The Chemistry of Heterocyclic Compounds, Small Ring Heterocycles (Part 3, Volume 42)

SMALL RING HETEROCYCLES - PART 3

This is the Forty-Second Volume in the Series THE CHEMISTRY OF HETEROCYCLIC COMPOUNDS

THE CHEMISTRY OF HETEROCYCLIC COMPOUNDS A SERIES OF MONOGRAPHS ARNOLD WEISSBERGER and EDWARD C. TAYLOR Editors

SMALL RING HETEROCYCLES Part 3

Oxiranes, Arene Oxides, Oxaziridines, Dioxetanes, Thietanes, Thietes, Thiazetes, and Others

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n 0

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S

Edited by

Alfred Hassner DEPARTMENT OF CHEMISTRY STATE UNIVERSITY OF NEW YORK AT BINGHAMTON and

BAR-ILAN UNIVERSITY, RAMAT-GAN ISRAEL

A N INTERSCIENCL@ PUBLICATION

NEW YORK

*

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JOHN WILEY AND SONS CHICHESTER BRISBANE TORONTO

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*

SINGAPORE

An Intcrscience@ Publication Copyright 0 1985 by John Wiley & Sons, Inc. All rights reserved. Published simultaneously in Canada. Reproduction or translation of any part of this work beyond that permitted by Section 1 0 7 or 108 of the 1976 United States Copyright Act without the permission of thc copyright owner is unlawful. Requests for permission or further information should be addressed t o the Permissions Department, John Wiley & Sons, Inc.

Libmry of Congress Cataloging in Publication Data: Main entry under title: Small ring heterocycles. (The Chemistry of heterocyclic compounds, ISSN 00693 1 5 4 ; ~42, . pt. 3- ) “An Interscience publication.” Includes indexes. 1 . Heterocyclic compounds. 2. Ring formation (Chemistry) I. Hassner, Alfred, 193011. Series: Chemistry of heterocyclic compounds; v. 42, pt. 3, etc. QD400 .S5 115 547‘.59 ISBN 0-471-05624-3 AACRZ

82-4790

The Chemistry of Heterocyclic Compounds The chemistry of heterocyclic compounds is one of the most complex branches of organic chemistry. It is equally interesting for its theoretical implications, for the diversity of its synthetic procedures, and for the physiological and industrial significance of heterocyclic compounds. A field of such importance and intrinsic difficulty should be made as readily accessible as possible, and the lack of a modern, detailed and comprehensive presentation of heterocyclic chemistry is therefore keenly felt. It is the intention of the present series to fill this gap by expert presentations of the various branches of heterocyclic chemistry. The subdivisions have been designed to cover the field in its entirety b y monographs which reflect the importance and the interrelations of the various compounds, and accommodate the specific interests of the authors. In order t o continue t o make heterocyclic chemistry as readily accessible as possible, new editions are planned for those areas where the respective volumes in the first edition have become obsolete by overwhelming progress. If, however, the changes are not too great so that the first editions can be brought up-to-date by supplementary volumes, supplements to the respective volumes will be published in the first edition. ARNOLDWEISSBLRGER Research Laboratories Eastman Kodak Company Rochester, New York

EDWARD c. TAYLOR Princeton University Princeton, New Jersey

Preface The chemistry of small ring compounds (three- and four-membered rings) has played a considerable role in the development of modern organic chemistry. Foremost among these reactive molecules are the small ring heterocycles. The presence of one or more heteroatoms in these strained rings imparts a measurable dipole moment to such molecules. It also adds a new dimension of intrinsic difficulty concerning the synthesis and stability of such heterocyclic analogs of cyclopropanes and cyclobutanes. If one considers the compressed bond angles (near 60" in threemembered rings and near 90" in four-membered rings), the mere synthetic challenge, especially for the unsaturated analogs of these heterocycles, seems enormous. Indeed, the small ring heterocycles possess much greater reactivity toward a variety of reagents than do their five- or six-membered ring analogs. The overwhelming amount of recent research literature in this field has made it necessary to divide this treatise on small ring heterocycles into several parts, with three- and four-membered rings sometimes interspersed. The current volume constitutes Part 3 in the series. Part 1 includes the three-membered rings containing one nitrogen or sulfur; thus it consists of chapters on Aziridines,Azirines, and Three-Membered Rings Containing Sulfur, which includes Thiiranes, Thiirenes, as well as their respective Oxides, Dioxides, and Onium salts. Part 2 is devoted largely t o four-membered rings containing nitrogen, for instance Azetidines, Azetines, Azetidinones (0-Lactams), Diazetidines, and Diazetines, as well as the three-membered ring Diaziridines. In this third part of the series the important group of three-membered rings containing oxygen, as well as four-membered rings containing two oxygens or one sulfur, are reviewed. Oxiranes, often referred to as Epoxides, are covered in the first chapter. They are among the most studied and stereochemically very valuable heterocycles. Recent advances in chiral epoxidation of olefins have made chiral oxiranes available as building blocks for important natural products. Unfortunately, coverage of the chemistry of oxiranes related to natural products is beyond the scope of this volume, and only the important basic features of oxirane chemistry can be dealt with here. However, a separate chapter on the biologically important arene oxides has been included. These compounds that undergo valence tautomerism with oxepins and that were unknown at the time of the 1964 edition of Three- and Four-Membered Rings Heterocycles now occupy an important role in understanding the metabolism of carcinogenic polycyclic aromatic compounds. The third chapter on Oxaziridines is an expos6 of this labile ring system containing both an oxygen and a nitrogen heteroatom and its equilibration with the isomeric nitrone system.

viii

Preface

Chapter 4 deals with the chemistry of the energyrich 1,2-dioxetane ring system; the isomeric 1,3-dioxetane systems still await exploration. The exploration of 1,2-dioxetane chemistry is also of recent vintage and the fact that they are cyclic peroxides explains their high reactivity. It is now established that such heterocycles are involved in bioluminescence. The final chapter involves the important chemistry of Four-Membered Ring Sulfur Heterocycles. This is a subject of considerable enormity. The subject matter covered includes not only the better known Thietanes and Thietes, but also the corresponding Sulfoxides, Sulfones, and cyclic Sulfonium salts, as well as the functionalized Thietanones, Iminothietanes, and Methylene-Thietanes. Furthermore, four-membered sulfur heterocycles containing additional heteroatoms such as N, 0, S, P, Si, and other elements, as well as selenetanes and telluretanes, are also discussed in this review. Specialists will appreciate the inclusion of four-membered ring sulfur compounds devoid of carbon, such as the dithiophosphonates (S2P2 ring system), which are useful in the preparation of thiocarbonyls, the S2N, ring system, and others. There has been a great deal of recent progress on regio- and stereoselectivity, as well as on photochemistry of these three- and four-membered rings. What is even more intriguing is their use as synthons for other functional groups as well as for larger ring heterocycles. Furthermore, there has been increasing interest in the biological properties and polymerization behavior of such molecules. An effort was made to briefly present the general state of the art and to emphasize research results of the past 15-20 years. Such an undertaking makes it necessary to be more selective than all-inclusive. Often it became more realistic to build on existing reviews of the subject. Editing this volume is especially meaningful to me because I had the privilege of being involved firsthand in the exciting explorations of some of these heterocycles during the past 20 years. I am indebted to the authors of the chapters for their splendid cooperation and patience and to my secretary, Joyce Scotto, for her invaluable help. Most of all, this book is devoted to my wife, Cyd, whose love has sustained me through this effort, and to the loving memory of our daughter, Erica, cruelly torn from us at a tender age.

ALFREDHASSNER Binghamton, New York September 1984

Contents 1.

1

OXIRANES M. Bartdk and K . L. Lbng

2.

197

ARENE OXIDES-OXEPINS Derek R. Boyd and Donald M. Jerina

3.

283

OXAZIRIDINES Makhluf J. Haddadin and Jeremiah P. Freeman

4.

1,2-DIOXETANES AND a-PEROXYLACTONES

35 1

Waldemar A d a m and Faris Yany

5.

FOUR-MEMBEREDSULFUR HETEROCYCLES

431

D. C. Dittmer and T. C. Sedergran Author Index

769

Subject Index

855

ix

Chemistry of Heterocyclic Compounds, Volume42 Edited by Alfred Hassner Copyright 0 1985 by John Wiley & Sons, Ltd.

CHAPTER I

Oxiranes M. BARTOK AND K. L. LANG

Department of Organic Chemistry, Josef Attila University, Szeged, Hungary

I. 11.

111.

Introduction . . . . . . . . . . . . . . . . Physical Properties of Oxiranes . . . . . . . . . . 1. Theoretical Models . . . . . . . . . . . . 2. Molecular Geometry . . . . . . . . . . . 3 . Energetics . . . . . . . . . . . . . . A . Heats of1:ormationandCombustion . . . . . B. Ring Strain . . . . . . . . . . . . . C. Ionization Potential . . . . . . . . . . D. Conformational Energy of the Oxirane Ring . . . 4 . Spectroscopic Properties . . . . . . . . . . A. Microwave Spectroscopy . . . . . . . . . B. IR Spectroscopy . . . . . . . . . . . C. UV Spectroscopy . . . . . . . . . . . D. NMRStudies . . . . . . . . . . . . a. Shielding, Chemical Shift . . . . . . . b. Coupling Constants . . . . . . . . . c. Shift Technique . . . . . . . . . . d. NMR in an Oriented phase . . . . . . . e. Resonance of Other Nuclei . . . . . . . 5 . Other Physical Measurements . . . . . . . . . A. Diffraction Measurements . . . . . . . . B. Raman Spectroscopy C. Dipole Moment Measurements . . . . . . . D. Optical Rotatory Dispersion . . . . . . . . E. Mass Spectrometry . . . . . . . . . . I;. Basicity . . . . . . . . . . . . . . G . Photoelectron Spectroscopy . . . . . . . . Synthesis of Oxiranes . . . . . . . . . . . . . 1. Oxidation of Alkenes . . . . . . . . . . . A . Oxidation with Organic Peracids . . . . . . B. Oxidation with Hydrogen Peroxide . . . . . . a. Oxidation with Alkaline Hydrogen Peroxide . . b. Oxidation with Hydrogen Peroxide and a Catalyst

1

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3 4 4 5 6 6 I

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8 8 8 8 9 10 10 11 11 12 12 13 13 13 13 14 14 14 14 15 15 15 25 25 29

2

Oxiranes C. D.

IV .

Oxidation with Organic Hydroperoxides . . . . . . . . Oxidation with Molecular Oxygen . . . . . . . . . . a . Oxidation with Oxygen with Metal Complex Catalysis . . . b . Oxidation withoxygen without aCatalyst . . . . . . E . Other Oxidation Methods . . . . . . . . . . . . . 2 . Preparation of Oxiranes from 1,2.Difunctional Compounds by 1,3. Elimination . . . . . . . . . . . . . . . . . . 3 . Preparation of Oxiranes from Carbonyl Compounds by Formation of Carbon-Carbon Bonds . . . . . . . . . . . . . . . A . Darzen’s Reaction . . . . . . . . . . . . . . . B . Reaction with Diazoalkanes . . . . . . . . . . . . C . Reaction with Sulfonium Ylides . Corey Synthesis . . . . . . D . Other Oxirane Syntheses . . . . . . . . . . . . . Reactions of Oxiranes . . . . . . . . . . . . . . . . . 1. Deoxygenation . . . . . . . . . . . . . . . . . 2 . Rearrangements and Isomerizations . . . . . . . . . . . A . BaseCatalyzed Rearrangements . . . . . . . . . . . B . AcidCatalyzed Rearrangements . . . . . . . . . . . C . Rearrangements Induced by Heterogeneous Catalysts and Metal Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . D . Other Rearrangements 3. Oxidation . . . . . . . . . . . . . . . . . . . 4 . Reduction . . . . . . . . . . . . . . . . . . A . Reduction with Metal Hydrides . . . . . . . . . . . B . Dissolving Metal Reduction . . . . . . . . . . . . C . Catalytic Hydrogenolysis . . . . . . . . . . . . . 5 . Ring Transformation of Oxiranes into other Heterocyclic Compounds . A . Ring Transformation into other Three-Membered Heterocycles . . B . Ring Expansion into Four-Membered Heterocycles . . . . . C . Ring Expansion into Five-Membered Heterocycles . . . . . D . Ring Expansion into Six-Membered Heterocycles . . . . . . 6 . Reaction with Organometallic Compounds . . . . . . . . . A . Reaction with Grignard Reagents . . . . . . . . . . B . Reactions with Alkylmagnesium and Alkylaluminium Compounds . C . Reaction with Lithiumdiorganocopper Reagents . . . . . . . . . . . . . . . D . Reaction with Alkyl- or Aryllithium E . Reaction with other Organometallic Compounds . . . . . . 7 . Other Reactions involving C - 0 Bond Opening . . . . . . . . A . Hydrolysis . . . . . . . . . . . . . . . . . R . TrazsfQrrr?ationswithAlroholsandPhenols . . . . . . . C . Transformations with SulfurContaining Nucleophiles . . . . D . Reaction with Halogen Acids . . . . . . . . . . . . E . Reaction with Carboxylic Acids and their Derivatives . . . . . I;. Reaction with Ammonia, Amines, and their Derivatives . . . . G . Miscellaneous . . . . . . . . . . . . . . . . 8 . Photochemistry . . . . . . . . . . . . . . . . . A . Alkyloxiranes . . . . . . . . . . . . . . . . B . Unsaturated Oxiranes . . . . . . . . . . . . . . C . Epoxyketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . a . a$-Epoxyketones b . P, y-Epoxyketones . . . . . . . . . . . . c . a$-Unsaturated y,6 -Epoxyketones . . . . . . . . D . Salts and Esters of Arylglycidic Acids . . . . . . . . . E . Aryloxiranes . . . . . . . . . . . . . . . .

30 34 34 36 38 40 47 47 51 52 54 57 58 61 62 65 71 75 76 77 78 83 83 87 87 88 90 96 98

99

101 106 110 113 115

118 119 120 121 122 123 125 126 127 129 131

131 136 139 140 141

Introduction Thermally Induced Reactions . . . . . . . . . . . . A. Alkyl- and Alkenyloxiranes . . . . . . . . . . . B. Oxiranes Containing a Croup Stabilizing the Ylide Intermediate. a. Aryl-Substituted Oxiranes . . . . . . . . . . b. Alkenyl- and Alkynyloxiranes . . . . . . . . . C. Miscellaneous . . . . . . . . . . . . . . . 10. Polymerization . . . . . . . . . . . . . . . . Abbreviations . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . .

9.

V. VI.

I.

3

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145 145 146 146 147 150 151 152 152

INTRODUCTION

The synthesis and chemical reactions of cyclic ethers with 3-6 ring atoms have been subjected to wide-range study. The class name for the three-membered ring monocyclic ethers is oxiranes. To preserve the name of a specific complex structure, the prefix epoxy is used in the substitutive nomenclature. Additive nomenclature is still used for oxiranes when they are described as the oxides of unsaturated compounds (ethylene oxide, styrene oxide). To describe oxirane formation, the expression epoxidation is still used instead of the more correct oxiranation. By virtue of the relative ease of their preparation and their readiness to undergo many kinds of reactions, the oxiranes stand out, and, are accordingly, thc oxacycloalkanes of most practical importance. The main task of this review is to present an account of the synthesis and most characteristic properties of the oxiranes. We shall deal mainly with the formation and chemistry of the oxiranes without going into details into the synthesis and reactions of oxiranes containing other functional groups.

(oxirane) (ethylene oxide)

The older literature on the synthesis and chemistry of the oxiranes was reviewed very systematically and in great detail by Rosowsky,' in a 1964 monograph that appeared in the series, The Chemistry of Heterocyclic Compounds. This was rapidly followed by two additional general reviews of the subject.233 Interest in the chemistry of the oxiranes did not wane in the 1970s, as indicated by the publication of several more monographs!-7 The most recent comprehensive survey of oxiranes was published in the series, The Chemistry of Functional Groups.8 Of the monographs that have appeared in the past two years, only those that give a more general account of the oxiranes have been mentioned. In the following section, we describe the reviews of individual special areas relating to the preparation and reactions of the oxiranes. Since some of the above monographs give a detailed treatment of the earlier results but merely touch on the more recent ones, we attempt to present the

Oxiranes

4

tremendous development now taking place in the chemistry of the oxiranes on the basis of experimental data mainly reported in the past few years (up to the end of 1982). Regarding results published after 1964, only those that are of a more general nature and those that were not dealt with by previous reviews for various reasons will be mentioned. Every year, a huge number of publications on oxiranes appear in the literature. As a consequence of the rapid development in synthetic methods, the investigation of chemical reactions, and hence utilization of oxiranes, oxiranes occupy a central position among cyclic organic compounds. For the above reasons, it is difficult to achieve completeness. We apologize in advance if we have inadvertantly omitted reference to work that the reader feels should have been included.

11. PHYSICAL PROPERTIES OF OXIRANES 1.

Theoretical Models

Because the oxirane contains a strained ring consisting only of two carbon atoms and one oxygen atom, a series of theoretical calculations and physical measurements have been performed in order to determine the exact molecular structure. The simplicity of the molecule permits the rather complex quantum-chemical calculations. It follows from the strained nature of the ring that it is a rigid one; good comparisons may therefore be made between the geometric data obtained via the various spectroscopic and other physical methods. The strain in the three-membered ring is one of its most important properties. It is also the basis of the explanation of many of the features of the molecule, for example, the high reactivity in ring-opening reactions and the low electron-donor ability. These properties can be explained in terms of the hybridization of the bonding and nonbonding electron orbitals and the angular strain in the transition state. A short account of the MO model with reference to the oxiranes is found in the work of Rosowsky.' The ground state and low excited state of the oxirane molecule have been described by a semiempirical SCF-MO method.' A b initio FSGO calculations have confirmed the chemical experience that the C-C bond displays an increasing tendency to bend the shorter the bond length, while the C-C bond is more flexible than the C-0 bond." An ab initio MO method in combination with the MollerPlesset perturbation theory (MP3) gives the result that, of the three C2H40isomers, acetaldehyde and vinyl alcohol (45 kJ/mol) are much more stable than the highenergy oxirane (1 14 kJ/mol). The ionization and excitation energies of oxirane together with its electron affinity have been calculated with a semiempirical HAM/3 method; the results fit well with those obtained from the electron spectrum." The structures and energetics of the possible C2H40 isomers have also been calculated via STO-3G and 4-31G programmes;" these data conform well with those derived from the rotation ~ p e c t r u m . ' ~

Physical Properties of Oxiranes

5

For substituted oxiranes, the effect of the substituent on the electronic structure of the ring has been computed with the CND0/2 method on the basis of orbital h y b r i d i z a t i ~ n . ' ~ .The ' ~ calculations revealed that the C-C bond is stronger than the C - 0 bond and that the C-0 bond is weaker when it is adjacent to a substituent. The computed dipole moment, total energy, electron configuration, and bonding energy are in good agreement with the experimentally found data. Quantummechanical studies on the triplet-state isomeric methyloxiranes have been d e s ~ r i b e d . lSb '~~~ In the past ten years, many investigations and theoretical calculations have been made with regard to the chemical nature of the bent bond. In contrast with molecular orbital theory, classical theory considers the bent bond to be connected only with the localized bond or the bond orbital. The Foster-Bogs method has been employed for the indirect generation of the localized orbitals and the resulting l7 orbitals have subsequently been analyzed from the aspect of the bent The FSGO (floating-spherical-Gaussian orbital) rnethodl8 in an ab initio computation procedure results in direct bond orbitals without base functions restricted to the atoms. When the degree of bond bending was calculated with this method, the following results were obtained:" 1. The C-C bond orbitals are more diffuse than in the similar unstrained systems. 2. The degree of bending of the C-C bond is in a simple correlation with the bond length. 3 . The C-0 bond is less flexible than the C-C bond. 4. The center of the C - 0 bond can be well followed via the electronegativity difference. 5. The computation does not lead any closer to the factors influencing the C-H orbitals adjacent to the ring. Reference will be made in the relavant subsections to the calculations necessary for a theoretical interpretation of the results of the individual experimental methods (microwave, photoelectron spectroscopy, nmr data, etc.).

2.

Molecular Geometry

A consequence of the rigid molecular skeleton is in close agreement with molecular geometry data obtained by different procedures. Information on the exact bond lengths and bond angles is provided primarily by microwave spectroscopy, electron diffraction, and, more recently, the nmr spectrum in the liquid-crystal phase. A fuller survey of the individual methods will be given in the appropriate sections; here, only the geometric data yielded by the various procedures are listed (Table 1). All of the measurements clearly demonstrate that the plane of the hetero-ring is perpendicular to the plane defined by the four hydrogen atoms. The two carbon atoms of the ring are symmetrically raised above the plane of the four hydrogen atoms.

Oxiranes

6 TABLE 1.

GEOMETRIC DATA OF THE OXIRANE RING MEASURED BY DIFFERENT METHODS

Reference 19

20

21

1

13

P

1.54 1.43 1.05 6 7" 51" 26'

7

-

1.472 1.436 1.082 6 1" 24' 59" 18' 159'25' 116"41'

1.4728 1.4363 1.0802 61"41' 59"9' 158'5' 116"51'

1.47 1.44 1.08 6 1"24' 59" 18' 158'6' 116' 15'

1.483 1.433 1.088 62.3" 58.85" 155.3" 114.5"

c-c c-0

C-H CY

6

117"28'

The C-C bond distance lies between those for a single (1.548) and a double (1.33 8) bond; similarly, the H-C-H bond angle lies between those for tetrahedral (109'28') and trigonal (120') bonding.13 The same situation is observed for the C-C-C bond angle in the event of substitution:

CH, r/ H2C=CH

CH3 f-1

H,C-CH2

1 12.4°22

CH3 7' HpC-CH

1 24.8°23

'd

121OZ4 1 1 8 * 3""

This suggests the model in Ref. 1, in which the two carbon atoms are apparently elevated above the plane of the four hydrogen atoms in response to the presence of the oxygen atom (in olefins the two caiboii atoms !is in thc plane of the hydrogen atoms).

3. A.

Energetics

Heats of Formation and Combustion

The stability of the three-membered ring is surprising, particularly if the bond angles are considered and the situation is further complicated by the nature of the nonbonding H-H interactions.26 The heats of formation and combustion of oxirane are given in Table 2 and are compared with those of higher homologues.

I

Physical Properties of Oxiranes TABLE 2.

Oxirane Oxetane Oxolane Oxane

HEAT OF FORMATION AND COMBUSTION O F OXIRANE AND ITS HIGHER HOMOLOGUES Heat of Formation" (kJ/mol)

Heat of Combustion'* (kJ/mol)

117.2

114.1 106.7 23.6 4.9

-

28.0 9.2

B.

Ringstrain

An examination of oxirane ring strain" showed that it depends primarily on the structure of the ring and its basicity. The ring-strain energy has been calculated as the difference between the experimental heat of formation (obtained from the heat of combustion) and the calculated total bond energy. The results for various ring systems are listed in Table 3." In a study of the ring strain relating to ring-opening with a secondary amine (dibutylamine) in an aprotic solvent,30 it was found that the reactivity of methylthiirane is greater than that of methyloxirane. C.

Ionization Potential

Photoionization indicated an ionization potential of 10.565 eV,31 which is in excellent agreement with the value of 10.5 eV calculated from the UV ~ p e c t r u m . ~ ' The oxiranes have higher ionization potentials than that observed for dimethyl ether (10.0 eV);33 this demonstrates the less effective nature of the delocalization of the 2p n-electron pair in the case of oxirane than in simple ethers. Support for this is provided by the experimental fact that the oxiranes exhibit a charge shift from the oxygen towards the carbon atoms,34which may cause an increase in the ionization potential of the 2p n-electron pair. Mass spectrometric measurements have been used to calculate the energy profile of the cation C2H50+.33Cleavage of the C-C bond here requires about 61 kcal/mol more energy than the corresponding C-0 ring-opening. This finding is supported both by theoretical calculations on oxirane and by the experimental facts.34i35 Furthermore, the C-0 bond rupture is favored not only in the ground state, but in the various excited states. TABLE 3 .

RING-STRAIN ENERGY OF OXIRANE AND ITS ANALOGUES Ring-Strain Energy (kJ/rnol)

Cyclopropane Aziridine Oxirane Thiirane

104.7 58.6 54.4 37.7

Oxiranes

8

The structures and formation enthalpies of the three ions CzH4O' have been determined;36-38 at the same time, the mass spectrometric measurements revealed that there is a fourth such ion, with a formation enthalpy of 202-205 kcal/mol, which is probably a product of rupture of the C-C bond.39

D.

Conformational Energy of the Oxirane Ring

Theoretical studies have indicated that the oxiranes display similar properties to compounds containing a double bond. For instance, the conformational energy of the A ring of 2,3-epoxylanostane is analogous to that of c y c l ~ h e x e n e . ~ ~ Dipole moment measurements have shown that, of the possible conformers of l-tert-butylpiperidine-4-spiro-2'-oxirane (l), the axial-0-conformer is preferred (1.1 kJ/mol). The conformational energy of the corresponding thiirane compound is 1.8 kJ/rnol more favorable than when the heteroatom is equatorial.

From nmr studies, a value of 1.13 kJ/mol was determined in the case of the cyclohexane deri~ative.~'

4.

Spectroscopic Properties

A.

Microwave Spectroscopy

This technique can be used extremely well to determine the geometry of the oxiranes. As long ago as the 1940s it was utilized in combination with dipole measurement to establish the bond lengths and bond angles in various substituted oxiranes. Simiiar data are found in the iiterature on deuterium-substituted o ~ i r a n e . ~ ~ ~ ~ ~ By means of microwave measurements, the ro, rs, and rm structures of oxygencontaining heterocycles have been determined.I3 The structure of 1,2difluorooxirane has been investigated via microwave spectroscopy from the aspect of fluorine ~ubstitution?~

B.

IR Spectroscopy

Oxirane exhibits three intense IR bands at 1265, 1165, and 865 cm-' 44,45 the last of which is the asymmetrical ring-stretching vibration. The overlapping ~

Physical Properties of Oxiranes

9

band at 1250 cm-' can be regarded as characteristic of the oxirane This band is probably attributable to the symmetrical stretching vibration. Steroid oxiranes do not yield the 1250cm-' band, but bands are observed at 900-800cm-' for some and at 1050-1035 cm-' for others.47If the oxirane ring is terminal, sharp bands are found at 910 and 840cm-' for fatty acids. With nonterminal oxirane rings, the absorption band is at 890cm-' for the trans compounds and around 830cm-' for the cis isomers.48 Perdeuterated ethylene derivatives have also been investigated in detail4' and the individual fundamental vibrations have been calculated. A review of the IR frequencies of the three-membered heterocycles is found in Katritzky and Ambler.49 The IR frequencies were more recently studied by Potts." Georges1 recorded the IR spectra of 16 straight-chain oxiranes for analytical purposes and reported their refractive indices too. IR (4000-200 cm-') and Raman spectra have been taken in the solid and the liquid phases for the conformational examination of alkyl-substituted o x i r a n e ~Studies . ~ ~ ~ have ~ ~ been made of the steric structure of oxirane-car box aldehyde^'^ and the low-temperature oxidation of cyclo.~~ have been carried out on the IR hexene in the presence of Co"' c h e l a t e ~Analyses spectra of oxiranes in the region of 850cm-' and the vibrational energy levels.56 Steroid oxiranes have likewise been subjected to IR investigation." Hirose13 published the rotational spectra of 10 oxiranes together with their evaluation and, in conjunction with the microwave spectra, determined the r,,, r,, and r , structures of the compounds. Bellamys8 and Jones et al.s9have made excellent surveys of the IR frequencies of substituted oxiranes. In these compounds, two fundamental effects may be differentiated: one involves changes in the vibrations of the oxirane ring by the action of the substituents and the other involves the effect of the oxirane ring on the absorption bands of the functional groups of the substituents. Rosowsky' gives a good account of the variations in the ring frequencies of oxiranes as the substituents are changed. In general it may be said that there is not a close correlation between the position of the oxirane band and the stereolectronic factors, which is primarily indicative of the determining role of the strained ring. In the second case, an important role is played by the absorption bands of an aromatic or olefinic functional group in conjugation with the oxirane ring. Since the oxirane ring has properties intermediate between those of a saturated function and an olefin, it is expected that the stretching frequency of a carbonyl group in the case of an (YJepoxyketone will lie between the frequencies for the corresponding saturated and a,P-unsaturated ketones. The concentration of an oxirane can be determined in the gas phase by the IR bands.60 Terminal oxiranes can be estimated with an accuracy of 1-2% in CC14 solution, via the bands at 6061 and 4545 cm-'.61

C.

UV Spectroscopy

Oxygen-containing heterocyclic homologues of ethers exhibit two absorption bands, with the exception of oxirane which has only one absorption maximum at

Oxiranes

10

1713cm-'. At the same time, its ionization potential (10.565eV) is higher than that of dimethyl ether (10.0eV) (see Section II.3.C.). The energy of the difference between the absorption bands for the higher cyclic ethers almost corresponds to this energy and thus it is probable that the lone p electrons are equally stabilized in oxirane, presumably by hyperconjugation with the methylene groups.62 values of substituted oxiranes are surveyed by Rosowsky.' In the The, , ,A majority of UV spectra of these systems, the conjugative effects are examined, which gives a reflection not of the ground state, but of the excited state. Accordingly, a comparative measurement is advisable, with a joint study of the corresponding olefins and cyclopropanes. Investigations of the UV spectra63 and acidities of substituted oxiranes and cyclopropanes have revealed that conjugation occurs in both systems and specific orientation of the cyclopropane ring is not necessary. This appears to refute the earlier assumption that a specific orientation is required for conjugation of the oxirane ring.@ The conjugative ability may be explained by the negative charge of the oxygen in the excited state, which is neglected in the ground-state calculation^.^^ D. a.

Nrnr Studies

SHIELDING, CHEMICAL SHIFT

In the nmr spectrum of oxirane,66 the protons /3 to the oxygen display a small chemical shift compared to that of the /3 protons of larger cyclic ethers; this can only be explained by the shielding effect of the abnormal electron density, which assumes a low electron density around the oxygen, as suggested earlier on theoretical grounds. The proton chemical shifts for various substituted oxiranes are given in a number of reviews and The oxirane ring exhibits similar anisotropy to that of cyclopropane. The literature contains only a single example of intense shielding above the ring: the chemical shift of proton 14 in 15/3,16/3-oxidobeyeral is found at 0.6ppm.69 Anisotropic shielding effects on the 19-methyl protons of steroids with the oxirane ring in various positions are listed by Tori.70The chemical shifts correspond quantitatively to the ring current model; however, their values are rather small, and it is necessary tc take inte ccnsideratim the canfanrr?,atiana! change occwring i ~ ?the sixmembered ring and the fact that an appreciable solvent effect can be observed even in chl~roforrn.~' Tabulated compilations of the chemical shifts of the protons in oxiranes are - ~ ~ structural conclusions are rarely drawn frequently found in the l i t e r a t ~ r e , ~ ' but from the chemical shifts as the coupling constant is a more exact means of establishing the configuration. Configurations and conformations of oxiranes derived from prostaglandin intermediates have been determined from 'H shifts with the aid of the ring current In phenyloxiranes, the protons adjacent to the aromatic ring absorb at lower field than the cis and truns protons. This low-field shift can be interpreted in terms of the ring current of the phenyl In 1,2-diphenyloxiranes there is resonance at lower field for the cis isomers. The effect of this has been calculated on

Physical Properties of Oxiranes

11

the basis of the ring current,79 but a quantitative description of the phenomenon has not succeeded.80 The phenyl ring conformation has been investigated on the same basis for many substituted oxiranes." Consideration was paid to the steric factors and solvent effects. The results agree well with the experimental proton shifts. In the oxides of styrene, stilbene, and stilbazole, the chemical shifts of the cis protons of the oxirane ring are larger than those for the trans isomers. This can be explained by the polarization effect of the electric dipole moment of one of the CH protons on the other CH.80 The anisotropc shielding of the ring in the case of oxiranes substituted with an aromatic group can be utilized well in the determination of the configuration.82 b.

COUPLING CONSTANTS

The most important datum that can be determined from the nmr spectrum of an oxirane is the coupling constant. Since the spectra are generally complicated and contain an ABM or ABX multiplet that cannot be interpreted directly, computer simulation is necessary. Abundant data on the coupling constants are to be found in the reviews referred to in Section I1 .4.D.a.67'68 MortimerE3 has determined the coupling constants in the various threemembered rings; these are listed in Table 4. It may be stated generally that the cis vicinal coupling constant is larger than that in the corresponding trans case.84This is in contrast with what is experienced for the larger rings, where Jmns >Jcis.67 The coupling constants strongly suggest the half-chair conformation in the 2,3and 3,4-anhydropyranosides, in which the conformational effect of the oxirane ringa5 is similar to that of a double bond (2,3-unsaturated pyranoside derivatives).86 The 13C-'H coupling constant can be determined from the I3C satellites of the proton spectruma7and from the 13C spectrum.83 c.

SHIFT TECHNIQUE

The occurrence of an appreciable solvent effect was observed for spectra of o x i r a n e ~ . Substituents ~~ can be distinguished by the benzene-induced shift Oxiranes can be studied well with the aid of lanthanide shift reagents since they are strong complex-formers. Primarily, the change in the chemical shift is informative since the coupling constant can generally not be determined as a consequence of signal b r ~ a d e n i n g . ~ ~ - ~ ' Chiral shift reagents are conveniently applicable to establish optical purity;'-" whiie the europium complexes are useful in determining oxirane configuration~.~'-~~ TABLE 4.

Oxirane Thiirane Aziridine

PROTON COUPLING CONSTANTS IN THREEMEMBERED HETERO-RINGS Jcis

Jtrans

Jgem

4.45 7.15 6.3

3.1 5.65 3.8

5.5 0.4 2.0

Oxiranes

12

d.

NMR IN AN ORIENTED PHASE

For molecules dissolved in a nematic thermotropic liquid-crystal, the direct coupling constants can be determined and from these the molecular geometry can be calculated. If the 13C satellites are determined, not only the proton structure but the carbon skeleton of the molecule can be established. Oxirane has been measured in two l a b o r a t o r i e ~ .It~ ~ proved ~ ' ~ possible to determine the orientation, the sign of the indirect coupling constant, and the geometry. Enantiomers can readily be determined by recording measurements in optically active liquid-crystals as solvents."' e.

RESONANCE OF OTHER NUCLEI

The 19F nmr spectra of the fluorine-substituted oxiranes have been reasonably well studied, for in the region of high chemical shifts, the fluorine nuclei readily yield spectra that can be interpreted directly. A further principle is that the longrange coupling constants can be measured well because of the large nature of the c ~ n s t a n t s . ' ~ ~In- 'the ~ ~ case of a fluorinated substituent, the linear Taft correlation may be used to determine the inductive and resonance substituent constants.lo6 In 31P nmr measurements, good use may be made of the fact that the stereospecificity of the P-C-C-H coupling is well d o ~ u m e n t e d . " ~For example, 2 and 3 can readily be differentiated on the basis of the 31P-1H coupling:'08 for 2 3Jp-C-C-H = 4.5 Hz, and 3 3Jp-c-c-H = 5 . 3 Hz.

0 MeO,; M e

0

0

H

o

/

~

MeO, 11 Ph MeOy'H

~

Ph

H O H 3

2

The resonance of the I3C nuclei may be employed extremely well in studies of oxirane structures.'09-"' Fr om the 13C spectra for 61 oxiranes an additivity rule was formulated for the chemical shifts.l12 Some examples are given in Table 5 . The conformation of cycloheptene oxide has been examined via the 13C nmr spectra of deuterated compounds on the basis of the temperature-dependence of the chemical shifts of the individual signal^."^ In phenyl-substituted oxiranes, the 13C shifts have revealed the inductive and hyperconjugative effects of the oxirane ring, and thus the ring behaves as an electron-accept~r."~ 'H-13C coupling constants have been measured for three-membered heterocycles and it has been observed that the coupling constant increases in the following TABLE 5.

_________

CHEMICAL SHIFTS OF OXIRANES IN PPM

~~

~

Compound

C-1

C-2

Ethylene oxide 1,2-Epoxypropane 1,2-Epoxypentane 1-Phenyloxirane 1,l-Diphenyloxirane

40.8 47.8 46.8 52.2 61.7

48.0 52.0 50.9 56.1

-

Physical Properties of Oxiranes

13

sequence: 0, N, S, CX2. This sequence correlates with the increase in the C-C bond length .l From the 13C nmr data on 42 aliphatic oxiranes, an additivity relationship has been derived for calculation of the chemical shifts.116An nmr investigation has been described on the addition products of indene derivatives and singlet oxygen.'0g Good reviews of the 13C nmr data may be found in the following references and in the papers cited thereir~.I'~-'~' Ex0 and endo oxiranes of bicyclo[2.2.l]heptane can be well differentiated on the basis of their 13C spectra.122 The effect of the molecular asymmetry on the chemical shift of the carbon in 0- and N-glycidyl compounds has been investigated.'23 In the study of stereoisomeric epoxyspirocyclohexane derivatives, the effects of the equatorial and axial oxiranes have been observed on the carbon atoms of the cyclohexane ring.'24 Relatively few publications have appeared on 1 7 0 measurements. The I7O chemical shifts have been measured for 21 oxiranes and compared with the corresponding 13C shifts.12' The results could be interpreted on the basis of the paramagnetic p and the diamagnetic y effects.

''

5.

Other Physical Measurements

A.

Diffraction Measurements

l-p-Bromophenyl-'26 and l - p - n i t r ~ p h e n y l - 'substituted ~~ oxiranes have been examined by x-ray diffraction. The dihedral angle between the phenyl ring and the oxirane ring was found to be 83" and 80.2", respectively. This can be explained through the pseudoconjugational interaction of the two rings.

B.

Raman Spectroscopy

The differences between the IR and Raman spectra were examined as long ago as the 1 9 3 0 ~ . ' ~ ~M1o' u~ s~~ e r o n 'later ~ ~ performed measurements on many oxiranes and identified the individual vibration bands. More recently, the results of solid-, liquid-, and gas-phase studies on the Raman spectra of a l k ~ l and - ~ ~vinyl-53substituted oxiranes have been reviewed.

C.

Dipole Moment Measurements

Oxirane has a higher boiling point (10.5") than cyclopropane (- 32.9"), which indicates its more polar character. Its dipole moment has been determined by numerous authors via the dielectric constant (e.g., R e f ~ . ' ~ l - ' ~ and ~ ) the Stark effect.40 The results agree well: 1.9D. The structures of aryl-substituted oxiranes have also been determined by means of dipole moment measurements.'34

Oxiranes

14

D.

Optical Rotatory Dispersion

The oxirane ring has been found to exhibit an ORD curve at 290 nm; this has the opposite sign to that of the alkyl

E.

Mass Spectrometry

The ring-opening modes have already been discussed in connection with the ionization potential of the oxirane ring (see Section 11.3).Mass spectrometric books present a detailed treatment of the properties of ~ x i r a n e s . ' ~ ~The - ' ~ ~individual fragmentation patterns have also been subjected to detailed discussion on the basis of the high-resolution mass spectra.I3' In the mass spectra of the oxiranes of terminal and nonterminal alkenes, the following characteristic fragments have been found: M-29,M-43,M-57.I4O A similar result emerged from more recent measurements, in the course of which the mass spectra of 16 straight-chain aliphatic oxiranes containing 7-1 2 carbon atoms were recorded." The mass spectra of 12 substituted methyloxiranes and 15 substituted 1,2-diphenyloxiranes have been compared with those of the corresponding aldehydes from the aspect of fragmentati~n.'~'It could be established that the oxirane fragmentation either gives rise to a symmetrical ion through the direct loss of one mole of aldehyde or ketone, or the molecular ion undergoes rearrangement to an isomeric carbonyl radical ion. Fragmentation of oxiranes has also been studied by chemical i o n i z a t i ~ n . 'In ~ ~the mass spectra of simple oxiranes, the fragmentation does not indicate electron-impact-induced isomerization towards a 1 d e h ~ d e .Even I ~ ~ radicals with lifetimes shorter than IO-'sec have been detected in the impact-activation mass spectra of oxiranes.'@ F.

Basicity

The basicities of cyclic ethers have been investigated widely, as they provide infermation not only on the natiure of the chemical reactions hut o n theoretical questions as well. Earlier monographs may be consulted for analyses and conclusions relating to the relevant

G. Photoelectron Spectroscopy From the photoelectron spectra, it is possible to calculate the ionization potential (see Section II.3.C). Ab initio SCF calculations145 have been used to ascribe the individual transitions in the photoelectron spectra of the 0 ~ i r a n e s . I ~ ~ The photoelectron spectra of halomethyloxiranes have also been p ~ b 1 i s h e d . l ~ ~ The photoelectron spectra have been utilized as the basis of a study of the effects of mono- and dialkyl, halomethyl, phenyl, and vinyl substituents on the

Synthesis of Oxiranes

15

ionization potentials of 0 ~ i r a n e s . lA~ halogen ~ substituent in the methyl group of methyl oxirane stabilizes all of the levels and increases the ionization potential. In methyl- and halomethyl-oxiranes, the ionization potentials of all four oxirane-type orbitals correlate with the electronegativity of the substituent. It may be concluded from the resulting linear correlation that inductive and hyperconjugative effects are manifested jointly in the oxiranes.

111.

SYNTHESIS OF OXIRANES 1.

Oxidation of Alkenes

In both the synthetic organic laboratory and industry, the first and foremost procedure for the preparation of oxiranes is the direct oxidation of alkenes. Significant new results have been achieved in the development of methods of oxidizing alkenes in the liquid phase. The major aim is the attainment of an oxidation reaction under the mildest possible experimental conditions, which allows an increase in the selectivity of oxirane formation and permits the selective oxidation of more sensitive compounds. Since the various methods of preparing oxiranes were reviewed quite recently,' the individual oxidation procedures will be mainly illustrated here with some more recent examples. Surveys concentrating on stereocontrolled epoxidations and assymmetric synthetic methods have been published.8ai'bisc

A.

Oxidation with Organic Peracids

The most frequently employed method for the conversion of alkenes to oxiranes is oxidation with organic per acid^.'>^^ 149-151a Th'is procedure was discovered by Prileshaev in 1909.152The usual oxidants are perbenzoic acid and its substituted derivatives, but aliphatic acids are also used, predominantly in industrial syntheses. It will be seen that the range of organic peracid derivatives is being increasingly extended with compounds in which there is an -0OH moiety in conjugation with a C=O or C=N, for example, 4 , 5 , and 6 . The oxidant is prepared from the corresponding acid by the addition of hydrogen peroxide; in preparations from weaker acids, the presence of catalytic amounts of mineral acids is sufficient. Because of the ease of decomposition of the perdcid, the latter is often prepared from the appropriate reagent in situ by the addition of hydrogen peroxide.

NH II

-C -0-0-H 4

0 It -NH-C-0-0-H 5

0

II

-0-C-0-0-H 6

Oxiranes

16

Of the percarboxylic acids, commercially available m-chloroperbenzoic acid (MCPBA) is generally the most favored; it is sometimes used at high temperatures in the presence of a radical inhibitor'53 and the yield may be increased with peracid stabilizer^.'^^ Inert solvents such as CH2C12, CHC13, and benzene are most commonly employed in the reaction Eq. 1. In basic solvents, the reaction rate decreases in proportion to the rise in basicity. With acid-sensitive olefins and in the preparation of acid-sensitive oxiranes, buffers are utilized; recent work involves the advantageous use of an alkaline two-phase solvent.'55

R-CH=CH2

+

P--o-o-H CHCI,

0

c1

R\/

(1)

0

Oxidation with the peracid is an electrophilic addition in which the driving force is provided by the electron-donor nature of the double bond and the electronacceptor nature of the -C020H group. The alkene is the nucleophile, the peracid is the electrophilic partner, and in the final step of the reaction, the peroxidic oxygen behaves as a nucleophile too. The reaction mechanism depends on the electrophilic or nucleophilic strengths of the two reactants. Quantitative studies have been performed on the basis of the linear free-energy correlation of the reaction rate and the structure of the alkene.lS6 Numerous authors have dealt with the role of the solvent in the r e a ~ t i o n . ' ~ ~ - ' ~ ' Even today, however, the fine details of the reaction mechanism have not been clarified in every respect. A stepwise mechanism is disproved by the stereochemical results. Oxygen transfer from the intermolecularly hydrogen-bonded peracid monomer'61 and 1,3-dipolar addition with a 1,2-dioxolane i r ~ t e r r n e d i a t e ' ~ ~are :'~~ not confirmed by the experimental results. Investigations have been carried out in solvents of various polarities and structures in order to shed light on the structure of the transition complex.'64 A kinetic isotope effect has led to the proposal of an open-chain structure 7 with strong charge separation, from which the rate of ringclosure is greater than that of rotation about the C-C axis.'65

7

Dryuk'66 attempted to solve the existing contradictions by performing wideranging reaction-kinetic examinations. The results of these can be summarized as follows: the course of the reaction, which is in competition with the formation of H-bonded complexes, is governed by the nature of the electron-donor-acceptor complex (EDAC) formed between the alkene and the peracid. The entire process is influenced by solvation effects. Oxirane formation is accompanied not only by the direct formation of a rearranged product, but by the induced decomposition of the peracids (Eq. 1a).

:'

Synthesis of Oxiranes

,+c, \

---H-0-0

\/

Ar-C-0-0-H

It

0

+

C II C

EA !c{

/\

0

C-Ar

' !I

- 'd4 ,

,C-C,

17

/

(1 a)

other transformation

In contrast with other electrophilic additions, the peracid epoxidation is synstereospecific. With sterically strongly hindered alkenes the reaction takes place on the less sterically hindered side. In other cases, the stereochemistry of the reaction is affected by polar effects or the geometry of the transition state. Important conclusions regarding the mechanism of the reaction can be drawn from the steric pathways in the synthesis of the oxiranes. This has been dealt with comprehensively by Berti? who reviewed the topic up to 1971, with special emphasis on the peracid oxidation. A noteworthy account of the topic of peracid epoxidation is given in a review by Rebek.& Ab initio molecular orbital studies have been carried out on the mechanism of epoxidation of alkenes with p e r a ~ i d s . ' ~Numerous ~ ~ ' ~ ~ examples have been reported of the formation of products where the stereochemistry differs from the known general regularities; some characteristic instances of these will be presented below.

T w o products, 13%

The stereoselective oxidation of cis- and trans-3-tert-butyl-4-cyanocyclohexenes can be explained on the basis of the energetic data and the geometry of the conformers Eq. lb.'69 An unexpected product is formed as a consequence of neighboring-group parti~ipation.'~'The syn directing effect of the methoxycarbonyl group is manifested in the epoxidation of adjacent double bonds in dihydrophthalates, the main product being 8.17'

W'-COzMe

b'

8

Oxiranes

18

In the case of a sterically hindered allylic methoxycarbonyl group, the epoxidation of substituted cyclohexenes-1,4-dienes occurs on the opposite side.'72 Further studies on the epoxidation of 0,y-unsaturated cyclohexenecarboxylic acids and esters indicate that the steric and polar effects of the COzMe group result mainly in anti-epoxidation while the carboxyl group in inert solvent exerts a syn directing effect . 73

'

OH

I

9

The direction of MCPBA epoxidation changes from syn to anti between the small ring (n = 2, 3) and the medium ring (n = 4) allylic alcohols 9.174The change from syn to anti direction is explained in terms of Witham's model for the transition-state geometry of peracid ep~xidation.'~'

10

Epoxidation of acyclic allyl alcohols with peracid and Mo/TBHP displays an opposite stereospecificity to that for the V/TBHP s y ~ t e m . ' ~ ~Trimethylsilyl''~~ substituted allylic alcohols give threo-epoxyalcohols with MCPBA and eiythroalcohols with VO(acac)2-TBHP, with high s t e r e o ~ e l e c t i v i t y . In ' ~ ~the ~ stereospecific epoxidatjon of ris- and trans-ally1 alcoholq, formation of a transition state is assumed with the development of two H bonds: between the hydrogen atom of the hydroxy group of the allyl alcohol and the oxygen of the peracid, and between the hydrogen of the peracid OH and the oxygen of the ether An analysis of the diastereometric transition-state interactions for stereoselective epoxidation of effect may be resacyclic allylic alcohols has been p ~ b l i s h e d . 'A~ conformational ~ ponsible for the unexpected cis major productg5in Eq. 2.

Synthesis of Oxiranes

19

Formation of the cis-oxirane 11 in the case of 1,6-disubstituted cyclohexenes can be justified by the occurrence of torsional strain (Eq. 2a).'%

-

I

(24 he

Me

11

oo

In contrast with the reactions of 2- and 3-carenes, the reaction of 12 is not stereospecific (Eq. 3).l8'

7 PBA r

(-$

+

(3)

,'

I

I

12

The exo-addition rule is not manifested in the case of 13 ((eq. 4).18'

13

1:1.8

/

Z

Z = C1, Br, COOCH3, C N 14

5,6-Disubstituted norbornene derivatives 14 give 2,3-exo-cis-oxiranes with MCPBA.la2 With the cyclopentane ring fixed in the envelope form, there is total stere oselectivity (Eq. 5) .183

Oxiranes

20

The trans-dioxirane 15 is formed in good yield from 1,4-dimethylenecyclohexane by peracid attack from the axial side.'84

0

15

Only the trans-oxirane is produced from a-pinene with PNPBA, the peracid attacking on the less crowded side (Eq. 6).185

8,

MNPBA

0

The kinetic and stereochemical results on 2-methylenecyclohexanol derivatives have been utilized to interpret the stereoselective epoxidation of aliphatic a-ethylenea l ~ o h o l s . ' ~The ~ ~main ' ~ ~ product in the oxidation of 4-a-chloro-3(10)-carene 16 is 17 (Eq. 7).lE8

Limonene is oxidized regioselectively by PBA (Eq. 8) and stereoselectivity can be observed for endo- and exo-dicycl~pentadienes.'~~

-0 6

+

Y

+

y M x i

17a, 17b

major products

The rate of epoxidation of 18 is influenced by the nature of R.

18

(8)

Synthesis of Oxiranes

21

The rate constant increases with increasing solvent dielectric constant." Bicyclo[2.2.2] octanes mainly give rise to the exo-oxirane (Eq. 9); endo-oxirane formation decreases as the temperature is l ~ w e r e d . ' ~ '

cF3c03"pJ+-f &c+o +

+yo

dC/O

45%

6C/O

I

24%

K0 0

(9)

Rate-strain relationship studies show 1,2-diphenylcyclopropene to undergo epoxidation more slowly than expected.'92 The relative rate of epoxidation of cyclopropenes fused to cycloheptane 19 revealed moderate backside interaction of the alllylic cyclopropene substituents (Eq.

19

Although a,@-unsaturatedketones are usually not oxidized with peracid, nmr data point to the formation of a cis-bisoxirane from 20 with MCPBA (Eq.1 l).'%

Me

I

-

I

Me

Me

Me'

20

a,B-Unsaturated esters are not used for epoxidation with MCPBA, but for the selective formation of @ - k e t o e s t e r ~ .Aryl-aliphatic '~~ oxiranes can be obtained in good yield (90-100%) in an alkaline two-phase system;'96 examples are 21,22, and

23.

21

22

23

Oxiranes

22

The reactions of dimethylcyclohexene derivatives substituted in the allylic position 24 are primarily governed by steric factor^."^

XMe, 24

Stereoselective synthesis of a sex pheromone (Z)-7,8-epoxy-2-methyloctadecane has been acheived by peracid oxidation.lg8 Epoxidation of highly hindered octalin 25 with PBA proceeds

Me@Me

25

predominantly on the less-hindered a-side.'" Following the epoxidation of 1,l'dicyclohexene and 1,l'-dicyclopentene with PNPBA, the structures of the diastereoisomeric bisoxiranes have been identified by resolution of the BH3/LiBH4 reduction products.200:'01

p@ @ 0

26

27

28

For the synthesis of oxiranes with more complex structures, the peracid method is combined with other epoxidation procedures; examples are the syntheses of (f)-crotoxirane, (*)-epicrotoxirane, and (+)-isocrotoxirane"' or the preparation of cis-trioxatris-(~)hornotropylidene?~~ a-Sulfoperbenzoic acid has been used for the stereoselective epoxidation of cholesterol.'" The selective epoxidation of cholest5-en-3-one too has been examined.205 In the synthesis of 25-hydroxycholesterol selective epoxidation occurs on AZ4 and 26 is forrned.'O6 The epoxidation of olefin propellanes 27 and 28 can be achieved with MCPBA. As a consequence of the secondary orbital interaction, syn-attack is more marked in the case of 28.'07 Epoxypropelladiene can be synthesized in accordance with Eq. 12.'08

n:o

Synthesis of Oxiranes

Me

NCS

Me

--

23

-

MCPBA- tert-BuOK

(12)

Me

An investigation has been made of the stereochemistry of epoxidation of the sesquiterpene i s o l ~ n g i f o l e n e .The ~ ~ ~a-epoxide structure 29 has been proved by x-ray crystallography.

(@

29

?$(

fo

,,OH

~

OH

OH

30

31

,OH

33

32

In addition to the main products 30, 31 in the epoxidation of (-)-a-terpineol with MCPBA, the 1,8- and 2,8-epoxy-l-ols 32 and 33 are also formed.210The epoxidation of tricyclic dienone 34 occurs selectively first to yield 35 and, subsequently, the bisoxirane 36 (Eq. 13). In dienol 37, rate acceleration by the action of the neighboring hydroxy group leads to the formation of 38 (Eq. 14).'11

(13) Ph

Ph.34

35

36

A medium-sized ring possessing neighboring hydroxymethyl or carboxyl functional groups give bicyclic ethers or lactones.2"a Studies have been carried out on the

Oxiranes

24

structures and stereochemistry of the reaction products of bicyclic phosphine oxides212and p h o s p h o l e n e ~containing ~ ~ ~ ? ~ ~sterically ~ hindered double bonds. Asymmetric epoxidation has been performed with optically active p e r a ~ i d . ~ l ’ - ~ l ~ and racemic oxiranes have been resolved on a glc column containing an optically active complex.218 The epoxidation of a l l e n e ~ ~has ~ ’ been examined, as have the reactive intermediates formed in the epoxidation of simpler allenes.220 Such intermediates have been isolated from sterically hindered allenes.221PNPBA epoxidation of a series of vinylallenes results in a-allenoxiranes and, as the main products, conjugated cyclopentenones.222 Polymer-supported peracids are also used effectively for the epoxidation of diand trisubstituted olefins. The ratio of the stereoisomers is similar to that for the products of the reaction of the monomer with aromatic per acid^.^^^ MCPBA epoxidation of homoallyl phosphonates has led to the preparation of 3,4-epoxyalkane phosphonates 39 in addition to the 1,2- and 2,3-epoxy derivatives.224Stereospecific peracid oxidation is one of the preparative methods employed in the synthesis of the structurally varied cyclic polyoxirane isomers, which are of interest from a biological aspect.225 (R0)2P-CH-CH2 I1

I

0

O R 39

In the procedures to date, the most frequent epoxidizing agent has been perbenzoic acid bearing an electron-attracting substituent. The use of p-methoxycarbonylperbenzoic acid prepared by photooxidative means has been reported.226 In industrial syntheses, in situ performic peracetic acid:28 and perpropionic aCid229,230have been utilized in a two-phase solvent. Imino analogues of the peracids, peroxyimidic acids formed from acetonitrile, or benzonitrile in situ by the addition of hydrogen peroxide have been used for e p ~ x i d a t i o n ~since ~ l - ~the ~ ~work of Payne.237’238Peroxybenzimidic acid is a much more reactive, but less selective epoxidizing reagent than MCPBA.239 Rebek gives an excellent survey of new epoxidation agents.& These new reagents, which are dealt with briefly below, can be used well for oxygen transfer to olefins. Formally, they are obtained via the dehydration of H202. Peroxycarbamic acid derivatives are very reactive epoxidizing agents that can be employed under mild conditions and are practically independent of the solvent effect; examples are the reagent (probably 40) prepared from carbonylditriazole with H 2 0 2 and N-benzoylperoxycarbamic acid 41 .240,241 The latter is very useful for the preparation of 2 - a ~ i d o o x i r a n e s . ~ ~ ~

N*N

0

LN-C-0-0-H J11 40

H-0-0,

t:

P hC - NH’ 41

c=o

Synthesis of Oxiranes

25

Use has recently been made of the ethers of peroxycarbonic a ~ i d . % ~ 0- t’h~er~ epoxidizing agents are disuccinoyl peroxide,245 bis(benzoyldioxyi~do)benzene?~~ and peracetyl nitrate.247Mainly in the terpenes, oxidation is achieved with benzeneperoxyselenic acids, prepared in situ from benzeneselenic acid with H202.248-250 Peroxymonophosphoric acidZ5laand the diethyl ester of peroxyphosphonic acid are of value as effective peracidsZ5l and the action of HzOz on ortho-esters generates intermediates capable of olefin e p o x i d a t i ~ n . ’Peracid ~~ oxidation has further been investigated in the presence of Mo(acac)z as catalyst.253New procedures have been introduced for the epoxidation of alkenes via dioxirane intermediates generated in the reaction of potassium caroate with ketones.253a Certain ally1 alcohols are epoxidized regio- and stereoselectively, the stereoselectivity being opposite to that of the V/TBHP system.253b B.

Oxidation with Hydrogen Peroxide

In the epoxidation procedures referred to in the preceding section, an important role was played by hydrogen peroxide in the preparation of the various epoxidizing reagents. An account will now be given of the use of hydrogen peroxide as a direct epoxidizing agent. The two procedures to be described are mainly applicable for the epoxidation of electron-poor olefins. These are consequently of great importance. The electrophilic character of alkenes in which the double bond is conjugated with an electron-attracting group (unsaturated ketones, acids, nitriles) means that they react with peracids only with great difficulty, if, at all; however, they do undergo epoxidation with hydrogen This method is an extremely important synthetic tool. Alkenes of a strongly electrophilic nature are oxidized by alkaline hydrogen peroxide. When the double bond is not so electron-poor, epoxidation can be achieved with hydrogen peroxide in the presence of a transitionmetal catalyst. a.

OXIDATION WITH ALKALINE HYDROGEN PEROXIDE

This method was first described by Weitz and S ~ h e f f e r . ’The ~ ~ oxidation begins with a reversible attack by the nucleophilic hydroperoxy anion on the conjugated system, and an oxirane conjugated with an electron-attracting group is formed by ring-closure following the loss of OH- from the intermediate enolate anion (Eq. 15). \ /

FP Col

/ \

6

C-

\ /

+

(-)OOH

C-OOH

I

C 7-53-

/

-:I

0

-

\ /

\c/

C

/

+

(-)OH

(15)

8

The reaction is generally not stereospecific. One of the causes of this is the lifetime of the intermediate enolate ion, which is usually long enough for rotation to occur around the Ca-C/3 bond, but polar and steric effects also influence the stereo-

Oxiranes

26

chemical course of the e p o x i d a t i ~ n .Good ~ ~ ~ yields may be obtained in the reaction, though this is subject to numerous factors; the main reaction is accompanied by side-reactions or the epoxidized product undergoes further transformation, as demonstrated by kinetic examinations.256 For steric reason. alkaline hydrogen peroxide yields only the trans-oxirane from cis- or trans-42 (Eq. 16):''

42

Mono- and polyepoxyalcohols have been prepared from phorone in very stereoselective syntheses.'86 The trans-oxirane 4 3 is formed from indenedione by participation of the C-1 carbonyl

-6

43 94%

0

& o

44

The polar interaction of a distant substituent has been observed in the reaction of 44.259If R' = R 2 = H, the p-oxirane is formed, while if there is a carbonyl group on C-11 and C-17, the yield of the a-oxirane is 85%. The naphthalenone 45 gives exclusively the trans-oxirane (Eq. 17).260

&- & \

/

\

I

(17)

.b

45

Great stereoselectivity is not observed in the case of bicyclic, tricyclic or steroidal a$-unsaturated ketones (Eqs. 18 and 19).261

1 :3-4

27

Synthesis of Oxiranes OMe

I

+

0

‘-0

1 :2

o&ql (19)

0

From the pregnane derivative 46 in alcohol, 21-alkoxy-16,17-monooxirane and a little bisoxirane 47 are produced (Eq. 20); more 47 is formed in dioxan.262

1,2-a-Epoxycholestadienone has been obtained from c h ~ l e s t a t r i e n o n e . ~ ~ ~ Bisoxiranes have been prepared in two-step oxidations from 48 and 49, the bicyclic molecular moiety being oxidized with MCPBA and the exocyclic double bond with

48

49

alkaline hydrogen peroxide .264 The nucleophilic oxidation of bicycloheptenyl vinyl ketones is similarly selective (Eq.21).265

Oxidation of bicyclo [3.1.I ] heptane derivatives containing an endocyclic double bond results selectively in the trans-oxirane 50 with respect to the geminal dimethyl bridge. The two diastereomers 51 and 52 are obtained from an exocyclic double bond.266Menthenone yields exclusively cis-(+)-menthenone oxide 53, with known absolute c ~ n f i g u r a t i o n . ~ ~ ’

Oxiranes

28

50

51

52

53

Kinetics demonstrate that in the epoxidation of the n-hexyl 0-alkylvinyl ketones 54 the possibility of nucleophilic attack decreases as the carbon chain in group R

becomes longer or more branched.268 The Hammett correlation has been studied in the reaction of 55 .269

55

54

Quaternary ammonium salts of alkaloids have been used for the synthesis of optically active oxiranes from electron-poor olefins under phase-transfer cond i t i o n ~ . ~The ' ~ enantiomer yield is inversely proportional to the dielectric constant of the solvent.271Asymmetric epoxidation in the presence of catalytic amounts of poly-(S)-amino-acids in a triphase system has been described with optical yields up to 96%.271a Addition of the hydroperoxy anion to the double bond in conjugation is promoted not only by the carbonyl group, but by other electron-attracting groups too. Good yields can be attained from nitroolefins (Eqs. 22 and23).272

85%

trans-a-Nitrostilbene does not react, coplanarity of the nitro group and the double bond being hindered for steric reasons. The epoxidation of a,P-unsaturated nitriles is accompanied by hydrolysis of the nitrile group to give an epoxycarboxamide .238i 273 Only the trans-oxirane is obtained from cis- and trans-56 (Eq. 24).274 Ph-CH=CH-S02C,H4Me 56

- pM

H 0 SO2CbH4-Me 94%

(24)

Synthesis of Oxiranes b.

29

OXIDATION WITH HYDROGEN PEROXIDE AND A CATALYST

Oxides of transition metals (W. Mo, V, Ti, etc.) are very effective catalysts in the epoxidation of electron-poor olefins with hydrogen p e r o ~ i d e . ’ ~ ’ Oxides , ~ ~ ~ -of~ ~ ~ tungsten and molybdenum are most frequently employed; in the presence of hydrogen peroxide these are oxidized to peracids and as a consequence of the catalytic activity of the peroxyanions (HWO;, HMoO;), the rate of the epoxidation is enhanced considerably. Pertungstic acid is formed rapidly: H2W04 + H202+ H2WOs + H 2 0 . Its anion exists in a cyclic form involving an intramolecular hydrogen bond (Eq. 25); accordingly it may behave as an electrophilic agent. The mechanism of the reaction with olefins has been reasonably well clarified,281-2m a transition complex being formed with the double bond (Eq. 26).

A fair number of articles have recently dealt with the kinetics and mechanism of the r e a ~ t i o n . ~ ~ It ~has - ~ been ~ ’ utilized among others for the stereospecific production of an antibiotic.2m The method is of great promise in industrial synthe. has the advantage that the side-product of the reaction is water. ses;291,292 it MolybdenumV1-peroxo complexes give oxiranes in high yields.293-295 For anhydrous hydrogen peroxide, a three-step mechanism is assumed, with an a-hydroxyhydroperoxide ir~termediate.”~Detailed studies have been made on the mechanism of the reaction of the Mo0(02),-HMPT complex with olefins (Eq. 27).297,298

The experimental results have led to the proposal of a 1,3-dipolar addition mechanism, the molybdenum atom being involved directly (Eq. 28).

Oxiranes

30

The structure and decomposition of the peroxomolybdenum-olefin complex have been in~estigated.’~’Further kinetic studies suggest the structure of the transition complex shown in Eq. 29. The double bond is attacked by a positively charged oxyger~.~@’ ‘*O labeling has demonstrated that the 0x0 oxygen is not affected in the reaction.301 A’Steroids are oxidized with surprising stereospecificity ;this is evidence in favor of the 1,3-dipolar mechanism.302

)~ Epoxidation of olefins with hydrogen peroxide in the presence of F e ( a ~ a c has been examined in the cases of stilbene, unsaturated alcohols, and fatty acids.303 From cis- and trans-olefins the main product is the trans isomer, formed via a biradical intermediate. Cholesterol undergoes f l - e p o x i d a t i ~ n . ~ ~ Boron-containing catalysts have also found a p p l i ~ a t i o n , with ~ ~ ~a- relatively ~~~ lower stereoselectivity. Cyclohexene oxides can be obtained with a selectivity of 97.5% in the H2O2-AszO3 system.309 Arsonated polystyrenes have also been employed as catalysts.310i311Epoxidation of olefins may be attained with hydroperoxide bound on an aluminium oxide surface .312

C.

Oxidation with Organic Hydroperoxides

Epoxidation of olefins with organic hydroperoxides in the presence of metal catalyst complexes has been widely developed in the past decade. The method began to be used only in the middle of the 1960s,313*314 but since the end of the 1960s an ever-increasing number of publications and industrial patents have appeared on this topic (primarily in connection with the production of methylo ~ i r a n e ) ; ~ ”it -is~ quite ~ ~ clear that this is a very effective and economically important reaction of value on both a laboratory and industrial scale. Many researchers are still occupied with the elucidation of the mechanism of the reaction. An appreciable number of monographs and reviews deal with the meth.d.151,275, 329-333 Th e large amount of experimental work that has been performed provides a possibility for establishing favorable conditions of epoxidation with regard to the roles of the catalyst, the organic hydroperoxide, the structure of the olefin, and the medium. Similar to the hydrogen peroxide-transition-metal complex reaction, this is an electrophilic reaction (Eq. 30).334 Application of the organic hydroperoxide in the reaction leads to many advantages. The reagent can be prepared from a cheap hydrocarbon source, it dissolves well in hydrocarbons (thus, the detrimental effects of polar solvents on the reaction can be avoided), its use is less dangerous than that of other epoxidizing agents, and, last but not least, a good yield and selectivity can be achieved.

Synthesis of Oxiranes

ROOH

+ catalyst LZ (ROOH

*

catalyst)

-

31

-

ROOH catalyst

,c=c

-

'\0/ ' + catalyst

\

C-C

/

Metals of the IVB, VB, and VIB Groups (mainly Mo, W, V, Ti, and Cr) are effective catalysts that promote heterolysis of the 0-0 bond in the hydrop e r o ~ i d e . ~Such ~ ~ metals , ~ ~ ~have - ~ a~high ~ charge, a relatively small size, and lowlying d orbitals that are partly unoccupied. The catalyst must be a good Lewis acid and must form complexes that are substitution labile. The metal in the active catalyst is in the highest oxidation state. The sequence of activities for the transition metals is Mo > W > T i , V. Metals of Group VIII are not good catalysts because they readily decompose peroxides by a one-electron pathway. Nontransition elements also are used, for examble, B338-342and Sn,343but these exhibit lower activities than the transition metals. The metals are employed in the form of well-soluble compounds (salts, acetylacetonate, naphthenate, carbonyl, oxalate, etc.). In a study of Mo-catalyzed epoxidation, Sheldonm showed that the ligand effect is only manifested in the initial stages of the reaction for the complex is converted in situ to Mo"' diolate. SapunovM5attributes greater significance to ligand exchange. The structure of the organic hydroperoxide does not have a dramatic effect on the rate of the epoxidation reaction either, but a certain sequence can be established. With M ~ O ~ ( a c a c )the ~ , reaction rate decreases in the following sequence: phenylethyl-, cumyl, tert-butyl and t e r t - a m y l h y d r ~ p e r o x i d e . ~ ~ ~ In regard to the selectivity of the reaction, the greatest role is played by the structure of the olefin. The reaction rate is strongly affected by the extent of alkyl substitution adjacent to the double bond and by changes in the number of electrondonating groups. A side-reaction lowering the yield, the metal-catalyzed homolytic decomposition of the hydroperoxide, is regulated by the olefin/hydroperoxide molar ratio.332 An olefin excess is accompanied by a higher selectivity. In the event of an organic hydroperoxide excess, the catalyst-hydroperoxide complex is stabilized by a small amount of barium oxide.3469347 Polar solvents disturb the reaction;336i348i349 this includes the alcohol formed as side-product. A temperature of 80-120" is generally used; high temperature favors the side-reaction involving radical decomposition. Ally1 alcohols may be epoxidized at room temperature. Besides hydrocarbon-soluble metal complexes, solid catalysts are also employed (Mo powder, Mo03);350-354in . the presence of hydroperoxides, some of this solid material may dissolve. Catalysts on SiOz or some other s ~ p p o r t have ~ ~ higher ~ - ~ ~ ~ activities as a consequence of the greater dispersity, but they are frequently quickly leached off the surface and, in effect, homogeneous catalysis occurs. True heterogeneous catalysis is observed on the Ti02-on-Si02catalyst363i3Hwith high oxirane selectivities.

32

Oxiranes

With a view to clarifying the mechanism of the epoxidation process, many research groups have carried out wide-ranging investigations involving reaction kinetics,%&349,365-388 the transition complex,298,’993 3’53 333-335, 389,391 the inter‘ and stereochemistry. mediates,344,366,392-397 inhibition,396 The first step in the reaction is the formation of the catalytically active species and then coordination with the hydroperoxide. This is followed by the ratedetermining oxygen-transfer step, for which two reaction pathways have been suggested. One of these is a mechanism involving a metal-oxide-containing active species,298’398 while the other involves an activated complex between the catalyst and the intact hydroperoxide molecule. The latter is confirmed by experiments with 180-enriched water3” and by the results of the steric effects. Regio- and stereoselectivity may occur on the basis of steric and polar factors as a consequence of the structure of the olefin substrate, while at the same time coordination of the functional groups with the reagent (with rigid geometry) also results in unexpected regio- and stereoselectivity. In the epoxidation of olefins not bearing a complexing group, there is not a great difference in stereoselectivity in comparison with the peracids. The cis-oxirane is Due formed from cis-butene-2 and the trans-oxirane from t r a n ~ - b u t e n e - 2 335a .~~~ > to steric hindrance, regioselectivity may be observed for nonconjugated d i e n e ~ .401 ~~’ In terpenes, the attack takes place from the less hindered Double bonds in bridged cyclic systems have an effect on the reaction rate.403 In the epoxidation of olefins containing functional groups, essentially different stereoselectivities are encountered, not only in comparison to the situation with the peracids,4w but also depending on the nature of the transition-metal complexhydroperoxide reagent8‘ Simpler olefins can be epoxidized more quickly with a Mo-containing catalyst. Olefins bearing a hydroxy group are epoxidized at a higher rate and with a better yield in the presence of a vanadium catalyst (Eq. 3 1).400,405

Mo(C0)6 111 VO(acac)2 4: 1

The geometry of the vanadium catalyst complex allows strong coordination of the alcohol ligands to vanadium. Sharpless links the stereochemistry of epoxidation of some acyclic allylic alcohols to rigid stereoelectronic requirements, in which a large role is played by the preferred 0-C-C=C dihedral angle of the allyloxy . ~ ~ at moiety.333 The stereoselectivity is almost complete with 2 - c y ~ l o h e x e n o l Even room temperature, V/TBHP brings about regioselective epoxidation of 57 and 5ti407 (Eqs. 32 and 33) and homallylic alcohols.408 Epoxidation of acyclic allyl alcohols with V/TBHP results in the opposite stereospecificity to that observed with the peracid and the Mo-catalyst system.’‘”’ 177 In contrast with the use of H P cis isomers MCPBA, epoxidation of cyclic allyl alcohols with V O ( ~ C ~ C ) ~ / T Bgives independently of the number of ring atom^."^^^^^ Highly stereoselective epoxida-

Synthesis of Oxiranes

33

tion of acyclic homoallylic alcohols has been described with a tetrahedral vanadate ester p r e d i ~ t e d " ~as a transition-state model for the V/TBHP system.409aRemote epoxidation directed by a Mo-template complex has been observed for steroids.410 Functional group-mediated stereospecific synthesis has been described for unsaturated acetates411 and steroid acetatesw'

c

(33)

58

With chiral ligands, the transition-metal catalyst-hydroperoxide complex yields optically active o x i r a n e ~ . " ~ ~One - ~ ' of ~ the most significant advances in the formation of chiral epoxides from allyl alcohols has recently been reported by the Sharpless Using (+)-tartaric acid, tert-butylhydroperoxide, and titanium isopropoxide, they were able to obtain chiral epoxides in very high enantiomeric excess. The enantiomeric epoxide can be obtained by employing (-)-tartaric acid (Eq. 33a).

The method is a very promising one; it has been demonstrated to be the best route to date for the synthesis of optically pure allyl alcohols. The Ti-alkoxidetartrate complex is more eythro-selective than V O ( ~ C ~ ~ ) ~ - T BinH the P;~~~~ absence of tartrate, the reaction is generally threo-selective. Ally1 alcohol epoxide intermediates of great use in the synthesis of natural products may be prepared."20b-420d The selective reduction of these provides a stereo- and regioTi'"-~ ~ ~ - ~ controlled route to di-, tri-, and polyhydroxylated ~ y ~ t e m A~new . ~ mediated diastereoselective epoxidation has been reported, with a pathway different from that prevalent under the Katsuki-Sharpless conditions.42oi Recent literature refers to the stereoselective and asymmetric epoxidation of allylic alcohols with organoaluminium peroxides:21 Ph3SiOOH epoxidizes ole fins with a stereoselectivity similar to that with p e r a ~ i d . ~Reports '~ have been made of a-substituted hydroperoxides (acids, esters, ketones, amides, and nitriles) as effective epoxidizing reagents4a:422-423a and the application of he~achloroacetone,4~~ t e t r a c h l o r a c e t ~ n e ? and ~ ~ ~hexafluoroacetone h y d r o p e r o ~ i d e , 4 ' ~ ~ as , ~ well ~ & as the H202-Vilsmeierreagent system ."24d

Oxiranes

34

D.

Oxidation with Molecular Oxygen

This procedure is primarily of industrial importance. It is sufficient to point out that oxirane, which is of great importance in industrial syntheses, is produced entirely by direct catalytic oxidation from ethylene. In the organic preparative laboratory, the direct epoxidation of olefins is carried out in the liquid phase. Independently of the reaction conditions employed, the reaction proceeds via a radical mechanism, generally with a poor yield, with low selectivity, and only rarely stereoselectively . There is already an extensive literature on this economically significant meth~ d . 151a3275, " ~ ~ 331,425-429 Many research groups have made efforts to elucidate the mechanism of the reaction and to discover new and effective catalysts. This is the subject of numerous patent descriptions. With regard to the nature of the radicalinitiating step, the method must be discussed in two separate sections. a.

OXIDATION WITH OXYGEN AND METAL COMPLEX CATALYSTS

The metal complexes used to catalyze the homogeneous or heterogeneous processes can likewise be divided into two groups. The metals in the first group (Group A) belong to Groups VII, VIII, and IB; of these, mainly the salts and complexes of Mn, Fe, Co, Ni, Rh, Ir, Ru, Pd, and Pt are used. The other group (Group B) comprises the metals of Groups IVB, VB, and VIB, of which Mo, V, W, and Ti are employed most frequently. Direct epoxidation with oxygen is greatly promoted by metal complex catalysts, which allow work at a lower temperature, with a more selective reaction and a higher yield. The two groups differ as concerns their catalytic properties. The complexes of the Group A metals are the more active and form dioxygen complexes more readily, but they give little oxirane with ole fin^.^^'-^'^ In Group B, the complexes have lower activities, but epoxidation is possible more selectively and with a better yield.M8-455 In the metal-catalyzed direct oxidation, an allylic hydroperoxide intermediate is assumed: the peroxy radical formed by the decomposition of the catalysthydroperoxide complex initiates the autoxidation through the abstraction of a hydrogen atom from the olefin (Eqs. 34-37).456

-

+ M" RO '+ M"+'(OH) ROOH + M"" ROO + M" + Ho \ 1 ' \ './ ROO + ,C=C -CH ROOH + ,C=C-C, I \ ,C=C-C, ' . / + 0 2 - ~ c = c - c -I o ~ ROOH

'

I

1

(34)

(35)

(37)

In the presence of the Group A complexes, the hydroperoxides undergo decomposition rapidly, but with the Group B complexes they are more stable.

35

Synthesis of Oxiranes

Another suggested reaction pathway is a direct reaction between oxygen and the metal complex, in which 0-peroxyalkyl radicals 59 are the key intermediates (Eqs. 38-40). M(acac),

+0

-

--

R+O,

ROO

+

\

,C=C'

\

+ CoZ + R'

Moxid

2

I

ROO-C-C, I

59

./

-

(38)

ROO

RO'

+

0

\

,C-C,

I\

(39) /

(40)

This mechanism has been introduced for models in which there is no abstractable allylic hydrogen in the compound.@' Co and Mn acetylacetonates initiate the chain of autoxidation by activating the oxygen molecule (Eqs. 41 and 42).439

M+O,&+)

+

o;(-)+

\

,C=C<

O:(-)

-

M6(+)+

(41 1 I

I

I

I

M 0 2 -C-C'

A mechanism has been proposed for chain-generation catalyzed by metal compounds in which oxygen is incorporated into the coordination-unsaturated complex and the metal-dioxygen complex forms a peroxy radical ROO' by opening a C-H bond.-' In the oxidation of cyclohexene, it is assumed that 60 and 61 are formed from the hydroperoxide intermediate, while cyclohexene oxide is produced by cooxidation with the aldehyde formed from the toluene solvent (Eq. 43).430

60

61

A further reaction pathway has also been put forward, which features an incompletely developed hydroperoxide intermediate (Eq. 44).443

Oxiranes

36

These mechanistic possibilities require further investigation. Some examples of how the reaction is influenced by the structure of the olefin, the catalyst, and the solvent are given. In the presence of MX(CO)(PPh3)2 (M = Rh, Ir; X = C1, I), the oxidation of a-and 0-methylstyrenes and cis- and trans-stilbenes permitted the establishment of an activity sequence dependent on the catalyst and the stucture of the 0lefin.4~' The solvent effect has been studied in the Ru complex-catalyzed oxidation of styrene and m e t h y l ~ t y r e n e In . ~ ~the presence of a Rh or Ir complex, the oxidation of tetramethylthylene is very selectivew and takes place at a faster rate than those of the less-substituted olefins. It emerges from this that a significant role is not played by the coordinative linkage between the metal center and the olefin. Examinations have also been made on the oxidation activities of metalloporphyrins, for example, the oxidation of cyclohexene with Co and Rh porph~rins.4~~~~~~ New oxygen-transfer complexes have recently been r e p ~ r t e d . ~ ~ ' -With ~~' (Phz),PtO2, norbornene has been epoxidized with a yield of 50% under mild conditions.460 Oxygen transfer from cobaltnitro complexes to terminal alkenes activated by thallium(II1) produces oxiranes?60a Cycloalkene oxiranes are formed in the presence of a nitropalladium complex, the catalyst having the nature of a nitronitrosyl redox [Fe30(OCOR)6L3]+-catalyzed regiospecific epoxidation of complicated olefins, for example, geranyl acetate, has been described.460d An increasingly greater role is being played by the Ag-catalyzed heterogeneous catalytic p r o c e d ~ r e s ; 4 ~the ~ ~ s~t-e r e o c h e m i ~ t r yand ~ ~ k~ i n t e t i c ~ of ~ ~the~ process -~~~ have been studied. A few patents may be m e n t i ~ n e d ? ~ ~ - ~ ~ ~ The catalyst-hydroperoxide complexes are more stable for the metals of Group B than for those of Group A. Epoxidation of the olefins proceeds more easily and more ~ e l e c t i v e l y . They ~ ~ - ~are ~ ~particularly significant in the industrially important epoxidation of propylene.454,455i480 Reference should be made to the very selective epoxidation of cyclohexene with a Mo complex452and to publications relating to the epoxidation of ethylene, hexene-l,@' and 0 c t e n e - 1 ~with ~ ~ a Cr complex. It is of interest to observe the different behaviors of the complexes C5H5Mo(C0)3 and C5H5V(C0)4 during the epoxidation of c y c l ~ h e x e n eIn . ~ the ~~ presence of the V complex cis-2,3-epoxycyclohexanolis formed with high stereoselectivity from the intermediate allylic hydroperoxide, whereas the Mo complex gives the oxirane and ally1 alcohol. Attempts have been made to utilize the favorable properties of the metal catalysts of Groups A and B by employing mixtures of these two catalysts types so as to enhance the activity and selectivity of the direct oxidation.406,482-489 b.

OXIDATION WITH OXYGEN WITHOUT A CATALYST

The processes without an external catalyst can be subdivided in accordance with the nature of the initiating step. Thermal, photocatalytic, and radical-catalyzed procedures may be differentiated. In recent years there has been an increase in the number of studies dealing with

Synthesis of Oxiranes

37

atomic oxygen. Theoretical investigations have been made of the addition of singlet oxygen to substituted olefins; the mechanism of the reaction has been assumed to occur with participation of peroxy radical, open 1,4-zwitterion and peroxirane intermediates. The procedure: ab initio calculations combined with a thermodynamic method determining substituent effects.490 MIND0/3 studies have been published on the possible mechanism of oxirane formation!919492 MO calculations on the reaction of vinyl alcohol with singlet oxygen illustrate the intermolecular attraction-directed orientation of the singlet oxygen atom.493 Comprehensive work has been carried out on the mechanism of dye-sensitized photooxidations with singlet ~ x y g e n . ~ ” ’Allylic ~ ~ ’ hydroperoxidation with simple olefins, 1,2-~ycloadditionto alkenes of low ionization potential, and 1,4endoperoxidation of conjugated dienes can occur.496-499The allylic hydroperoxidation is cis-stereospecific. Examinations have been made on the stereochemistry of epoxidation of olefins with fixed conformation and on the effect of the hydrazide function.500 If epoxidation is performed with carbonyloxides obtained from diazo compounds, the formation of carbonyl compounds can be avoided or these are c o o ~ i d i z e d . ’ ~Recent ~ publications relating to photoepoxidation deal with the effects of the sensitizer, the wavelength of the light used, and the With an appropriate sensitizer, a radical cationic process was first observed with singlet oxygen.503 The photochemical synthesis of fluorinated simple epoxides has been described.5w’505 A number of theoretical studies have appeared on the mechanism of the oxiraneforming reaction of olefins and O(3P).506-509A kinetic investigation of the reaction of oxirane and the O(’P) atom has shown that H-abstraction occurs rather than insertion to form a dioxetane intermediate.’1° The thermal and photochemical epoxidation of propylene in the presence of sulfur dioxide and acetonitrile have been reported.510a Photooxidation suitable for the epoxidation of aromatic olefins also occurs with a-diketones (benzil, biacetyl), b e n z ~ p h e n o n e , ’benzoin, ~~ and a - k e t ~ a c i d s . ~ ” ~ ’ ~ ~ ~ ~ Isotopic mechanistic studies point to a reaction via a b i r a d i ~ a l . ~’13’ ~ ’Photooxidation with an a-diketone or a-ketoacid recently has been interpreted in terms of a photochemical a-cleavage leading to an acylperoxy radical, which can have similarly effectively transfer an oxygen atom to o l e f i n ~ .511b ~ ~ ’Vinylallenes ~~ been photooxidized in the presence of b i a ~ e t y l . ~ ~ ~ Thermally initiated epoxidation with dienones proceeds selectively (Eq. 45)’15

15%

The autoxidation is probably initiated by a reaction between triplet oxygen and During thermal epoxidation of the bicyclo [3.1 .O]hex-2-ene system, epimerization of one of the isomers occurs by the opening of the cyclopropane ring. Accordingly, one major oxirane isomer is formed (Eq. 46).516

Oxiranes

38

Ph ‘

v

p

h

phv

”*,,

*

-k

Ph

Ph

(46)

Ph

The synthesis of butadiene dioxide with air at 250” has been described.’I7 The epoxidation of 2-butene takes place partly stereospecifically t o trans-2,3epoxy butane .518 Stereospecific epoxidation of olefins with radical 6 2 , produced in a mixture of tetramethyltetrazene-ZnCl’ and oxygen, is a radical-catalyzed p r o c e ~ s . ” ~ I

ZnC1,

R

62

63

II

Oxiranes may also be prepared by the cooxidation of aldehydes and 01efins.~~’ There are two assumptions as regards the mechanism: the oxidation occurs via either an acylperoxy radical or a pera~id.’’~-”~The peracid oxidation is stereospecific. Experiments carried out with a view to assessing the radical versus nonradical mechanism indicate that the extent of the radical epoxidation depends on the structure of the olefin and the olefin/aldehyde ratio.’24 Cooxidation in the presence of oxygen was achieved by irradiating the aldehyde and carrying out the reaction with the alkene after a suitable quantity of peracid had been obtained.”’ Enantioselective epoxidation has been described in the reaction of (l-phenylalky1idene)malonitriles 63 catalyzed by optically active tertiary amine~.’’~ E.

Other Oxidation Methods

The epoxidation procedures described here are not general ones; they are used in special cases to prepare stereoisomers that are difficult to obtain by other means. 2,4-Disubstituted-6-hydroxymethylphenols have been oxidized with good yields t o spirooxirane derivatives with sodium periodate in the case of bulky substituents, for example, when R’ = R’ = tert-butyl (Eq. 47).527

Synthesis of Oxiranes

39

Periodate compounds have been used for the epoxidation of simple olefins too (MI04, MHJ06, or MZH3106;M = Li, Na, K, Rb, Cs, e t ~ . ) . ~In’ alkaline ~ medium, xenon-trioxide epoxidizes alkenes stereoselectively; there is no cis-hydroxylation as when other inorganic oxides are employed.529 Olefins with hindered double bonds may be transformed stereospecifically to oxiranes by treatment with ozone.53o The epoxidation of propylene has been achieved with alkoxyalkyl-hydroperoxides obtained by the ozonization of olefins in the presence of alcohol.531 The yield depends on whether the alcohol is a primary, secondary, or tertiary one. The low-temperature (- 70”) epoxidation of olefins with a yield of about 30% has been performed with electrophilic intermediates produced in the course of the ozonization of alkynes; these intermediates are probably five-membered cyclic trioxides. This epoxidation is almost totally stereospecific .532 Chromic acid oxidation of olefins can rarely be used for the preparation of oxiranes because they occur as intermediates that rapidly undergo further transformation. From an investigation of the mechanism of oxidation of triarylsubstituted olefins, it was concluded that a carbonium ion or cyclic chromate ester is a possible intermediate.533,534Selective epoxidation of compounds containing conjugated double bonds is attainable by means of chromic-acid oxidation (Eq. 48).535Exclusively cis product was obtained from a highly substituted octalin with NazCr04, KMn04, or ozone (Eq. 49).lg9

Hypochlorous acid and its salts may be utilized for the epoxidation of electronpoor olefins. The reaction is stereospecific; the reaction mechanism is assumed to involve concerted attack by OH- and HOCl.536A new transition-metal-catalyzed epoxidation occurs with NaOCl in the presence of manganese-porphyrin in a phasetransfer In contrast to epoxidation with alkaline hydrogen percr &-unsaturated sulfones give the cis product on reaction with HOC1.537 Whereas nitroolefins undergo a stereoselective reaction with the HOO- anion,272 their epoxidation with HOCl leads to a mixture of (Z)- and (E)-oxirane~.’~~ Presumably rotation occurs before the ring-closure of the carbanion formed in the attack by the OCI- anion. 3,4-Epoxybutanone is obtained in good yield at PH 8-8.5 .538 The osmium tetroxide-catalyzed epoxidation of olefins with sodium chlorate has been reported. It was proved that the epoxy-oxygen originates

Oxiranes

40

exclusively from the chlorate. Incorporation of an alkyl substituent into the alkene increases the reaction rate.539 Chiral oxiranes have been prepared with sodium hypochlorite by alkaloid-assisted asymmetric synthesis under phase-transfer conditions.540 In a solvent of low polarity, epoxidation of olefins with thallium acetate occurs in good yield. Formation of the oxirane involves neighboring-group participation, while the side-product carbonyl compound is obtained via a carbocation resulting from heterolysis of a metal-carbon bond in the intermediate.s41’s42

-

- 95%

+

PPh,O

Oxiranes can be prepared by electrochemical oxidation.543Regioselective w epoxidation of polyisoprenoids will take place with excellent yields on sodium bromide-promoted electrochemical oxidation in neutral or basic medium.544This has now been described as a general method.544a Hexafluoropropylene oxiranes have been produced by electrochemical means.s45 The deoxygenation of dioxetane to oxirane with triphenylphosphine has been described (Eq. 50).546

2.

Preparation of Oxiranes from 1,2-Difunctional Compounds by 1,3-Elimination

Three-membered cyclic compounds can generally be prepared from difunctional compounds by 1,3-elimination. In the formation of oxiranes from 2-substituted alkanols, the alkoxide produced in the basic medium participates in an internal nucleophilic attack, which promotes the departure of the substituent on the adjacent carbon atom leading to ring-closure. A stereochemical condition for the reaction is that the reacting groups should be in an antiperiplanar conformation relative to each other (Eq. 5 1).

x = C1, Br, I, O S 0 2 R , OCOR, N R f ) ,

N F ) , OH

Oxiranes are usually prepared from halohydrins. A general method of obtaining chloroalcohols from olefins is by the addition of hypochlorous acid formed in situ form N-chloramides or tert-butyl hypochlorite. Bromoalcohols are produced from alkenes with N-bromosuccinimide or N-bromoacetamide, while iodoalcohols are prepared with iodine in the presence of oxidants (iodic acid, oxygen, and nitrite).

Synthesis of Oxiranes

41

The hydroxy function may originate from the reduction of an a-halogenated carbonyl compound or a Grignard reaction. The oxirane oxygen is not always incorporated directly from a hydroxy group; for instance, in the case of a carboxylic acid ester, it is derived with neighboring-group participation from an ortho-monoester intermediate. From the preparative point of view the stereochemical result of the reaction is important. The configuration of the oxirane is not changed compared to that of the starting olefin. Both the addition and elimination steps are stereospecific. This well-known ring-closure method has been thoroughly reviewed!-6 We shall deal here with those recent publications that are of interest for preparative, stereochemical, or other special reasons. Oxiranes cannot be prepared directly from 1,2-diols by dehydration. Formation of the oxirane intermediate has been studied in connection with the mechanism of the pinacolic rea~angement.'~'Oxiranes can be prepared stereoselectively from the acetals and ketals of 1,2-diols. D-(+)-2,3-epoxybutane has been obtained from an optically active diol via conversion of the ketal 64 to a halohydrin ester (Eq. 0-C-OMe II

Me HXo\c
pcI,_ $H

c1

-

(52)

&H

Me

64

The stereospecific preparation of cis- and trans-oxiranes can be achieved from the same diol via the acetal. The trans-oxirane is obtained via the glycol monotosyl ester and the cis-oxirane via the bromohydrin ester (Eq. 53).549

+ Me

Me PhCHO

(53) Me

H

M0elMr;'e

With TDAP in CC14 1,2-diols give the oxirane or the spirophosphorane, depending on the configuration of the glycol. The trans-oxirane is formed from meso-65 and the spiro compound (phosphorane) from dl-65 (Eq. 54).550,551

Ph-CH-CH-

I

I

OH

OH 65

-Ph

(54)

Oxiranes

42

Quantitative yields of oxiranes can be obtained from vicinal diols by the joint application of triphenylphosphine and DEAD (Eq. 5S).”, Me-CH-CH, Me-CH-CH,

O1 H ’OH

/

-

\

Me,

CH-CH,

DEAD

EtO’

C

\N/

\

H

PPh,

I

HN-C0,Et

-

(55)

OPPh,

0 EtO,C -N-NH--CO,Et PPh3=0

+

Me-CH-CH2

\ / 0

At temperatures around 200°, a-hydroxyacetates are transformed to oxiranes via a tautomeric ortho-monoester with neighboring-group parti~ipation.”~ By the action of heat. CO, is split off the carbonic acid esters of 1,2-diols and oxiranes are formed.554~555 Disecondary or ditertiary 1,2-diols react with diaryldialkoxysulfurane 66 by antiperiplanar intramolecular nucloephilic displacement via a 0-hydroxyalkoxysulfonium ion intermediate 67 (Eq. S6).556 OC(CF,),Ph 66

L

67

From the corresponding diols, cis- and trans-divinyloxiranes can be prepare2 by elimination of the monotosylate obtained via the disodium a l ~ o h o l a t e . ~In ~’ a similar manner, cis- 68 and trans-2-phenyl-3-vinyloxiranes 69 have been prepared from the erythro- and threo-diols with total s t e r e o ~ e l e c t i v i t y . ~ ~ ~

pv

Ph

0

68

69

Vinyloxiranes of (Z)-configuration can be obtained by 1,3-elimination in a multistep synthesis.559

Synthesis of Oxiranes

43

The ring-closure mechanism of 2-chloroethanol has been studied on the basis of kinetic and equilibrium chlorine isotope effects.560 Epoxidation of the terminal double bond of farnesyl acetate has been achieved via the bromohydrin, obtained with NBS.56’ A stereospecific method has been elaborated for the preparation of 1-alkynyloxiranes, starting from the monotosylate ester of acetylenic di01s.~~’ 1-Alkynyloxiranes are also formed from a-hydroxy quaternary ammonium salts in alkaline medium (Eq. 57).563

The base-catalyzed transformation of small-ring cyclic P-hydroxyalkyl-mercurichlorides is a 1,3-elimination reaction Eq. 57a.564/3-Bromooxiranes can be obtained from ally1 alcohols in excellent yield by bromine addition in dilute alkaline solution (e.g., Eq. 58).565

57%

43%

The Payne rearrangement is cited on p. 79, Eq. 114, Ref. 739. Fully substituted fluorooxiranes have been prepared from an a-haloketone with a Grignard reagent followed by hydrogen bromide elimination (Eq. 59).’04

Et-C-C-Me /\ F Br

6

- --HBr

MeMgBr

(59) 0

A new method of preparing fluoroepoxyalkanes has been described by Soviet authors (Eq. 60).566

Halohydrin has been produced in the presence of a free radical initiator for the preparation of oxirane fluorinated in the side-chain (Eq. 61).567

44

Oxiranes

Ye FzCH -CFz-C-OH

cI'_

I

CHZ -C1 I A FzCH-CFz-C-OH -w FzCH-CF2-C-0

Me

Me I

h e (61)

Bicyclo [2.2. Ilheptane-iodolactone can be converted to an oxirane in an aprotic solvent (Eq. 62).568

trans-Diaxial bromohydrins and iodohydrins containing a 3-substituted cyclohexane skeleton with futed conformation are readily transformed to oxiranes with silver carbonate in the presence of elite.'^' With Ag20 at room temperature, a- and 0-oxiranes can be formed via the i ~ d o h y d r i n . ~A~modified ' iodohydrin procedure is a useful model for the stereocontrolled preparation of acyclic compounds: when the diethylphosphate ester of homoallyl alcohols is reacted with iodine, the elythrooxirane is predominantly formed (Eq. 63).'17

I I

cp? -

The mechanism of the transformation of 2-cycloalkenols to chlorooxiranes with hydroxy group participation has been studied by taking into consideration stereoelectronic requirements (Eq. 64).572

p,,oH

WQ, 1.y OH t-BuOCl

(64)

In a similar way, 5a,6~-dichloro-3~,4/3-epoxycholestane has been obtained from the ally1 alcohol formed in the chlorination of cholesterol (Eq. 6S).573 An important field of application of the 1,3-elimination method concerns those compounds where oxiranes can be obtained with configurations opposite to those of the oxiranes resulting from the peracid method. Examples are the stereoselective epoxidation of a methylenecyclohexane derivative with NBA/KOH,574 the epoxidation of 3-alkylcyclopenteneg5 and 3,4-dialkyl~yclopentene~~~ with NBS/KOH, and the 0-epoxidation of bicyclo[3.3.0] octene and bicycl0[4.3.0]nonene.~~~ The different stereoselectivities can be interpreted on the basis of the mechanisms of the

Synthesis of Oxiranes

45

-

HO

c1

c1

C'

c1

reactions. A triterpene oxide with configuration opposite to that produced in the peracid oxidation has been obtained by halogenation of the double bond in DMF. The 0-oxirane was formed from the trans-halohydrin 0-formyl derivative.576 20,3@-Epoxypinane is produced stereoselectively from the trans-rnonotosylate (Eq. 66).577

An exception to the anti-elimination rule is the formation of the oxirane from the cis-monotosylbornane derivative (Eq. 67).578

In the syntheses of aryloxiranes and oxabicycloalkanes via a sulfonium salt intermediate, the leaving group is SR; (Eqs. 68 and 69).579,580 Br 0

1:l

Oxiranes

46

From the in situ reaction between RSe02H and H 3 O 2 , selenic acid and alkenes interact to yield 0-hydroxyselenides, which undergo selective transformation to oxiranes (Eq. 70).581 R-CH=CH2

+

[PhSeO,H

+ H3P02]

R-CH-CH,-Se I OH

@

,Me ‘Ph

-

RCH-CH,SePh bH

Me1

R - Y07

2,3-Epoxyindanone can be prepared most conveniently via the b r ~ r n o h y d r i n . ’ ~ ~ Epoxysulfonamides have been made from their c h l ~ r o h y d r i n sHydroxychlorina.~~~ tion of 70 with chlorine water gave 71, from which the epoxyphospholane oxide 72 was obtained by elimination (Eq. 71).584

0

Me

Me

d he I0

4\

fv\

0 Me

0 Me

71

72

1,3-Elimination has also been used to produce b i s e p o ~ y a l k a n e s . ~ ~ ~ - ~ ~ ~ Finally, mention may be made of those articles in which this method is utilized in the synthesis of optically active oxiranes for example, the simple synthesis of monosubstituted ( S ) - o x i r a n e ~ and ~ ~ ~the ~~~ asymmetric ~ cyclization of some chlorohydrins catalyzed by optically active cobalt (sa1en)-type or in the enantiomeric selection of racemic oxiranes via h a l o h y d r i n ~ ’and ~ ~ 0-hydroxy sulfides.593A useful three-step synthesis has been worked out from (S)-amino acids ~ ~ ~as~ enantiomer ~~~~ resolution for chiral oxiranes by to ( R ) - a l k y l o ~ i r a n e sas~ well complexation gas chromatography .s93c, 593d

Synthesis of Oxiranes 3.

41

Preparation of Oxiranes from Carbonyl Compounds by Formation of Carbon-Carbon Bonds

This method offers very varied possibilities for the preparation of oxirdnes and their derivatives. The essence of the process is the condensation of aldehydes and ketones in a basic medium with nucleophiles possessing a good leaving group. The alkoxide ion generated in the intermediate creates a bond with the neighboring carbon atom bearing a leaving group X so that an oxirane is produced (Eq. 72).

X

X I

RI-CH~

_Bo_

I

RI-CHO

R2 R3 :$.. \/ -+R~-cH-c, + 0

<-A

/R2 3-

R'-CH-C

,R'

The method is discussed in separate sections, depending on the structure of the compound providing the nucleophilic reaction partner. This reaction type is dealt with in a number of monographs and reviews, both in general and from special

aspect^.^-^, 594

A.

Darzen's Reaction

This long-known procedure is used mainly for the synthesis of glycidic esters (Eq. 73).

+

CICH2C02Et

0 R'\ Rz/C-cHCo2Et

(73)

a-Halogen derivatives are required in which proton abstraction as well as heterolysis of the halogen atom is promoted by an electron-attracting substituent group, for example, carbonyl, carboxylate, acid amide, cyano, etc. The base employed in the reaction may be sodium alcoholate, potassium alcoholate, lithium amides, etc. Benzene, THF, or HMPT is used as solvent, but the reaction can be carried out in a protic solvent and even in an aqueous medium. Good yields have similarly been described in a phase-transfer milieux.595-596a The mechanism of the reaction is well-known. The first step is formation of a carbanion, followed by nucleophile addition to the carbonyl carbon atom; halohydrin alcoholates are produced; finally, ring-closure takes place by intramolecular substitution. The stereochemistry of the reaction is much disputed; the reason why a unified viewpoint has not emerged is that the configuration of the end-product is influenced by the structure of the starting compound (including steric hindrance), the base employed, and solvation by the solvent, sometimes in an unclear manner.4 The stereochemical course o f the reaction is controlled by the kinetic and thermodynamic factors in the second step; the structure of the oxirane formed is decided by the reversibility of the aldolization and the reaction rate of the ring-closure.

Oxiranes

48

Stereochemical examinations have been carried out on the reaction depicted in Eq. 74, with variations in the cation of the base (Na, K, Li) and the solvent (HMPT, benzene, THF).597

PhCHCN I

c1

73

+

(74)

The reaction was always accompanied by retroaldolization. In the solvent (HMPT) in which the extent of reversibility of the aldolization was the highest, isomer 73 was formed practically quantitatively, via the least-crowded transition state. These results are in contrast with those obtained with benzaldehyde and chloroaceto599 where stereoselectivity was not observed in HMPT. Examples are presented below to illustrate the varied possibilities of utilizing the method. Glycidic esters can be prepared from the a-bromo esters with LiN(SiMe3),; mainly (72-86%) the trans isomer is formed (Eq. 75).600

+

R-CH-COzEt I Br

Ryy

R' RZ

fi'

\I

p780ce

RZ

0

+

RR

R'

COzEt

(75) COzEt

a-Haloglycidates 74 have been obtained from dihalo esters.

X = Br, C1 74

The bromo derivatives are less stable.60"602In a protic medium, dichloroacetonitrile gave a-haloglycidimic esters (Eq. 76).603

CHC1,CN

+

R R' // C

8

R 0 C1

f l ,0-i-Pr

i-PrOH

i-PrOK-

(76)

NH

The preparation of glycidic nitriles has also been described under phase-transfer conditions (Eq. 77).604

CICHzCN

+

5 0 % NaOH

Et,RCH,Ph

]

Clo

e

Synthesis of Oxiranes

49

An isomer mixture is obtained from an asymmetric carbonyl compound,6°4awhile KCN on solid absorbents yields cis-oxirane stereoselectively.6Mb Formation of diazoketoxiranes is shown in Eq. 78.605 0 ClCHz-C-CHN, + Ph-CHO *::: PhLC-CHN, (78) II 0

6

The trans-epoxysulfone is exclusively produced from toluylchloromethylsulfone; the stereoselectivity is motivated by solvation and steric reasons (Eq. 79).6062607

p-Me-C,H,SO,CH,CI

+

PhO H PhCHO

t-BuOH t-BuOK*

\ / \ /

c-c

’

(79)

\ SOzC6H4-Me - p

By means of a Darzen’s synthesis, glycidyl thioesters 75 can be prepared from a-halogenated thiol ester tert-butylate and benzaldehyde .608

R 75

With aldehydes, a-halogenated sulfides give thioether ~ x i r a n e s . ~ ”a-mercaptocarbonyl compounds react with chloracrylonitrile to yield dihydrothiophene oxirane derivatives; under phase-transfer conditions the leaving group is incorporated intramolecularly (Eq. 80).610

With ketones, a-chlorosulfoxide forms a-epoxysulfoxides (Eq. 8 l), which may be transformed by action of heat to homologous a,P-unsaturated aldehydes.611

Reduction of the condensation product obtained from a-halosulfoximines and carbonyl compounds leads to homologous aldehydes and ketones.612 A modified variant of the Darzen’s reaction has been described for the production of new derivatives by conjugate addition of nucleophiles to haloolefins (Eqs. 82 and 83).613

Oxiranes

50

Y For example, C< ,Cl

C 6H

+

,

70,Et

HC-Me I C0,Et

-

Since the discovery of phosphomycin, interest has turned to phosphoruscontaining ~ x i r a n e s .The ~ ~ ~Darzen’s reaction of a-halomethylphosphorus compounds with carbonyl compounds leads to such oxiranes (Eq. 84).

a

R, P-CH2CI

T-

n-RuLi

0

R,P-CHCl

8

+ PhCHO

-

R, I,P V P 0 0

h (84)

A study has been made of the stereochemistry of the reaction.615 Chiral chalcones are formed in the reaction of phenacyl halides and p-substituted benzaldehyde or sodium cyanide in the presence of cinchona alkaloid salts under phase-transfer conditions.540In a similar reaction, the asymmetric induction and the stereoselectivity have been investigated on a polymer matrix, when predominantly (E)-derivatives 76 were formed.616

76 (chiral)

A high enantioselectivity was attained with chiral quaternary ammonium salts in the reaction of p-toluylchloromethylsulfone and ketones in a two-phase system with a catalyst bound to a polymer matrix.617

Synthesis of Oxiranes

51

Reaction with Diazoalkanes

B.

Two types of products are generally obtained by reaction of ketones with diazoalkanes: a homologous carbonyl compound and a small amount of oxirane. The reaction scheme is presented in Eq. 85.

Addition of the diazoalkane nucleophile is followed by an S N i reaction with ringclosure or a homologous ketone is formed with a 1,2-alkyl rearrangement (shift). Spirooxiranes are produced from cyclic ketone derivatives with diazomethane (Eq. 86).61x

I

OR Which homologous diazoalkanes, a mixture of cycloheptanones and spirooxiranes results.61xIn cyclic ketones equatorial attack is usually favored! A perfluoro-enol also reacts with diazoalkanes (Eq. 87).619

CF\,

/CO,Et

,c-c\ / H'

F2HC

0

66%

Oxiranes

52

The reaction of a diazoalkane with an ester carbonyl group has been reported (Eq. 88). It was found that the reaction is promoted by the presence of a nitro group in the cY-position.620 C.

Reaction with Sulfonium Ylides.Corey Synthesis

Oxiranes can be prepared in excellent yield from carbonyl compounds by alkylidene transfer with sulfonium ylides. The reaction is generally carried out with dimethylsulfonium methylide 77, dimethylsulfoxonium methylide 78, or related compounds such as anionoid species originating from sulfylimines 79 and sulfoximines 80 that can undergo addition to the electrophilic carbonyl carbon.

78

19

80

A betaine intermediate is formed, the fragmentation of which leads to formation of an oxirane ring by intramolecular substitution by the anionic oxygen (Eq. 89). The sulfonium ylides also react with other types of compounds containing an electrophilic unsaturated bond (C=C, C=N), giving cyclopropane derivatives and aziridines.

This ylide chemistry is treated in a number of monographs and The formation and properties of 77 and 78 were first dealt with by Corey et al.624 Reactive ylides are prepared from dialkyl sulfide and dialkyl sulfoxide in a nonaqueous medium. The solvent for the epoxidation reaction may be an aqueous basic solution.625 No side-reactions occur in a two-phase system626 or under the more recent phase-transfer condition^.^^' While the mechanism of the reaction has been clarified in accordance with the scheme outlined in Eq. 89,628-631its stereochemistry is not known in every respect. The sulfoxonium ylides are more stable and behave as better leaving groups than the sulfonium ylides. Choice of the reagent is governed by stereochemical considerations, because their stereoselectivities differ.43632In general, 77 attacks from

53

Synthesis of Oxiranes

the more-crowded side and 78, 79, and 80 from the less-crowded side. Attack by the sulfoxonium ylide on the carbonyl site is reversible and the structure of the product is under the kinetic control of the betaine step. With the sulfonium ylide, the reaction is irreversible and the end-product is the result of thermodynamic control.629 Accordingly, with qfl-unsaturated ketones; sulfoxonium ylids 78 react to form cyclopropylketones, whereas the sulfonium ylids 77 prefer to give unsaturated epoxides (Eq. 90).

78

+ R-C-CH=CH-R I1 0

77

+ R-C-

II

0

C=C-R

-R-:TR 0

(90)

R-C-CH=CH-R

’ 1

0

Cyclopropyloxiranes 86 have been produced from chalcones with ylide 78 via a cyclopropylketone.642’643 With 4-tert-butylcyclohexanone, sulfoxonium ylides (78,80,81, 82)630give (Z)o x i r a n e ~ , whereas ~ ~ ~ , ~mainly ~ ~ (E)-oxirane is formed from 77. The N-p-toluylsulfonimidoyl-stabilized carbanions 83 are similarly regio- and stereoselective.

0 I1

0

Ar- S@CH,

I N Me’ ‘Me 81

?@

?@

0 Me-S -CH2 I

0 Ar-S-CH,

82

83

N Et’ ‘Et

I1

NTs

Sulfonium ylides permit the incorporation not only of the methylene group, but The synthesis of oxaspiropentanes has been a ~ h i e v e d ~ ~ ” ~ ~ ~ of other alkyl as shown in Eq. 9 1.

By equatorial attack on the carbonyl, a single stereoisomer is formed from tertbutylcyclohexanone. In the presence of sodium alcoholate, 84 is formed from a butadienyl-sulfonium salt with an aldehyde.637 The reaction is stereospecific with 85; for instance, with aldehydes the trans product is obtained.638 An interesting stereospecific intramolecular methylene transfer has been observed for a decalone derivative.639 Stereoselective epoxidation has recently been described with 79; predominantly, the trans product results.640’641Epoxidation can be carried out in a one-pot procedure at room temperature, with Me$ + Me2S04, then NaOMe formed in situ.644

Oxiranes

54

%R R

Q-gHAr

CH20R 84

85

86

Information on the details of the reaction is provided by the reactions of tricarbonylchromium-complexed sulfonium ylides with carbonyl compounds.645 Regenerable sulfonium salts anchored to polymers react with carbonyl compounds under phase-transfer conditions to give oxiranes in high yield.@' Dialkylamino-aryloxosulfonium alkylides may be employed for enantioselective epoxidation if the ylide with its chiral sulfur center is resolved into its enantiomeric f ~ r m . ~ An ~ ' enantioselective , ~ ~ oxirane is obtained by means of a chiral phasetransfer catalyzed procedure with dimethylsulfonium methylide.@' The utilization of arsonium ylides was reported some time ago.650,651A h'ighly stereoselective synthesis of mans-epoxides with triphenylarsonium ethylide has recently been described.651a Optically active arsonium ylide has been used in the asymmetric synthesis of d i a r y l ~ x i r a n e s . ~ ~ ~

D. Other Oxirane Syntheses Oxiranes can be produced in a similar way as in the Corey synthesis, but with different reagents.653The key reagents (PhSCH2Li, CH3SCH2Li, PhSC(Ph)HLi, etc.) give products of type 87 with carbonyl compounds. These products form sulfonium salts with methyl iodide, from which oxiranes are obtained by collapse of the betaine formed on treatment with base.654,655This reaction type has the advantage that it is possible to prepare oxiranes even from the ketones that do not undergo the Corey synthesis because of enolization in basic medium; additionally, the /3-hydroxysulfide stage is suitable for resolution of diastereomers.

OH I -C-CH2

'

SR (Ar)

87

A similar principle is observed in the reaction of seleno-anions 88 with ketones and aldehydes Eq. 91a.656-''0

Y

= SeR,

SR, O R , N R 2 , Si(CH3)3

Synthesis of Oxiranes

55

The chemoselective synthesis of alkenyloxiranes can be achieved from a,O-unsaturated ketones.661 If the carbanionic carbon atom in a-halolithium compounds is reacted with carbonyl compounds, a C-C bond is created; this provides a convenient, general oxirane synthesis (Eq. 92).662,663

X = C1, Br, J

Bisoxiranes can be prepared from dioxo compounds.664With geminal chloromethylallyllithium the synthesis of new a-vinyl tri- and tetrasubstituted oxiranes has been developed (Eq. 93).665

Reaction of his-(trimethylsilyl) bromomethyllithium with benzophenone gives the corresponding oxirane derivative.666 A general method has been elaborated for the preparation of 1,2-epoxyalkane phosphonates starting from 1-chloro-1-lithioalkane phosphonates produced by chloro-lithium exchange from a 1,l-dichloro derivative (Eq. 94); a mixture of cis and trans isomers is formed.667

c1

c1 I

0 R' ll I /RZ (RO), -P-C-C \R3 0 An almost quantitative yield was attained in a one-step synthesis when a monochloro derivative 89 was treated with n-butyllithium at - 70°, a carbonyl compound was added, and the mixture was heated to room temperature.668The prophosphoncedure is also suitable for the synthesis of l-substituted-1,2-epoxyalkane ates (Eq. 95).668

T

'\P-CH2 X' I C1 89

Y = 0,S X = EtO, (CH3)2N

Oxiranes

56

0 EtO, /I EtO/P-CH2C1

1) n-BuLi - 70°

7 + ~

70",

o

Et0,ll ,P EtO

20°

0 Me

Me

-cI1 -c 1

EtO'

Li

(95)

This reaction also can be effected in one step without the isolation of an intermediate. Another possibility for the preparation of an oxirane derivative is presented in Eq. 96.669 ArCHCH CO R

21)) (i-Pr),NLi I,, - 7 8 O

I

* ArCH$yZR 0

OH

The intermediate in the reaction is presumably complex 90 produced from the enolate of the 0-hydroxyester.

R

O

A

;

0.. 0 I .Lf

Li

90

Oxiranes may also be prepared from the reaction of aldehydes with trivalent phosphorus derivatives, as in Eq. 97.

2 ArCHO + (R2N)3P

-

A

r

T Ar

+ (R2N)3P=0

(97)

0

The interpretation of the mechanism of the reaction is that the trivalent phosphorus attacks the oxygen of the aldehyde, after which diastereomeric dioxaalkane intermediates 91,92 are obtained with another molecule of aldehyde. Oxirane and phosphine oxide result from the opening ofthe five-membered ring of 91 and 92.4,550'551

dr 91

Ar 92

a-Haloglycidyl esters and amides can be synthesized in excellent yield from aliphatic aldehydes with TDAP.670,671 The mechanism of a-halooxirane formation is illustrated in Eq. 98.

Reactions of Oxiranes

(Me,N),P

R'

+ R'CCl,

-

0

(Me,NI3P I

0

C-R I

c1 c1,

-

57

R21C,0 H'

(98)

= C 0 2 R , CONHz

It has been established that the alcoholates formed are very reactive. The aldolization is always reversible and, regardless of whether direct or secondary cyclization occurs, only the trans product is obtained. If the ring of the aromatic aldehyde bears electron-attracting substituents in the ortho position, the reaction with TDAP proceeds more easily, but the stereoselectivity diminishes.672

X = C1, Br, C1O4 L = pyridine, etc.

A new catalytic redox procedure has been devised for the preparation of oxiranes from ketones or ketoalcohols with Cu" alkoxides (e.g., Cu(OCH3)Clpyridine) (Eq. 99).673

IV.

REACTIONS OF OXIRANES

The chemical behavior of oxiranes is governed by two factors: the strain in the ring and the basicity of the ring. The extent to which these two factors contribute to the reactivity, either separately or jointly, can be assessed from the results of the reaction under various conditions. The reactions generally involve heterolytic opening of the C-0 bond (Eq. 100, 1). This opening, most often induced by an electrophile, is accompanied by attack from a nucleophile (a) or a 1,2-rearrangement (b). Other, comparatively rare reactions are the homolytic splitting of the C-0 bond ( 2 ) or the C-C bond (3). The biradicals formed undergo rearrangement (c) or conversion to ylides (d). The latter then suffer fragmentation (e) or lead to a Ring-opening to an ylid can occur directly or via 1,3-dipolar addition product (0. the homolytic mechanisms by photochemical, thermal, or radical initiation. Another reaction pathway involves deoxygenation to olefins.

Oxiranes

58

\

/

1.

C=O+

:c;

Deoxygenation

Deoxygenation of oxiranes to olefins is an important method in organic synthesis and in proving structures. A varied series of reagents have been used for this purpose in the past decade. In principle, the reaction may involve different pathways, depending on the nature of the reagent and the substrate. There may be a radical mechanism, via oxygen complexation or C-0 bond insertion, or nucleophilic attack on the a- or 0-carbon atom. The transformation may occur in one or several steps. Depending on the conditions applied, it may proceed stereospecifically with retention or inversion; in some cases there is complete loss of stereochemistry. The deoxygenation of oxiranes with metals or metal-containing compounds has been the subject of wide-ranging investigations. Nonstereospecific reductive elimination has been described with Cr" complexes (Eq. 101).674

93 is the probable transition stare or intermediate. Stereoselective reduction is observed with nondefined low-valency tungsten halides, namely, soluble reagents ' ~ the WC16-LiAIH4 prepared in THF from WC16 and a l k y l l i t h i ~ m , ~with Olefins have been obtained in varying vields by the use of a magnesium-bromide-

Reactions of Oxiranes

59

94

magnesium amalgam.677 A single-step reductive elimination with limited stereochemistry has been reported with a Cu-Zn couple; the rate of rotation of the C-C bond is close to the rate of olefin formation.678Oxiranes bearing electron-attracting substituents are converted stereospecifically to trans-olefins by Nio complexes,679 presumably via electron-transfer cleavage. Stereospecific deoxygenation has likewise been achieved with C O ~ ( C O )for ~ ; example, the epoxides derived from cis- and trans-dimethyl methyl succinates give the corresponding trans- and cis-olefins with inversion.680 A cobalt-containing five-membered heterocyclic intermediate 94 may be involved in the reaction. Fe(CO)5 transforms steroid, aliphatic, and aromatic oxiranes to olefins.681 The nonstereospecific nature of the reaction points to a radical intermediate. Low-valency titanium (from TiCl,-LiA1H4) is an effective deoxygenating agent.682 The lack of stereospecificity is explained in terms of a several-step radical reaction mechanism. Deoxygenation has been performed with low-valency reactive metallocenes in which the sequence of reactivity of the metals is Zr Ti 9 Mo > W.683 With bis(benzene)titanium in THF, methyloxirane is converted quantitatively to p r o ~ e n e . ~ ~ ~ Deoxygenation can be achieved with transition-metal atoms (Ti, V, Cr, Co, Ni) in a high vacuum at low temperature, V and Cr being the most active; cis-trans mixtures are obtained with low conversions.685The reaction of cyclohexene oxide of the with transition-metal complexes has been studied on a zeolite complexes examined, the copper-phthalocyanine and cobalt-diamine complexes are the most active. With arc-generated carbon atoms the deoxygenation is not ~tereospecific,6~~ because of the high energy of the singlet carbon atom. Oxiranes have been converted to olefins with appreciable stereospecificity with atomic carbon obtained by the thermal decomposition of tetrazole.681 Nucleophilic reagents will also effect deoxygenation. Di- or trisubstituted oxiranes have been transformed to olefins stereospecifically with inversion via a phosphobetaine (Eq. 102).688

-

Another possibility in the method is the reaction via a fl-hydroxydiphenylphosphine oxide.689Deoxygenation takes place with retention by means of triphenylphosphine derivatives Ar3P=X (X = S, Se). (Eq. 103).6w'691Triphenylphosphine itself has often been employed in deoxygenation of oxiranes and thiiranes.

Oxiranes

60

9, RZ

R'

% p

t-( -A

R'

RZ

X

-Ph,PO

RZ

R'

rRmRz (103)

If use is made of the five-membered cyclic phosphorus derivatives, the geometry of which is more suitable than that of the triphenylphosphine, formation of the phosphorane intermediate is more favored and the yield of olefin increases.692 Deoxygenation with KSeCN in mildly alkaline medium can similarly occur by heteroatom exchange; retention is observed as a consequence of double inversion.693Open-chain compounds react with good yields, but cyclic oxiranes yields vary considerably with the number of ring atoms, due to steric hindrance. Alkali metal 0,O-diethylphosphorotellurates are very useful reagents for the conversion of terminal oxiranes, Eq. 104694but the reaction does work for other types. In the case of oxiranes formally derived from acyclic olefins, the (Z) compounds react more readily than the (E)-oxirane s .694 a

RCH=CH,

+ T e + EtO,

-P-ONa

8

With methyltriphenoxyphosphonium iodide in the presence of BF3-Et20 oxiranes are deoxygenated with retention of stereochemical integrity via the intermediate 95 .695

96

Sodium cyclopentadienyl-dicarbonylferrate 96 and tetrafluoroboric acid react with oxiranes to give olefins with the same stereostructure, after decomposition of the iron-alkene complex.696With 96, diary1 and dialkyloxiranes are transformed to the olefins with inversion, by thermal decomposition of the intermediate a l k ~ x i d e .Oxiranes ~~~ interact with CF3C(0)I to yield olefins with the same geometry via a ~ - i o d o t r i f l u o r ~ a c e t a t e . ~ ~ ~ With trimethylsilylpotassium the deoxygenation is accompanied by inversion (Eq. 105).699 (Me), Si K

R

R

Hp:e3 R

R

-

R

R

(105)

Reactions of Oxiranes

61

Depending on the reaction conditions, the (E)- or (Z)-isomers of heteroatomsubstituted olefins are formed from a,p-epoxysilanes (Eq. 106).700

-

/o\ RCH-CHSiMe,

HX

OH X

I

I

RCH-CH-Si(Me),

or

acid

R-CH=CH-X (1 06)

X = Br, OAc, NHAc

Aryl- and vinyloxiranes and a,P-epoxycarbonyl compounds may be deoxygenated under mild conditions with diphosphorus tetraiodide with retention of stereochemistry.701 Other authors have also reported regio- and stereospecific deoxygenation with P44, PI3, and Me3SiI for di-, tri-, and tetrasubstituted terminal ~ x i r a n e s . ~KI, ' ~ Zn, and P205 in DMF have been employed for the deoxygenation of oxiranes in good yields in the carbohydrate field.703aJ-Epoxysilanes react with lithium di-n-butyl cuprate to give 0-hydroxyalkylsilanes in a regio- and stereospecific manner; these intermediates may be transformed to olefins through a p-elimination r e a ~ t i o n . ~ "A similar reaction has been reported with Grignard reagents.705 Another group of compounds converting oxiranes to olefins consists of lithiumalkyls; deoxygenation here is accompanied by the introduction of the alkyl group (Eq. 107).706

t-Bu 0

\L1

+

t-Bu-Li

-

'-BurCH

:

-

OLi Li t-"qlH \

2-Bu

Oxiranes undergo biotransformation to olefins in the r u m e r ~ . ~ ' ~

2.

Rearrangements and Isomerizations

The enhanced reactivity of oxiranes due to geometric strain is manifested in their acid- and base-catalyzed reactions, in their rearrangements in the presence of metals and metal compounds, and in their thermal and photocatalytic transformations. These reactions permit the development of new and varied methods of synthesis and the preparation of derivatives that in many cases are difficult to obtain by other routes. The main products of the isomerization reaction are unsaturated alcohols and carbonyl compounds. Great progress has been made in this area of organic chemistry during the past 20 years (The reader is referred to some relevant reviews,5,6,708-712

Oxiranes

62

A.

Base-Catalyzed Rearrangements

These processes take place by a mechanism of 0-or a-elimination. Ally1 alcohols may be formed in the course of p- or a-elimination (Eq. 108).

B:,

' Cd

I 00

(1 08)

&-Elimination occurs via a carbene intermediate (Eq. 109), which may be stabilized by transannular insertion or formation of a ketone.

The unusual rearrangement of oxiranes to allyl alcohols on the action of strong bases was first observed in the reaction of cyclooctatetraene oxide.713 The investigations have been extended to phenyl-substituted ~ x i r a n e s , ~medium-ring '~ cycloalkene oxides,715 and open-chain ~ x i r a n e s . ~These ' ~ studies have contributed to the understanding of the reaction mechanism. It has been established that the rearrangement to allyl alcohol is very selective. trans-Olefins are formed stereoselectively from open-chain oxiranes. On the action of the base, a proton is abstracted from the least-substituted carbon atom. Examinations have been made to elucidate other pathways in the reaction with lithium d i a l k ~ l a m i d e . ~ ' ~ - ~ ' ~ D-labeling experiments have demonstrated the stereo- and regioselectivity .722 A study has been carried out on the behavior of cyclohexene oxide with lithium alkylamides substituted under various condition^."^ The cyclohexanol yield was highest with diprimary alkylamide. Formation of the ketone was favored by a bulky base. Bimolecular substitution leading to aminoalcohol formation was also observed, mainly with lithium monoalkylamides. In the reactions of medium-ring oxiranes, bicyclic systems were obtained through transannular r i n g - c l ~ s u r e .718 ~ ' ~It~has been proven724 that these are produced via transannular insertion from carbene-type intermediates formed by &-elimination. The carbenoid insertion reaction proceeds smoothly in molecules with favorable geometry (Eq. 1

Reactions of Oxiranes

63

If the transannular reaction is hindered and p-elimination is not possible either, isomeric ketones are produced. The reaction following the carbenium pathway is 727 Thi, procedure has provided a new strongly temperat~re-dependent.~'~' possibility of synthesizing bicyclic compounds that are otherwise difficult to obtain. An example is the synthesis of pentacyclododecanol. (Eq. 11

Numerous instances have been described in the literature on the base-catalyzed isomerization of oxiranes with various structures. The product in the reaction of benzocycloalkene oxiranes with lithium diisopropylamide depends on the ring size: it is either a transannular insertion product or a transannular product and some a-ketone or only a 0-ketone (Eq. 112).729

&+a &membered ring

Studies have been made of the rearrangement of oxiranes containing an acetylenic ~ i d e - c h a i n , isoprene ~~' oxides,73' and y,6 ansaturated ~ x i r a n e s . ~ ~ ~ The kinetics of the reaction of tert-BuOK with aryl-substituted oxiranes follow a linear Taft correlation.733Steroid 5a,6a- and SP,6P-oxiranes react with pyridine to give 97 (Eq. 113).734

Oxiranes

64

97

The rearrangement of P,y-epoxyketones with diethylamine has been examined under mild condition^.^^ a,P-Epoxyketosteroids undergo the Favorskii rearrangement.736 The rearrangement of three stereoisomers of caryophyllene ketooxirane has been followed in a tert-BuOH-H20-KOH system.737

OH I

Me-CH-CH-CH

\0/

,Me

BQ

f)\

Me-CH-CH-C

'Me

/Me

,\Me OH

('I4)

On the action of base (NaOH-H20 or Et3N-CHC13), five- and seven-membered /3-epoxysulphones lead to y-hydroxy-cu,P-unsaturated s ~ l f o n e s . ~In~ *the case of a-hydroxyalkyloxiranes, base causes reversible oxirane migration (Payne rearrangement) (Eq. 114).739 Such an isomerization has also been observed in sugar chemistry in response to sodium methylate (e.g., Eq. 1 Me I

Epoxysilanes are converted by strong bases to silyl aldehydes and ketones.741 The stereospecific transformation of oxiranes on exposure to organoaluminium 743 Isomerization of transamides under mild conditions has been described.742> epoxycyclododecane has been investigated with dialkylaluminium N,N-dialkylamides of various compositions (Eq. 1 16).744

The best yield (99%) was obtained with DATMP in benzene or hexane. Under similar conditions 98 is transformed into 99 in good yield (Eq. 117), in contrast to reaction with lithium amide where the yield is only 5%.

65

Reactions of Oxiranes

Information on the stereochemistry of the isomerization under basic conditions is provided by Eq. 118(a) and 1 18(b).744

C4H?

F5H11

"CH-C'

\01\Me

-

$HZ

C4H9-CH-C-C5Hll I OH

(118a)

96%

83%

In both cases, only a single product is formed by means of a concerted synelimination. B.

Acid-Catalyzed Rearrangements

Proton donors or Lewis acids result in the transformation of oxiranes to carbonyl compounds. The first step is the binding of the electrophilic agent followed by the splitting of the Cp-0 bond (Eq. 119).

BFP

Oxiranes

66

(C,-0 bond splitting can also occur with R3 or R4 migration.) The bond splitting is followed by the development of a classical carbonium ion and the migration of some R group; in some cases, these two steps proceed synchronously.74s

100

t-Bu

Much attention has been paid to the mechanism via the carbonium ion intermediate.746-749Detailed studies have been performed on the dependence on the migrating group. In the BF3-catalyzed rearrangement of the 1,l-disubstituted oxirane 100 (Eq. 120),750,751it has been proved that the H atom cis to the methyl group migrates as a consequence of the interaction between the bulky tert-butyl and the OBF; group. In this case, 102 is the favored conformer.

M e w t - B u

101

102

Rearrangement of deuterated derivatives of n-hexyloxirane has been investigated in order to clarify the mechanism for oxiranes not containing a tertiary carbon atom.752Selective migration of the H atom trans to the alkyl group was observed. A fair number of publications have appeared on the isomerization of alkyl- and aryl-substituted oxiranes also containing other functional groups (e.g. ref^.^'^-^'^). Ph-,, % -’C .H ‘t/

0

/\

103

,,-Ph SPh

8

H-.. /0\ --Ph Ph/c-c&SPh

8

104

Migration of the functional group can also be observed in the Lewis-acid-promoted rearrangement of oxiranes containing a carbonyl group. The products of the rearrangement of thiol esters 103 and 104 clearly show the stereochemistry of the isomerization processes. The main product is obtained from the (E)-isomer by aphenyl group migration; three products are formed from the (Z)-isomer (by migration of the thiol ester group, the a-phenyl group, or the 0-phenyl group) in a concerted mechanism with an expanded cyclic transition-state structure.7s7The rearrangement reaction involving carbethoxy group migration is temperature- and solventdependent.7s8A study of the optically active isomers of oxiranes 105 and 106 has confirmed a concerted pathway. On the action of BF3, 1,2-acyl migration occurs in the case of 1057s9and 1,2-vinyl migration in the case of 106,760via transition states developing with participation of the carbonyl group and vinyl group, respectively.

67

Reactions of Oxiranes

10.5

106

BF3 also causes the very stable allenemonooxirane derivative to undergo rearrangement (Eq. 121).761

rBu

5 CH,=C-C-C-CH, I

t-Bu'

I

11

-t-Bu

(1 2 1 )

Me Me 0

The main products formed from the oxiranes 107 and 108 on the action of BF3 are the corresponding ketocyclopropane isomers; in addition, however, with doublebond participation and ring expansion, 109 is also obtained.762Similar transformations have been observed in the cases of 110 and 111 as we11.763-765 -CO,Me 107

\0/ 108

110

111

The rearrangement of oxiranes with various structures in the presence of AICI3, ZnCl,, and other Lewis acids has been examined by taking into consideration the strengths of the Lewis acids, the molecular structure, and steric and electronic factors.7667767 The effects of Lewis acid and the solvent have been investigated in the rearrangement of 1-n-octenoxirane to the aldehyde.768 By means of Mg12,

Oxiranes

68

a-haloglycidic ester and asymmetric a-chloroepoxyketones can be converted to a-ketoester and asymmetric 1,2-diketones, re~pectively.~~’ a,fi-Epoxysulfones rearrange in the presence of MgBrz to a-bromaldehydes and ketone^.^^'-^^^ a-Silylketones can be obtained from silyloxiranes via MhBrl-catalyzed ringcleavage.771 In the presence of MgI2, the (2S,3S)-isomers of 2-trimethylsilyl-2,3dialkyloxiranes yield a-trimethylsilylketones, while the (2S,3R)-isomers give not only ketones but also silylenol ether^.'^''^^^ Vinyl ether oxiranes 112 form bicyclic systems stereospecifically. The regio- and stereospecific synthesis of 113 from 112 has been described under mild conditions (Eq. 122).775

112

113

Isomerizations involving ring contraction have similarly been investigated.776 One such reaction is presented in Eq. 123.777

2-Carene oxide can be converted to limonenol with metatitanic acid (Eq. 124).778

In 1,2-epoxyoctane and its unsaturated derivatives the effects of the double bonds and various Lewis acids on the rearrangement have been examined.779The effects of Lewis acids on the regioselectivity have also been considered for oxiranes prepared from cycloalkenes. Equation 125 (where R = Ph and n = 6) illustrates isomerization processes in which ketone is formed on the action of ZnClz and mainly aldehyde on the action of A1C13.766

Reactions of Oxiranes

69

Isomerization of cyclic oxiranes has been dealt with in great detail with very many model compounds, because of the highly varied nature of the transformations.780-794 The individual reactions are influenced considerably by the reagent employed, the experimental conditions, and the electronic and stereochemical factors inherent in the structure of the reactant. Oxiranes with a contiguous cyclopropane ring have been subjected to detailed studies (Eqs. 126-128).782'783

Ring-expansion reactions with different, but essentially similar mechanisms have been found in the acid-catalvzed isomerization of cyclic oxiranes (Eqs. 129-

ph+ Ph

Ph

n

130)

70

Oxiranes

Very interesting isomerizations have also been observed in the case of spiro~ x i r a n e s ; ~ these ~ ~ - ~are ~ ’presented in Eqs. 133- 135.

New results have likewise been reported on the acid-catalyzed rearrangement of steroid o x i r a n e ~ . ~ ’Three ~ - ~ ~different ~ types of rearrangements are depicted in Eqs. 136-138. A new fragmentation is observed and isopropyl group migration occurs besides the oxirane + carbonyl isomerization (Eq. 136).795

15%

(136)

Reactions of Oxiranes

71

As a consequence of steric crowding, ring expansion takes place, as exemplified in Eq. 137.796 The oxirane + unsaturated alcohol isomerization is accompanied by methyl migration (Eq. 138).797 A methyl group likewise migrates in a BF3.AczO-induced rearrangement in a series of p r e g n a n e ~ .A~ long-range ~~ effect has been observed in the rearrangement of 5 , 6 - e p o ~ y s t e r o i d s . ' ~ ~ C.

Rearrangements Induced by Heterogeneous Catalysts and Metal Complexes

The results found in the literature relate predominantly to research into the catalytic activities of various metals, metal oxides, phosphates, and zeolites. In regard to the metals, the isomerizing activities of transition metals have been investigated in the cases of some model compounds. Isornerization to give carbonyl compounds is a characteristic transformation. Wide-ranging work has been carried out with the aim of understanding the mechanism of the catalytic reaction. On oxide catalysts (Al2O3, SiOz, MgO, TiOz, ZnO) oxiranes are isomerized to carbonyl compounds and unsaturated alcohols, depending on the surface state of the catalyst . Studies on the isomerizing effects of phosphates have extended to the catalyst Li3P04. The experimental results lead to the conclusion that this is a general method for the preparation of unsaturated alcohols from oxiranes. The above general statements will now be illustrated with some examples. Alumina, modified alumina, and silica-gel-induced oxirane rearrangements have been examined in the cases of 114-118;8°0-803

114

115

116

117

118

On silica gel, the rearrangement mainly proceeds via a typical carbonium ion. Various types of reactions have been observed on an alumina surface. A characteristic reaction is presented in Eq. 139; the yield is 75%.804

Oxiranes

12

n = 1,4

Japanese authors have made comprehensive investigations of the rearrangements of oxiranes in the presence of solid acids, bases, and salts.805-809The model compounds employed were cyclohexene oxide and 1-methylcyclohexene oxide. The effects of the acidic and basic properties of the catalysts on the selectivity were interpreted on the basis of the products obtained. The main products are carbonyl compounds and ally1 alcohol isomers. Rearrangements of d-limonene oxide over similar ‘ research acids and bases were studied on five different types of A1203;810-812 has been carried out on 2- and 3-carene oxides,813 cis- and trans-carvomenthene oxides814and a-pinene oxide.815 Reports on rearrangements on Li3P04 catalyst have mainly been made by Soviet authors.816 For di-, tri-, and tetraalkyl-substituted oxiranes, the ring-opening takes place at the carbon atom bearing the most s u b ~ t i t u e n t s The . ~ ~ ~mechanism of the reaction of monoalkyl-substituted oxiranes has been examined via the kinetics and the Taft correlatiow818 The methyl group in the p position undergoes migration (Eq. 140).819(HB are the acidic and basic sites on the catalyst).

Studies have been made on the regioselectivity of the isomerization in the case of 2-methyl-3-isopropyloxirane.820 The proton in the position is eliminated at a higher rate (Eq. 141). Me I

CH,=CH--CH-bHMe 1 OH

M~CH-CH=C-M~ I OH

Reactions of Oxiranes

73

The interest in oxirane isomerization is reflected in the patent literatUre.804,816,821,822

There has recently been an upsurge in the research into the role of metals in the isomerization of oxiranes. This research is in part of a synthetic nature and in part of theoretical significance in that the aim is the understanding of the stereochemistry and mechanism of metal catalysis. Cyclododecanone has been synthesized from epoxycyclododecane on a Pd catalyst.823Comprehensive work has been carried out on the hydrogenolysis and isomerization of methyloxirane on various metals. The results have been compared with those for oxacycloalkanes with larger rings.824 The transformations of 1,ldimethyloxirane and 1-methylepoxycyclopentene have been followed on Pd, Pt, Rh, Cu, and Ni catalysts.825 The mechanisms of the catalytic reactions have been dealt with in detai1.826-829It ha s been demonstrated that the isomerization of the oxiranes on metals is the primary process, occurring in parallel with hydrogenolysis. The pathway of the reaction depends on the nature of the metal. Deuteration has been utilized to establish the role of hydrogen. Kinetic examinations have been made in order to shed light on the reaction mechanism.830 For oxiranes with asymmetrical structures isomerization takes place in both directions (Eq. 142).828

RCH,CHO

H@

TR 0

M+H,

x

R-C-Me

Experimental proof has been obtained that the mechanisms of the isomerizations to aldehydes or ketones differ. Aldehydes are formed on the action of the acidic sites of the metal catalysts.831i832 while the formation of ketones is a hydroisomerization process,833 and can thus be ascribed to the effects of the metal and the hydrogen chemisorbed on it (Eq. 143).

Stereochemical research has made a considerable contribution to the elucidation of the mechanisms of the isomerization processes.834 Investigations on the transformation of tetramethyloxirane on various types of supported and support-free metals provided the first experimental proof that 1,2bond shift isomerization on noble metals also takes place in the case of compounds containing C - 0 bonds (and not only for hydrocarbons) (Eq. 144).835

Oxiranes

14

Me

Me

Me

\ /

0 I Pt

I \Me Pt

I

Pt

\+

Pt

\Me

Me

Pt

2Pt

Me Me I / Me- C-C-Me I I OH H

Me Me I I Me-C-C-Me I I 0- Pt

Me\ Me’

/Me ( 144)

C-c1 \Me 0

Me

I

+,Me

Me-C-C\ I 0 ‘Pt-

Me

Me Me I I -O=C-C-Me

C

Pt

I

Me

An interesting reaction has been observed during the transformation of epoxydiazomethyl ketones in the presence of Cu (Eq. 145).836

It has been found quite recently that the isomerization to carbonyl compounds of oxiranes containing a n-electron system is catalyzed by certain metal comThe experimental data acquired so far suggest that only the pentacyanocobalt complexes are active towards the isomerization of aliphatic and alicyclic oxiranes.u6

Reactions of Oxiranes

75

Two reactions differing from the customary ones are observed in the presence of rhodium carbonyl chloride (Eqs. 146 and 147).837,838 O:C/H

Cyclic epoxyalcohols undergo RhH(CO)(PPh3)3 (Eq. 148).847

D.

geometric isomerization by the action on

Other Rearrangements

A general method for the conversion of oxiranes to ally1 alcohols under very mild conditions involves the use of a selenium reagent (Eq. 149).848

KOCN causes five- and six-membered cyclic oxiranes to isomerize to the geometrical isomer of opposite configuration (Eq. 150).&49~850

This procedure can be employed to advantage in the field of steroids in particular. Configurational isomerization with OH group participation is illustrated in Eq. 15 1. In this several-step process, the oxirane configuration is not changed.851

Oxiranes

76

Regioselective rearrangement to allyl alcohols can also be attained with dialkylboryltrifluoromethane sulfonate in the presence of tertiary amines (Eq. 152).852

RCHz2kMe

-

Me

RCH,CH -C=CH, I I OH Me

The electrophilic conversion of oxiranes in a mild milieux has recently been described with organosilicon and other reagent^.^^^-^^^ With a reagent prepared in situ in acetonitrile solvent, cyclic di-, tri-, and tetrasubstituted oxiranes are opened regioselectively; treatment with weak organic bases then gives the corresponding allyl alcohols.853 a,P-Unsaturated alcohols have been prepared in good yields from cyclic and substituted acyclic oxiranes with CF3SO3SiMe3-diazabicyc1oundecene systems.854,854ay854b A less-sensitive reagent is ISiMe3-diazabicyclononene. Morehindered allyl alcohols are obtained from trisubstituted o x i r a n e ~ . ~8’5~5 a>

3.

Oxidation

Few publications deal with the oxidation of the oxiranes. This method is used for synthetic purposes if it is difficult to prepare the desired compound by other means. Alkaline hydrogen peroxide induces splitting of a C-C bond in most terminal oxiranes. The result of the reaction is a disubstituted ketone via a 0-hydroperoxyalcohol (Eq. 153)t5’ monosubstituted oxiranes yield glycols.

The mechanism and conditions of the process have been clarified. Trioxane derivatives are obtained in similar oxidations occurring through 0-hydroperoxyalcohols (Eq. 154).858

The intermediate produced from phenyloxirane by action of catalytic amounts of acid, reacts with benzaldehyde to yield an unsymmetrical trioxane derivative (Eq. 155) .859

I1

Reactions of Oxiranes

Oxiranes can be converted to dialdehydes with hydrogen peroxide in the presence of a boric acid ester or phosphoric acid ester.860 The base-catalyzed oxidation of oxirane and alkyl-substituted oxiranes with tert-butylhydroperoxide has been reported. With increased substitution the molecule undergoes fragmentation.861 With DMSO in the presence of tert-butylhydroperoxide and strong acids, a-ketols are formed via a sulfonium salt (Eq. 156).862 Ph

H

Ao

t-BuOOH

CH,CHPh I I@ OH OS(Me),Aa

-HA

CH,CPh I I1 OH 0

(156)

Oxiranes can be opened with periodic acid in a phase-transfer system;863in an aqueous medium, a dialdehyde is produced (Eq. 157); in the case of a dienemonooxirane, the double bond remains unchanged in the reaction.8w

Simple aliphatic oxiranes are oxidized by nitric acid to an oxalic 4.

Reduction

The most frequently employed reducing agents in modern synthetic organic chemistry are the metal hydrides and the complex metal hydrides. These reagents are used most often in the reduction of oxiranes to alcohols. NaBH4 and LiAlH4 have been constantly applied since their discovery nearly 40 years ago, but numerous variants of metal hydrides have also been produced. As a consequence of the effective work of a number of research groups, a wide-ranging literature is now available; this has led to the recognition of the mechanisms of the processes, and the reagent most suitable for a given purpose can now be selected. Very extensive work relating to the field of reduction with metal hydrides has been continued by H. C. Brown and his colleagues. The results of their activities earlier reviews and those of other authors have been treated in a recent exist as we11.6, 708,709,867 Another important reductive method is the utilization of dissolving metal reagents. These reagents perform reduction with high selectivity and, by virtue of their individual properties, are of use in carrying out special tasks.868

0xir an es

78

The past decade has also seen the publication of many articles on the catalytic reduction of oxiranes. An account of the mechanism and stereochemistry of the hydrogenolysis is presented in various reviews and papers discussed in the next section.406’7093869 A review that appeared recently on the reduction of oxiranes to alcohols covers all of these methods.870 A.

Reduction with Metal Hydrides

The metal hydrides exhibit different reducing properties. The complex metal hydrides (LiAIH4, NaBH4) are nucleophilic in character; hydride is transported from the complex anion to the electron-deficient centers of the functional groups. Another group of metal hydrides (boranes, alanes) are strong Lewis acids; they interact with centers that are relatively richer in electrons. The selectivity of the reduction can be improved and the scope of its application can be extended by the joint use of these two types (mixed hydrides). Within the nucleophile group, LiAIH4 stands out because of its strong reducing powers, although this diminishes the selectivity in multifunctional molecules.871In contrast, NaBH4 is a very mild reducing agent; for instance, it reduces oxiranes only very slowly. The reducing effects of the metal hydrides can be enhanced by variation of the cation and the solvent, and by the introduction of substituents that bestow new properties on it for steric or electronic reasons. Examples of such newly developed reagents include alkoxyaluminohydrides, such as Li(OMe)&1Ha7’ and L i ( t - B ~ 0 ) & l H ; 8 ~alkoxyborohydrides, ~ for example, K ( ~ S O - P ~ O ) ~ B H ; ~ ~ ~ a l k y l b o r o h y d r i d e ~ ,for ~ ~ ~example, Li(Et)3BH with its special hydride-transfer p r 0 p e r t y ; 8 ~or ~ ,the ~ ~ mild ~ reductant Na BH3CN.878i878a In the group of electrophilic reagents the reducing power of B2H6is increased by the addition of a catalytic amount of NaBH4 or BF3;8793880 the reaction is accelerated, but at the same time the reaction pathway is changed. New alkylboranes have been developed, for example, thexylborane 1 19881and 9-borabicyclo [3.3.llnonane (9-BBN) 120.882 Me I CH-C -BH2 Me/ 1 Me Me,

119

120

The reactivity of A1H:83 has been varied by the preparation of alkyl- and alkoxy alane s.884-886 The mechanism and stereochemistry of the reduction with metal hydride has been dealt with in many articles. It may be stated in general that the structure of the oxirane and the nature of the reducing agent exert great effects on the rate and pathway of the reaction.

Reactions of Oxiranes

79

the complex anion Reduction with LiAlH4 is an SN2-type attacks as a hydride-carrier on the side opposite to the oxirane ring; if there is no steric hindrance, the ring is opened regiospecifically at the least-substituted carbon atom and yields the more-substituted alcohols. The reactivity increases in the sequence LiBH4, LiAlH4, and Li(sec-Bu)zBH. Examinations on optically active l-aryl-l,2-epoxypropane and 2-aryl-2,3-epoxybutane, and 1-phenyl- and 1-cyclohexyl-l,2-epoxycyclopentaneand -cyclohexane modelsam have shown that the stereoselectivity of the reaction in the aliphatic series is controlled by the steric hindrance between the substitutens; the reactivities of the cyclic derivatives are influenced by the ring strain and the substituent effect. In studies on models similar to the above with A1H3, A1ClZH,and their deuterated d e r i ~ a t i v e s , ~ ’ it~ ~was ~ ’ ~found that besides the intramolecular attack by the metal hydride after its coordination to the oxygen atom of the oxirane, the a- or P-carbon atoms may undergo intermolecular attack by another hydride molecule. After the opening of the oxirane ring, rearrangement has also been demonstrated. Rearrangement involving ring contraction took place in the case of cyclic compounds. The reaction mechanism has been elucidated in studies on the reduction of asymmetric oxiranes with alkoxyaluminium hydrides8% and optically active phenylo~irane.*’~ Metal hydride reduction may therefore occur through an intramolecular or intermolecular mechanism and the reduction may be accompanied by rearrangement.8 In support of these general remarks, some examples will now be presented to illustrate the research results of recent years. Hydrogenolysis of a-3,4-epoxycarenes with LiAlH4 takes place on the leasthindered carbon atom (Eq. 158).896

Oxiranes with a rigid conformation, containing a neighboring OH group, are opened regioselectively (Eq. 159),897whereas flexible systems give a mixture of diols.

The reduction of cis- and trans-121 generally proceeds via trans-diaxial opening as a consequence of the effect of the XMe3 g r o ~ p . ” ~

Oxiranes

80

X

= Si, Ge, C

M@o

XMe,

121

An alcohol mixture is formed from tert-butylcyclohexene oxide, that is the reaction is not regio- or stereoselective (E. 160).898

.Q '\

LiA'H4,

+Q

ij

+ bH

'3

50%

0

+

Q

(160)

OH

H 0' 35%

15%

Opening of the oxirane ring in Eq. 161 takes place on the least-hindered side.171

(161)

0'

I

OH

LiAlH4 has also been successfully applied for the reduction of halogenated oxirane s. ' 0 0 8993

0 I / PhCH-CHZ

-

PhCHMe

I

OH

Li(t-Bu0)aH-Et3B is a suitable reagent for the instantaneous and quantitative opening of oxiranes (Eq. 162),'01 though it is less regioselective than Li(Et)3BH,877i902which can be used well for the reduction of hindered and rearrangement-susceptible oxiranes (Eqs. 163 and 164).

99%

Reactions of Oxiranes

81

Epoxyketones can be reduced to epoxyalcohols with a mild reductant zinc boroh ~ d r i d ewhich , ~ ~ means that the reduction leaves the oxirane ring intact.

122

Reversed regioselectivity has been observed in reduction with lithium 9,9-di-nbutyl-9-borabicyclo [3.3.llnonate 122. This compound reduces aryl-substituted oxiranes (Y to the aryl groups (in the most-hindered position) and aliphatic oxiranes in the least-hindered position (Eqs. 165 and 166).904 PhCH-CH2

\0/

122

PhCHZCH, I OH

A study has been made of the regio- and stereochemistry of the reduction of 123 by various hydride reagents (Eq. 167).905

All three products were obtained with LiA1H4, whereas the other two reagents proved selective. Vinyloxiranes are reduced very selectively by diisobutyl-aluminium hydride (Eq. 168).* Without regard t o the configuration (exo, endo), the reduction of norbornane diepoxides with LiAlH4 proceeds in such a manner that the norbornane moiety remains intact in the reaction.905a(Eq. 168).%

Oxiranes

82

123a

Me

Me

Me

95:5

The dissolving metal reduction (Ca/NH3) occurred with reversed stereoselectivity. The anomalous hydride reduction of hexamethyl-Dewar benzene oxirane has been reported.w7 With AlH3, a-allene substituted oxiranes give a- and P-allenyf alcohols.90x The reducing properties of B2H6 differ from those of the metal hydrides discussed so far.’” The oxirane ring tends to be opened at the more sterically hindered side,%’ although the reaction is not completely regio- and stereoselective (Eq. 169).x79

o-ze -oMe aMe B,H, H,O,

*OH

+

(1 69)

+

OH

OH

B2H6 has also been employed to study the behavior of styrene oxide, 0 - a n d p methylstyrene oxides, 1-phenylpropene oxide isomers, and 2-methyl-lphenylpropene oxide.’lO’’I1 Styrene oxide yields mainly the primary alcohol. Phenyldimethyloxirane is transformed in accordance with Eq. 170.912

The configuration of the produced diol is influenced by the relative stabilities of the benzyl- or alkylcarbonium ions formed during the reaction. Similar reactions were investigated earlier.901,913i914 The rate and stereochemistry of the diborane reaction is altered by a small quantity of LiCl.”’ Wide-ranging research has been performed with regard to the mechanism and stereochemistry of the diborane reduction in connection with cyclic916 and a l i p h a t i ~ ”a,P-unsaturated ~ and allylic epoxides, on diterpene models,91x-920and by study of the reduction of epoxym e t h y l e n e c y ~ l o h e x a n eand ~ ~ ~2 ,3-epoxy-3-methylcyclohexanone.922

83

Reactions of Oxiranes Dissolving Metal Reduction

B.

Alkali metal reduction is performed with Li, Na, and occasionally Ca in liquid ammonia, ethylamine, or especially diethylamine. The regio- and stereoselectivity of the reaction is satisfactory. Two such reactions are presented in Eqs. 171 and 172,923,924

OH Phenyloxirane is readily reduced to 2-phenylethanol with Na/NH3.’” These reagents open the oxirane ring at the sterically more hindered side, and the reductions are accompanied by retention of the configuration. The alkali metal procedures can be employed as a comparatively simple and clean method of reducA general synthetic method has been ing sterically hindered oxiranes.89899233924 developed with this procedure for the preparation of 2-ethynylcycloalkan01s.~~~ In the case of polycyclic compounds, the oxirane reduction is accompanied by rearrangements involving changes in the ring system (Eq. 173).927

H C.

Cetalytic Hydrogenolysis

The early investigations on the hydrogenolysis of the oxiranes were performed in the liquid phase, with a view to establishing the regiochemistry of ring-opening of the asymmetrically substituted oxiranes and primarily leading to formation of primary alcohols. It was found that mainly NiY2’ but also Cu9293930 catalysts conveniently yield primary alcohols. A number of authors have dealt with the industrial application. Methyloxirane is reduced on a Ni catalyst,931 straight-chain ~ ~ phosphorus-containing 1,2-epoxyalkanes in the presence of metal b o r a t e ~ ’ over metals,933and 1,2-epoxyhexane on metal-containing zeolites.gMA small amount of acid or base exerts a considerable influence on the regioselectivity of the process.

Oxiranes

84

This is presumably the explanation of the initially rather contradictory results.’ In an investigation of the hydrogenolyses of 1,2-epoxydecane and methyloxirane, M i t s ~ i ’ found ~~ that the primary alcohol is formed in greater quantity on a Ni catalyst, but the secondary alcohol on a Pd catalyst. Vapor-phase studies have the advantage that the problems caused by the solvent effect can be avoided.936Such studies have revealed that Pt and Pd catalysts cleave the C-0 bond from the less sterically hindered direction, while Ni and Cu do so from the more hindered side; Ag, Au, and Rh occupy an intermediate position. The fundamental difference observed in the regioselectivity can not be directly correlated with the electronic structures of the metals. Only the activity can be connected directly with the electronic structure; thus, the activities of Ag, Au, and Cu are much lower than those of the metals with unfilled d - o r b i t a l ~ . ’ ~ ~ Besides the catalyst, the substrate also exerts a considerable effect on the regioselectivity. The probability of cleavage of the more sterically hindered C-0 bond is higher in the presence of a tertiary or a benzyl carbon atom. In the hydrogenolysis of 1,l-dimethyloxirane, Ni, Cu, and Rh catalysts cause total cleavage from the sterically more inhibited direction, while Pt does practically as regioselective and Pd does so to an appreciable extent.8252-Phenylethanol is likewise the product in the hydrogenolysis of phenyloxirane on both Ni and Pd catalysts.937 More extensive breaking of the more sterically hindered C-0 bond can similarly be observed for other compounds.8259 826, 938 One possible explanation of the formation of the primary alcohol is that the oxirane isomerizes to aldehyde in the first step (Eq. 142) the aldehyde then being hydrogenated to alcohol.’ This is not probable, for oxiranes participate in hydrogenolysis under conditions where 0x0 compounds do not react at all with hydrogen or only very ~ l o w l y ~ ~ moreover, ~ ~ ’ ~ ’ the reduction of the 0x0 compound does not occur on a surface covered with the ~ x i r a n e . ’ Thus, ~~ formation of alcohols and 0x0 compounds is the result of simultaneous processes. Equation 174 presents an illustrative example of the roles of the various catalysts on the selectivity and regioselectivity in the hydrogenolysis of oxiranes containing other functional groups that can be hydrogenated.w Ph

O H OH

I

1

7

Ph- CH-CH-CH2Ph

-$vPh

0

Kaney Ni

1

0

OH OH I I Ph-CHCH,CH+h

TOH

I Ph-CH-

(1 74) CH-CH-

\0/

Ph

It should be mentioned that the supported Pt catalysts prepared via impregnation with H2PtCI, are acidic in nature,831probably because of the chloride content. Much more aldehyde and alcohol-1 is formed on such catalysts than on a supportfree Pt catalyst. The chemisorbed aldehyde formed on the acidic sites is presurnably hydrogenated before desorption.

Reactions of Oxiranes

85

The mechanism of hydrogenolysis of oxiranes was first investigated in detail by Study of the deuterolysis of 2,3-epoxybutane has revealed that d l butanone and d2- and d3-butanols are formed as primary products (Eq. 175). I t is assumed that the dl-butanone and d3-butanol are produced from a common intermediate, a triadsorbed species, while the d2-butanol arises from a diadsorbed species. Since deuterium-exchange and configurational isomerization are not observed for the oxiranes, the oxygen is presumed to adsorb first. (The strong poisoning effect, similar to ethers, can otherwise be explained by the strong dative bonding of the oxygen.) d,-butanol I

Me

Me

Me

\

Me/

O4 M

d -butanone

/

CHDC=O (175)

c

\ d3-butanol

Butane has been found t o be the primary product in desoxygenation. The formation of do-butene indicates that the process involves an associative mechanism. For the metal catalysts examined (Pt, Pd, Ni, and Rh), the mechanism did not differ fundamentally. With regard t o the stereochemistry of hydrogenolysis of the oxirane ring, it was earlier claimed that the hydrogenolysis proceeds with retention.' This was not confirmed by later research. For example, on a PtO, catalyst, the hydrogenolysis can be accelerated by acid-catalysis and the cis- and trans-alcohols are formed in almost indentical amounts."' The deuterolysis of cis- and trans-epoxysuccinic acids takes place with inversion."' In the case of phenyl-substituted benzyl alcohol^,"^ Pd causes inversion, but Ni causes retention in the hydrogenolysis of the C-0 bond. Analogous behavior has been observed in the hydrogenolysis of 2,3-diphenyl-2,3epoxybutane (Eq. 176).944 Ph

I

HO- C-Me I

O$M'

Ph

Me

Ph

3L

I

Me-C -OH HC-Me I I Ph

z

I

Me

Oxiranes

86

The cause of the differences in behavior regarding the stereoselectivity and the regioselectivity is considered to be that Pd displays a lower activity than Ni towards the electro-negative elements. As a consequence of the low activity of Pd towards oxygen, the hydrogenolysis is directed by the stereoelectronic factors and inversion occurs via an S N type ~ reaction (Eq. 177)."'

I'd

Ph-C-CI I

"2

00 I 1 PhZC-C-

l

1

M

-

00

I

Ph-C-C-

1

M

/

I

-Ph-C-C-

OH

I

H

H

I I

(177)

The strong adsorption of oxygen on Ni causes the process to take place via an SNi mechanism (Eq. 178). I

Ph-C-C-

i

\o/

I

I

& H, Ph.-C-C-

4

I

1

+Ph-C-C-

i

0-M

M

M

I

1

1

1

I

---+ Ph-C-C-

I

I

H OH

H 0-M

M

(178)

As a result of the addition of NaOH, inversion also occurs on the Ni catalyst. This is explained in that the adsorption of the oxygen is decreased by the action of the NaOH. Suzuki9& did not observe such effect by NaOH in the hydrogenolysis of rnonoterpene oxiranes. The different behavior of Ni could also be demonstrated in the case of oxiranes not containing a phenyl s u b ~ t i t u e n t .In ~ ~a~study on l-methyl-l,2-epoxycyclopentane, S B n C ~ h afound l ~ ~ ~that mainly the trans-alcohol is formed on a Ni catalyst, whereas a Pt catalyst yields a mixture with proportions corresponding to the equilibrium distribution. The dz-alcohol is obtained in the course of deuterolysis. Valuable results relating to the stereochemistry of the hydrogenolysis have also been provided by other investigation^.^^^^^^^^^^^ The most recent results on the hydrogenolysis of I-methyl-2,3-epoxycyclohexane are summarized in Eq. 179.938

0 O

M

e

+ Hz%

M OH e

O

+

01;+

a

30.5%

19%

M 13%

(179) e OH

The cis addition is explained in terms of the hydrogenation of the Cornet diadsorbed species. Assuming that roll-over is possible without desorption of the species, trans addition can also be explained. Examination of the hydrogenolysis of 1,2-epoxy-4-tert-butylcyclohexaneisomers revealed axial alcohol formation, while deuterolysis indicated the entrance of hydrogen by trans addition (Eq. 1

0

0

+ D z

dD (180)

OH

Reactions of Oxiranes

87

The hydrogenolysis of 4-tert-butyl-methylenecyclohexane epoxides was studied on Pd, Pt, Rh, and Ni catalysts,938a as was that of C,-,, 1,2-epoxyalkanes on Co, Ni, and Pt cat a l y ~ t s . ~ ~ ~ ~ It emerged from a study of the correlation between the configuration and reactivity of the o ~ i r a n that e~~ cis-2,3-dimethyloxirane ~ undergoes hydrogenolysis at an appreciably higher rate than the trans isomer on Pt and Pd catalysts, whereas on a Ni catalyst no difference could be detected. This phenomenon can be explained if the strong Ni-0 interaction results in at least partial breaking of the C-0 bond prior to adsorption of the metal at the carbon atom, so that no difference is expected 6etween the cis and trans isomers; the C and 0 atoms are adsorbed simultaneously on the Pt and Pd catalysts, and thus the cis isomer has a considerable advantage over the trans isomer. The given mechanistic conception accords well with the differences in regio- and stereoselectivity observed for the above catalysts.”8 Comparatively few publications have appeared on kinetic investigations of the hydrogenolysis of oxiranes. The vapor-phase hydrogenolysis of oxirane has been studied on a Pt catalystwg and the hydrogenolysis of 1,2-epoxybutane on a Pt/C catalyst.830 The effects of alkyl substituents in the oxirane on the reaction rate have been e ~ a m i n e d . ~ ~ Because ’ , ~ ~ ’ of the differences in kinetic behavior and the different effects of the structure of the oxirane on the reaction rate, it is assumed that the isomerization and the hydrogenolysis are independent reactions, but they occur on the same sites. It has been concluded from the independence of the rate of hydrogenolysis on the structure of the oxirane that the splitting of the C-0 bond is not the rate-determining step. On a Pt catalyst, the hydrogenolysis of tetramethyloxirane is accompanied by a 1,2-bond i ~ o m e r i z a t i o n(See ~ ~ ~Eq. 144).

5.

Ring Transformation of Oxiranes into other Heterocyclic Compounds

The publications that appeared up to 1975 on the transformations of oxiranes into other heterocyclic compounds are reviewed in detail in the monograph by van der Plasg51 and the relevant chapters of other review^.^'^^^^^^' A ccordingly, we merely supplement the earlier data with more recently reported results and, at the same time, present some of the varied transformations of the oxiranes. The possibility of stereoselective synthesis of heterocyclic systems was broadened considerably by 1,3-dipolar cycloaddition reactions. Heterocycles are formed if the ylide intermediates produced from oxiranes in photolytically or thermally induced reactions are made to react intramolecularly or with external dipolarophiles. Reactions of these types will be treated in Sections IV.8 and IV.9.

A.

Ring Transformation into other Three-Membered Heterocycles

A single-step synthesis of aziridines has been described by nucleophilic attack of an amidophosphate ester anion on the least-substituted carbon atom of oxiranes (Eq. 181).953

Oxiranes

88

Ph I

0

H\ H-’

N

.c --c I\

00 I

/H *.

‘Ph

+ O=P(OH), (181)

A new synthetic method involves reaction with an N-substituted iminophosphorane, which is accompanied by oxygen-nitrogen heteroatom exchange (Eq. 1 Me 0 P h A

+

Ph,P=NMe

- P h A

N

t

Ph,P=O

(182)

With phenoxymethyloxirane the reaction takes place through a five-membered cyclic intermediate (Eq. 183).954 R I 0 PhOCH2 Ph,P=NR Ph3P’Nl ‘0 CH,-OPh

-

A+

R N PhO-CH,A

+

Ph,P=O

Oxygen-sulfur heteroatom exchange has been achieved with 3-methylbenzenethiazole-2-thione in the presence of trifluoroacetic acid955 and with l-phenyl-5-mer~aptotetrazole.~~~ Thiirane can be prepared from oxirane on a support impregnated with alkali metal salts, by decomposition of the dithiocarbonether, perhydrobenzo-18ate formed with carbon d i s ~ l f i d e .A~ ~macrocyclic ~ crown-6, plays a role in the nucleophilic reaction of oxirane with KCNS, which leads to thiirane in good yield.9s8 Seleniranes have been obtained with tri-n-butylphosphine selenide in the presence of trifluoroacetic acid (Eq.

0

+

Bu,PSe

Se

+

Bu,P=O

(184)

Under the same conditions triphenylphosphine selenide was ineffe~tive.~” B.

Ring Expansion into Four-Membered Heterocycles

A general method has been elaborated for the synthesis of oxetanes from oxiranes by means of carbene insertion, with an a-selenoalkyllithium reagent that has also been utilized for the regioselective preparation of the oxirane itself from a carbonyl compound (Eq. 185).960

Reactions of Oxiranes

89

fx

K- Se -C -Li

0

0

Oxetanes can similarly be produced from oxiranes by using an excess of dimethylN-(p-toluenesulphony1)sulfoximereagent (Eq. 186).96'

a-

%)

Me-S.,

f-00

p - T s - N v

R R'

R

R'

- 0)

(186)

R R'

Oxetanes are formed by intramolecular ring-closure of 3,4-epoxyalcohols and their methyl analogues in basic medium. The alkoxide anion attacks regioselectively on atom C-3 (Eq. 187).9623963

base Me,SO

W

C

H

O

H

( ' 87)

1

R The stereochemistry of the reaction has been studied in rigid and in nonrigid system^.^^^^^^ A new route to functionalized 1,2-dioxetaneshas been described.gwa Lactones can be obtained by oxidation of the intermediate complex formed from dienemonooxiranes by carbonyl group insertion with pentacarbonyliron (Eq. 188).966

Oxirane can be converted into germaoxetanes via a radical-mechanism reaction with germylenes (Eq. 189).967By dimerization, digermaoxocanes are formed.

0

2a

+

PhCeCl

-

Ph I

C1CH2CH2-Ge 0

( 1 89)

Oxiranes

90

C. Ring Expansion into Five-Membered Heterocycles Benzofuran derivatives have been prepared through phenolate neighboring-group participation (Eq. 190).968

-

Another reaction giving rise to benzofuran derivatives is seen in Eq. 191.969

On the action of BF3, a steroid oxirane undergoes rearrangement to a tetrahydrofuran.w6 y-lactones are formed from oxirane by nucleophilic ring-opening (Eqs. 192- 194).970-972

Me0

NaCH(CO,Et),

* M e 0w L : 1 9 2 )

Me

Me

Rearrangement of a,p-epoxydiazoketones takes place on catalysis with BF3; this is followed by ring-closure (Eq. 195).756 Ph BF, E t 2 0

Ph

CCHN, 0

excess

--

EtOH

1:l

Ph

Reactions of Oxiranes

91

A y-lactone is produced from an epoxyketone in the Wittig-Horner reaction (Eq. 196).973

0 4 (MeO)2i-CHzC0,Me -

&

=Q+

0.

b’

b-

C0,Me

COzMe (196)

HO

Cyclic orthoesters are obtained in one step from oxiranes and ketene acetals (e.g., Eq. 197).974

124

The proton-catalyzed hydrolysis of 124 leads to y-lactones. 4,5-Dihydrofuran derivatives are formed from the reaction of a-nitrooxiranes and malonic acid dinitrile (Eq.

Tetrahydrofuran derivatives have been prepared from oxiranes with pyruvaldehyde acetal imines 125 or hydrazones (Eq. 199).976

OMe

OMe I

Me-C -CH- OMe I1

X-N

X = N(Me)*

LiNEt,

b

I

H,C $-CH-OMe Li+ X-N 125

(199)

Oxiranes

92

The preparation of dioxolanes has been reported by the condensation of oxiranes with a carbonyl compound under neutral conditions976a and in the presence of Lewis acids?77-980the mechanism of the reaction has been studied in detail.981Equation 200 depicts the general scheme of the reaction.

In the presence of anhydrous copper sulfate, aliphatic oxiranes react stereoselectively with acetone, but (E)- and (Z)-aryl-aliphatic oxiranes give the same isomer mixture.982 A study has been made of the kinetics of formation of dioxolanes from oxiranes and aromatic aldehydes in a neutral medium.983 Dioxolane and dioxan isomers are obtained from the reaction of 2,3-epoxybutane and carbonyl cornpounds.984 The reaction of oxiranes and COz yields 1,3-dioxolanones in the presence of various catalysts, such as organic antimony compounds,985 organic tin cornpounds,986 M O C I ~ - P a~ mixture ~ ? ~ ~ of phenols, alkali metal iodides, and metal oxides,988and Nio complexes (Eq. 201).989

0

A one-step synthesis with a good yield has been reported in which the conditions are mild, with Et&JBr as catalyst.989a Experiments on Cu and Ni catalysts with labeled compounds proved that the Cu-catalyzed reaction takes place with retention.'" Work has also been carried out on the kinetics of carbonate formation.991-993 Pyrrolidines have been successfully synthesized from epoxy amino-nitriles (e.g., Eq. 202).994

I

Me

Me

A pyrrolinium iodide has been obtained via the reaction of 2-methyl-2-alkynyloxirane with dimethylhydrazine (e.g., Eq. 203)."'

Reactions of Oxiranes 0

HC=C

+

Me,N-NH,

Me

-

93

OH I

Me

' 0 0

HC=C-C-CH,-N-NH 1

Me

I

Me

Me,$,Me HO

Unsymmetric diacetylenic oxiranes react with amines to give pyrrole derivatives (Eq. 204).996

I

Me

A number of authors have reported the acid-catalyzed synthesis of five-membered heterocycles containing nitrogen and oxygen (oxazoles) from oxiranes, with acetonitrile and benzonitrile. The stereochemistry of the reaction has also been dealt with in Refs. 997-999. By the reaction of oxiranes with RSCN in the presence of BF3, alkylthiooxazolines have been obtained (Eq. 205).'000,1001 ___)

0

MeS

Chalcones undergo a similar type of reaction.'00'" Various oxazolidine derivatives can be prepared from carbodiimide and oxiranes with HBF4.1m2 Oxiranes are converted to oxazolidines by the most different reactants. Examples of such reactions are presented in Eqs. 206-210. Oxiranes react with Schiff bases to give 1,3-oxazines (Eq. 2O6).'Oo3

CH,OPh The cycloaddition of oxirane to hexafluoroacetone N-benzenesulfonylimine similarly yields 1,3-oxazine derivatives (Eq. 2O7).'Oo4

Oxiranes

94

The preparation of 2-oxazolidones from aryloxirane with urea in DMF is illustrated in Eq. 208.'Oo5

Electron-accepting substituents promote the formation of 5-substituted isomers, while electron-donating groups promote the formation of 4-substituted isomers. Oxazolidones are produced by the reaction of oxiranes and isocyanates (Eqs. 209 and 210).'006,1007 Ph, \J(CH~)Z-CO~B~

PhNCo

0

Ph-OCHZ

7

+

L>(CHz)z0 0

C0,Bu (209)

Ph \ PhNCo

0

Ca(OEt), or AICi,

+

- OPh ( 2 10)

A>CHz 0 0

With phenyloxirane as starting material, both 4- and 5-substituted oxazolidones can be prepared.lW8 The reaction of geminal dicyanooxirane and thioamide leads to the formation of nitrogen- and sulfur-containing heterocycles (Eq. 2 1 l).'Oo9

wCN + CN

Ph

PhCSNHPh

0

-

Ph

00

s""

NO

H

\Ph

+

2HCN (211)

I

Ph Examples of the preparation of heterocycles containing oxygen and phosphorus are given in Eqs. 212-215. Phosphorus ylides are suitable reagents for opening the oxirane ring (Eqs. 2 12-2 14).'0'0-10'2

A+

Me3P=N-PMe3 I1 CH2

-+

M e/ \ \ p/a M~ Me3P=N

(213)

Reactions of Oxiranes

95

The products shown in Eqs. 213 and 214 have a rigid bipyramidal structure. Epoxy-ylides formed by the reaction of phosphorane and epichlorohydrin undergo ring-closure intramolecularly (Eq. 2 15).'O13

I

reflux toluene

A Azaphospholes can be obtained from azidooxirane with a tricoordinated phosphorus compound (Eq. 216).'0'4

The reaction of oxiranes with the sodium salt of malononitrile dimer gives rise to bicyclic compounds, for example, dihydrofuropyridines (Eq. 2 17).'0'5

Oxiranes

96

A new synthesis o f nitroimidazo-oxazoles from oxiranes has been developed in accordance with the method in Eq. 218.'0'6

CH2-CH-R I OH

The preparation o f trithiocarbonates from aliphatic and cyclic oxiranes can be achieved with sodium 0-ethylxanthate (Eq. 219).'O17

Germadioxolanes are formed from the reactions of germylenes and oxiranes via the corresponding four-membered germaoxetanes (Eq. 220).10'8

The means of preparing the reagent dialkylgermanone is shown in Eq. 221

0

+

Et,GeNEt,

D.

-

-,C=C,

\

/

+ E t 2 G e = 0 (221)

Ring Expansion into Six-MemberedHeterocycles

Valerolactones are obtained in the reaction of oxiranes with dianions produced from phosphorus compounds (Eq. 222).'0'9

Reactions of Oxiranes

97

(222)

Perchloric acid hydrolysis of glycidonitriles leads to spirolactones (Eq. 223).'OZ0

The reaction of oxiranes and isocyanides has been reported to give 1,3-oxazines (Eq. 224).'02'

A

R'

+

R3CHzNC

R2

n-BuLi

NC

OH

I

R3CH-CH-dII-R2

Y

I

R'

EtONa

Q:.

A

(224)

H

Procedures involving the reduction of oxirane and ammonia in the vapor phase over an A1203-Si02 catalyst have been patented for the preparation of pyrazine, piperazine, and m ~ r p h o l i n e . The ' ~ ~ ~formation of quinoxalines is illustrated in Eq. 22 5 .lo23

'aNH2+ Ph

NH2

(225) Synthesis of the perhydropyridazine skeleton is outlined in Eq. 226.loz4

d2v

+PhNH-NH2

(226)

Oxiranes

98

From the reaction of divinylketone monooxirane and H2S, thiopyranone is formed (Eq. 227).'02'

(227)

i-PrOH NaOAc

Starting from oxiranes, oxygen-containing macrocycles can also be prepared; a good example of this is the formation of the ten-membered oxygen-containing heterocycle 126 via the condensation of chloral hydrate and oxirane using the phasetransfer technique.'026

126

6.

Reactions with Organometallic Compounds

Oxiranes are converted by organometallic compounds t o alcohols. This reaction, which is one of the most important methods for the formation of a C-C &-bond, proceeds by nucleophilic attack of an organic carbanionic species on the leastsubstituted carbon. (Eq. 228). MeCH-CH, \/ 0

RM=H20

+ MeCH-CH2R I

(228)

OH

Clear-cut results are expected only for the homologues of oxirane and with halogenfree organometallic compounds. The type of alcohol formed and its yield and the regio- and stereoselectivity of the reaction depend on the alkyl (aryl) substituents and other functional groups near the oxirane ring. These substituents determine the basicity of the oxygen atom of the oxirane and the electrophilic character of the carbon atoms. Furthermore, the reaction pathway, the direction of attack, and the occurrence of side-reactions involving rearrangement are controlled by the basicity of the organometallic compound employed or the strength of its electrophilic and nucleophilic centers. The role of the solvent is not negligible. Besides the well-known Grignard compounds, other magnesium, aluminium, lithium, and copper-lithium organometallic compounds have been used as reagents - most recently, ate complexes of aluminium have been introduced.

99

Reactions of Oxiranes A.

Reaction with Grignard Reagents

Many publications have appeared in this field but attention is primarily drawn to some reviews.” ‘OZ7 When Grignard compounds react with substituted oxiranes, it is necessary to consider the formation of various products, predominantly the “normal” and “abnormal” alcohols. The Grignard compound itself is a reagent that simultaneously displays both nucleophilic and electrophilic character; in addition to the organometallic compound, electrophilic magnesium halides are always present (2 RMgX + RzMg MgX2), and these induce rearrangement. The reactions of methyl oxirane’OZ8and higher h o m o l ~ g u e s with ’~~~ Grignard compounds have been investigated systematically from the aspects of the nature of the halogen, the proportion of the reagent and the type of the solvent. In the case of cycloalkene oxides, those containing more than five ring atoms undergo ring contraction (Eqs. 229 and 230).’030,‘03’

+

RMgX*

CH-R

(229)

I

OH

In a side-chain containing a double-bond /3 to the oxirane, double-bond migration has also been observed.’032 The effects of the solvent and the reagent have been examined in the reaction of vinyl-magnesium bromide and p h e n y l ~ x i r a n e . ’ ~ ~ ~ Acetylenic oxirane gives a complicated mixture of products with a Grignard reagent, but the Cur halide-catalyzed reaction leads to an allene alcohol (Eq. 23 1 i . 1 0 3 5

Me I Me-CX-C-CH, \I 0

EtMgBr)

cuI

Me Me >C=C=C’ Et ‘CH, OH

(23 1)

Although a regioselective reaction occurs with butadienylmagnesium chloride, the selectivity in the formation of the normal addition product is not total (Eq. 232).’OM

CH,= CH-C-CH-CH-OH CH,=CH<%H,I MgCl

R’--RZ 0

11

I

CH, R’

+

CH,=C=CH-CH,-

k2

(232)

CH -CH -OH I

R‘

I

RZ

Oxiranes

100

Similar products have been reported by other authors.'036 The very stereoselective synthesis of 1,s-dialkadienes takes place with a good yield. The newly formed double bond exhibits (E)-geometry (Eq. 233).'03'

(233)

(E):(Z) 95:s

Homoallyl alcohols have been obtained in the presence of a catalytic quantity of CuI (Eq. 234).'03'

\ IR + 0

CH,=C-MgBr I

SiMe,

Cul

R I CH,-CH-C=CH, I

(234)

I

OH

SiMe,

The catalytic effect of CuI is illustrated in Eq. 235.'03'

M e Me

A

R

R'

-t

e

R

,

R Me

Other authors have also described copper catalysis in the Grignard reaction. In the presence of copper salt, cyclohexene oxide reacts with phenylmagnesium chloride under mild conditions to give trans-2-phenylcyclohexanolin good yield; in the absence of the catalyst, the conversion is low. At the same time, benzylmagnesium chloride led to a yield of 90% even without the catalyst.'w The reactions between epoxynitriles and Grignard reagents have likewise been studied in The reaction is governed by the nucleophilic character of the oxygen atom and the electrophility of the carbon atom of the cyanide group, which depends on the nature of the substituents. a-Chlorooxiranes react with abnormal opening on the side not containing the chlorine atom,'043 and indeed some compounds react only with organolithium compounds.lM a-Chloroepoxycarboxylic acids lead to chlorocarbonyloxiranes (Eq. 236). 045

'

Reactions of Oxiranes

101

c1

c1 R'MgRr

0

*

K 1 0- d c'R3

(236)

d

*o

The a-alkylation and arylation of aJ-unsaturated ketones has been achieved by Grignard reagents on the epoxyketone-N,N-dimethylhydrazoneintermediates (Eq. 237).lM6

Me,N-NH,

--PhMgBr - HOH

(237)

0

Ph

The reaction of 0-aroylacrylic acid oxiranes with Grignard compounds can be seen in Eq. 238.1W7

On the action of Grignard compounds, a,P-epoxysilanes undergo rearrangement to a-silylcarbonyl compounds, erythro-0-hydroxysilanes being formed in a very stereoselective reaction.7w The one-step synthesis of p-dihydroxyethylbenzene has been elaborated by means of an oxirane Grignard reaction (Eq. 239).lW8

fi i-

2 0

p-C,H,(MgBr),

-'TH1; +

HO(CH2): e C H 2 ) , l H (239)

B.

Reactions with Alkylmagnesiumand Alkylaluminium Compounds

Many publications deal with the reactions of oxiranes with the organic compounds of magnesium and aluminium.'027~1M9~1051 The review by Boireau et al.1052provides a comprehensive survey of the mechanisms of reaction of the two reagents. Studies with symmetric alkylmagnesium compounds indicate that nucleophilic attack occurs on the least-substituted carbon atom of the oxirane (Eqs. 240 and 241).

Oxiranes

102

Me- CH- CH, Et I

OH Me -CH-CH2

\0/

Me -CH- CH,-CH, I

-

CH=CH,

OH

Two products are formed from vinyloxirane (Eq. 242).

CH2 CH-CH-CH,

\0/

Et,Mg

Et I

CH2 CH-CH-CH1 I OH

+ CH2-CH=CH-CH2 I I OH

Et

(242)

3: 1

Phenyloxirane yields only primary alcohol (Eq. 243).'OS3 P h A

R2Mg

*

I:

OH

Ph-CH-CH,-

(243)

The variation in regioselectivity in the case of substituted 1,2-diphenyloxiranes is illustrated in Eq. 244.

10%

The reaction seen in Eqs. 242-244 are controlled by polar effects.1052A reactionhas revealed that the reaction kinetics investigation on l-phenyl-2,3-epoxypropane with organomagnesium compounds proceeds in two steps. The first, fast step is a process between the oxirane and the solvated reagent, leading to an equilibrium.

Reactions of Oxiranes

103

The second, slow step is attack by a further dialkylmagnesium molecule from the opposite direction. The result is inversion on the reacting carbon atom. Breaking of the C-0 bond of the oxirane is always preceded by the development of a new C-C bond (Eq. 245).Ios4

S

RMgR

OMga

OH

The stereochemistry of oxirane opening has been studied in the reactions of cis127 and trans- 128 l-phenyl-1,2-epoxypropaneswith dialkylmagnesium. 128 reacts on the carbon atom adjacent to the phenyl group and exclusively threoalcohol is formed. In the case of 127, the reaction also takes place on the other carbon atom and an alcohol mixture is obtained.'055 The importance of steric factors is demonstrated in studies with mircenemagnesi~rn.'~~~

127

128

Medium-ring oxiranes are opened by diethylmagnesium through interaction of the double bond on carbon atom C-6 (Eq. 246).los7

Q

+ H OH 33%

67%

In the reaction of epoxynitriles with R2Mg, the oxirane ring is maintained (Eq. 247).1058Epoxyketones may be prepared this way. Me

Me

NMgR

HOH

Meb C -0 R Me 0

(247)

104

Oxiranes

The basicity of the solvent influences the course of the reactions of dialkylmagnesium; solvents more basic than diethyl ether solvate the reagent strongly.'052 The reactions of the organoaluminium compounds differ essentially from those of the magnesium compounds.'052 When organoaluminium compounds are used, nucleophilic addition proceeds on that carbon atom of the oxirane ring on which there are more substitutents (Eq. 248).'05'

This stereochemically unfavorable reaction permits the conclusion that the formation of the product depends on electronic factors. In the course of the reaction; the C-0 bond is opened more quickly than the new C-C bond is formed. A carbonium ion results, which is stabilized by interactions with the neighboring groups. Boireau et al. comprehensively examined every detail of the reaction.'052 1-Phenyl-2,3epoxypropane and derivatives substituted on the phenyl group give alcohols of the same type, but the substituents exert considerable effects on the reaction. The value of p calculated from the Hammett function is 5.8. The results for 1,2diphenyloxirane derivatives are presented in Eqs. 249 and Zj0.'052

100%

80%

The ring-opening is regioselective in the reactions of a-and 0-alkoxy e p o x i d e ~ . ' ~ ~ ~ ~ The stereochemistry of the reaction has been examined, among others, in the cases of trans-l-phenyl-2,3-epoxybutane and trans-l-p-tolyl-2,3-epo~ybutane.~~~~~ After the reaction with triethylaluminium 80% erythro-3-benzylpentan-2-01 and 82% erythro-3-p-methylphenylpentane-2-01, respectively, were found in the mixture of alcohols. This proved that the attack by the ethyl group took place on the benzyl carbon atom and with retention of configuration. Since 80-82% erythro isomer was found in the mixture of alcohols the reaction is stereoselective. The mechanism of the reaction is shown in Eq. 2jl.'OS5

105

Reactions of Oxiranes

-.c-c'

I-

/ \ / \

0

z

AIR3 I

1

I

1

-C-C-OH

R

I \ /

3 -C-C-Q-blR, I

R R,Al-R ,

fast I

R,AP However, as in Eq. 245, the reaction takes place with inversion for those compounds in which there is not sufficient stabilization of the positive charge (e.g., pure aliphatic oxiranes). Organoaluminium compounds are stronger Lewis acids than organomagnesium compounds and form complexes with basic solvents. In ethers, for instance, R A 1 either does not react at all with oxiranes or gives a very low yield of product and, accordingly, hydrocarbons are preferred as solvents. Important roles are played in the reaction by the molar ratio of R3Al to oxirane and the nature of the R substit~ents.'~~~ Organoaluminium compounds have been utilized for alkynylation of alicyclic oxiranes in prostaglandin synthesis and for the preparations of cis-alkenols (Eq. 252).'060>'061

Regio- and stereoselective ring-opening has been reported in the reaction of cyclopentadienemonooxirane. The desired main product is obtained by the correct choice of the solvent (10% ether in hexane) (Eq. 253).'06'

Formyloxiranes react with rearrangement to give a 0-propiolactone with a diepoxyester as a side-product (Eq. 254).'063 JCHO

0

*IR3

0

Me $ T H - O V O

R

0

+

/?

Me +-OCH,b 0

Me

0 (254)

Oxiranes

106

C.

Reaction with Lithium Diorganocopper Reagents

Nucleophilic ring-opening of oxiranes by lithium dialkylcuprates occurs at the sterically less-hindered side and the corresponding alcohol is formed.'064-'066 The reaction can be carried out under mild conditions and the side-reactions observed with other organometallic compounds can be avoided. The mechanism of the transformations has been treated in detai1.'065~'067With MezCuLi the reaction proceeds stereoselectively and the new C-C bond is formed on the side opposite the C-0 bond of the oxirane (Eq. 255).'065,1065a

HO Me CuLi

Me

h

Me

(255)

Me

89%

Selective oxirane opening takes place in the presence of a ketone group (Eq. 256).1067

0

OH I

Me,CuLi

B

MeCH2CH(CH& -C-Me

(256)

The high stereoselectivity has been employed to advantage in prostaglandin precursor synthesis.'06' In the case of electron-acceptor substituents, the attack occurs mainly on the more electrophilic carbon atom. Tetrasubstituted oxiranes do not react, probably because of steric hindrance. The directing effect of the oxygen function has been examined in derivatives of cis- and trans-2-hydroxycyclohexene oxides (Eqs. 257-259).

Me,CuLi

oo QH

Me,CuLi

Me,CuLi

83%

0:: OH

85%

6: 49%

15%

107

Reactions of Oxiranes The results indicate conformational control.'069 Alkenyloxiranes react regioselectively (Eqs. 260 and 26 1).

Me,CuLi

* M&OH

(261)

Conjugated addition predominates and trans-ally1 alcohols are formed.'0703'07' In contrast, 1,3-cyclohexadienemonooxiranereacts less selectively (Eq. 262).'07'

Me 3 5%

42%

23%

Besides the 1,4-addition product, a direct-opening product and a rearrangement product are obtained. However, only a single product is formed from 1,4cyclohexadienemonooxirane with Me2CuLi (Eq. 263).1073

1,4-Alkadienols are produced in the very stereoselective reactions of alkenyloxiranes and olefinic lithiumorganocopper reagents (Eq. 264).'03'

OH

96 :4

a-Acetylenoxiranes give rise to allene alcohols (Eq. 265).'074

~ - BuCE C Me

Me,CuLi

OH n-Bu, 1 C=C=C-CH, I Me' Me

(265)

In the presence of lithium acetylide, a vinylcopper compound reacts with oxiranes to give homoallyl alcohols (Eq. 266).'075

Oxiranes

108

0 A +

LCu Bu L , O \ Pr

B

u

Li-czc-Pr,

H (266)

Besides the expected 1,2- and 1,4-acrylate adducts, an unexpected product is also obtained in a 52% yield from 1,3-cycloheptadienemonooxirane with a mixed lithium organocuprate (Eq. 267).'076

The strongly electron-withdrawing acrylate ligand is responsible for this high regioselectivity of 1,4-addition. However, it has been demonstrated experimentally (Eq. 268) that the regioselectivity is ligand-dependent.

+

SH2

?

Me-Cu-C-C-OMe

+

I

Li 97%

Me

One of the steps in a route leading to prostaglandin synthesis is a reaction of lithium vinylcuprate (Eq. 269).1077

CH,=CH-Li CUI

(269)

\ I

0

Appropriately substituted fl-hydroxyketones may be produced from epoxyketones containing a protected carbonyl group (Eq. 270).'078

Reactions of Oxiranes

109

The a-alkylation of a,P-unsaturated ketones can be performed via an oxirane intermediate (Eq. 271).'079

a-Alkylketones can be prepared from acetoxyoxirane (Eq. 272).'O8'

Asymmetric compounds found in natural products undergo regio- and stereoselective transformation with Me2CuLi (Eq. 273).'OS1

CH20H P h c H 2 0 a 0 . H

Me

Me,CuLi

Me

* ' h C H 2 O ~ 0 H 3 ) OH

H

A stereoselective step in a pheromone synthesis is the formation of an erythroalcohol from a trans-epoxydiester in accordance with Eq. 274.'Oa2

( 6 )

(2S, 3R)

An interesting transformation is illustrated in Eq. 275

r-Bu-i7 0 +

([gzcuLi *- .

a

u

~

o

(275)

H

Mq- Mqo Lep: @" Oxiranes

110

The reagent RCu(CN)Li leads to alcohols in good yields,'084 though the reaction is not selective for oxiranes with more complicated structures (Eq. 276).'OS5

R(CN)CuLi

0

Me

CH,R

CH, R

R-CH,-C-Me I

276)

OH

A reagent of general formula R2Cu(CN)Li2 reacts with epoxides with good yields, the ring-opening occurring on the less-hindered The silyl enol ethers of a,P-epoxycyclohexanones react with alkyl- and phenylcyanocuprate reagents in a regio- and stereospecific manner to give 1,4-trans-adducts (Eq. 276a).'085b9'085C

The reaction represents a new strategy involving an umpolung reactivity for carbon atoms (Y to the carbonyl group. Sequential trans-l,4-opening of cyclohexene epoxides and hydroxy-directed epoxidations provide general methodology for the functionalization of five carbon atoms of a six-carbon unit. P-Hydroxysilanes are formed from a,P-epoxysilanes.'0s6 An investigation has been made of the transformations of epoxynitriles with lithium d i a l k y l c ~ p r a t e s . ' ~ ~ ~ D.

Reaction with Alkyl-or Aryllithium

Organolithium compounds are less reactive than lithium organocuprates. A number of publications deal with the differences observed between the two reagents in the ring-opening reaction of o x i r a n e ~ . '1067, ~ ~ ~'0707 ' 1072,1073 The reaction of 1,3-cyclohexadienemonooxiranewith methyllithium is seen in Eq. 277.'073

MeLi

GHeMe a'" +

37%

(277)

63%

With asymmetrically substituted oxiranes the alkyl group is incorporated here on the more easily approachable side. The action of phenyllithium on chlorooxiranes has been examined.'088 Depending on the structure of the oxirane, the transformations found in Eqs. 278-280 take place; these could be of value for preparative purposes.

Reactions of Oxiranes

A-

PhLi

Bu

Cl

Ph, C1'

111

A

OLi I CH-CH B 'u

Ph

Bu

(278)

By variation of the solvent, not only alkyl-substituted oxiranes but also a,Punsaturated alcohols can be obtained from halooxiranes (Eq. 28 l).'Osg

/R' t-BUT C H \ R 2

+

t-BuvX

(281)

R2,CH-Li R'\

0

t-Bu - CH -CH=C I

OH

X = halogen

/R' 'R2

A general method for the preparation of P,y-substituted ally1 alcohols with (Z)configuration has been developed with a l k y l l i t h i ~ m .The ' ~ ~ regioselectivity ~~ of the ~ ~ ~the effects of the solvent and reactions of alkynyllithium and o x i r a n e ~ 'and (Me2N)J'0'091 have been investigated with regard to the formation of homopropargyllic alcohols. The stereochemistry of the process has been studied in the reactions of cis- and trans-neopentylallyllithiurn with cyclohexene oxide and trans-2,3-butene oxide. 'Og2 Phenyllithium effects proton abstraction from medium-ring oxiranes (Eq. 28 2) 1057

(2

PhLi

*

c 3 OH

(282)

0

The reaction of alkyllithium with oxirane yields the same products as in the reaction with the Grignard reagent (Eq. 283).'039

98%

In the presence of CuI the reaction is not selective (Eq. 284).

112

Oxiranes

45%

55%

With alkyllithium, expoxynitriles give two types of products, depending on the basicity of the organolithium (Eq. 285).1093

Pathway (a) is followed in the case of the more weakly basic reagents (LiCHzCN, LiCH2C02Et,etc.) and pathway ( b ) with strongly basic reagents. Nucleophilic opening has been reported with the trimethylsilylacetonitrile anion (Eq. 286).""

The conversion of oxiranes containing various functional groups has been studied with organolithium compounds.'095 /.?-Substituted ally1 alcohols are formed stereoselectively with n-butyl-lithium from 1,2-epoxyalkyl phosphonates (Eq. 287). Og7 Me

The most varied types of organolithium compounds are nowadays used in syntheses. For example, 2-lithio-l,3-dithianes, as protected acyilithium derivatives (Eq. 288), are suitable reagents for hydroxyalkylation with oxiranes (Eq. 288).1098,1099

Reactions of Oxiranes

113

OH y-Butyrolactone can be prepared in good yield from the lithium salt of oxazoline (Eq. 289)."O0

<>CH2R1

[KJ-yH-Rl

;CEcH-R-lI Li

Ljthiation of a-heterosubstituted oxiranes 129 has been investigated and favorable reaction conditions have been established with the aim of preparing nucleophilic oxirane molecules that can be employed in organic syntheses.'"'

R1& RZ

E.

129

R = SiPh3, SOZPh, CN, P(O)(OEt)* R' , RZ = H, alkyl, aryl

Reaction with other Organometallic Compounds

Sodium tetraethylaluminate and lithium tetrabutylaluminate alkylate oxiranes stereo- and regioselectively. In the case of aliphatic oxiranes, the reaction takes place on the less-substituted carbon atom, while in the case of a phenyl substituent, it occurs at the benzylic position, always with inversion. In the presence of a catalytic quantity of nickel salt, the reaction is accelerated c ~ n s i d e r a b l ~ . " ~ ~ ~ " ~ ~ With trans-alkenyltrialkylaluminates, 0-hydroxy-trans-alkenes are obtained (Eq. 2 90).l1O4

Oxiranes

114

The reaction of lithium trialkylalkynylborate and oxiranes has been de~ c r i b e d . " ~ ~A , " ~small ~ amount of air initiates the 1$addition of the organoborane and the oxirane by a radical mechanism to produce allenic derivatives (Eq. 291).'lo7

Et,B

+

/"\

HC-C-CH-CH,

-

EtCH=C=CHCH,OH

(291)

Oxiranes are transformed by tris(ethy1thio) borane to sulfur-containing derivatives.'lo8 With selenoboranes, terminal or a,P-disubstituted epoxides yield 0-hydroxyselenides; trisubstituted epoxides give allyl In the presence of Me3SiK, cyclohexene can be hydroxyethylated in the allyl position with oxirane (Eq. 292)."09

Phosphobetaines are formed from oxiranes with lithium triphenylpho~phine.~''~ ''lo On the action of acid, P-triphenylstannyl and P-triphenylplumbyl alcohols originating from the reaction of oxiranes and triphenylmetal-alkali metal undergo deoxymetalation reactions."" With phenyloxirane in the presence of MgBr2, dialkylcadmium and dialkylzinc give the corresponding alcohol in good yield.1053 Trimethylchlorosilane"'2' and trimethyliodo~ilane'~'~ with oxiranes give 1,2halohydrin trimethylsilyl ethers, while with trimethyliodosilane generated in situ a selective elimination mechanism is reported.1113a In the presence of magnesium bistrimethylsilyloxy derivatives are f ~ r m e d . " ' ~The reactions of oxiranes with organic isothiocyanat~silane~~~~ and trimethylsilyl cyanide"'631116a have been reported. The addition of trimethylsilyl cyanide to epoxides is strongly dependent on the nature of the Lewis acid catalyst. With Znlz, a new synthetic route to isonitriles has been derived."'6b 0-Siloxyalkyl phenyl selenides have been obtained from oxiranes with trimethylsilyl selenide in the presence of a catalyst (Eq. 293)."17

+

Me,SiSePh

ZnI,

,-SePh OSiMe,

Reactions of Oxiranes

115

A similar reaction has been described for the preparation of thioethers with aryland alkylthiotrimethyl ~ i l a n e s . " ' ~ ~Ring-closure occurs with w-bromo-l,2epoxyalkanes on the action of magnesium and lithium in the presence of CUI. By this means, cyclobutanol, cyclopentanol, and cyclohexanol can be prepared."" (e.g. Eq. 294).

An intramolecular oxirane ring-opening reaction can likewise be seen in Eq. 295."19

X = halogen

7.

Other Reactions involving C - 0 Bond Opening

This section will primarily treat those cases of nucleophilic addition in which the oxirane ring is opened with compounds of type HX, as illustrated in Eq. 296. The reaction products are 1,2-difunctional compounds; depending on the nucleophile, they are 1,2-diols or 2-substituted alcohols.

X = OH, SH, halogen, O R , OAr, O z R , S R , R C O l , etc.

The mechanism of the ring-opening and its regio- and stereoselectivity are areas of great interest in the chemistry of oxiranes. A very considerable number of literature data area available and the topic is dealt with in several review^.^'^^^^'"^^ The mechanism of the reaction has been studied in basic; acidic, and neutral ~ the mechanism media. In basic medium, the reaction is a substitution of S N type, and stereochemistry of which have been reasonably well clarified. In asymmetric oxiranes, the attack by the nucleophile generally takes place with inversion on the less-substituted carbon atom (Eq. 297).

Oxiranes

116

The mechanism of the opening in acidic medium is not so simple. Although a general reaction scheme can be written, the pathway is influenced to a great extent by the structure of the oxirane, the steric and electronic effects of the substituents, and the solvent also plays an important role. Ever-increasing attention is being paid to the concept of the microscopic structure of solvation in binary solvents. In binary solvent mixtures, the structure of the solvent around the molecule in the solvent shell differs from that of bulk solvent. In acidic medium, the first step is the preequilibrium addition of a proton to the oxirane; in the course of this, an oxonium ion is produced that can react further in two ways (Eqs. 298 and 299).

0

+

fast

Ha

R'\

Y i>o,,RZ

1

H/C--C,R4

(298)

H !

1 slow

+

R',

OH

,R3

I

H/c-&2

X

In the acid-catalyzed reactions, the nucleophile is linked to the carbon atom bearing the larger number of substituents and inversion normally occurs on this carbon atom; retention has been observed only rarely. If the breaking of the C-0 bond becomes complete and the carbonium ion has a relatively long lifetime, racemization also occurs. The mechanism of the reaction is bimolecular, or monomolecular, or the intermediate borderline A2. The mechanism and stereochemistry of these reactions taking place in acidic medium are currently of great interest. The contradictions observed in this field can be explained by the individual characteristics of the models examined and by the great variety of milieux employed. In most of the publications, attempts were made to clarify the polar, steric, and conformational effects influencing the mechanism of opening of the oxirane ring, by selecting suitable models and establishing the proportions of the stereochemical and regiochemical products. The results of kinetic investigations were also subjected t o detailed analysis. Attention was drawn to this technique in the fundamental study by Parker and Isaacs,"" which is a frequently cited reference.

Reactions of Oxiranes

117

The results of solvolysis in acidic medium in comprehensive examination of methyloxirane, phenyloxirane, and their derivatives have been interpreted on the basis of activity parameter^."^^-"^^ Studies on the reactions of methyloxirane, 1 , l dimethyloxirane, and epichlorohydrin"26 have led to the proposal of a new mechanism, denoted A;.1127 From research on dimethyloxirane in aqueous and nonaqueous media, a new mechanistic conception has been put forward; in this, a role is played by the ion-pair formed between the substrate and its conjugated acid."30 An A2 mechanism has been accepted for the reactions of primary and secondary aliphatic oxiranes, but further work is suggested as regards tertiary and monoarylsubstituted 0 ~ i r a n e s . l Wide-ranging '~~ investigations over the entire pH interval have been reported by Pocker et al.'13' The hydrolysis of tetramethyloxirane has been reexamined.' 128, 12' A large-scale series of examinations have been made in connection with the opening of aryl- and alkyl-substituted oxiranes in acidic medium.1133-"40 It h as been established for cis- and trans-1-phenyl-4-tert-butylcyclohexeneoxides that the reaction rate and steric course of acidic hydrolysis depends to a considerable extent not only on the configuration of the substrate, but on the nature of the solvent.1133 With hydrochloric acid in a solvent of low dielectric constant, the two isomers undergo mainly or exclusively cis opening, with retention of configuration. In water or alcohols, the stereospecificity is lower. The retention is attributed in part to formation of a solvent-protected ion-pair, while it is also in part a result of thermodynamic control. In studies on 1-aryl-substituted oxiranes, close attention has been paid to the extent of steric and conjugative effects, to configurational and conformational stereoselectivity, and to solvent effects."41 The effect of substituents on the stereoselectivity has been studied in the acidcatalyzed hydrolysis of a series of a r y l ~ x i r a n e s . " Work ~ ~ on the influence of temperature on the steric course of the reaction"38 has demonstrated that the tendency towards retention is explained by the high degree of carbocationic nature in the transition state leading to the cis products, the favorable entropy content of the transition state of cis addition, and the relatively low enthalpy barrier of the benzyl C-0 bond. At the same time, almost complete trans selectivity can be observed in aliphatic and cycloaliphatic oxiranes and ionization of the C-0 bond is associated with high enthalpy values. Attempts have been made to separate the inductive, 3,4-Epoxytetrahydropyranwas conformational, and stereoelectronic used t o study the inductive effect while the corresponding cis- and trans-methyl derivatives were employed to examine the stereochemical and conformational factors.""" Nucleophilic participation of HMPT has been reported in dipolar aprotic solvents.1145Formation of a sulfonium salt has been observed in an acid-catalyzed reaction in DMS0."463"47 Another research group has examined the nucleophilic splitting of stereoisomeric 3-methoxycyclopentene and hexene oxides."48 Detailed studies have been performed on the geometry of the transition state in the reactions of cyclopentene and cyclohexene oxide^,"^' and their competitive opening by charged and neutral nucleophiles in acidic aqueous methanol.1148 Other authors have dealt with the opening of epoxynorbornenes and the nature of the inter-

Oxiranes

118

mediate carbonium ion, other results have recently been published on the stereochemistry of the acid-catalyzed reactions of 2,3-epoxybicyclooctanes.11so~11sz Instructive kinetic measurements have been made in a binary ~ o l v e n t . " ~ ~ ~ ~ ' ~ ~ A contribution towards the understanding of the regioselectivity of oxirane ringopening has been achieved by application of the hard-soft acid-base theory, the results being in good agreement with pra~tice."~'Ab initio calculations have been carried out relating to the catalytic effect of H-bonding on the opening of the oxirane ring. The oxirane-nucleophile interaction has been examined in the acidcatalyzed reaction of oxirane with ~ a t e r . " ~ ~Computed '"~~ data have been published on the structure of oxirane and on the most stable structures for interactions of cis and truns types between protonated oxirane and a water molecule. Further theoretical studies have dealt with bimolecular nucleophilic opening of ~ x i r a n e , " ' ~ its acid-catalyzed opening.11s9 proton addition,"60 and the reaction with HF.l16' In this latter reaction a concerted mechanism has been proposed for the gas phase, but this mechanism is probably manifested even in the reaction in solution. Theoretical calculations have also been performed on the most likely rearrangement pathway for the cation obtained by vertical ionization of the oxirane molecule."62 In addition to these considerations of a general nature, we present below some examples that illustrate recent research results.

A.

Hydrolysis

Oxiranes are converted by hydrolysis to diols. Steroid oxiranes yield diols by cis opening with neighboring-group p a r t i ~ i p a t i o n . " ~ ~ - "cis-Ketoglycols ~~ have been obtained from cyclic ketooxiranes by utilizing the semicarbazone."66 The synthesis of 1,2,3-trisubstituted diols with cyclopentane and cyclohexane skeletons has been described.1148 In a,P-epoxysilanes, ring-opening occurs next to the trimethylsilyl group in the a! position."67J1168Chromone oxiranes can be converted to 1,2-diols by acid Lactone is formed from cholestane derivatives by stereospecific ring-opening with neighboring-group participation (Eq. 300).1170

In l-aryl-l,2-epoxycyclohexenes, a significant salt effect has been observed in favor of the formation of cis-diol products.1171 A diol is obtained from hexamethyl Dewar-benzene oxide via an intermediate with carbonium ion character (Eq. 3 0 1y 1 7 2

119

Reactions of Oxiranes

o&( ' eMMe

'Me Me

H,O@

- Me

--t \V I

Me

Me

-

Remote epoxy-oxygen participation has been experienced in the solvolytic reaction to be seen in Eq. 302."73

Many authors have dealt with the kinetics of epoxide h y d r o l y ~ i s , " ~ ~ , " ~pro~-'~~~ ducing results important towards an understanding of the reaction mechanism. B.

Transformations with Alcohols and Phenols

The main product in these reactions is the corresponding 1,2-diol monoether. With alcohols, side-reactions may occur during the conventional acid catalysis. For this reason, BF3.Et20 is a preferred acid catalyst; the use of heteropolyacids has also been r e ~ o m m e n d e d . " The ~ ~ base-catalyzed opening of oxiranes is also accompanied by rearrangement. The selectivity is more favorable on the opening of 2,2dialkyl-substituted oxiranes. In acid catalysis, the site of attack by the nucleophile is changed by electron-attracting substituents: secondary alcohols result instead of primary alcohols.1180 The ratio of the cis and trans products in the reaction of l-phenyl-l,2-epoxycyclohexene depends on the acidic or basic ~atalyst."~'With methanol in trifluoroacetic acid, a,P-epoxysilanes are transformed to P-hydroxy-amethoxy-silyl derivatives."68 Alcoholysis has also been carried out without affecting other functional groups in the molecule (Eq. 3O3).'lE1 M e . V C H = CHC0,R

0

BF R'OH

HOCH-YH-

CH=CHCO,R

I

Me O R '

(303)

Oxiranes

120

Meon

In the presence of sodium borohydride in methanol, epoxycholestanes are opened regioselectively (Eq. 304)."82

OH

MeOH, NaBH,,

BO

(304)

HO

H

The reaction seen in Eq. 305 results in oxetane derivatives by means of neighboringgroup participation (Eq. 305).1183

The role of steric factors has been examined in the opening of polyfluorinated o ~ i r a n e s . " Accounts ~~ have been given of the alcoholysis of steroid oxiranes and their transformation with phenol."857 The kinetics of the reactions of oxiranes with alcohols and phenols have been reported in a number of publications.1186-1188 The catalytic influence of transition metals has been examined."88a A secondary deuterium isotope effect has been studied in the course of m e t h a n o l y ~ i s , "and ~ ~ the solvent effect has been considered in reactions with phenols."87

C.

Transformations with Sulfur-ContainingNucleophiles

The reaction of oxiranes with thiols permits the preparation of a-hydroxyalkyl thioethers. Reactions with thiophenols are presented in Eqs. 306 and 307.1190,1191

OAc '-OAc

-

CH, OCOPh OAC

PhSH

HO

I

'-OAc

PhS-'

I

SPh

.CH,OCOPh OAc

1:l

"OAc

OH

(307)

Reactions of Oxiranes

121

An account has also been given of the reaction between benzylmercaptan and cisbenzene t r i ~ x i d e . " ~With ' a-mercapto esters, p-substituted phenyloxiranes undergo normal opening, without being affected by the substituents on the benzene ring.1193Chalcone oxides react with mercaptan with accompanying C-C bond cleavage (Eq. 308).""

The great variety of transformations that can occur with other sulfur-containing nucleophiles are illustrated by the following experimental observations. Oxiranes react with sulfurated borohydrides in a similar way as the hydrogen sulfide in a basic medium: symmetric bis hydroxyethyl disulfides are formed.119s cis-benzene trioxide gives di- and triadducts with N,N-diphenylthiocarbamide.'19' Reports have butadieneappeared on the reactions between oxirane and n-decylrner~aptan,"~~ monooxirane derivatives and m e r c a p t a n ~ , "and ~ ~ methyloxirane and sulfite ion.1198

D.

Reaction with Halogen Acids

Simple aliphatic oxiranes can be converted to fluorohydrin with hydrogen fluoride only with great difficulty, but the reaction can be carried out in systems with rigid conformations (e.g., steroids, 9,10-epoxydecalin)."99 Good yields can be attained from cyclopentene and cyclohexene oxides with 42% pyridinepolyhydrogen fluoride'200 and in a series of terpene oxides with an amine-hydrogen fluoride complex.8s6 The reactions can be performed more simply with hydrochloric acid and hydrobromic acid. The reaction between terpene oxides and hydrochloric acid has been examined, for example, in the cases of p-mentadiene dioxide,lZo1 a-3,4-epoxycarane,'202 and a - 4 , 5 - e p o ~ y c a r a n e . ~Studies ' ~ ~ have been made of the reactions of steroid oxiranes with hydrochloric acid and hydrobromic acid.1204'120sa~b The acidic opening of compounds containing two oxirane rings can be carried out selectively and in good yield (Eq. 309)."06

The selectivity is influenced considerably by the nature and stereochemistry of the substituents. For instance, under conditions similar to those used in Eq. 309, 130 does not react."06

Oxiranes

122

130

The stereospecific synthesis of trisubstituted olefins has been described in the concerted ring-opening reaction of cyclopropyloxirane (Eq. 3 1O)l2O7 as a novel adaption of the Julia-Johnson olefin synthesis.'207a

o$Epoxysilanes are transformed by hydrobromic acid t o the corresponding bromoh y d r i n ~ . " ~ " " ~In~ th e presence of hydrobromic acid and potassium bromide, cisbenzene trioxide gives 1,2,4-triol-3,5,6-tribromocyclohexane isomers.'208 E.

Reaction with Carboxylic Acids and their Derivatives

With trichloroacetic acid'209 and trifluoroacetic acid"" epoxyfatty acid esters are converted to dihydroxy esters. The opening of alkyl- and aryloxiranes with aryl carboxylates has been investigated in the presence of tertiary amine (Eqs. 3 11 and 3 12).1211 0

NR: TCH-CH, I

+ R\ CH-CH,OAr RZC02'

R2-C-OAr 0 R:N

phT R2C0,ArF 0

RZCO2CH-CH2OAr I

Ph

+

+ R:N (311)

RZCO2CH,-CHOAr I

Ph

(312)

Equation 3 11 shows a possible reaction pathway of the process. The opening of cyclohexene oxide with monochloroacetic acid is not a selective reaction: bis(trans-2-hydroxycyclohexyl)ether mono(ch1oroacetates) and trans-2(ch1oroacetoxy)cyclohexanol are formed.'212 In an aprotic solvent with benzoic acid, indene oxide gives only trans p r ~ d u c t . " ' ~The reaction of oxirane with monochloroacetic acid esters is shown in Eq. 313.1214

Reactions of Oxiranes

0

+

MeCONMe,

ClCH,CO,R

ZnCI,

123

* CICH2CH20CH,C02R (3 13)

Monoesters of diastereomeric 1,2-diols can be prepared from oxiranes with camphanic acid.'215 The acetolysis of epoxycyclopentanes and further transformations of the unexpected product of acetolysis (Eq. 314) have been followed in acidic and basic media.1216

The process in Eq. 315, the transformation of a steroid oxirane with acetic acid or benzoic acid, is regio- and stere~selective."~~

OH I

OH 1

The corresponding hydroxyalkyl derivatives can be obtained with carbanions originating from tertiary amides (Eq. 3 16)."17 MeCH2- C-NMe, It

0

NaNH,/NH,

0

- fi

+

HO(CH,),-

CH -C -NMe, I

Me

(3 16)

I1

0

Oxiranes yield oxazolines with nitriles in the presence of strong acids. The reaction proceeds with inversion, with complete s t e r e o s p e c i f i ~ i t y A . ~ ~new ~ application of the Ritter reaction has been reported; the opening of epimeric steroid-16,17oxiranes in acidic medium with acetonitrile.'218 The reactions of unsaturated hydroxynitriles formed from a-ethylenic oxiranes have been inve~tigated.'~'~ Numerous publications have appeared on the kinetics of reactions with carboxylic acids and their derivative^.'^^^-'^^^

F.

Reaction with Ammonia,Amines, and their Derivatives

The ring-opening of oxiranes with ammonia and amines is one of the general methods for the preparation of 1,2-aminoalcohols. This procedure has acquired great importance in practice too. The process is illustrated in a new example in Eq. 317.'226

124

8

Oxiranes

+

" 6 N H 2

NH,,

M

G

i

H (317)

8 0 :2 0

trans-2-Dialkylamino-3-cyclohexan-l-ols are synthesized in yields of 61-95% by the reaction of 1,2-cyclohexene oxide and secondary amine~.''~' 1-Acetylcyclohexene oxide reacts with amines by trans-diequatorial opening.'228 The configuration of 0phenyl-glycidic acids has been determined via their a m m o n ~ l y s i s . The ' ~ ~ ~2-amino4-tert-butylcyclopentanol isomers have been synthesized and identified by transformation of the corresponding o x i r a n e ~ . ' ~The ~ ' absolute configuration of enantiomeric 1,2-epoxy-1-phenylcyclohexane has been established after conversion to a dimethylamino derivative. lZ3' When oxiranes are reacted with enamines, y-hydroxyketones are formed (Eq. 318).'232 /-(5H2)tI

+

0

/\

Me

-

DMF-hydrolysis A

*

(3 18)

(CQH~~

The effect of a heteroatom (3 to the oxirane ring has been studied in the reaction of monosubstituted oxiranes 131 and ben~ylamine.''~~ If X = 0, the reaction occurs via the transition state 132 with neighbouring-group participation. Neighboringgroup participation has similarly been observed in the reactions of mono- and trisubstituted oxiranes and o-substituted primary amines.'zM The product ratio of the aminoalcohols formed from the reactions of a-vinyloxiranes and primary amines depends on the geometry of the 0 ~ i r a n e . l ~Base-catalyzed ~' addition of oxiranes to oximes leads not only to 0-alkyl but to N-alkyl derivatives (Eq. 3 19).'236

RXCH2CH-CH2

\0/

X=O,S,N

OH

I

CH,Ph 132

131

R'' ,,C=NR

H'

?

EtO@

R' RZ/'C=N-OCH,CHOH

R' @,CH~CHOH 'C=N R2/ 0 '0

+

Reactions of Oxiranes

125

Oxiranes react with 1,2,4-triazoles in the presence of acetic acid or formic acid (Eq. 320).'237

A comprehensive study has been made of the kinetics of the reaction of oxiranes and amines, with special regard to the side-reactions and the role of the secondary products.'238 The reaction of methyloxirane and dibutylamine has been investigated in an aprotic solvent to acquire information on the orientation of the ring scission.'239 Some kinetic studies relating to this field are also worth of mention,124&1243 The synthesis of carbamic esters of 1,2-diols has been achieved by reacting oxiranes and amines in an atmosphere of carbon dioxide under various experimental conditions.'24431245 G.

Miscellaneous

Oxiranes can be opened stereo- and regiospecifically under mild conditions with alcohols, thiols, amines, and acetic acid, with simultaneous activation of the nucleophilic and electrophilic centers on an alumina D'101s have been obtained on silica gel in the presence of water'250 and adsorbed FeC13.'251On an ion-exchange resin, the opening of oxirane isomers to diols and the separation of the latter,'252 e t h a n ~ l y s i s , " ~the ~ reaction with and catalytic a m m o n ~ l y s i s ' have ~ ~ ~ been described. Hydrolysis and methanolysis catalyzed by Nafion-H, a perfluorinated resinsulfonic acid have been reported.'255a Cyclohexene oxide and its 0-hydroxy derivatives have been opened regio- and stereospecifically with p h o s p h o d i e s t e r ~ . ' ~The ~ ~ mechanism of the reaction of oxiranes with sodium dialkyl ph~sphite"~'and d i p h e n y l p h o ~ p h i n e s 'has ~ ~ ~been studied. Cyclopropanecarboxylic acid derivatives have been obtained from substituted oxiranes with triethylphosphonoacetate anion.'259 The mechanism of formation of isomeric alkoxyalkylacetates from oxiranes with alkyl halides and mercuric acetate has been discussed.'260 2-Thiocyanato-2-cyclohexenone is formed regioselectively'261 (Eq. 321a) from 2,3-epoxycyclohexanone.

Oxiranes can be converted stereospecifically to chlorohydrins with FeC13 in ether.'262 The stereochemistry of opening with AlC13 is to a large extent solventdependent.'263 A number of publications have appeared on the Friedel-Crafts

Oxiranes

126

alkylation of aromatics with o x i r a n e ~ . ' ~ @ "Work ' ~ ~ ~has been carried out on the conditions of asymmetric induction,'266 the stereochemistry of the reaction,'267 and the side-reactions occurring as a consequence of isomerization.'268 Stereospecific synthesis of dihalogen derivatives from oxiranes has been achieved with various reagents: in a Ph3p-CC14 system,'26y (Eq. 321b) with 2-chloro-3ethylbenzoxazolium tetraflu~roborate,'~~'and with triphenylphosphine dihalides.'271912nDifluoro derivatives have been prepared by the reaction of oxiranes and SF4 (Eq. 321c). With hydrogen peroxide and hydrochloric acid, glycidyl sulfides give dichloro derivatives via a persulfurane intermediate (Eq. 322).'274

0 +Ph,P-CCI,

-

SE', RT CH,CI,, NaF * 0 H,O,, HCI

RSCH,CH-CH, \/

*

R-CH-CH,F I

3

F

R-S-CH-CH,-CI I

-

CH20H

0

(32 1b) (32 1 c)

(322)

RSOzCH(CH2Cl)z

C1 O-CH, If a chlorine complex of thioanisole is used to open oxiranes, a-chlorocarbonyl derivatives may be synthesized in a single step (Eq. 323).'275

OH

Cycloalkanone derivatives can be prepared from cycloalkenoxiranes by ringexpansion as illustrated in Eq. 324.'276i1277

LiCH(SMe), TsCI, base

hydrolysis, ~

8.

(324)

Photochemistry

Ever-greater interest is being demonstrated in the photochemical transformations of the oxiranes. The first studies relating to this field date from the 1950s. The publications that appeared up to the middle of the 1960s were r e v i e ~ e d . ' ~ ~ ~ - ' ~ ~ ~

Reactions of Oxiranes

127

With regard to the past decade, attention is drawn to two reviews covering rather short periodssi6 and two detailed monographs that give comprehensive analyses of the results.'281' lZ8' The reactivity of the oxirane ring is strongly manifested in the excited state too, in close correlation with the ring strain, the ring atom hybridization, and the interactions with the unsaturated and aromatic functional groups in the molecule. The primary process is homolytic C-0 or C-C bond cleavage, which may be accompanied by isomerization, rearrangement, and f r a g m e n t a t i ~ n . 'Since ~ ~ the functions linked to the oxirane ring have characteristic influences on the transformations of the molecule, it is convenient to classify and discuss the reactions of the individual models on the basis of substituents.'281i'282

A.

Alkyloxiranes

The first publications dealt with simple a l k y l o ~ i r a n e s ,lZa3, ' ~ ~ ~n~ The photochemical behavior of oxirane, methyloxirane, and ethyloxirane has been investigated by direct irradiation or mercury-sensitized photolysis. The products formed by cleavage have been analyzed, but the nature of the primary processes has not been touched on. A free-radical mechanism has been proposed.'285 A free-radical chain mechanism has been established on the basis of the products obtained on direct irradiation (254 nm) of pure methyloxirane.'286 Experiments with the aim of clarifying the primary Fhotochemical processes were published recently, with Mainly propanal was irradiation of methyloxirane in the gas phase at 185 obtained with a little acetone and traces of ethanol and propanol. An outline of the reaction mechanism is presented in Eq. 325.

1

Me

Me

From the excited-state oxirane, mainly propanal is formed by hydrogen abstraction via a biradical. With the increase of pressure, the excited state is quenched and, at the same time, there is a rise in the quantity of acetone. The two products are therefore not formed from the same intermediate. Acetone formation is conceived

Oxiranes

128

via a free-radical initiator, which abstracts a hydrogen atom from the methyloxirane. Production of a higher amount of acetone is expected on the basis of the stabilities of radicals 133 and 134.

133

134

The gas-phase mercury-photosensitized decompostion of oxirane has been investigated. The quantities of Hz, CO, CzH4, and alkenes obtained have been determined as functions of the pressure, the additives, and the p h o t ~ i n t e n s i t y . ’ ~ ~ ~ ’ ~ ~ ~ The results have 1.d to the proposal of possible mechanisms. An account has been given of the isomerization and decomposition of methyloxirane in response to intense CO, laser light.12g0 The photochemical bromination of alkyloxiranes has been described (Eq. 3 26). 291 BrCCI,

Me&,Me Me

CCI,

Me

*

k V M e

(326)

Me Br 0

The bromoketone is formed from the oxirane on action of UV-light by a regiospecific free-radical mechanism.’292 It has been established from esr spectra that oxiranyl radicals with pyramidal configuration undergo inversion, while alkylsubstituted radicals are rearranged through ring-opening to a-ketoalkyl radicals (Eq. 327),1293from which the brominated products are formed.

Bromooxiranes are produced in the presence of NBS.lZg1 Isomeric adducts are obtained in UV-irradiation or dibenzyl-sensitized addition reactions (Eq. 328).””

+ MeO,CCsCCO,Me

Reactions of Oxiranes

129

Several papers report the photoaddition to oxiranes in protic solvents (Eq. 329) .1295-I299

The phenomenon has been ascribed to photogenerated acid catalysis. Recent investigations indicate that the true catalyst is not the solvent but the metal ion in it, for example, Fe"' (Eq. 330), for in a solvent purified with EDTA no alcohol addition occurs.13oo

dk

(j(+)

F$f;I)*

>Llc + F e W )

MeoH

*

4-9 OMe (330)

OMe

B.

Unsaturated Oxiranes

Rearrangements to unsaturated ketones with hydrogen or alkyl migration have been observed in the acetone-sensitized reactions of cyclic and alicyclic 3,4-epoxyolefins (Eq. 33 l).1301

A similar rearrangement and geometric isomerization occur in the case of 2,4hexadienemono~xirane.'~~~ Irradiation of the spirooxirane 135 leads to cumulene, 135a, ally1 alcohol 135b, and oxetane derivatives 135c.1303 Cumulene formation is interpreted as occurring via a cyclopropylcarbene.

: * eM Me

0 135

JMe Me-

-\Me

Me 135a

Me I

/

C=CH,

M e rC>OH Me M e 135b

Me

135c

130

Oxiranes

In acetonitrile, exoepoxynorbornene derivatives undergo intramolecular (27~+ 20) photocycloaddition (Eq.332).'-

In other solvents (ether, cyclohexane, acetone), the cycloaddition does not take place, only reduction of the double bond is observed.'304 As regards the two monooxiranes of endo-bicyclopentadiene, in the course of acetone-sensitized photolysis only endo-4-oxatetracycloundec-9-ene 136 is changed. Photoreduction of the double bond proceeds by a free-radical mechanism; there is no interaction between the triplet-state excited olefin and the oxirane part.'305

136

Photoinduced valence isomerization has been observed.1306 An example is the process given in Eq.333.1307

The valence isomerization of cyclooctatetraene oxide to all-cis-oxacyclononatetraene is of interest both theoretically and p r a ~ t i c a l l y . ' ~ ~ - ' ~ ' ~ Dimethylsilylene produced by photolysis reacts in accordance with Eq. 334 in vinyloxirane as solvent.

It has been proved that the reaction takes place via the zwitterion 137.1311

/ \

Me Me 137

Reactions of Oxiranes

13 1

Studies have been made of the photochemical reactions of vinyloxiranes with iron carbonyl. The four diastereoisomers of 2,4-hexadienemonooxirane take part in photochemical reactions that are stereospecific. The structure of the iron complex has been determined by x-ray c r y ~ t a l l o g r a p h y . ' ~Complexes ~~ formed from dienemonooxiranes with iron carbonyl can be oxidized to lac tone^.^^^^'^^^

C.

Epoxyketones

The photochemical reactions of a,P-epoxyketones have been treated in detail in . ~past~decade, ~ ~there ~ has ~ been ~ an ~ upswing ~ , in ~ several r e ~ i e w ~In the interest in the reactions of compounds bearing relatively more separated functions: 0 , ~and- y,6 -epoxyketones. a.

a,P-EPOXYKETONES

Geometric isomerization may occur on irradiation.1316The characteristic photoreaction is photorearrangement to 0-diketones (Eq. 335).1317-1319

0 Ph-;/\/*

0

0

0

I1 II Ph-CCH2C-Ph

Ph

(335)

The findings led to the mechanism of the rearrangement being written in the form given in Eq. 336.1320The C,-0 bond undergoes cleavage; breaking of the Cp-0 bond is rarely observed.'321

a

\

In rearrangements of this type, a biradical intermediate is formed, predominantly from the singlet [S,] state. Further examples are to be seen in Eqs. 337 and 338,1316,1320

~

~

~

d-

Oxiranes

132

- J1f hv

+

(337)

40%

40%

An examination of the readiness of the 0-substituent to take part in migration gave rise to the following sequence: benzyl > hydrogen > methylene > methyl S phenyl. Numerous examples of the photochemical transformations of a,&epoxyketones to 0-diketones are to be found in the literature, including a series of steroid syst e m ~ . ' ~ The ~ ~formation " ~ of ~ unsaturated ~ ~ ~ ketoalcohols ~ ~ ~ ~has ~been ~ observed in the case of aroyl substituted oxiranes (Eq. 339).1317 R A Me

H C-Ph

8

hv

YHz

R

* R-C-CH-C-Ph I

OH

~

(339)

R = M e , Ph

If R = Ph, the cis isomer does not change under the same condition. Irradiation in aqueous ethanol transforms the trans isomer to the cis isomer and yields acetophenone and hydroxyacetophenone.'282 The photochemical rearrangement of steroid spiro aJ-epoxyketones 138, 139 has been investigated. Epimerization has not been observed in the course of the irradiation; b-diketones are formed as main products, via C,-0 bond ~ 1 e a v a g e . l ~ ~ ~

RZ R'

R' R Z 138

R' = H , RZ = Ph R' = Ph, RZ = H 139

The photolysis products of 139 depend on the stereochemistry of the comp o u n d ~ . The ' ~ ~ rearrangement ~ of steroid a,P-epoxylactone and a,0-epoxylactam to 0-diketone has been described (Eq. 340).1327,1328

~

-

Reactions of Oxiranes

133

Not only C,-0 and rarely Co-0 bond breaking but C,-Cb bond splitting may be observed.’31591329 A consequence of this is the very stereoselective epinierization of benzylidenecyclohexanone oxide.’330 The stereochemistry of photolysis of optically active dypnone oxide has been studied and the possibility of C-C bond cleavage has likewise been proposed.’331 C-C bond splitting has also been observed during examinations of chalcone oxides; transformation to dibenzoylmethane, trans-cis isomerization, and photofragmentation occur via ylides and acylcarbene intermediates (Eq. 341).1332

Ai The trans-ylide formed by disrotatory opening of the C,-Cp bond has been proved by reaction with methyl acrylate, when a substituted tetrahydrofuran is produced. Possible mechanistic pathways to account for the duality of the oxirane ring cleavage have been discussed.’333With a view to discovering the influence of the localization of the excitation energy on the photochemistry of a,o-epoxyketones, epoxyketones with various structures have been irradiated in solution at 366nm. Depending on the nature of the excitation and the localization of the reactive triplet state, the fragmentation gives rise to aldehydes and products that rearrange to a- or f l - d i k e t ~ n e s . ’ ~ ” ~ ’Ylides ~ ” ~ figure as intermediates in the formation of aldehydes. Their existence is confirmed by their low-temperature absorption spectra and their room-temperature reactions with d i p ~ l a r o p h i l e s . ’1335a ~~~~ A number of authors have also examined cyclic epoxyketones. The irradiation of cyclohexadienonemonooxirane with r,n* singlet excitation leads to a single product, a diketone (Eq. 342).’“

Oxiranes

134

*

A striking solvent effect is observed in the irradiation of epoxyketone in accordance with Eq. 343.'336

-i(

0

(343)

Investigations were recently begun on the photochemical behavior of epoxynaphthoquinones 140 and 141. Two types of photoaddition have been observed with olefins. In the case of 140, a spirooxetane is formed from the nn* excited state as a consequence of reaction between the carbonyl group and the olefin, without opening of the oxirane ring. In the case of 141, 1,3-cycloaddition occurs via an ylide, with opening of the C2-C3 bond of the epoxyquinone (Eq. 344).1337y1338

@o

a 0 R 0

0 R=H,Me

141

+

R=Me

140

+ hv

L

q

:

141

e Me

(344)

Reactions of Oxiranes

135

A reaction of similar type to Eq. 344 takes place between 141 and aldehydes or ke tones.’339 When a,P-epoxydiazomethylketonesare irradiated in benzene, they rearrange to butenolides, whereas in a large excess of methanol they are converted to y-hydroxya,P-unsaturated esters, via epoxyketenes (Eq. 34.5).lm Ph2C -CH- CHC0,Me I

OH

& Ph

80-95%

90%

(345)

Another characteristic general photochemical reaction of a,P-epoxyketones is the transformation of disubstituted cyclopentenone oxides to 2-pyrone derivatives (Eq. 346).’”’”M2

y $ :

Ph

> 260nrn

(346)

0 Irradiation of 3,5-dimethyl-4-pyrone in trifluoroethanol leads to cyclopentenoneoxirane, which on further irradiation is converted to a 2-pyrone derivative and a O-diketone. A photoadduct is also formed with the solvent (Eq. 347).IN3

1 0-

M e f i e

0

“fYe 0

(347)

Oxiranes

136

It was earlier discovered" that when tri- and tetraphenylcyclopentenone oxides are irradiated at 320-390 nm, colored compounds are formed; these are decolorized above 450 nm. The phenomenon is the photochromic valence isomerization of the compounds, with splitting of the C-C bond of the oxirane ring to yield a dipolar pyryllium oxide that is in photoequilibrium with the starting substance (Eq. 348).1345"346 Ph

320--390 nm

____)

(348)

450 nrn

Ph

Ph

0

The dipolar pyryllium oxides have been separated in the form of perchlorate salts and trapped with d i p ~ l a r o p h i l e s . ~lM8~ ' ~ b.

0,yEPOXYKETONES

The behavior of acyclic 0 ,y-epoxyketones has been investigated in detail by Padwa et a1.1349y1350As Eq. 349 shows, the transformation is not selective. The main product is the diketone formed by isomerization.

+

PhCH2C02H

+ H Ph"

(349)

O

D "Ph

The photocatalytic isomerization is explained by intramolecular hydrogen migration. The reactive state is an n-n* triplet and the products arise from a common biradical intermediate. The cis isomer does not react. Irradiation of oxiranes not containing the phenyl group gives rise to cyclobutanol epimers (Eq. 350).1351

28%

Reactions of Oxiranes

137

The formation of the products is interpreted in terms of excitation of the carbonyl, y-proton abstraction, and clockwise and anticlockwise rotation around the C1-Cz bond in the 1,4-biradical. On irradiation of 2,2-dimethyl derivatives, small amounts of epoxycyclobutanol and benzoic acid are formed (the latter originating from C, opening, facilitated by the geminal dimethyl group) (Eq. 35 1).

O

S

P

“Me ‘)“Orh

h

Me

(35 1)

0 The photochemical transformation of 3,4-epoxy-2-methyl-l-phenylbutan-l-ones 142 proceeds by the same mechanism, but the configuration of the end-products is regulated by the spatial requirements of the substitutents on C1 and C2.1352

142

Several accounts have been published on the photochemistry of cyclic

PJ-

epoxy ketone^'^^^-'^^^ and a general reaction mechanism has been proposed.1356The main steps in this are: Norrish type I bond cleavage with formation of a biradical (step 1); ring-opening leading to an acylalkoxy biradical (step 2); competitive ringclosure to a lactone (step 3 ) or with hydrogen transfer to a dioxo compound (step 4). If these steps cannot occur for geometric reasons, decarbonylation is observed, the products of which are obtained through disproportionation (steps 5 and 6) (Eq. 352).

hv

I

1

a

c6

7.

5

Oxiranes

138

A concrete example may be seen in Eq. 353.1355

H The photolysis of 2-oxiranylcycloalkanones has been used for the preparation of unsaturated macrolides (Eq. 354).13”

0

A discussion of the mechanism of the photocatalytic process outlined in Eq. 3551358has provided new data relating to the behavior of 1,4-acylalkoxy radicals and a,P-unsaturated aldehydo-ketenes.

8 OHCCH =CH(CH,),CH=C=O OHCCH=CH(CH2),CH=C=0

Photolysis of diastereomeric P , y-spiroepoxyketones gives the same products (Eq. 356),1359in contrast with their cyclopropane analogues, where stereoelectronic control can be observed in the reaction.

Reactions of Oxiranes

139

C. a,P-UNSATURATED y,6 -EPOXYKETONES The vinylogues of a,P-epoxyketones have also been examined extenAn example is given in Eq. 357. 0

The mechanism of the transformations has been supported by deuterium labeling experiments.'363 Excitation is followed by C,-0 opening; the y,6 -epoxyketones are then transformed further by ring contraction. In the study of photoreactions of two analogues containing fewer methyl groups, it was possible to observe two new reaction products that facilitate establishment of a general reaction mechanism (Eq. 358).'364,1365

*. C -4 -0 cleavage

'.-

I

I .

0

c,

Oxiranes

140

Depending on the methyl substitution, the biradical produced by C4-0 opening undergoes isomerization in one of four different pathways; the route depicted in Eq. 358 leads to formation of the enol lactone. The two epoxyketones obtained by selective oxidation of bicycloheptadienone are transformed in different ways in the course of the photolysis (Eqs. 359 and 360). 1366

Since 1968, a systematic, extensive series of experiments has been carried out on appropriately selected models in the field of the photochemistry of a,P-unsaturated The great complexity of this subject and the innumerable variations in the products formed mean that we must forego a survey of these investigations. D.

Salts and Esters of Arylglycidic Acids

On irradiation, the sodium salt of phenylglycidic acid gives phenylacetaldehyde as the primary product (Eq. 361).'377

hw

Ph

H

HOH

PhCHZCHO

+ CO, + PhCHZCHzPh + PhCHO (361)

A higher selectivity is experienced in the photolysis of phenyldimethylglycidic acid. In this case also, the catalytic decarboxylation is followed by isomerization to a carbonyl compound (Eq. 362).'377

Co?Na@ ""H Ph Me

& HOH

P h CI H - CI1- M e f C O , Me 0

(362)

Reactions of Oxiranes

"R

0 C0,Et

PhCHO+

Ph

Me

141

-

H

Ph C'' 0' 0 ' H-.tfe

hU

254 n m benzene

Ph

(363)

COzEt

Under different experimental conditions C-C bond splitting is observed (Eq. 363). The dioxolane derivative is formed from carbene and benzaldehyde produced in the course of fragmentation of the 0 ~ i r a n e . l ~ ~ '

E.

Aryloxiranes

Aryloxiranes undergo the following characteristic photocatlytic reactions: splitting of the C - 0 bond of the oxirane ring and subsequent rearrangement with hydrogen migration; opening of the C-C bond followed by isomerization and fragmentation in an elimination reaction of type (3 + 2 1). The reaction of phenyloxirane differs from the general transformations of the aryloxiranes. When irradiated in a fluid medium it yields acetophenone, together At 77"K, benzyl radical, phenylacetaldehyde, and with 1- and 2-phenylethan01.'~~~ styrene are produced.'379 Photolysis of monoaryloxiranes starts with formation of a biradical; the end product results by hydrogen migration. Some examples are presented in Eqs. 364366,1281,1380,1381

+

gw" \

Oxiranes

142

Vicinal diaryloxiranes and oxiranes bearing several aryl substituents undergo (3 + 2 1) cycloelimination reactions, and are fragmented to arylcarbenes and carbonyl compounds (Eq. 367).1382-'3w Carbene formation has been confirmed by esr and luminescence spectra.'385

+

R' and R2 may be H, methyl, cyclopropyl, cyano, or ester g r o ~ p s . ' ~ The ~~-'~~ phenylcarbene formed on irradiation of trans-l,2-diphenyloxiranehas been trapped and identified in the form of a cyclopropane derivative in methanol in the presence of benzyl methyl ether and a l k e n e ~ . ' ~ ~Photolysis ~ , ' ~ ~ ~ in the presence of 2,3dimethyl-2-butene proceeds by cycloaddition with the formation of cyclopropanecarboxylic acid and oxetane derivatives (Eq. 368).13"

+)+&A +TI Ph C0,Me

Ph 0 C 0 2 M e

)4

Me0,C

Ph

C02Me

Ph

(368)

For nonsymmetrically substituted oxiranes, the fragmentation pathway depends on the nature of the substituents. Groups capable of stabilizing an anion become part of the carbene fragment. Conclusions may be drawn about the mechanism of photolysis from the mode of the fragmentation. It has been suggested that the C-C bond is split in a concerted disrotatory manner with retention of the orbital symmetry;1393-1396 ylides are formed that are zwitterionic in structure (Eq. 369), and they cause the photochromic behavior exhibited by 2,3-diaryloxiranes at low temperature.

This structure was also proposed by Huisgen et a1.'397 From a very strained molecule, strikingly stable ylides can be produced photolytically or thermally (Eq. 370). 398

'

Reactions of Oxiranes

143

Studies have been made on the photolysis of 3,3-dicyanostilbene oxides in the ~ ~ ~the aim of establishing the (3 + 2 1) cycloeliminapresence of a l k e n e ~ 'with tion route on the basis of the products formed as in Eq. 371.

+

H:

Ph 0 CN CN

hu

+

R = H , Ph

+

Ph

R

CN

The results demonstrate that the carbene formation stems from photoopening of the carbonyl-ylide intermediates, in accordance with Eq. 372.

The fragmentation may be the result of concerted or consecutive processes, including opening of the C-0 bond. Photoexcited acyclic formation of ylides has also been proved directly in the course of their regioselective and stereoselective addition with dipolarophilic alkene~,'~"in the same way as ylides formed in the thermally induced ring-opening of aryloxiranes have been trapped and identified.'4011'm2 Results have likewise been reported on similar reactions with electrondeficient dipolarophiles. It has been found that carbonyl-ylides are formed both from the singlet and the triplet excited state. In contrast with the low yield from singlet excited oxiranes, the formation is quantitative in a new triplet-sensitized reaction mixture.'403 The triplet-sensitized reaction provides the same product from cis- and trans-1,2-diphenyloxirane. The trans-cis isomerization of some a-cyanoQarylglycidates via ylides has been described at 110" and at low temperature (77°K) in an inert matrix. The epimer ratio has been determined by nmr analysis (Eq. 373).'404

Oxiranes

144

H

phRo2Me H

C0,Me

CN

It

(373)

Photolysis of a-cyanostilbene oxides has been examined in cycloaddition reactions with the dipolarophile dimethyl fumarate.1405 The stereochemistry of the tetrahydrofuran adduct prepared from the ylides formed in the disrotatory electrocyclic ring-opening predicted by Woodward and Hoffman points to cis-trans isomerization of the carbonyl-ylide, probably via conrotatory cyclization. An account has been given of the photolysis of phenyl-substituted epoxyethylphosphonates (Eq. 374) and it has been established that the reaction pathway leading to phosphono-substituted carbenes is the more f a ~ 0 r e d . l ~ ' ~

Ph2C: Ph

P(OEt),

6

Ph-C

0 0

+ Ph-C-P(OEt), -

POEt,

(374)

+ Ph2C=O

The [4n + 21-cycloaddition reactions of the photo- and thermo-induced carbonyl ylides of numerous symmetrically substituted 2,3-diaryloxiranes have been examined with a variety of d i p o l a r ~ p h i l e s . ' ~ ~ ~ ~ The reaction of ring-bridged stilbene oxides has also been in~estigated.'~'~ These compounds are more photostable than the open derivatives; carbene has not been detected in the primary products, although their photochromic behavior has been observed at 77°K. Their rearrangement leads to the formation of an unsaturated ketone by hydrogen abstraction through a biradical with Norrish type I1 cleavage (Eq. 375).

n = 1,2

Reactions of Oxiranes

145

H ~ i s g e n has ' ~ ~made ~ theoretical and reaction-kinetic studies in connection with the electrocyclic ring-opening of oxiranes with particular regard to orbital control of the ring-opening and to the steric course of the reactions. Theoretical considerations have been published on the photochemical ring-opening and fragmentation of o ~ i r a n e .1409 ~ ~ ,A similarly comprehensive theoretical survey recently appeared dealing with the structures and reactions of ylides formed from substituted oxirane~.'~~'

9. A.

Thermally induced Reactions

Alkyl- and Alkenyloxiranes

Flowers et al. have dealt with the thermal gas-phase reactions of methylo ~ i r a n e , ' ~ ' 'other methyl-substituted o ~ i r a n e s , ' ~ ' ~and - ' ~ e~t~h y l ~ x i r a n e . ' ~The '~ kinetics of the processes have been compared. Pyrolysis of these compounds is a first-order, homogeneous, nonradical process; the reaction rate is not affected by ' ~ thermochemical behavior radical scavengers. A biradical mechanism h 0 1 d s . l ~ The of cyclopentene oxide'417 and cyclohexene oxide'418 is similar. The primary products are the corresponding carbonyl compounds and unsaturated alcohols. Two mechanistic possibilities have been discussed: they are obtained from a common biradical intermediate or the alcohol is formed directly from the oxirane in a concerted manner.'417 Thermolysis of spirooxiranes leads to ketone derivatives via biradicals with homolytic bond cleavage (Eqs. 376, 377).'419i1420

Trie- yoMe Me-C

Me-

c

/

Me

,Me

Me

+

Me

0

Me Me

Me Me Me-

Me

H

Mf=

Me

O

a

(376)

e Me

1,5-Hydrogen migration has been observed during gas-phase pyrolysis,'421 in the process given in Eq. 378.

Oxiranes

146

Isomerization of a medium-ring oxirane at a relatively low temperature leads to heptatrienaldehyde as the main product (Eq. 379).14"

Aromatic compounds are formed from cyclooctadienemonooxirane above 500" ; this has been interpreted as occurring via a bicyclic intermediate in a permitted pericyclic reaction. 14" B.

Oxiranes Containing a Group Stabilizing the Hide Intermediate a.

ARYL-SUBSTITUTED OXIRANES

The thermal transformation of oxirane derivatives bearing an electron-attracting substituent takes place via ylide intermediates with breaking of the C-C bond of the oxirane ring.'423 Convincing evidence of this is provided by the reaction of t e t r a c y c a n ~ o x i r a n e . 'It~ ~has ~ been experienced that the intermediate is somewhat ionic in character and the opening and closing of the oxirane ring comprise a reversible process. A kinetic study of the geometric isomerization and racemization of optically active cis- and trans-2-phenyl-3-p-tolylo~iranes'~~~ has proved the conrotatory mode of thermal opening, which was to be expected from orbital symmetry consideration^.'^^^ A simultaneous investigation was carried out on cis- and trans-2,3-dicyano-2,3-diphenyloxiranes. Their epimerization thermally gives cycloaddition compounds with acetylenic and olefinic products via ylides.lM2 The structures of the cycloadducts obtained in the thermal reactions of a-cyanostilbene oxides lend support to the electrocyclic cleavage of the C-C bond and the preferential conrotatory route of the ring-opening.'M1 It has emerged from a kinetic examination of the cycloaddition reactions of these compounds that the opening of trans-a-cyanostilbene oxide proceeds exclusively by conrotation and the reaction with dimethyl fumarate is stereospecific. The cycloadducts formed from the cis isomer permit the conclusion that geometric isomerization of the ylide takes place with conrotation or the partial disrotation of the cis isomer.'408' 142691427 When 2-aryl-3,3-dicyanooxiranes are reacted with aldehydes, 1,3-dioxolanes are obtained via ylide interrnediate~.'~'~ a-Keto-a-cyanooxiranes are rearranged similarly to dioxols, but in an intramolecular process (Eq. 380).14*'

147

Reactions of Oxiranes The probable mechanism of the rearrangement is shown in Eq. 381.

dE b.

(381)

ALKENYL- AND ALKYNYLOXIRANES

In the thermally-induced rearrangement of 2-vinyloxirane (Eq. 382), dihydrofuran is formed by thermolysis of the oxirane C-C bond via an ylide intermediate. 1430

(382) Butenal is produced by C - 0 bond splitting. A biradical mechanism has been suggested for this process.'430 A number of authors have dealt with the reactions of divinyl~xiranes.'~~~-~~~~ It has been found that dihydrooxepine and 2,vinyldihydrofuran are formed from trans-vinyloxirane at 170-220" (Eq. 383).

For clarification of the reaction mechanism, the rearrangements of cis- and transphenylvinyloxiranes have been investigated,1434to avoid the formation of dihydrooxepine. cis-Dihydrofuran derivatives are formed by conrotational opening of the oxiranes through a carbonyl-ylide intermediate. The experimental results outlined in Eqs. 384 and 385 permit considerations of the stereochemistry of the processes.143s In every case a cis product is obtained. 4,s-Dihydrooxepine derivatives are formed from cis-oxiranes in an intramolecular concerted 3,3-sigmatropic reaction, while trans-oxiranes yield not only the dihydrooxepines but also dihydrofurans, the latter by isomerization via an ylide intemediate.

Oxiranes

148

Isotopic examinations indicate that the products obtained from trans-divinyloxirane are formed from a common ylide intermediate.1436 Further work on the thermal behavior of cis- and trans-vinylaryloxiranes has revealed that the stereoselectivity of the reactions depends primarily on the configuration of the ethylene bond (Eq. 386)

In the thermolysis of phenylvinyloxiranes stabilized with a cyano group, the ylides have been confirmed in the cycloaddition reaction with d i p ~ l a r o p h i l e s . ' ~ ~ ~

phy P

h

COzMe

143

q C0,Me

144

The study of the vinyloxirane + dihydrofuran isomerization has been extended to other di- and trisubstituted butadienyloxirane derivatives.1439 The cis-2,3dihydrofuran obtained stereospecifically from the cis and trans isomers 143 and 144 is produced by conrotatory opening via an ylide, as in Eq. 387.'@'

The conclusions given above are supported by the following experimental data. A trisubstituted hexatrienoxirane rearranges to a mixture of diastereomeric 2,3dihydrofurans (Eq. 388).'@l

149

Reactions of Oxiranes

Me0,CJ Me0,C-

\CO,Me

,

M e 0 C*',Me0,C'-

(Z)-Styryloxiranes give 2,7-dihydro-3,4-benzoxepineswith phenyl ring participation by cycloaddition via an extended dipole (Eq. 389).'@'

A

1.5 - H

(389)

An example of intramolecular cycloaddition through a carbonyl-ylide is also shown in Eq. 390.1a3

Both vinyldihydrofurans and dihydrooxepines are formed from substituted (Z)butadienyloxiranes, whereas the (E)-isomers are converted only to vinyldihydrofurans.'* The process occurring in the case of a vinyloxirane with fixed geometry is shown in Eq. 391.1*5

C0,Me

-

___)

Me0,C

MeOzC

C0,Me

T) (39 1 )

The intermediate ylide has been trapped with a dipoIarophile,'446 and the resulting addition products are discussed on the basis of orbital symmetry. Further detailed studies have been made with several thermally induced ring-expansion reactions of butadienyloxirane.'4a> 1446b

Oxiranes

150

In the thermolysis of trans-a-ethylene-a'-acetylenoxirane, four electronic conrotatory openings occur and three products are formed via an intermediate ylide.lM7 The cis isomer also yields similar products (Eq. 392). In the gas- and liquid-phase reactions of substituted derivatives it has been verified that the initial product in these thermolyses is the oxacycloheptatriene.'448

Aryl-substituted contiguous cyclopropyloxiranes are converted to dihydropyran derivatives (Eq. 393).IM9

toluene loo0

+

/ \7

1

W

R (393)

Miscellaneous

C.

a-Halooxiranes readily undergo rearrangement.712 The thermal rearrangement of 2-chloronorbornene-exa-oxide has been studied on one of the optically active enantiomers; the transformation takes place with chlorine migration (Eq. 394).14'0

2,3-Chlorooxiranes give a,&'-dichlorocarbonyl compounds. The products are explained by heterolysis of the C-0 or C-CI bond (Eq. 395).14'l

0 II Me-C-CH

0

O Me-r/-\HCI C1 I

/

\

I

CIo -MeCCl,C/''

-t

c1

0 Me-C-CHCl / \

0

+

H '

(395)

0 CI0 -Me-C

I1

-CHCI,

On the action of heat, trimethylsilyloxiranes are rearranged to silylenol ethers (Eq. 396).14', Me,Si

-

CH,=CH-OSiMe,

(396)

Reactions of Oxiranes

151

If the mixture of epoxysilanes obtained on the epoxidation of vinylsilanes is subjected to destructive pyrolysis, only one of the isomers is decomposed.’453 It should be noted that besides the processes with radical mechanisms induced photolytically and thermally, studies have also been performed on oxirane transformations initiated with various radicals.’280’1454-1459 10.

Polymerization

The polymerization of oxiranes, a reaction of importance for both industry and commerce, has been abundantly described in the literature. Several hundred articles are published in this field annually. The quantity and great variety of themes discussed mean that a survey of this immense literature material exceeds the scope of the present review. Accordingly, we shall merely mention some of the works attempting to clarify the situation regarding the mechanism of polymerization reaction^.'^^'-'^^^ We shall also outline the fundamental types of oxirane polymerizations. These can be classified into three groups: with anionic,1477,1478 c a t i o n i ~ , ’ ~ and ~ ~ -coordination’485 ’~~ 31486 mechanisms. The base-catalyzed reaction is one of the longest known polymerization processes. Stepwise anionic polymerization proceeds as in Eq. 397. (a)

(h)

CH,-CH, \ / 0

HOCH,CH,O@

(c)

+ OH8 +

CH ,-CH \ /

0

-

HOCH,CH,OB

,

-

IIOfCH,CH20f,CH2CH,00

HOCH,CH,OCH,CH,O@

+

CH,-CH, 0

-

(397)

HOf CHzCII,O j n + l C H 2 C H 2 0 ~ Cationic polymerization is induced by Lewis acid catalysts. This type is mainly used in connection with higher cyclic ethers, since oxiranes produce only lowmolecular-weight polymers. The propagation step is illustrated in Eq. 398.

Oxiranes

152

Since the discovery of coordination catalysts based on various metal alkoxides (Fe, Zn, Al), such catalysts have proved of great value for the preparation of highmolecular-weight polymers. Many studies have been devoted to coordination polymerization, but the mechanism has not yet been fully elucidated. Depending on the type of the catalyst and the metal employed, we can speak of coordinate cationic and coordinate anionic processes.

V. acac B DATMP DEAD DMF DMSO EDAC HMPT LAH M MCPBA MNPBA NBA

NBS

PY PPA PBA PNBA t TBHP TDAP THF TMC Ts

Acetylacetone Base Diethylaluminium 2,2,6,6-tetramethylpiperidide Diethyl azodicarboxylate Dime thylformamide Dime thylsulfoxide Electron donor-acceptor complex Hexamethylphosphortriamide Lithium aluminium hydride Metal m-chloroperoxybenzoic acid m -nitroperoxybenzoic acid N-bromoacetamide N-bromosuccinimide Pyridine Peroxyacetic acid Peroxybenzoic acid p-nitroperoxybenzoic acid

tert

t-BuOOH

Tris(dimethy1amino)phosphine Tetrahydrofuran Tetramethylcarbamide p-toluenesulfonyl

VI. 1.

2. 3.

ABBREVIATIONS

REFERENCES

4.Rosowsky, in A. Weissberger, Ed., The Chemistry of Heterocyclic Compounds, Irol. 19, Wiley-Interscience, New York, 1964. 2. Dittus, in Houben-Weyl,Merhoden der Organischen Chemie, Vol. VI/3, Thieme, Stuttgart, 1965, pp. 367-487. R. J. Gritter, in S. Patai, Ed., The Chemistry of the Ether Linkage, Wiley, London, 1967, pp. 373-410.

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Chemistry of Heterocyclic Compounds, Volume42 Edited by Alfred Hassner Copyright 0 1985 by John Wiley & Sons, Ltd.

CHAPTER 11

Arene Oxides-Oxepins DEREK R . BOYD Department of Chemistry. The Queen’s University. Belfast. Northern Ireland

DONALD M . JERINA Laboratory of Bioorganic Chemistry. National Institutes of Health. National Institute of Arthritis. Diabetes. and Digestive and Kidney Dkeases. Bethesda. Maryland. U.S.A.

I. I1.

111.

IV.

V. VI .

Introduction . . . . . . . . . . . . . . . . . . . Structure and Synthesis . . . . . . . . . . . . . . . 1. Structure . . . . . . . . . . . . . . . . . . 2 . Synthesis . . . . . . . . . . . . . . . . . . A . Benzene Oxide . . . . . . . . . . . . . . . B. Mono-and Polysubstitutcd Benzene Oxides . . . . . . C . Arene Oxides and Oxepins of Polycyclic Aromatic Hydrocarbons D . Arene Polyoxides . . . . . . . . . . . . . . Reactions . . . . . . . . . . . . . . . . . . . . 1 . Isomerization t o Phenols (Aromatization) . . . . . . . . . 2 . Isomerization t o Nonphenolic Products . . . . . . . . . 3 . Addition Reactions (Solvolytic. Nuclcophilic, Cyclo-) . . . . . 4 . Oxidation-Reduction Reactions . . . . . . . . . . . Biochemistry of Arene Oxides . . . . . . . . . . . . . . 1. Enzymatic Formation . . . . . . . . . . . . . . 2. Hydration t o trans-dihydrodiols . . . . . . . . . . . 3 . Reaction with Glutathione . . . . . . . . . . . . . 4 . Arene Oxides and Cancer . . . . . . . . . . . . . 5 . Diol Epoxides and the Bay-Region Theory . . . . . . . . Acknowledgements . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . .

197

198 198 198 204 205 205 213 223 230 231 238 241 252 255 255 259 266 266 269 270 270

Arene Oxides-Oxepins

198

I.

INTRODUCTION

Two comprehensive reviews of arene oxides-oxepins have been produced to date. The first review in 1967l dealt mainly with the concept of valence tautomerism in the monocyclic arene oxide-oxepin series, while the second article in 19732 also included the arene oxides of polycyclic aromatic hydrocarbons (PAH) and placed more emphasis upon their chemistry and biochemistry. In addition, a number of more specialized reviews dealing with aspects of arene oxide-oxepin chemistry including oxepins and h y d r o o x e ~ i n s ,solution ~ chemistry: and roles in metabolismSy6have appeared. The profusion of papers associated with the title arene oxides-oxepins that have appeared since 1973 (> 300 papers) allied to the significance of advances contained therein has prompted the present chapter. Particular stress is placed upon the material appearing during the period 1973-1982, with appropriate cross-references to the earlier literature.'-6

11. STRUCTURE AND SYNTHESIS 1.

Structure

Many arene oxides are in dynamic equilibrium with their oxepin forms. The parent molecules, benzene oxide l a and oxepin l b , are related as valence tautomers that interconvert by an allowed disrotatory electrocyclic reaction. Structural identification of l a and l b was based initially upon spectroscopic evidence' and chemical transformation to stable products of known structure.' Thus the areneoxide structure was inferred from its typical dienoid (4 2 7 ~cycloaddition) and epoxide (ring-opening, aromatization) reactions, while the oxepin structure was deduced by catalytic hydrogenation of the triene oxepin to form oxepane.

+

la

lb

Structural identification of arene oxides-oxepins by such chemical transformations to stable products does not, however, provide any information on the relative proportions of the contributing valence tautomers where the barriers to tautomerization are low and a state of dynamic equilibrium exists. Ultraviolet spectroscopy was used initially to establish that a rapid equilibration of l a and l b occurred at ambient temperature and that the distribution of tautomers was markedly temperature and solvent-dependent.' Thus, the less conjugated arene oxide form l a was favored at low temperature or in polar solvents and was a colorless liquid. In contrast, the more conjugated bright yellow oxepin l b formed

Structure and Synthesis

199

on warming the sample or dissolving it in a nonpolar solvent. Nuclear magnetic resonance (nmr) spectroscopy at ambient temperature did not indicate discrete signals for protons in either l a or lb, as anticipated for a fast dynamic process.' At lower temperatures the individual proton signals could be distinguished, and activation energies were measured for the forward and reverse reactions (9.1 and 7.2 kcal mol-'). The entropy difference (AS on isomerization of l a + l b was measured by the nmr method (+ 10.5 2 8.3 e.u.) and is a measure of the conformational mobility of the oxepin tautomer. Further structural investigations of the arene oxide-oxepin isomers have been carried out with the aid of 13C nmr and have confirmed the temperature dependence of the arene oxide-oxepin equilibrium.'-' It has not yet, however, proven possible to estimate accurately the proportion of each tautomer at ambient temperature. Structural information in the crystalline state can be obtained directly by x-ray diffraction studies, but this method has not been used extensively in the arene oxide-oxepin series since the majority of the monocyclic arene oxide-oxepins synthesized to date have been liquids and since chemical instability at ambient temperature is a common feature of many mono- and polycyclic arene oxides. X-ray crystal structure analysis has been carried out on the relatively stable K-region arene oxides 2-4.'OY1' Similarly, an x-ray analysis of 5 , a crystalline annelated benzene oxide (which, however, exists in both arene oxide and oxepin form in solution), has and indicates that the six-membered ring is almost planar. The been 'reported oxepin ring in compound 6 has been shown to exist in the boat conformation both in solution and in the crystalline state.13 The structural information thus obtained in the crystalline state is totally consistent with the spectroscopic data and the chemical reactivity of the arene oxides in solution and has been used in theoretical studies of the arene oxide-oxepin ~ystern.'~-'' Additional evidence for the rapid equilibration in the benzene oxide-oxepin system la-lb has accrued from a range of molecular orbital (MO) c a l ~ u l a t i o n s . ' ~ - ' ~

''

Me 2

3

4

Me /

Arene Oxides-Oxepins

200

Preferred geometry of the benzene oxide-oxepin system can be predicted by molecular orbital methods. Thus benzene oxide l a is predicted to be markedly nonplanar (with the epoxide ring at an angle of 73" to the benzene ring), while the oxepin l b has been predicted to prefer a shallow boat structure (MIND0/3) or a planar structure (ub initio)." AS previously mentioned, the proportion of each tautomer present at equilibrium is both temperature and solvent-dependent. Molecular orbital calculations have been used to rationalize the solvent effects, both in terms of the more polar character of the arene oxide that is favored in polar solvent^'^ and the strengthening of the oxirane C-C bond upon coordination of the oxygen atom lone pair in polar solvent^.'^ Thus values in the range 1.5-2.0 D and 0.76-1.36D for the dipole moments of arene oxide l a and oxepin l b have been calc~lated.'~

la

lb

lb

la

A further factor that has a marked influence upon the arene oxide-oxepin distribution is the effect of substituents. With the numbering system shown below, arene oxides, monosubstituted arene 1,2-, or 3,4-, and 1,2 disubstituted 1,2-oxides prefer their oxepin forms whereas arene 2,3-oxides prefer their oxide tautomers. These observations concur with MIND0/3 calculations and may be rationalized" in terms of the maximum number of low-energy valence-bond structures for 7 ~ electron-donating or withdrawing substituents (Figure 1).

X

X

X

Bridging substituent groups also influence the preference for either the arene oxide or the oxepin valence bond tautomer.' Thus, when n = 3, indan 8,9-oxide 7 exists exclusively as the oxide form. With n = 4 , tetralin 9,lO-oxide 8 is dominant over its oxepin form while similar amounts of the arene oxide and oxepin are present when IZ = 5 (9).

Structure and Synthesis

201

n-Electron Donor [XISubstituted Arene Oxides-Oxepins Monosubstituted Arene 1,2-Oxides

‘.-..

/

Monosubstituted Arene 2,3-0xides

X

X

XO

XO

Monosubstituted Arenc 3,4-0xides

O

0

1,2-Disubstituted Arene 1,2-Oxides

X

.x

X

XO

n-Electron Acceptor [XISubstituted Arene Oxides-Oxepins

Monosubstituted Arene 1,2-Oxides

bo-&

Monosubstituted Arene 2,3-0xides

X

‘

XQ

---

3

eo-(-J X

XO

x ~ 0 2 y Jxco o -xc Monosubstituted Arene 3,4-Oxides

0

‘

4

Figure 1.

/

/

O

\

c

-__.I

Resonance forms of arcne oxides and oxepins that bear either electron-donating -withdrawing substituent.

01

Arene Oxides-Oxepins

202

In addition to the temperature, solvent, and substituent effects, a preference for either the arene oxide or oxepin form may be achieved by localization of one double bond as part of an aromatic ring system. Thus the reluctance t o form a cyclobutadiene ring causes 10 to exist preponderantly as its oxide form.” Naphthalene 1,2oxide 11 is the simplest arene-oxide member in the polycyclic aromatic hydrocarbon (PAH) series and exists exclusively in that tautomeric form.” In contrast, naphthalene 2,3-oxide exists exclusively as the oxepin form 12 since the C4-C5 bond in the oxepin ring forms part of an aromatic ring.”

10

11

12

Although results obtained by spectroscopic methods such as UV and nmr may imply the presence of a single valence-bond tautomer, such methods cannot detect a very minor portion of the other tautomer in a state of rapid equilibration. One method of attempting to identify the presence of such an equilibrium with a very small amount of the oxepin tautomer would be to test whether a chiral arene oxide racemizes. This has been done for optically active naphthalene 12-oxide 11,which is optically stable at ambient temperature.21323Studies of the configurational stability of discrete enantiomers of arene oxides of polycyclic aromatic hydroarbo on^^^,^^-^^ have established that equilibration occurs at ambient temperatures in some cases and not in others. A theory has now been devised that allows a prediction of whether or not an optically active arene oxide will racemize.’’ Perturbational molecular orbital calculations of the loss in resonance energy associated with the isomerization of arene oxide to its corresponding oxepin tautomer [AAE = E (substituted oxepin) - E (substituted oxirane) --E (oxepin) + E (benzene oxide)] give the values shown (kcal mol-’) in parentheses in Figure 2. The total energy for this process may be considered to consist of two parts, (i) an energy of reorganization which is very similar for all compounds in the series and (ii) a 7~ electron resonance energy which is the most important variable factor throughout the series.

203

Structure and Synthesis

& oomomo \

\

1 ( 0 00)

14 (10.5)

17 (14.4)

20 (50.5)

23 (14.4)

Figure 2.

\

\

\

\

/

13 (30.5)

11 (20.0)

I

\

/

/ 15 (10.5)

2 (40.0)

O &\

/

16 (14.1)

18 (7.2)

19 (7.2)

21 (24.9)

22 (24.9)

24 (14.4) 25 (17.1) Arene oxides that have been studied both experimentally and theoretically for their configurational stability.

2 04

Arene Oxides-Oxepins

26 (17.1)

28 (ca. 6.0) Figure 2.

Continued

The nearly constant part of the energy change is close to zero as shown for the finely balanced equilibrium between benzene oxide and oxepin. Thus the 71 electron resonance energy alone may be taken as a good measure of the total energy change. In accord with the theoretical predictions, experimental results indicate that arene oxides 11, 13,20-22,25, and 27 exist as enantiomers that do not racemize at room temperature and thus must be present exclusively in the arene-oxide form.23J ~ - ~ ~ In contrast, arene oxides 14-19 racemize s p o n t a n e ~ u s l yas~predicted.24i25 ~~~~~~~~~~ Spontaneous racemization of 18 and 19 has been observed by the authors but not yet reported. On the assumption that the barriers to racemization for arene oxides are of the same relative order as A A E and that values of or below 10.5 kcalmol-' represent examples where racemization should occur too fast for optical activity to be detected. It was theoretically predicted that arene oxides 14-19,23,24,28, and 29 would racemize. In the cases of 16 and 17, the actual barriers to racemization (E,) could be measured and were found to be 25.2 kcal mol-', r e ~ p e c t i v e l y . ~ ' , ~ ~ The corresponding entropy of activation values (AS*) obtained during racemization of 16 and 17 (+ 3.7 ? 1.1 and 0.7 f 0.6 e.u., respectively) are fully consistent with the intermediacy of oxepins. One interesting feature of the calculations is that all K-region arene oxides are predicted to be configurationally stable, although this has to date only been verified experimentally for arene oxides 20 and 4.27,34

+

2.

Synthesis

For clarity, the term arene oxide has been used in the following discussion (and arene-oxide structural formulas have been used in Tables 1 and 2), although a

,

Structure and Synthesis

205

tautomeric arene oxide-oxepin equilibrium is either assumed or known to exist in certain cases.

A.

Benzene Oxide

Evidence for the direct oxidation of benzene (or substituted benzenes) to benzene oxide (or substituted benzene oxides) by enzymatic (Refs. 5 and 35 and references therein) and chemical (Refs. 35 and 36 and references therein) methods is available both from the observation of the migration and retention of ring substituents during aromatic hydroxylation (NIH shift):' and from the nature of the isolated products (phenols, trans-dihydrodiols). As a direct consequence of its thermal instability and high reactivity, benzene oxide 1 has not yet been isolated as an oxidation product of benzene. The most general synthetic route to benzene oxides-oxepins is that initially developed by Vogel' for 1. 1,4-cyclohexadienes (readily available from [2+4] cycloaddition of alkynes and butadienes, lithium-ammonia reduction of arenes, or dehydration of cyclohexenols) were converted to dibromoepoxides, the immediate precursors of benzene oxides. Modifications of this route have been used to prepare l c and Id. Treatment of the monosubstituted arene oxide 43 (Figure 3) provide addiwith (Et)4NF37,38 or thermal isomerization of 3-o~aquadricyclane~' tional synthetic routes t o l a . Similarly, the thermal (or photochemical) isomerization of the monoepoxide of Dewar benzene yielded la.42

DBN

~,5-Diazabicyclo[4.3.O]non-5-ene

D

&J 0

B.

L

1

-

h*or A

0

0

Mono- and Polysubstituted Benzene Oxides

The wide range of monosubstituted benzene oxides that have been synthesized using halogenoepoxide' or related routes is illustrated by the examples given in Figure 3. This general route (Figure 4) has been used in the synthesis of mono-

206

Arene Oxides-Oxepins

Monosubstituted Arene 1,2-Oxides

3947

4

0

~

~

I

414R

SiMe3

4337,38

Monosubstituted Arene 2,3-0xides

C02Bu‘

Figure 3.

CH,OCOPh

CHzOCOEt

Structures of synthesized monosubstituted bcnzenc oxides. References t o each synthesis are superscripted.

Structure and Synthesis

207

Monosubstituted Arene 3,4-0xides

M

e

o

o o-

5237,S0,51,S7

\

C% ' \

5 343 54s8

Figure 3.

Figure 4.

Continued

0

208

Arene Oxides-Oxepins

substituted arene 1,2- and 3,4-oxides. Thus arene 1,2-oxides with weak electrondonating substituents 29, 30, 39, 41, and 43 were synthesized from the requisite dienes by sequence A whereas the arene 1,2-0xides with electron-withdrawing substituents 31-33 and 37 were obtained via sequence B. Arene 3,4-oxides 52, 53, 55, 57, and 59 were obtained via route C (or D). Facile chemical transformations of substituent X may be effected to yield the arene 1,2oxides 34 (X = -CO,H), 35 (X = -CH20H), 36 (X = -C(Me),OH), 37 (X = -CN), 38 (X = -CHO), and 40 (X = -CH = CHC0,Me) using essentially the halogenoepoxide route (Figure 5). Arene 2,3-oxides 44,s03s145,5248,” and 5lS6 (Figure 3) were all synthesized by base treatment of haloepoxide intermediates. As with monosubstituted arene oxides, most of the di-, tri-, and polysubstituted benzene oxide-oxepins (Figure 6) have been prepared by methods similar to those outlined.

CHZOH 34

Figure 5 .

0

CH 2 OH

D

-35

Established modifications of a substituent X prior to synthesis of 1-substituted benzene oxides. See Figure 3 for product arene oxides.

209

Structure and Synthesis

Me I

Disubstituted Benzene Oxides

Me

Me

Me

I

I

I

a

Me

Me

0 H m

7364

7464

@

CHzOCOMe

CH,OCOMe

76'

7P4

Br

n,

HN OH

NC'

H

Figure 6 .

Structures of synthesized di- and polysubstituted benzene oxides. References to each synthesis are superscripted.

210

Arene Oxides-Oxepins

Polysubstituted Benzene Oxides

c1

M e 0 2 C ~ : Me02C

%o

M e z O C b oM e O z C b o

\ 86 70

Me02C

\ 8Y7l

\

MeOzC

8865

c1

8965

\

C02Me

Ph

9976 Figure 6 .

Continued

\

Structure and Synthesis

21 1

Among examples of single-step chemical transformations of substituted arene oxides t o yield alternative types of arene oxides are: SiMe,

84 ( R = Me, R 1 = H) 85 ( R = H , R' = Me)

I

R' COzMe 34 ( R = R' = H)44

R' The synthesis of arene oxides 44, 46, and 47 via cyclohexane bromo-0-lactone epoxide intermediates constitutes a novel synthetic approach t o arene 2,3Although the final consecutive dehydrobromination and thermal decarboxylation steps in the synthesis of 44,46, and 47 proceed under mild conditions, they do not, however, permit the isolation of 1 from the corresponding bromo-0-lactone epoxide.

0

0

R = - M e (44) R = -CH,OCOPh (46) R = -CHZOCOEt (47) DBU

1,8-Diazabicyclo[5.4.0lundec-7-ene

Arene oxides 42 and 49 were obtained as minor products by an unusual thermal Although the isomerization of the photooxide of 3-diphenyli~obenzofuran~~ thermal isomerization reaction of 3-0xaquadricyclane~~ has been used in the synthesis of benzene oxide 1, this route to benzene oxides was initially limited t o specifically substituted derivatives owing to the unavailability of the unsubstituted 7-oxanorbornadiene. Thus most of the substituted arene oxides prepared by this route contained electron-withdrawing substituents X [X = -CF3 (77), -CO,Me (76, 86, 88-92, 94), and -C02Et (93)] which increased their thermal stability.

Arene Oxides-Oxepins

212

@: \

\

I

Ph

0

-

42i-49 iother products

Ph

Diphenylisobenzofuran

The arene oxides 76, 77, 86, and 88-94 have all been formed by direct thermal isomerization of the corresponding oxaquadricyclanes. Transition-metal-catalyzed isomerization of oxaquadricyclanes, however, yields arene oxides with alternative substituent patterns; for example, 95 .74

While the tert-butyl substituted oxepins 96-98 result from the acid-catalyzed dehydration of a series of 1,4-disubstituted 2,6-ditert-butyl-2,5-cyclohexadiene-1,4diols, this route is of limited synthetic value for arene oxide-~xepins.~’ Ring expansion of a pyrylium salt using ethyl lithio diazoacetate and a Pd complex proceeds via a carbene intermediate to yield arene oxide-oxepin 99. Due t o severe nonbonding interactions between the But groups, the oxepin valence tautomer only was observed.76

HO R’

But,

k

R OH Arene oxide 80 has been reported as a stable metabolite of 5,s-diphenylhydant0in.6~ Since no substituted benzene oxides have previously been isolated as metabolites and since an oxirane hemiacetal structure would be predicted to be highly the structural assignment in this report is highly questionable.

Structure and Synthesis

213

The mass spectral data upon which the structural assignment largely depends would be much more consistent with an isomeric structure such as that shown below.

OH

0

OH

An early attempt68 to synthesize the phenolic benzene oxide 81 failed to dctect any of this enol structure but yielded a product whose spectral data were consistent with the keto isomer.

C. Arene Oxides and Oxepins of Polycyclic Aromatic Hydrocarbons The simplest member of the polycyclic aromatic hydrocarbon (PAH) series, naphthalene, may in principle form four possible arene oxide-oxepin tautomeric pairs (A-D). In practice, the valence tautomers that have an intact aromatic-ring structure 11, 12, 100, 101 predominate. This discussion of arene oxide synthesis

11

12

100

101

214

Arene Oxides-Oxepins

will however be mainly concerned with PAH analogues of structural type A. The terminology K-region, non-K-region, and bay-region arene oxides is exemplified by reference to the phenanthrene ring. Thus epoxides at the bonds indicated in phenanthrene form a set of three arene oxides of differing chemical reactivity. Kregion arene oxides tend to be the most stable arene-oxide type. In fact, the first , ~ ~ formed at the K-region arene oxide synthesized, phenanthrene 9,1 O - ~ x i d e was of phenanthrene.

&

Non-K(bay)-region arene oxide

\

[Ol

1

Non-K-region arene oxide

<’

/

K-region arene oxide

A number of K-region arene oxides have been detected as intermediates in the metabolism of the corresponding PAHs in liver systems; for example, phenanthrene, benz [a] anthracene, pyrene, benzo [a] pyrene, and diben~(a,h)anthracene.~These K-region arene-oxide metabolites were generally only detected by trapping the radiolabeled intermediate. The arene-oxide metabolite 102 obtained from (Ynaphthoflavone was found to be sufficiently stable with respect to isomerization and resistant to attack by epoxide hydrolase so that it could be isolated and identified spectroscopically.7s-80

0 102

The direct oxidation of PAHs as a synthetic route has been confined mainly to the more stable K-region arene oxides. However, the first isolation of an arene oxide resulting from direct chemical oxidation of a PAH (and to date the only example of a non-K-region arene-oxide synthesis by this route) was achieved in low yield by photolysis of pyridine N-oxide in the presence of naphthalene36i81to form naphthalene 1,2-oxide 11. The relative susceptibility of non-K-region arene oxides to further epoxidation is one of the reasons for the lack of generality of this approach. Direct epoxidation of unsubstituted (or substituted) PAHs and azapolycyclic aromatic hydrocarbons has produced a wide range of K-region arene oxides (Figure

Structure and Synthesis

215

7) in yields up t o 9S%.82-85The decomposition of K-region arene oxides under acidic conditions was minimized by the use of meta-chloroperoxybenzoic acid (MCPBA) as an oxidant in CH2C12 solvent in the presence of aqueous NaHC03. This two-phase system gave arene oxides 2, 103, 104, 115, and 116 in yields within the range 9-S9%83 as well as the azaarene oxides 128, 129, and 130.'09 With the combination of aliphatic carbodiimides (e.g., Pr') and hydrogen peroxide, it was possible to form peroxyimidic acids in situ that are capable of direct oxidation of PAHs t o K-region arene oxides 2 and 115, both in acceptable yield (-30%) and under essentially neutral condition^.^^ The preparatively most useful direct route t o K-region arene oxides utilized aqueous sodium hypochlorite in the presence of a phase-transfer ~ a t a l y s t . ~This ' neutral oxidizing agent has since provided a convenient synthetic route t o the known arene oxides 2, 115, and 116, to the previously unreported substituted arene oxides 107 and 108, and t o those derived from azapolycyclic aromatic hydrocarbons 124-128 in acceptable yields.8591079108 A low yield of arene oxide 2 was obtained by y-radiolysis of liquid CO, in the presence of ~ h e n a n t h r e n e . ~Relatively ' low yields (3-7%) of the K-region arene oxides 2 and 115 were also obtained by oxidation of phenanthrene or pyrene with tetraphenylporphinato iron (111) chloride and iodosyl benzene." The K-region arene oxide 134 has been formed by an intramolecular oxygen atom transfer process from the carbonyl oxide intermediate.'"

[O]

MCPBA/NaHC03

ioi = P?NH - c

NPr' \

(Ref. 83)

(Ref. 84)

OzH

(01 HOCl/Bu4NHSO4

(Ref. 85)

The earliest synthetic route to K-region arene oxides involved ring-closure of This method has 2,2'-biphenyl dialdehydes using @is-dimethylamin~phosphine.~~ been highly successful in the synthesis of 2, 3, 20, 108, 116-120, and 123 as well as the azaarene oxide 131. A modification of the latter condensation method using aroyl cyanides has been used in the synthesis of K-region arene oxides 110112." More convenient and versatile synthetic routes t o K-region arene oxides

216

Arene Oxides-Oxepins K-Region Arene Oxides

d&d \

Ph

0

Ph

1t493

\

1 1584-86,8S,89,98

\

\

0

20??,88,89

Figure 7.

\

\

Me I 1777

11683,85,89,99,100

0

\

CH,OH

0

1 18'01

Structures of synthesized K-region arene oxides of polycyclic hydrocarbons. References to each synthesis are superscripted. See also Figure 1.

217

Structure and Synthesis

Me CH~OH 1191°2

Me 387,88,102

12088,103

0 486-88

1291°9 and

N-Oxide

130109

1331°9

Figure 7.

Continued

218

Arene Oxides-Oxepins

-

110-

NaOMe/MeOH

111

H,SO,MeOH

* 112

(Figure S), based upon the ready availability of K-region cis-dihydrodiols (from cis-hydroxylation [Os04] of the parent hydrocarbon), has been developed. The cis-dihydrodiols were treated with trimethylorthoacetate to yield 2-methyl-2methoxy-l,3-dioxolanes which in turn yielded chlorohydrin acetates on treatment with trimethylsilyl chloride. Treatment of the chlorohydrin acetates with dry NaOMe in ether gave arene oxides 2-4, 20, 115, and 120 in overall yields of 4356% from the cis-dihydrodiols.8s The azaarene oxide 133 has also been synthesized by this method.log This synthetic method has particular advantages in that (i) all of the reactions from the cis-dihydrodiol can be carried out in the same flask without need for isolation or purification of intermediates and that (ii) syntheses of chiral K-region arene oxides are possible.27330734 Since the absolute configuration at the chiral center bearing a C-0 bond remains constant in the sequence cisdihydrodiol + 2-methoxy-1,3-dioxolane + trans-chloroacetate + arene oxide,88opti-

Structure and Synthesis

219

cally active cis-dihydrodiols of known absolute stereochemistry have been used to form optically active arene oxides 4 and 20 of known configuration. Alternatively, the cis-dihydrodiols were converted to the trans-isomers prior to cyclization to arene oxides 2-4, 115, 116, and 123 using the dimethylacetal of dimethylforma n ~ i d e , ' and ~ ~ ~t o~ arene oxides 2, 4, 20, and 115 using diphenyl di(1,1,1,3,3,3he~afluoro-2-phenyl-2-propoxyl-sulfurane.~~~ The K-region arene oxide 121 has also been synthesized from a trans-dihydrodiol. The monotosylate was generated in situ and cyclized t o 121 using NaH.lw A similar reaction sequence has been applied"' to a trans-dihydrodiol t o yield the non-K-region arene oxide 25. A recently developed route t o K-region arene oxides results from the observation that trans-bromohydrin acetates at the K-region can be formed from several polycyclic aromatic hydrocarbons by reaction with N-bromoacetamide in acetic acid.'13 This method has been used t o synthesize both enantiomers of chrysene-5,6-oxide 116.1i4

0

f'rerny's Salt

I 4

NaBH,

OH

( i ) NaH

(ii) Tosyl irnidazole

Higher thermal instability and chemical reactivity of the benzo-ring (non-Kregion and bay-region) arene oxides in Figure 9 has precluded application of most of the synthetic methods reported for K-region arene oxides. The direct oxidation " ~very limited of naphthalene t o 11 by photolysis of pyridine N - ~ x i d e ~is~ of synthetic value because of the low yield. Similarly, the partial deoxygenation of naphthalene 1,4-endoperoxide (PPh3, - 78°C) to yield 11, although of considerable interest, is not an attractive synthetic route in view of the number of steps required in the peroxide ~ r e p a r a t i 0 n . l ~ ~

00

Arene Oxides-Oxepins

220

LIAIH,

MeC(OMe),

OH

OMe

(MeO),CHNMe,

Figure 8.

Synthesis of K-region arene oxides from cis and trans K-region dihydrodiols.

The halogenoepoxide route to benzene oxides has been used in the synthesis of arene oxides 11,19'1 13,"' 14,116,'1721,"l 25,"' and 26l" as well as the azaarene oxide 140.123 The major problem of this synthetic route to non-K-region arene oxides is typified by the results obtained by early attempts to prepare 1311' and 15.l16 Thus, the tetrahydroepoxide116 and bromoepoxide"' intermediates were highly unstable under the required reaction conditions and yielded a highly impure

lq 0

11, 13-15, D"N21,25,26

KCO,K

Br NBS

N-Bromosuccinimide

DBN

1,5-Diazabicyclo[4.3.01non-5-ene

form of arene oxide 13 upon base treatment. The problem has since been circumvented by utilization of bromohydrin ester intermediates.1167117This method has been highly successful when applied to the preparation of the arene oxides in Figure 9 that include one azaarene oxide 141. This general synthetic route has been modified to utilize chiral bromoester intermediates [menthyloxyacetates or rnethoxytrifluorornethylphenylacetates(MTPA)] that are separable into diastereo-

22 1

Structure and Synthesis Non-K- and Bay-Region Arene Oxides

1323,115

424,1 16,117

& \

0

29,120

Figure 9.

18119

1632

1524,26,116,117

19118,119

/

2230

23lI8

Structures of synthesized non-K-region arene oxides of polycyclic aromatic hydrocarbons. References to each synthesis are superscripted. See also Figure 2.

Arene Oxides-Oxepins

222

0

\

/

/

140124

141lZ4 Figure 9.

Continued

isomers by chromatographic and crystallization methods. Arene oxides 11, 13, 15-17, 21, 22, and 25 were thus obtained in optically active form by the bromohydrin ester m e t h ~ d . ' ~ -728-33 '~

,d

N BA

NBA

OCOMe

N BS

__z

OCOMe

[ao

-

@ B r

NaOMe

Br

N-Bromoacetamide

3-Benzoxepin 12 has been prepared by methods similar to those already discussed for arene oxides. Thus photochemical isomerization of 1,4-epoxy-l,4dihydronaphthalene to an oxaquadricyclane intermediate followed by thermal

rearrangement yielded 12.lZ6 Similarly, 12 was derived from a dialdehyde using a Wittig reaction.lZ7 Dehydrohalogenation of a bromoepoxide using KOBU' has also been used in the synthesis of 12.' The pyrolysis of 1,2-dihydronaphthalene

Structure and Synthesis

CHO Ph$-CH2

\ /

0

223

NaOMe

*

MeOH

12

CHO Ph3P-CH2 0 BrQ 2-hydroperoxide provides a further route to 12.12* 1-Benzoxepin 100 and 1,6oxide[ 1Olannulene 101 have been prepared via bromoepoxide i n t e r r n e d i a t ~ .>' l~3 O~ Br I

Br

Br D.

Arene Polyoxides

The term arene oxide is frequently assumed to apply only to monoepoxides of aromatic compounds. Dioxides 142, 143 and trioxides 144, 145 may in principle be formed by oxidation of benzene and are discussed. None of the di- 142, 143 or tri- 144, 145 oxides of benzene have been synthesized by direct chemical epoxidation, but all have been obtained from the corresponding bromohydrins or bromo-

t

142

143

144

145

Arene Oxides-Oxepins

224

acetates. The synthesis of trans-benzene dioxide 142,131 cis-benzene dioxide 143,13' trans-benzene trioxide 144133J34 andcis-benzene trioxide 145,133,135 shown in Figure 10, were all dependent upon three dibromoepoxide intermediates that were readily interconverted. An alternative synthetic route to 142 and 144 starting from p-benzoquinone appears to offer significant advantage^.'^^ Interestingly,

KOH

0

0

0

144

dH

cis-benzene trioxide 145 acts as a tridentate ligand to form crystalline crown-ethertype complexes with a range of cations including Li, Na, K, Rb, Cs, Ca, Sr, and Ba.'37 The synthesis of 144 by thermal rearrangement of the endoperoxide adduct obtained from singlet oxygen reaction with 1133J38is noteworthy since this method

has been extended138 to give triepoxide 146. Alternatively, the isomeric trunstrioxide 147 was obtained by treatment of the endoperoxide with triphenylphosphine followed by oxidation with MCPBA. The monosubstituted cis-benzene dioxide 148 was isolated after dehydrobromination of a dibromodiepoxide intermediate with sodium in liquid a m m ~ n i a . ' ~The ' first naturally occurring benzene dioxide moiety 149 has been shown to have antibiotic activity and has a monosubstituted cis-diepoxide structure analogous to 148.140 The cis-benzene dioxides 150 and 151 have recently become available by a Diels-Alder cycloaddition route.141

225

Structure and Synthesis

TosO

OH -

!

THF

Br

oLHb

Br

0

Figure 10.

HO

Br 0

KOH

145

Br

$/ *

I

Br Synthesis of benzene dioxides and trioxides.

142

Arene Oxides-Oxepins

226

A

~

144

0

0 MCPBA

0.’

Br

147

148

Br

b0bobo COzH

0

0

149

CHO

0

150

151

Relatively few arene dioxides and trioxides have been reported from PAHs. Arene dioxides in the naphthalene 152, 154, 155 and anthracene 157 series have been formed in good yield by direct epoxidation of the parent h y d r 0 ~ a r b o n . l ~ ~ These arene dioxides 152, 154, 155, and 157 were formed by MCPBA epoxidation

Structure and Synthesis

R

R

-

R=Me

221

154

155

-

MCPBA

R

R

R R=H R=Ph

156 157

via arene monooxide intermediates that could not be isolated. The cis-dioxide 153 was not found among the oxidation products of naphthalene. Neither the intermediate monoarene oxide, nor the dioxide 156 in the anthracene series could be synthesized by this oxidation route due to oxidation to 9,lO-anthraquinone. The trans-anthracene dioxide 157, in which the 9,lO-positions are blocked, was isolated after epoxidation of 9,10-diphenyl anthracene. Alternative synthetic routes to the naphthalene dioxides 152 and 153 using bromoacetates gave relatively poor yields (1-8%).'43 The enantiomerically pure trans-arene dioxides 142 and 152 have been synthesized (via their bromo MTPA ester diastereoisomers) and assigned absolute stereochernistry.l4 A synthetic route to the cis-naphthalene dioxide 153 (which was not available by direct epoxidation of naphthalene) based upon a [ 4 + 2 ] n cycloaddition reaction of benzyne and a butadiene derivative has been r e ~ 0 r t e d . l ~ ~

Br

Br

qoA Br

~

o

A

c

N

1

3

OAc

s

,

%,

KOH

OAc

Br

152

228

Arene Oxides-Oxepins

1

MesCl

OAc

OAc Direct reduction of naphthalene 1,Cquinone with diisobutylaluminum hydride produces the free ~is-1,4-dihydrodiol.~~ Cis-naphthalene dioxide 153 and compound 158 have been obtained by the photooxidation of 1,6-imino[lOIannulene, An interfollowed by thermal isomerization and reaction with nitro~ylchloride.'~~

esting pair of phane-type bridged molecules, cis arene di- 159 and trioxides 160, has been obtained by treatment of the isomeric endo peroxides with a cobalt tetra-

Structure and Synthesis

159

229

160

phenylporphyrin ~ a t a 1 y s t . lTriphenylene ~~ triepoxide, obtained by direct epoxidation of triphenylene, was found to have trans stereochemistry by x-ray diffraction analy~is.'~'Photochemical isomerization of the 9,lO-anthracene endoperoxide with longer wavelength (> 435 nm) U.V. light gave the cis-diarene oxide of anthra-

161 cene (161) as a rather unstable (tl,2 6.5 h at 28°C) p r 0 d ~ c t . Arene l ~ ~ dioxides of PAHs may have both the oxirane groups on one benzene ring as in 152-159 or on different rings. Examples of the latter category include the K-region diepoxides 162-164 which are formed by an identical route t o that used previously; that is, condensation of dialdehydes in the presence of tris-(dimethy1amino)phosphine (e.g., 2, 3,20, 108, and 116-123).

230

Arene Oxides-Oxepins

To date, the only natural product containing a benzene dioxide moiety is the antibiotic 149.140 In addition to this cis dioxide, there is evidence that trans naphthalene dioxide 152 may be an intermediate in the hepatic metabolism of na~htha1ene.l~'The reactivity of the cis (153) and trans (152) naphthalene dioxides with nucleophiles and the relative stereochemistry of the adducts has been determined.151 The possibility that arene dioxide intermediates form during metabolism of PAHs has been discussed f r e q ~ e n t l y . ' ~ ~ ~Indeed, ~ ~ ' - ' the ~ ~ detection of a trans-diol epoxide such as that derived from arene oxide 25,'563'57or the isolation of a trans-diol oxepin (e.g., 165) is mechanistically consistent with the formation of two epoxides on either the same or different rings. However, presently available evidence would suggest that it is most unlikely that either diol metabolite was derived from an arene dioxide intermediate. Involvement of dioxide intermediates in the metabolism of PAHs will require further experimental verification.

111.

REACTIONS

Arene oxides show the characteristic reactions of epoxides (isomerization to ketones, reductions to alcohols, nucleophilic additions, deoxygenations) and olefins or conjugated dienes (catalytic hydrogenation, photochemical isomerization, cycloaddition, epoxidation, metal complexation). Where a spontaneous, rapid equilibration between the arene oxide and oxepin forms exists, reactivity typical of a conjugated triene is also found.

Reactions

1.

23 1

Isomerization to Phenols (Aromatization)

The most widely studied aspect of arene-oxide chemistry is the aromatization reaction to yield phenols. The acid-catalyzed, spontaneous, and thermal rearrangements of epoxides to ketones have a parallel in the isomerization of arene oxides to dienone intermediates with subsequent aromatization to phenols. Prior t o their availability by chemical synthesis, arene oxides were postulated as initial inter-

1

mediates in the metabolism of aromatic hydrocarbons by the cytochrome P450 system in mammalian liver.’59 The obligatory role of arene oxides in hepatic metabolism was unequivocally established by the detection of 11 among thc biotransformation products of naphtha1encl6’ and the migration of the labeled hydrogen (deuterium or tritium) from the site of aromatic hydroxylation to a neighboring carbon atom (NIH shift, Refs. 2, 35, and 162). The validity of this

X

= ’H or 3 H

N111 SHIFT

mechanism for the NIH shift was confirmed by the synthesis of deuterium-labeled samples of arene oxides 5257and 11’63 and subsequent examination of the labeling pattern after aromatization. The percent of deuterium label retained during aromatization was almost entirely dependent upon the kinetic-isotope effect ( k H / k ” ) during enolization of the intermediate ketone. Other factors known to affect the magnitude of the NIH shift include the presence of an ionizable ring substituent and the pH of the reaction medium. Evidence for the intermediacy of a dienone was deduced from studies on arene oxides 5zs7and ll.i63This intermediate was also observed in the low temperature (- 198°C) photolysis of ll.38The dienone intermediate was detected by infrared spectroscopy prior t o isomerization to 1naphthol and by detection of an isomeric ketene photoproduct of the dienone. Further confirmation of the epoxide +ketone rearrangement of arene oxides was obtained by isolation of stable dienones upon isomerization of arene oxides 61,” 82,@ and 137.5’ The NIH shift mechanism has now been established for over 100 examples of enzyme-catalyzed aromatic hydroxlyations in plants, animals, and microorganisms. Reviews of the NIH shift in biological ~ 6 3 3 5 9 1 6 2 1 1 6and 4

232

Arene Oxides-Oxepins

blH Me

Me

I

2H

0

52

(40-85% 2H retained)

(about 80% * H retained)

1

1

L

references contained in recent papers,92i165-'74some of which demonstrate halogen migrations, provide a more detailed treatment of this topic. A wide range of chemical oxidizing agent^'^'"^^ has also been shown to hydroxylate aromatic rings via the NIH shift mechanism (Table 1). While the NIH shift is generally associated with the initial formation and aromatization of transient areneoxide intermediates, it has been proposed'@' that the NIH shift observed for one chemical oxidizing system [Fe(C104)2/H202] could also be explained by oxidation of a radical adduct to a cyclohexadienyl cation leading to the isolation of a phenol having a large retention of label.

Reactions

61

137

82

-

23 3

-

CO,Me &Me

On the basis of the evidence discussed, the rearrangement of arene oxides to phenols clearly involves dienone intermediates. However, from kinetic results it is evident that several carbonium ion intermediates must also be involved.’86-’88 The evidence for involvement of carbonium ion intermediates is:

1. The kinetic data for isomerization of a range of arene oxides in both the mono- and polycyclic aromatic series as a function of pH showed that the process can be acid-catalyzed ( k H ) in all cases. A pH-independent spontaneous aromatization in the neutral to alkaline region (k,) was also found for arene oxides (generally too slow to be observed for K-region arene oxides). The kinetics of these isomerizationslE6obey the rate law: kobs = k H OH

+ k0

These pathways are illustrated in Figure 11. 2. The rates of aromatization by both the acid-catalyzed (kH) and spontaneous (k,) pathways were found to decrease in solvents of lower dielectric constant as ancipitated for a reaction having a transition statelE6more polar than the reactant. TABLE 1.

CHEMICAL OXIDANTS KNOWN TO HYDROXYLATE AROMATIC RINGS VIA THE NIH SHIFT MECHANISM

Oxidant

Reference

RC0,H N-oxidcslhv o(~P) Carbene/O, HOF SnC1,/0, MO(CO),/BU~O,H CrO,(OAc), Fe(C104),/H,0, Tetraphcnylporphinatoiron (111) chloride iiodosyl benzene

163, 177 36,81,163,178,179 180 81 181 182 81 183 184 92.185

Arene Oxides-Oxepins

234

R

RY

QH I

Acid-catalyzed mechanism

(kid

loH

R

x

\

bH R

x

I

oo

R

I

Spontaneous mechanism (ko)

QH0

I

OH

I

R

R

OH

00

'H Figure 11.

Pathways involved in the acid-catalyzed ( k ~and ) spontaneous ( k , ) isomerization of arene oxides to phenols.

3. Substituent effects upon the rates of aromatization of arene oxides, both by the acid-catalyzed and spontaneous pathways, gave large negative p+ values (- 5.5 to - 6.0) indicative of transition states possessing significant carbonium ion ~ h a r a c t e r,188 .~ 4. The virtual absence of a primary kinetic isotope effect ( k H / k D= 1.OO to 1.05) in the rates of aromatization of normal (kH) vs. deuterated arene oxides (kD) is consistent with the development of a carbonium ion in the rate-limiting step and the absence of a rate-limiting transfer of hydrogen or deuterium.1873189

23 5

Reactions

5 . The direction in which unstable arene oxides open to phenols is consistent with the most stable carbonium ion intermediates. The effect of substituents on the direction in which arene oxides open t o form phenols was initially studied with methyl-substituted benzene oxides (R = methyl). The cationic species A (Figure 12) is stabilized by the methyl substituent and thus dominates the aromatization process since species B is not stabilized by the methyl substituent. The methyl substituent and other electron-donating substituents thus facilitate formation of carbonium ion A leading to para-substituted phenol^.^^^^^^^ Conversely, electron-withdrawing substituents (e.g., R = -CO,H) favor the intermediacy of carbonium ion B, which leads t o meta-substituted phenol^.^^^^^^^^^^ Naphthalene 12-oxide 11, upon protonation, may form a carbonium ion, centered at either the benzylic or allylic positions (which does not destroy aromaticity in the neighboring aromatic ring), from which naphthols are produced. Since the lessstable benzylic carbonium ion leads to 2-naphthol, the latter phenol is found as a minor product (Figure 12). Non K-region arene oxides of PAHs such as 11 yield only phenolic products under acidic conditions while the more stable K-region arene oxides give both phenols and dihydrodiol Generally, non-K-

R

R

R

($

__c

\

B

& R

OH

/

OH

11

Figure 12.

Rearrangements of arene oxides to isomeric phenol? via pairs of cationic species.

Arene Oxides-Oxepins

236

region arene oxides isomerize to phenols in a fashion such that the oxygen atom is retained at the benzylic carbon of the starting arene oxide. The only known exception t o this is benzo[a]pyrene 9,lO-oxide 26 from which 9-hydroxy-benzo[a]pyrene predominate^"^"^^ because of the unusual electronic properties of the pyrene ring system. The importance of carbonium ion intermediates during aromatization of arene oxides has also been deduced from the migration and loss of a range of areneoxide substituents. Aromatization of polymethylated arene oxides, for example, 61, 63, and 65,5°751162in each case yielded phenols where methyl migration occurred. Related arene 1,2-oxides have been extensively studied since their aromatization may involve both substituent loss and/or migration.379389w-47~191 The mechanism of aromatization of deuterated and otherwise substituted arene 1,2-oxides to phenolic products has been studied in detail (Figure 13). Pathways leading to phenols A and B correspond to substituent loss, whereas phenols C and D represent substituent migration. Type A phenols are most commonly formed and have been isolated from aromatization of a range of monosubstituted arene 1,2oxides: for example, 29,373389191 33 and 34,w94535 and 36;’ 37,46 38:’ 39,47 and 40,47 where a proton is lost (see Figure 3). The loss of substituent X duringaromatization has been found where X is carboxyl 34,44 trimethylsilyl 43,37938 formyl 38,45 hydroxymethyl 35 p5 and 2-hydroxyisopropyl 36.45 The aromatization pathway leading to phenols of type C involves a single migration step for carboalkoxy 32, 33, 7 2 , * ~and ~ ~carbomethoxymethyl 3947 substituents. The doublemigration sequence leading to the formation of a phenol of type D has to date only Me

65 Me

Me

Me

OH

Me

hoH+ (34-57%)

(54-37%)

0

Me

( j/ f i e

/

Me

61

(21%)

Me

Me

Me 63

( 1 3%)

Me

(27%)

OH

Me (87%)

Reactions

23 7

been found for the carbomethoxy group 32.@ The pattern of substituent loss and migration observed during aromatization of the monosubstituted arene 1,2oxides37338,@-46 and the polymethylated arene facilitates an understanding of the mechanism of aromatic hydroxylation in biological systems. One noteworthy example of the aromatization of an arene oxide to yield different phenols by the kH (acid-catalyzed) and ko (spontaneous) pathways is indan oxide 7.'923'93The mechanisms for the aromatization reaction of arene oxide 7 appear to be more complex than those found for arene oxides discussed previously. Thus, 4-hydroxy and 5-hydroxyindan were reported to have been formed via a dienone and a diol intermediate, respectively. Alternative or additional mechanisms for the formation of these phenols involve oxygen-walk pathways, which will be examined in the following section.

R'

R

R'

A

I

"-b' R' C Figure 13.

R'

R'

R +X

R'

0

R' I)

Potential pathrvays involved in the migration, retention, or loss of subFtituent X during t h e C O U I S ~of isomerization of I - and/or 2-substituted arcne 1,2-oxides.

[a- p Arene Oxides-Oxepins

23 8

OH

r

OH

1

HO

2.

Isomerization to Non-Phenolic Products

The spontaneous tautomerization of arene oxides and oxepins generally found in members of the benzene oxide series has been included as a structural aspect of arene oxides. Other types of arene-oxide isomerizations that yield nonphenolic products generally do not proceed spontaneously under ambient conditions. The term oxygen-walk mechanism was coined'92 for one such process and has been used234~1937'w to describe the ring-opening reactions of an arene oxide followed by ring-closure of the resultant carbonium ion intermediate to form an isomeric arene oxide. In this type of molecular rearrangement, the epoxide oxygen atom migrates around the periphery of the ring. Product studies support an oxygen-walk mechanism in the isomerization from indan 8,9-oxide (7, R = H) via alternative arene-oxide intermediates leading to 4- and 5-hydroxyindane (R = H).'92 A similar study has been carried out using arene oxide 70,63 which yielded related hydroxy indan products. The initially postulated arene-oxide intermediate (indan 3a,4oxide), obtained by thermal isomerization of 7, has now been isolated and characterized by an alternative ~ y n t h e s i s . ' The ~ ~ formation of both oxepins 100 and 101 from base-catalyzed dehydrohalogenation of a common tetrabromoepoxide pre-

X

X

X

X

x

Reactions

239

I

7(R=H) 7 0 ( R = 011)

OH

D

D

D

D

Id cursor'z9 may be a further example of an oxygen-walk process. Photolysis of 3,6dideuterobenzene oxide l d t o yield I ,4-dideuterobenzene oxide provides an example of a photochemically induced oxygen-walk process.39 Further examples of oxygen-walk mechanisms have been found in the photochemical rearrangement Arene oxide 79 was of a series of K-region arene oxides t o oxepins.39'94,98'196i197 found to undergo a thermal oxygen-walk process over the temperature range (80-100°C).66 A review of the oxygen-walk phenomenon as part of a wider range of circumambulatory rearrangements has appeared.'99 An electrocyclic photochemical rearrangement of oxepins to cyclobutene ringcontaining valence isomers has also been reported. Thus 2-oxabicyclo- [3.2.0] hepta3,6-diene has been isolated upon photoisomerization of 1.' Similarly, when 1benzoxepin 100 was irradiated, the valence tautomer 3,4-benz-2-oxabicycl0[3.2.0]hepta-3,6-diene was formed?00 While the isomerization of benzene oxides to oxepins occurs spontaneously at low temperature, the analogous mobile valence tautomerization of cis-benzene dioxide 143 (Figure 10) t o the 10-n-heterocycle, 1,4-dioxocin, was only evident at temperatures > 50°C.132 The latter process is symmetry-allowed and is formally equivalent to a retro-Diels-Alder reaction. The mobile equilibrium at 60°C appeared

Arene Oxides-Oxepins

240

2,108,110,112

@ \

0-

hV

/

115 1 - (hu- p

100

143

to favor 1P-dioxocin (95%). The cis-benzene trioxide 145 was irreversibly isomerized to cis, cis, cis-I ,4,7-trioxonin upon heating at elevated temperatures (> 200°C).'33,135 The trans-dioxide and trioxide of benzene, 142 and 144, showed no evidence of isomerization to 1,4-dioxocin and cis, cis, cis-l,4,7-trioxonin, respectively, even upon heating to high

24 1

Reactions

145

3.

Addition Reactions (Solvolytic, Nucleophilic, Cyclo-)

In general, K-region arene oxides behave rather like aliphatic epoxides and thus readily undergo hydration reactions, whereas benzene oxides and non-Kregion arene oxides form dihydrodiols much more reluctantly. Kinetic studies of the mechanism of solvolysis of phenanthrene 9,lO-oxide 2 have been carried out in several l a b o r a t o r i e ~ . ' ~ ~ Be1 - ' ~ow ~ pH 7 the hydrolysis reaction was acidcatalyzed and the products included the trans- and cis-9,lO-dihydrodiols along with a preponderance of 9-phenanthrol, while above pH 7 the reaction proceeded via the spontaneous mechanism ( k o )to yield mainly the trans-dihydrodiol. Hydrolytic studies with other K-region arene oxides 3 , 20, 4, and 109 have been reported.202-2w A comparative investigation of the mechanism of the solvolysis and rearrangement of K- and non-K-region arene oxideslS9 showed that dihydrodiols were not produced from non-K-region arene oxides and the exclusively formed phenols resulted mainly from the vinylogous benzylic carbonium ions.

2

OH

OH

1,2-Dihydrodiols have not been obtained from hydrolysis reactions of benzene oxides; however, evidence for the formation of 1,4-dihydrodiols has been obtained from acid-catalysis studies on 1,4-dimethylbenzene oxide 63188!'05 and 8,9-indan oxide 7.19' The mechanism of acid-catalyzed rearrangement and hydrolysis of benzene oxide has been investigated theoretically using the semiempirical allvalence electron MIND0/3 methodzM and the perturbational MO method;07 both from the viewpoint of product stabilities and reaction pathways. The aromatization reaction was found to be much more exothermic than the hydrolysis and thus would be the preferred reaction, as was found experimentally.

24 2

q

3'-+

Arene Oxides-Oxepins

Me

Q-

HO

=

Me

Me

Me

OH

OH

+OH

Me

Me

63 Addition of ethanol solvent to benzene oxide la is reported to occur at an extremely slow rate (incomplete reaction after 60 days at ambient temperature). The analogous reaction of 1 with methanol solvent proceeded readily at ambient temperature in the presence of a [Rh(CO)zC1]z catalyst to give the methyl ether adduct

EtOH

OEt (7% yield) among other products.208 This solvolytic type of reaction was found to occur much more readily (25"C, l h , Et,O) under the catalytic influence of basic alumina to yield trans adducts in good yield. Thus naphthalene 1,2-oxide 11 reacted with methanol-doped alumina to give both I-naphthol and trans-l-hydroxy-2methoxy-l,2-dihydronaphthalene.209Addition of methoxide anion in methanol

44%

34%

solvent and phenoxide anion in tert-butyl alcohol has been found to give exclusively trans-l,2-adducts with l.40Methoxide also readily adds to 11.'l0 Attempts to add

0 PhO

t-BuOH

OPh

Me0

Q

MeOH

OMe

hydroxide anion to arene oxide 1 or 2 were unsuccessful although attack of this nucleophile on 4-carbo-tert-butoxybenzene oxide 57 yielded tert-butyl trans-2,3dihydroxy-2,3-dihydrobenzoate.60 This successful hydration of a benzene-oxide

Reactions

243

'BuO 2C

'Bu02C 0 HO ay.

dioxane

OH 57 derivative was the consequence of the presence of an electron-withdrawing substituent that increased the rate of nucleophilic addition relative to rearrangement. An alternative route to a trans-dihydrodiol product from attack of an oxygen nucleophile on an arene oxide was provided by the attack of hydroperoxide anion?' The trans-dihydrodiol ultimately produced was obtained by borohydride reduction of the intermediate hydroperoxide adduct.

In general, nucleophilic addition reactions of arene oxides with nonpolarizable oxygen and nitrogen nucleophiles are very slow. Thus both NH3 and NH, nucleophiles failed to add to benzene oxides under a range of conditions.403211 Amine nucleophiles have, however, been found to react very slowly with benzene oxide.

n-RuNH,

NH,NH,

crq

NHNH2

NIlBu

Thus reaction with n-butylamine gave the trans adduct in 56% yield after standing at ambient temperature for eight months.212 Using amines in the presence of an alumina catalyst provides a more convenient method for the opening of arene oxides by weak nitrogen nu~leophiles.~'~ This particular alumina-promoted nucleophilic reaction of 11 gave a mixture of trans adducts along with 25-30% of 1-

OH

-A1203

PhNH,

31%

11%

11

n-BuNH,

BuNH

OH

NHPh

\

/ 25%

25%

Arene Oxides-Oxepins

244

naphthol in contrast to the reaction of methanol-doped alumina. The addition of the more polarizable azide ( N 3 ) nucleophile, unaided by alumina, occurred much more readily to yield a trans adduct.40121' Addition of azide to 3,6-dideuteriobenzene

D

OH D

D

D

OH

40%

60%

Id OH 11

NaN,

oxide (Id) occurred both by trans-1,2- and trans-l,6-ring opening. A range of amine nucleophiles including trimethylamine adds to arene oxide 57 t o yield detectable but relatively unstable adducts that readily arornatize.'l3 A general synthetic route to K-region arene imines has been developed involving reaction of azide anion with

K-region arene oxides 2, 4, 20, 117, and 123. The trans-azido alcohols yielded aziridine products on treatment with tri-n-butylpho~phine.~~~''~

2

Reactions

24 5

Intramolecular nucleophilic attack of an amine group o n an arene oxide has been proposed t o account for the biosynthesis of a range of epipolythiopipcrazinediones (e.g., gliotoxin, bis-dithiobis-(methylthio)dehydrogliotoxin, spirodesmins, e t ~ . ) . ” ~ - ’With ~ ~ the amine-substituted arene oxides 50 and 55 (Figure 3), synthe-

sized4’ as models for this biosynthetic step, cyclizations of the type proposed t o occur in uiuo were not observed. This observation does not exclude nucleophilic attack of an aniine on an arene oxide under enzyme catalysis. Gliotoxin has been synthesized b y a reaction pathway having as one step the Michael reaction of a nucleophilic nitrogen atom on arene oxide 57.219,220

COzBu‘

0 C0,Bu‘

-

~gliotoxin

Me

57

The polarizable thiolate anion reacts readily with a wide range of arene oxides Contrary t o earlier reports, the to give trans-thioether adducts.39~204~210,211,221-224

- Do” Q

RS

1

SR

24 6

Arene Oxides-Oxepins

adduct obtained by attack of thiols on arene oxides of PAHs occurs by attack at C-2 rather than at C-l."53'10 Decomposition of the trans-thioether adduct to a 1-thioethyl-substituted PAH occurred possibly via an episulfonium intermediate. OH

SEt

The latter reaction sequence was of importance since addition of the thiol glutathione to arene-oxide intermediates under control of hepatic glutathione-S-epoxide transferase enzyme(s) is a very important metabolic transformation.', 353"47"5 It would appear probable that most of the structures of the arene oxide-glutathione adducts (premercapturic acids) reported in the literature before 1975 are incorrect with respect to the position of the hydroxy and thioether substituents (they should now be reversed). Addition of thiomethoxide anion to arene oxide 70 may occur via 1,6- and 1,4-addition, although one of these thioether adducts could also be accounted for by the alternative arene-oxide intermediate obtained from an oxygenwalk.63 Styrene 3,4-oxide (53) has been observed to react with ethanethiol to yield three adducts which appear to aromatize to three isomeric ethylthiostyrenes without the formation of episulphonium intermediates.''6 59

Reactions

241

The reactions of strong carbon nucleophiles with arene oxides 1 and 11 leads to rapid adduct formation.'@ Methyl lithium and dimethyl magnesium react with arene oxide 1 by 1,6-addition to give cis-adducts. Trans-adducts were also obtained from reaction of dimethyl magnesium and methyl lithium with arene oxides 1 and 11, respectively, by the more usual 1,2-truns addition mechanism.m

OH

Diene cycloaddition reactions have frequently been used to characterize relatively unstable arene oxide-oxepins. The reactions of 1 with maleic anhydride or dimethyl

C02Me

0

acetylenedicarboxylatel occurred with the arene-oxide tautomer. A pericyclic reaction of benzene oxide-oxepin with 3,4-diazacyclopentadienone forms an unstable cycloadduct .227 Although the trimethylsilyl-substituted 1,2-arene oxides 43 and 85 formed are directly analogous with Diels-Alder adducts with 4-methyl.~~ 1,2-dimethyl1,2,4-triazolinedione, 84 reacted as the oxepin t a ~ t o m e r Similarly, benzene oxide 61 preferred to form cycloaddition products between the oxepin form and dimethyl azodicarboxylate.2z8A series of 1-benzoxepins were also reported to form cycloadducts with tetra~yanoethylene.'~~

Arene Oxides-Oxepins

248

SiMe, MeN Me

SiMe3

84

The cycloaddition reaction of benzene oxide-oxepin 1 with singlet oxygen to yield an endo-peroxy adduct has been studied in several laboratories.'33313832301231 This endo-peroxide rearranged readily to form the trans-benzene trioxide 144 and gave trans-benzene dioxide 142 upon reaction with triphenylphosphite. A similar addition reaction occurred between singlet oxygen and indan 8,9-oxide 7 to yield a further e n d o - p e r o ~ i d e . 'An ~ ~ endo-peroxide adduct of an oxepin was also formed when singlet oxygen reacted with I-benzoxepin 100. Upon deoxygenation with trimethylphosphite, the latter peroxide yielded an aldehyde.232

24 9

Reactions

0

(QMe

It

Me0

N C0,Me N II C 0 , M e

*

Me0

4'N

0 A a

Me Me

@Me

Me 61

Ph

R'

$ R4

100

The cycloaddition reactions of arene oxides-oxepins already discussed have all been done with dienophilic reagents; that is, [4+2]71 cycloadditions. The reaction of oxepin 1 with a dienone provides a further example within this category, but the ~ ~ ~ 2,5-dimethoxycarbonyl-3,4-diphenylcyclooxepin acts as a d i e n ~ p h i l e .When

Arene Oxides-Oxepins

250

CO ,Me p Ph h* o-

C0,Me

0

Ph

0

1

pentadienone was stirred in the presence of 1 the analogous endo-[4+2].rr cycloadduct was also formed as the major product.234 A minor component was a novel exo-[6+4]n adduct, indicating that benzene oxide-oxepin 1 may also function as a 6n donor. Cycloaddition of oxepin (1) with a tetrazine can also occur by a [2+4]n mechanism to yield a dihydrooxepino[4,5-d]pyridazine or by a [6+4]n mechanism to give a p h t h a l a ~ i n e . ’ ~ ~

I

N

0

C02Me

Reactions C0,Me

25 1

0

Ph

1

The unusual reaction of 1with trichloro(nitroso)ethene to form cis-epoxyepimino1,3-cyclohexadiene may result from an initial [4+2] n cycloaddition reaction between the arene oxide and the nitroso group followed by a spontaneous rearrange-

c

o

I

11 0

0 1

n ~ e n t . ' This ~ ~ cycloaddition and isornerization reaction seems to be similar to the reaction of 1 with singlet oxygen to yield an endo-peroxide and, ultimately, 144. In contrast, however, the anticipated cycloaddition reaction between 1 and p chloronitrosobenzene did not occur and a nitrone product was isolated.237 Diazomethane also undergoes addition reactions with a range of benzene oxides to yield cis-mono, cis-bis- and trans-bis-l-pyraz~lines.~~ Ar \

AT-N=O

252

Arene Oxides-Oxepins

4.

Oxidation-Reduction Reactions

The epoxidation reaction of arene oxide-oxepins has been encountered in the formation of the arene dioxides of naphthalene and anthracene rings 152-157.'42 A similar approach to the synthesis of epoxides of benzene oxide-oxepin using a peroxyacid oxidant, however, was u n s u c c e s s f ~ l (Z,Z)-muconaldehyde ~~~ was isolated presumably via an oxepin-epoxide intermediate. The disubstituted benzene

oxide-oxepin 61 upon oxidation again yielded a (Z,Z)-diketone product without the oxepin-epoxide intermediate being detected.238 The tetrasubstituted benzene oxide-oxepin 93 (a very stable compound due to the two electron-withdrawing carboethoxy groups) on peroxyacid oxidation, yielded isolable mono- and d i e p o x i d e ~ . ~ ~ These results supported the earlier proposal that arene oxide-oxepins may be epoxidized during the biosynthesis of aranotins in fungi to form substituted symoxepin oxide intermediate^.^^^ The parent sym-oxepin oxide was first prepared

Reactions

253

from 7 , 7 - d i e t h o ~ y n o r b o r n a d i e n e In . ~ ~the ~ final step, thermal extrusion of CO and CO, from a bis-epoxide yielded sym-oxepin oxide (80%)and 1 (20%), respectively. An alternative synthetic route t o sym-oxepin oxide involving benzene oxide as a

-

0

~

-0

A(42Oo C )

HOAc/H,O

0

0 + 1

0

starting material and a spontaneous thermal extrusion of nitrogen from a bisepoxide in the final step has been r e p ~ r t e d . Both ~ ~ , ~sym-oxepin ~~ oxide and

several alkyl-substituted analogues were found t o undergo a facile Cope rearrange,243 This isomerization process ment process yielding isomeric oxepin

does not, however, occur in the bridged sym-oxepin oxide derived from arene oxide 7 due t o stereochemical constraints.244

254

7 -

Arene Oxides-Oxepins

- - yI _

-

\ I

0

V

The earliest reduction reactions of arene oxides to be reported involved catalytic hydrogenation of 1 (H,-Pd) to yield oxepane' and reaction with lithium aluminium hydride to give cyclohexa-l,3-dien-5-ol.'An alternative type of reduction reaction

LIAIH,

of arene oxides is the removal of an oxygen atom; that is, deoxygenation. Treatment of benzene oxide 1 with thiocyanate yielded only benzene, possibly by extrusion of a sulfur atom from the intermediate benzene ~ulfide-thiepin.~'Sirnilady, an attempted direct synthesis of benzene sulfide-thiepin produced only

benzene and The latter sulfur analogue of 1 has not t o date been isolated, although thiepins stabilized by two bulky tert-butyl groups have been ~ y n t h e s i z e d . 2 ~ ~ A series of K-region phenanthrene oxides have also been deoxygenated to the parent hydr~carbon.'~' Thus 2 was deoxygenated t o yield phenanthrene using thiones (thiourea, thioacetamide, or thiosemicarbazide). J~~

Pyridine is also capable of deoxygenating arene oxides 110 and l12.248The chromium, and deoxygenation of benzene oxides in the presence of catalysts has been studied, and a mechanism for the reduction process has been proposed.'" Deoxygenation of K-region arene oxides is also catalyzed

255

Biochemistry of Arene Oxides

Me

Me

Me

by enzymes in mammalian liver.251-254Reduction reaction on the oxepins tautomer have not been widely investigated. Attempts to deoxygenate the stable bridged oxepin of 93 were unsuccessful.255 Alkali metal reduction of the oxepin form of arene oxide 61 occurred by a one-electron transfer mechanism to yield octa-4,6dien-2-one and 4 - o c t e n - 2 - 0 n e . ~ ~ ~

IV.

BIOCHEMISTRY OF ARENE OXIDES

The principal pathway by which unsubstituted and many substituted aromatic hydrocarbons are metabolized in mammals consists of the initial formation of arene oxides, which undergo a variety of enzymatic and nonenzymatic reactions prior to excretion of the resulting more polar, oxidized hydrocarbons via bile or urine.53257 Taken together, these pathways represent an attempt on the part of the animal to detoxify or eliminate such nonpolar xenobiotic substances for which it has no apparent use. Although detoxification is the probable role of the arene oxide pathway, it is equally clear that chemically reactive species mediate this process. Thus, studies over the past several years have either implicated or established arene oxides in a causative role in such adverse biological reactions as cytotoxicity, mutagenesis, and carcinogenesis via covalent interaction of arene oxides with biopolymers.

1.

Enzymatic Formation

The endoplasmic cytochrome P450 system, localized primarily in liver, constitutes the major site of formation of arene oxides in mammals. Studies on the

256

Arene Oxides-Oxepins

solubilization, purification, and reconstitution of this ~ y s t e r n ' ~ have ~ - ~ estab~~ lished an absolute requirement for two enzyme components, a flavoprotein reductase and a cytochrome P450 terminal oxidase which is a hemoprotein, as well as membrane lipid. The reactions involved consist of NADPH-supported r e d x t i o n of one atom of the dioxygen molecule to water with concurrent incorporation of the other atom of the dioxygen molecule into Present studies indicate that there may be as many as a dozen different cytochrome P450 isozymes that are either indigenous or may be induced by treatment of animals with barbiturates, aromatic hydrocarbons, sterols, etc. Of these various cytochromes P450, the isozyme cytochrome P450c isolated from rat liver263is of the most relevance to the present report in so far as it has much higher catalytic activity (50-200 fold) for oxidation of polycyclic aromatic hydrocarbons compared to the other known isozymes. Polycyrlic aromatic hydrocarbons, 0-naphthoflavone and polychlorinated biphenyls are potent inducers of cytochrome P450c. Although certain arene oxides of the polycyclic aromatic hydrocarbons racemize readily,25 many of them do not. Since the expression of biological activity and the rates of subsequent enzymatic transformation are often highly dependent on absolute configuration, it has become critically important to anticipate which enantiomer of an arene oxide will be formed by the cytochrome P450 system. A steric model has been developed to this end for the catalytic binding site of cytochrome P ~ ~ O CThe . ' ~construction ~ of this model is based on a superimposition of the arene oxides of known absolute configuration that are formed from benzo[a]pyrene by cytochrome P450c.27334~265-270 Conceptually, since each of these arene oxides was formed in the catalytic site, their superimposed steric requirements must represent a minimal boundary of the binding site. Benzo[a]pyrene was selected since it was the largest hydrocarbon for which adequate stereochemical information was available (Figure 14). The site model has proved to be quite useful in predicting the stereochemical outcome of a number of cytochrome P450c catalyzed oxidations of polycyclic aromatic hydrocarbons. For example, the model predicts that benz[a]anthracene should convert to the (+)-(5S,6R)- and (+)-(8R,9S)-enantiomers of the 5,6- and 6,8-oxides, respectively (Figure 15). Experimentally, these enantiomers are favored to the extent of > 97%.'" In addition, the model is capable of predicting which diastereomer (isomer-1 in which the benzylic hydroxyl group and epoxide oxygen are cis and isomer-2 in which these groups are trans) of a bay-region diol epoxide (see later) will be formed from a given enantiomer of a benzo-ring dihydrodiol with a bay-region double bond. Thus, for the optically active isomers of the trans-dihydrodiols at the 7,8-position of b e n ~ o [ a ] p y r e n e 'and ~ ~ the 1,2-positions of chrysene'" and ~ h e n a n t h r e n e ? ~ the ~ diol epoxide-1 diastereomer predominates from the (S,S)-dihydrodiol; conversely, the diol epoxide-2 diastereomer predominates on metabolism of the (R,R)-dihydrodiol as illustrated for the chrysene example in Figure 16. Cytochrome P450c, as predicted by the model, forms predominantly diol epoxide-1 from the (-)-( 1R,2R) dihydrodiol of benz(a)anthracene and the diol epoxide-2 diastereomer from the (+)-(I S,2S)-dihydrodiol of benz(a)a n t h r a ~ e n e . ' ~Additionally, ~ the model predicts that cytochrome P450c should be highly stereoselective in forming the (+)-(I R2S)-enantiomer of anthracene 1,2-

Biochemistry of Arene Oxides

B[ a ] P (4S,SR)-oxide

Figure 14.

B[a]P ( 7 R , 8S)-oxide

257

B [ a ] P (9S, lOR)-oxide

Superimposition of the predominantly formed enantiomers of benzo[ a ] pyrene 4,5-,7,8-, and 9,lO-oxides. The hypothetical hydrocarbon skeleton represents the minimal shape of the catalytic-binding site of cytochrome P450c. Shaded areas rcpresent regions forbidden to binding whereas dashed rings are known areas of allowed binding based on studies of other hydrocarbons.

oxide but much less stereoselective in forming the enantiomers of naphthalene 1,2oxide. Such has recently been found to be the case.275Although the model is useful for predicting which of a pair of enantiomers or diastereomers would form from a substrate that fits into the site, it cannot be applied to predictions regarding which metabolites will actually form. Thus individual sterically acceptable metabolites need not form at comparable rates from a given substrate. For example, liver microsomes from 3-methylcholanthrene-treated rats form the 3,4-diol-l,2-epoxide-2 diastereomer from benz[a]anthracene (3R,4R)-dihydrodiol, yet form virtually no 3,4-diol-l,2-epoxide from the (3S,4S)enanti0mer.~~~ Similarly, chrysene is readily accommodated into the site in an orientation such that the K-region 5,6-double

Arene Oxides-Oxepins

258

W

(+)-BA (SS,6R)-oxide

___)

(+)-BA (8R,9S)-oxide Figure 15.

The catalytic-binding-site model predicts that opposite enantiotopic faces of bcnz[a]anthracene (BA) must be epoxidized by cytochromc P450c t o produce the observed stereochcmical outcome. Formation of the opposite enantiomers in either case would require the hydrocarbon to be bound in such a fashion that at least one ring would occupy a rcstricted region.

bond would be epoxidized, yet the K-region oxide is at best a trace metabolite with these m i c r o ~ o m e s .On ~ ~the ~ other hand, certain positions on a given substrate may be excluded from epoxidation by the model when it is not possible to position the substrate such that the appropriate double bond lies over the site of oxidation.'' In addition to the studies with rat liver microsomes and homogeneous cytochrome P450c, numerous other preparations have been utilized to study the metabolism of the environmental carcinogen benzo[a]pyrene. For example, the specificity of several different purified forms of rabbit liver cytochrome P450 appears to be different from the rat cytochrome P450c on metabolism of benzo[a]pyrene and benzo[a]pyrene 7 , 8 - d i h y d r o d i 0 1 . ~Although ~ ~ ~ ~ ~ ~ these forms have < 5% of the catalytic activity of cytochrome P450c and may be only minor contributors to the overall metabolism of benzo[a]pyrene in the rabbit, cytochrome P450LM6 in the rabbit has high catalytic activity for the metabolism of benzo[a]pyrene. Unfortunately, information comparable to that of cytochrome P450c in the rat, concerning the specificity of P450LM6 is presently unavailable. Numerous preparations from human tissue catalyze the formation of arene oxides, dihydrodiols, and diol epoxides from b e n z o [ a ] p y r e n ~ , 2 ~ although ~ , ~ ~ ~ little is known about the number and specificity of their cytochromes P450. Interestingly, prostaglandin synthetase is capable of oxidizing benzo[a]pyrene 7,8-dihydrodiol t o 7,8-diol-9,10e p o x i d e ~ , J~~ 2 ~ ~ but seems to be incapable of forming arene oxide^^"^^^^ from benzo[a]pyrene. In contrast, certain fungi have the full complement of enzymes necessary to convert aromatic hydrocarbons to arene and dihydro-

Biochemistry of Arene Oxides

Chrysene ( 1 R,2R)-dihydrodiol

259

Chrysene 1,2-diol-3,4epoxide-2

c Chrysene ( 1 S,2S)-dihydrodiol Figure 16.

Chrysene 1,2-diol-3,4-epoxide-l

Predicted and observed epoxidation of the enantiomeric chrysene 1,2-dihydrodiols to diastereomeric bay-region diol epoxides. In this case, the same diastereotopic face of the dihydrodiol enantiorners is epoxidized. Put in other terms, the specificity of cytochrome P450c is such that a single face of the dihydrodiol substrate(s) is epoxidized regardless of the relative or absolute configuration of the hydroxyl groups.

diols.164 ,174,297 For example, Cunninghamella elegans oxidizes benzo[a]pyrene to its 7,8-oxide, hydrates the 7,8-oxide to the 7,8-dihydrodiol, and metabolizes this as ~ - ~ ~stereochemical ~ consewell as the 9,lO-dihydrodiol to diol e p o x i d e ~ ' ~ with quences quite similar to those observed for liver microsomes from the 3-methylcholanthrene-treated rat ?709302-306

2.

Hydration to trans-dihydrodiols

The term dihydrodiol is widely used in reference to vicinal dihydroxydihydroderivatives of aromatic hydrocarbons. Although most known and potential benzene oxide or substituted benzene oxide metabolites tend t o be quite unstable, a recent study has described the isolation of a relatively stable arene oxide metabolite of 2,2',5,5'-tetrachl0robiphenyl.~~~ Perhaps because of the generally high susceptibility of benzene oxide 1 and many substituted benzene oxides to isomerize to phenols, relatively little has been reported on the kinetics and regiospecificity of their rtiicrosomal epoxide hydrolase (EC 3.3.2.3) catalyzed trans hydration to dihydro-

Arene Oxides-Oxepins

260

diols. By contrast, a wealth of information exists on the hydration of K-region (Figure 7) and non-K-region (Figure 9) arene oxides of polycyclic aromatic hydrocarbons. Like the cytochromes P450, epoxide hydrolase is a microsomal enzyme.308 It has been purified to apparent h ~ m o g e n e i t y , ~ has ~ ~ -no ~'~ metal-ion requirement,309 and functions through the participation of an unionized imidazole moiety in the rate-determining step of the reaction.314 Additional f a ~ t o r s , ~ ' ~such - ~ las~ kinetic solvent isotope effects, entropy effects, and aryl substituent effects (Hammett rho values), generally favor a mechanism in which the imidazole functions as a general base assisting in the removal of a proton from an attacking water molecule, possibly with the aid of a general acid catalyst that assists in the dispersal of developing negative charge on the oxirane oxygen (Figure 17) Perhaps the most compelling experiment in favor of general base catalysis has been the observation that trans3 -bromo-l,2e poxycyclo hexane is converted to truns-2,3-epoxycyclohexanol by epoxide h y d r o l a ~ e . ~A' ~partial N-terminal sequence of the protein has been reported.319 Various aspects of the enzyme have been the subject of a recent re view .320

;O\

H. ..His-Enz

The primary goal of initial studies of the microsomal and purified epoxidehydrolase catalyzed hydration of arene oxides of polycyclic aromatic hydrocarbons was an attempt to identify structure-activity relationships. To this end, some selected values for the hydration of a series of arene oxides3" are given in Table 2. One of the more obvious aspects of this study was that there is no apparent relationTABLE 2.

COMPARISON OF EPOXIDE HY DROLASE ACTIVITY IN LIVER MICROSOMES FROM PHENOBARBITAL-TREATED RATS WITH THAT O F THE PURIFIED ENZYME INTHE PRESENCE OF LIPID FOR A SERIES OF ARENE OXIDES321

Substrate Naphthalene 1,2-oxide Phenanthrene 9,lO-oxide Benz[a)anthracene 5,6-oxide Bcnzo[a]pyrene 4,5-oxide Benzo [ a ] pyrene 7,8-oxide Benzo[a]pyrene 9,lO-oxide Benzo [ a ] pyrene 11,12-oxide 3-Methycholanthrene 11,12-oxide Dibenz[a,h] anthracene 5,6-oxide

Rate (nmol/min/mg protein)

Microsomes

Purified enzyme

21 89 29 19 15 15 1.7 2.7 1.0

94 2 26 23 1011 445 321 39 0 31 41 13

26 1

Biochemistry of Arene Oxides

Figure 17.

A possible mechanisni for the hydration of phcnanthrene 9,lO-oxide by epoxide hydrolase. Thc pseudo-second-order rate constant for the cnzyme-catalyzed reaction kJK, has been estimated to be 10' times greater than the corresponding hydroxide-ion rate with this substrate.31s

ship between solvolytic reactivity of the substrates and their rate of enzymatic hydration, despite a 100-200 fold range in substrate activity. Unstable non-Kregion arene oxides can be hydrated either faster or slower than the much more stable K-region arene oxides. Styrene 7,8-oxide and the very stable octene 1,2-oxide are hydrated at comparable rates.3z1 The described studies were conducted at low conversions of racemic substrates. Epoxide hydrolase displays marked differences in its stereospecificity and regiospecificity toward K-region vs non-K-region arene oxides. Based on studies of naphthalene 1,2-0xide,'~' benzo[a]pyrene 7,8- and 9,l O - o ~ i d e s and , ~ ~on~ ~ ~ ~ ~ benz[a]anthracene 8,9-0xides,'~' it now appears that epoxide hydrolase catalyzes the trans addition of water with only one known exceptionz7' at the norbenzylic position of non-K-region arene oxides, regardless of the absolute configuration of the substrate. Within experimental error, individual enantiomers of a given arene

P

H2O 0

\\\\

HO

OH

oxide lead t o the expected product dihydrodiol by inversion at the non-benzylic oxirane carbon. In the case of benzo[a]pyrene 7,8-oxide, the kinetics of hydrolysis of the individual enantiomers have been examined.268 Although the (-)-(7S,8R)oxide that forms the (+)-(7S,8S)-dihydrodiol is a three- t o fourfold better substrate (k,) than the (+)(7R,8S)-oxide, the enzyme has a tenfold higher affinity (l/Km) for the (+)-oxide. As a result, racemic 7,8-oxide is metabolized preferentially to the

Arene Oxides-Oxepins

26 2

(-)-(7R,8R)-dihydrodiol from the (+)-(7R,8S)-oxide at low conversion. A similar situation has been proposed to explain the kinetics of hydration of the enantiomers of styrene 7,8-0xide.~'~ For K-region arene oxides, a different situation pertains in that the regioselectivity of the enzyme is dictated by the substrate The fascinating consequence of this change in regiospecificity with change in enantiomer is that both enantiomers of benzo [a] pyrene 4,5-oxide produce predominantly (85-99%) the same product enantiomer (Figure 18). The preference for attack at an oxirane with (S)-absolute configuration is not as high for the enantiomers of benzlalanthracene 5,6-oxide; 87% and 42% on the (+)- and (-)- oxides, respectively.34 Based on the presently available data, epoxide hydrolase generally exhibits a kinetic preference for the addition of water at the oxirane carbon having (S)absolute configuration. Nonetheless, it is clear that each new K-region arene oxide that is examined will have to be treated as an individual case. The combination of a large number of chemical resolution and assignment studies (Table 3) of benzo-ring trans-dihydrodiols along with studies designed to define the stereochemical course of metabolism of b e n z 0 [ a ] p y r e n e , 2 ~ ~benz[a],~~~ anthraa n t h r a ~ e n e ? ~ '~ h r y s e n e , ' ~~~h e n a n t h r e n e ? ~benzo[c]phenanthrene,338 ~ cene,l15*275 and naphthalene'613275has led to the conclusion that the combined action of cytochrome P450c and epoxide hydrolase has a marked preference for the formation of (-)-(R,R)-dihydrodiols. This result pertains even when the initially

OH

0'

\

Figure 18.

H

Stereochemical c a m e of the microsomal epoxide-hydrolase catalyzed hydration of (+)- and (-)-benzo[a]pyrene 4,5-oxide. About 99% of the attack by water occurs at the (5S)carbon of the (-)-(4K,SS)-oxide and about 85% at the (4s)carbon of the ( + ) - ( 4 S , 5 K ) - o ~ i d e . ~ ~

Biochemistry of Arene Oxides

263

formed arene oxide is subject t o rapid racemization as is the case of phenanthrene 1,2-oxide,benz[a] anthracene 1,2-oxide, and benz [a] anthracene 3,4-oxide (Table 3). Although the subject deserves further study, epoxide hydrolase either selects the enantiomer of the arene oxide in the racemic mixture that leads to the (R,R)dihydrodiol or captures this enantiomer before it has a chance to racemize. The argument, of course, presumes that all benzo-ring arene oxides are enzymatically hydrated by attack of water at the nonbenzylic position as discussed above, and '~~ that the steric model for the catalytic-binding site of cytochrome P 4 5 0 ~ predicts correctly which arene oxide enantiomer will be formed. Configurational assignments for known K-region derivatives are given in Figure 19. In contrast to the benzo-ring trans-(R,R)-dihydrodiols, the K-region trans-

Figure 19.

Absolute configurations and signs of rotation (tetrahydrofuran) for resolved Kregion derivatives of polycyclic aromatic hydrocarbons. References are superscripted. Rotation of the free cis-4,S-dihydrodiol of benzo[a]pyrene was not determined because of facile autoxidation which resulted in colored solutions. With liver microsomal enzymes from 3-methylcholanthrene-treated rats, the frans-(R,R)dihydrodiol greatly predominates (96%) from b e n z ~ [ a ] p y r e n e , * ~ ~ ~' t o be the minor enanpredominates (68%) from benz[ a l a n t h ~ a c e n e , ~appears tiomer from 12-methylben~[a]anthracene,~~~ and is the minor enantiomer (42%) from p h e n a ~ ~ t h r e n e . ~ ~ ~

P

O\

p3

+ 214"

Anthracene 1,2-(13) (D)23,327

(C)325,326

Benz[a]anthracene 8,9-(21)

8R,9S

(C)"

racemizes118

Benz[a]anthracene 1,2418)

+ 115"

- 614" ( ~ ) 1 1 9 , 2 7 4

(+)-racemizes (cI3' 4R,3S

Chrysene 3,4-(17)

Benz[a]anthracene 3,4419)

4R,3R

(+)-racemizes (C)32 1R,2S

Chrysene 1,2-(16)

(T)329

- 273" (T)z9,119 8R,9R

4R,3R

- 363"

1R,2R

- 313"

(T)33a

105" (T)329 lR,2R

(+)-racemizes (C)24-26 4R,3S

Phenanthrene 3,4-(15) -

-443" (T)277 4R,3R

r a c e m i ~ e s ~,328 ~+

- 312" (T)277 1R,2R

160" 1R,2R

-

167" 1R,2R

-

Dihy dro diol

Phenanthrene 1,2414)

1R,2S

(C)23

+ 149" (QZ3

Naphthalene 1,2-(11)

1R,2S

Arene Oxide

163" (C)32

(T)297119

-130" (QZ9 8S,9R

- 97" (C)"8 45,3r

+ 2" (T)329 4R,3R + 66" 8R,9R

15,2r

-

109" (c)31,329 45,3r - 1700 (c)ll8,335,336

15,2r

-

45,3r

- 156" ( c ) 2 6 3 3 2 8

- 9" (T)1l8,335 1 R 2R

~- 23" (T)31 4R 3R

+ 78" (T)329329 1R,2R

- 33" (T)277g Z s 4R,3R

140" (~)24,328 15,2r -

+ 35" (T)328 1R 2R

(C)" - 151" ( c ) 2 3 + 8

1 S,2R

- 135"

15,2r

(033

Tetrahydroepoxide

+ 44" (C)23 1R,2R

1R,2R

+ 110"

Tetrahydrodiol

ABSOLUTE CONFIGURATIONS AND SIGNS OF ROTATION ([ 011 D) FOR ENANTIOMERICALLY PURE, NON-K-REGION DERIVATIVES OF THE PAHS. The enantiomers shown for the arene oxides and dihydrodiols are either known or are expected t o be those which predominate by the combined action of cytochrome P450c and epoxide hydrolase. The tetrahydrodiols result either by reduction of the dihvdrodiols or bv trans hvdrolvsis of the tetrahvdroeooxides in which attack bv water occurs at the benzvlic oxirane carbonu

Hydrocarbon Position

TABLE 3.

vl

m

N

-

(+) racemizes (C)"'

Benzo[a]pyrene 9,10-(26)

Benzo[ clphenanthrene 3,4-(23)

~~

(T)269

~~~~

~

-300" (T)"' 4R.3R

-56" (T)333 4R,3R

10R,9R

- 294"

-432" (T)332 7R,8R

- 35" (T)331 1 lR,lOR

(C), dioxane (D), and tetrahydrofuran (T).

4R,3S

7R,8S

a Rotations were determined in chloroform

Dibenz[c,h)acridine 3,4-

+ 175" (C)"

Benzo[a]pyrene 7,8-(25)

llR,lOS

+ 383" (C)30

Benz[aJanthracene 10,11422)

- 78" (C)"" 4S,3R

+ 29" (T)333 4R,3 R - 38" (T)334

185" (C)'19 10S,9R

+ 55" 1OR,9R -

144' (C)" 7S,8R

-

(C)30 11S,lOR

- 142"

+ 63" (T)" 7R,8R

+

98" (T)303331 1lR,lOR

Arene Oxides-Oxepins

266

(R,R)-dihydrodiols known to date have positive values of [.ID. In addition, the enantiomer composition of the K-region dihydrodiols formed from various PAHs by liver microsomes from 3-methylcholanthrene-treatedrats is dependent on the substrate (see Figure legend). Present results suggest this is due entirely to a change in the regioselectivity of epoxide hydrolase rather than a change in the enantio~ e l e c t i v i t y ' of ~ ~cytochrome P4SOc.

3.

Reaction with Glutathione

A family of soluble proteins, collectively known as the glutathione S-transferases, are widely distributed throughout animal tissue. Along with a wide variety of other displacement reactions, they are capable of catalyzing the addition of the naturally occurring tripeptide glutathione t o arene Unfortunately, relatively little is known about the mechanism of action or the stereoselectivity of the homogeneous proteins toward arene oxide substrates. As might be expected, the addition to arene oxides occurs in a trans fashion to produce mercapturic acid precursors. For non-K-region arene oxides, both chemical and enzyme-catalyzed attack generally occurs at the nonbenzylic carbon as is the case for epoxide hydrolase. As discussed earlier, such thiol adducts undergo a novel 1,2-migration upon acid-catalyzed hydroly~is."~ Recent interest has focused on stereochemical aspects of the addition of glutathione to arene oxides. Reaction of a racemic Kregion arene oxide with the optically active tripeptide can result in a mixture of four diastereomers via attack at either epoxide carbon atom in each enantiorner. Development of a suitable HPLC separation procedure for such diastereomers allowed identification of a single isomer as the product formed when the addition of glutathione to racemic benzo[a]pyrene 4,5-oxide was catalyzed by an enzyme preparation from marine fish.'" The chromatographic technique, using either N-acetylcysteine or glutathione, has been successfully utilized to identify the enantiomers of benzo[a]pyrene 4,s-oxides of benz[a]anthracene 5,6-and 8,9-oxides, of anthracene 1,2-oxide, and of naphthalene 1,2-oxide formed from the respective hydrocarbons by cytochrome P ~ S O C .,2719275 ' ~ ~ In addition chromatographic properties of diastereomeric glutathione adducts of phenanthrene 9,lO-oxide and pyrene 4,s-oxide have been d e ~ c r i b e d . ~More ~ ' recent studies have established the absolute configuration of adducts formed from other K-region arene oxides by homogeneous to epoxide hydroforms of the rat liver glutathione S - t r a n ~ f e r a s e s In . ~ ~contrast ~ lase, these enzymes show a preference for attack at the oxirane carbon with (R)absolute configuration. The structures of two glutathione conjugates of brornobenzene oxides formed from bromobenzene in viva have been defined.344 J~~

4.

Arene Oxides and Cancer

A principal criterion for a chemical carcinogen is that it has the ability to bind covalently to cellular macromolecule^.^^^ Arene oxides, as known reactive metab-

Biochemistry of Arene Oxides

261

olites’ of carcinogenic polycyclic aromatic hydrocarbons, were thus strong candidates as ultimate car~inogens.’’~Although a comprehensive survey of the metabolism-induced binding of polycyclic aromatic hydrocarbons to biopolymersW6 is beyond the scope of the present article, a brief discussion of K-region arene oxides is appropriate. Most of the early efforts centered on K-region arene oxides, since they were the first to become available synthetically.’ Perhaps the most definitive structural studies of bound adducts of K-region arene oxides have been done with 7,12-dimethylbenz[a]anthracene5,6-oxide 3 . Reaction of the racemic arene oxide with guanosine in acetone-water resulted in the formation of six products, two of which were characterized as having resulted from attack by the 2‘-ribosyl hydroxyl group at positions 5 - and 6- of the arene oxide. In addition to the novel but precedented attack on a ribose hydroxyl group, evidence was presented indicating that only the (5R,6S)-enantiomer of the racemic arene oxide participated in the formation of these a d d ~ c t s In . ~ a~ subsequent ~ study, the remaining four adducts have been characterized.W8 They consist of two

0

0

diastereomeric pairs of cis (minor) and trans (major) adducts that result from the attack of the guanosine C-8 and 5-position of both enantiomers of the racemic arene oxide. The relative configurations of the cis and trans-adducts are illustrated. The sum of the two ribose 2‘-hydroxyl adducts and one of the guanosine C-8 adducts account for < 10% of the total 7,12-dimethylbenz[a] anthracene bound to the RNA of rat liver cells when exposed to the hydrocarbon in culture. The K-region 4,5-oxide of benzo[a]pyrene 4 is also known to bind to nucleic although little is known about the structures of the bound adducts. Interestingly, 9-hydroxybenzo [a] pyrene, a spontaneous isomerization product of the metabolically formed benzo [a] pyrene 9,10-oxide, also binds to DNA on further metabolic a ~ t i o n . ~ ’ ~Although -~’~ the evidence is largely indirect, the K-region 4,s-oxide of 9-hydroxybenzo [a] pyrene seems to be responsible for this binding.

Arene Oxides-Oxepins

268

ribose

ribose

Synthesis and biological testing of this putative metabolite should prove to be rewarding. Although it should be emphasized that tumor studies in animals are the only known method to determine whether or not a compound is carcinogenic, mutagenesis studies with bacteria and mammalian cells in uitro are useful indicators of possible carcinogenic activity. Since covalent modification of DNA generally represents the first step in mutagenesis, such short-term assays for potential carcinogenic activity are of chemical interest. Table 4 compares the mutagenic activity of a series of K-region arene oxides toward the Ames bacterial tester strains S. typhimurium TA98 and TA100. The comparison is meant to be representative rather than comprehensive and is based on data from several different experiments, albeit done in the same laboratory. The most useful conclusions that may be drawn from this data are that there is practically no correlation between mutagenic

TABLE 4.

RELATIVE MUTAGENIC ACTIVITY OF SELECTED K-REGION ARENE OXIDES TOWARD HISTIDINE-DEPENDENT STRAINS OF S. fyphimurium Relative activitf

Arene Oxide Phenanthrene 9,lO-oxide Chrysene 5,6-oxide Benz[a]anthracene 5,6-oxide Benz[c]acridine 5,6-oxide 3-methylcholanthrene 11,12-oxide Benzo [ c ] phenanthrene 5,6-oxide Dibcnz[a,h]anthracene 5,6-oxide Benzo[e]pyrene 4,S-oxide Benzo[a]pyrene 4,5-oxide

Strain TA98 0

Strain T A l 0 0

< 1%

- 13%

- 1% - 15% < 1% - 11%

< 10%

< 10%

100%

100%

nil

- 3%

nil

nil nil

'Data are relative to benzo[a]pyrene 4,5-oxide

< 2% 3%

Reference 360 360 361 362 363 364 365 105, 105,365-367

(2,300-2,700 histidine revertants per nmol in the two tester strains) which appears to be the most mutagenic K-region arene oxide known in this test system.

Biochemistry of Arene Oxides

269

response and either carcinogenicity of the parent hydrocarbon or solvolytic reactivity of the arene oxides. Other factors, such as physical properties or topological features of these arene oxides, seem to be more important than gross chemical reactivity to binding and mutagenesis. Relatively little is known about the tumorigencity of arene oxides of polycyclic aromatic hydrocarbons; initially because of the lack of synthetic accessibility and subsequently because of evidence that they are not ultimate carcinogens. Although several lines of evidence had implicated K-region arene oxides as ultimate carcinogens, tumor studies established them to be considerably less active than the parent hydrocarbons from which they were derived.257i368-3RThe only arene oxide thus far found to have high tumorigenic activity, although still only 20% of the parent hydrocarbon, is the non-K-region benzo[a]pyrene 7 , 8 - 0 x i d e . ~Interestingly, ~~ the (+)-(7R,8S)-enantiomer, which is metabolically formed in a 20 fold excess over the (-)-enantiomer by rat liver enzymes268>270 is about 20 times more active in causing lung adenomas in newborn mice? As indicated in the next section, subsequent tumor studies have established that certain non-K-region arene oxides and their resultant dihydrodiols are proximate rather than ultimate carcinogens. Thus, interest in the tumorigenicity of arene oxides has dwindled. 5.

Diol Epoxides and the Bay-Region Theory

Continued studies from several laboratories of the binding, mutagenicity and tumorigenicity of benzo [a] pyrene and its derivatives led to the identification of (+)(7R,8S)dihydroxy-(9S, 10R)-epoxy-7,8,9,lO-tetrahydrobenzo [a] pyrene (a diol epoxide-2 diastereomer) as the principal metabolite responsible for the carcinogenic Only one of the four metabolically possible activity of b e n ~ o [ a ] p y r e n e . '9157,374 ~~ isomers of the 7,8-diol-9,1O-epoxide was found to have high tumorigenic activity.375 Bay Region

Reflections on the chemical reactivity of epoxides on saturated angular benzo-rings and a reevaluation of existing tumor data resulted in the proposal that diol epoxides of angular benzo-rings in which the epoxide group formed part of a bay-region of the carcinogenic hydrocarbons would be prime candidates as ultimate carcinogens if metabolically formed! 7376-378 Subsequently more than a dozen hydrocarbons have been found to tit the predictions of the bay-region theory.3743379

270

Arene Oxides-Oxepins

VI. ACKNOWLEDGEMENTS We are particularly grateful to our colleagues at the Queen’s University of Belfast, Hoffmann-La Roche Inc., and the National Institutes of Health for their contributions to the studies described and for their examination of the text. We especially wish to thank Dot Dougherty for her typing and assembly of the manuscript. We take great pleasure in acknolwedging NATO for a travel grant (1807) and the Nuffield Foundation for support (to D.R.B.) without which this review would not have been possible. We also wish to thank R. T. Kimber (Science Library QUB) for conducting a comprehensive computer search of the topic, G. A. Berchtold (MIT) and J. M. Sayer (NIH) for numerous readings and helpful suggestions regarding the chapter.

VI. 1. 2. 3.

4. 5. 6. 7. 8. 9. 10. 11.

12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22.

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Arene O x i d e s - O x e p i n s R. N. Armstrong, W. Levin, and D. M. Jerina,J. Biol. Ckem., 2 5 5 , 4 6 9 8 (1980). R. P. Hanzlik, M. Edelman, W. J. Michaely, and G. Scott, J. Am. Chem. soc., 98, 1952 (1976). P. M. Dansette, V. B. Makedonska, and D. M. Jerina, Arch. Biockem. Biopkys., 187, 290 (1978). G. Bellucci, G. Berti, M. Ferretti, F. Marioni, and F. Re, Biockem. Biopkys. Res. Comcum., 1 0 2 , 8 3 8 (1981). G. C. DuBois, E. Apella, R. N. Armstrong, W. Levin, A. Y. H. Lu, and D. M. Jerina, J. Biol. Ckem., 254,6240 (1979). A . Y. H. Lu and G. T. Miwa, Ann. Rev. Pkarmacol. Toxicol., 2 0 , 5 1 3 (1980). A. Y. H. Lu, D. M. Jerina, and W. Levin,J. Bid. Ckem., 2 5 2 , 3 7 1 5 (1977). D. R. Thakker, H. Yagi, W. Levin, A. Y. H. Lu, A. H.Conney, and D. M. Jerina, J. Biol. Ckem., 252,6328 (1977). S. K. Yang, P. P. Roller, and H. V. Gelboin,Biockemistry, 16, 3680 (1977). T. Watabe, N. Ozawa, and K. Yoishikawa, Biockem. Pharmacol., 30,1695 (1981). J. Booth, E. Boyland, and E. Turner, J. Ckem. Soc., 1 1 8 and 2808 (1950). R. Miura, S. Honmaru, and M. Nakazaki, Tetrahedron Lett., 5271 (1968). P. Sims, Biochem. J., 9 2 , 6 2 1 (1964). S. K. Balani, D. R. Boyd, E. S. Cassidy, G. E. Devine, J. F. Malone, K. M. McCombe, and N. D. Sharma, J. Chem. Soc., Perkin Trans. I , 2751 (1983). H. Yagi, K. P. Vyas, M. Tada, D. R. Thakker, and D. M. Jerina, J. Org. Chem., 47, 1110 (1982). K . P. Vyas, H. Yagi, W. Levin, A . H. Conney, and D. M. Jerina, Biockem. Biopkys. Rex Commun.,9 8 , 9 6 1 (1981). D. R. Thakker, W. Levin, H. Ya@, S. Turujman, D. Kapadia, A. H. Conney, and D. M. Jerina, Ckem.-Biol.Interact., 2 7 , 1 4 5 (1979). H. Yagi, H . Akagi, D. R. Thakker, H. D. Mah, M. Koreeda, and D. M. Jerina, J. Am. Ckem. Soc., 9 9 , 2 3 5 8 (1977). H. Yagi, D. R. Thakker, Y. Ittah, M. Croisy-Delcey, and D. M. Jerina, Tetrahedron Lett., 24, 1349 (1983). R . E. Lehr, S. Kumar, N. Shirai, and D. M. Jerina, manuscript submitted. D. M. Jerina, P. J. van Bladeren, H. Yagi, D. J. Gibson, V. Mahadevan, A. S. Neese, M. Koreeda, N. D. Sharma, and D. R. Boyd, J. Eng. Ckem., in the press. D. R. Boyd and N. D. Sharma, J. Ckem. SOC.,Perkin Trans. 1, in the press. E. Huberman, L. Sachs, S . K. Yang, and H. V, Gelboin, Proc. Natl. Acad. Sci. U.S.A., 7 3 , 6 0 7 (1976). Y. Ittah, D. R. Thakker, W. Levin, M. Croisy-Delcey, D. E. Ryan, P. E. Thomas, A. H. Conney, and D. M. Jerina, Chem.-Bid. Interact., 4 5 , 15 (1983). P. P. Fu, M. W. Chou, and S. K. Yang, Biockem. Biopkys. Res. Commun., 106, 940 (1982). W. B. Jakoby, Advances in Enzymology, Vol. 4 0 , Wiley-Interscience, New York, 1978, pp. 383-441. D. M. Jerina and J. R. Bend, Biological Reactive Intermediates, Plenum, New York, 1 9 7 7 , ~207-236. ~. 0. Hernandez, A. B. Bhatia, and M. P. Walker, J. Liquid. Chromatoy., 6 , 1693 (1983). D. Cobb, C. Boehlert, D. Lewis, and R. N. Armstrong, Biochemistry, 2 2 , 805 (1983). T. J . Monks, L. R. Pohl, J . R. Gillette, M. Hong, R. J. Highet, J. A. Ferretti, and J. A. Hinson, Chem. Biol. Interact., 41, 203 (1982).

References 345. 346. 347. 348. 349. 350. 351. 352. 353. 354. 355. 356. 357. 358. 359. 360 361. 362.

363. 364. 365 366. 367 368. 369. 370. 371. 372. 373. 374.

28 1

E. C. Miller and J. A. Miller, Molecular Biology of Cancer, Academic, New York, 1974, pp. 377-402. P. L. Grover, Chemical Carcinogens and DNA, CRC Press, Baco Raton, FL, 1979. H. Kasai, K. Nakanishi, K. Frenkel, and D. Grunberger, J. Amer. Chem. SOC.,99, 8500 (1977). K. Nakanishi, H. Komura, I. Miura, H. Kasai, K. Frenkel, and D. Grunberger, J. Chem. Soc. Chem. Commun., 8 2 (1980). W. M. Baud, R. G. Harvey, and P. Brookes, Cancer Res., 35,54 (1975). S. H. Blobstein, I . B. Weinstein, P. Dansette, H. Yagi, and D. M. Jerina, Cancer Res., 36,1293 (1976). H. W. S. King, M. H. Thompson, and P. Brookes, Int. J. Cancer, 18, 339 (1976). €3. Jernstrom, H. Vadi, and S. Orrenius, Chern.-Biol. Inferact., 20, 311 (1978). B. Jernstrom, S. Orrenius, 0. Undeman, A . Graslund, and A. Ehrenberg, Cancer Res., 38, 2600 (1978). R. A. Lubet, J. Capdevila, and R. A. Prough, Int. J. Cancer, 23,353 (1979). P. Vigny, Y. M. Ginot, M. Kindts, C. S. Cooper, P. L. Grover, and P. Sims, Carcinogenesis, 1 , 9 4 5 (1980). M. Boroujerdi, H.-C. Kung, A . G. E. Wilson, and M. W. Anderson, Cancer Res., 41, 951 (1981). S. W. Ashurst and G. M. Cohen, Int. J. Cancer, 27, 357 (1981). I. S. Owens, G. M. Koteen, and C. Legraverend, Biochem. Pharmacol., 28,1615 (1979). M. Nordenskjold, S. Soderhall, P. Moldeus, and B. Jernstrom, Biochem. Biophys. Res. Commun., 85,1535 (1978). A. W. Wood, R. L. Chang, W. Levin, D. E. Ryan, P. E. Thomas, H. D. Mah, J . M. Karle, H. Yagi, D. M. Jerina, and A . H. Conney, Cancer Res., 39,4069 (1979). A. W. Wood, R. L. Chang, W. Levin, R. E. Lehr, M. Schaefer-Ridder, J. M. Karle, D. M. Jerina, and A. H. Conney,Proc. Natl. Acud. Sci. U.S.A., 14, 2746 (1977). A. W. Wood, R. L. Chang, W. Levin, D. E. Ryan, P. E. Thomas, R. E. Lehr, S. Kumar, M. Schaefer-Ridder, U. Engelhardt, H. Yagi, D. M. Jerina, and A . H. Conney, Cancer Res., 43, 1656 (1983). A. W. Wood, R. L. Chang, W. Levin, P. E. Thomas, D. Ryan, T. A . Stoming, D. R. Thakker, D. M. Jerina, and A. H. Conney, Cancer Res., 38, 3398 (1978). A. W. Wood, R. L. Chang, W. Levin, D. E. Ryan, P. E. Thomas, M. Croisy-Delcey, Y. Ittdh, H. Yagi, D. M. Jerina, and A . H. Conney, Cancer Res., 40,2876 (1980). A. W. Wood, W. Levin, P. E. Thomas, D. Ryan, J. M. Karle, H. Yagi, D. M. Jerina, and A. H. Conney, Cancer Res., 38, 1967 (1978). A. W. Wood, R. L. Goode, R. L. Chang, W. Levin, A. H. Conney, H. Yagi, P. M. Dansette, and D. M. Jerina,Proc. Natl. Acad. Sci. U.S.A., 12, 3176 (1975). R. L. Chang, A. W. Wood, W. Levin, H. D. Mah, D. R. Thakker, D. M. Jerina, and A . H. Conney, Proc. Natl. Acad. Sci. U.S.A., 16,4280 (1979). E. C. Miller and J. A. Miller, Proc. Soc. Exp. Biol. Med., 124, 915 (1967). E. Boyland and P. Sims, Znt. J. Cancer, 2,500 (1967). P. Sims, Int. J . Cancer, 2, 505 (1967). K. Burki, J. E. Wheeler, Y. Akamatsu, J . E. Scribner, G. Candelas, and E. Bresnick, J. Nat. Cancer Inst., 5 3 , 9 6 7 (1974). P. L. Grover, P. Sims, B. C. V. Mitchley, and F. J. C. Roe, Br. J. Cancer, 31, 182 (1975). W. Levin, A. W. Wood, H. Yagi, P. M. Dansette, D. M. Jerina, and A. H. Conney, Roc. Natl. Acud. Sci. U.S.A., 13, 243 (1976). W. Levin, A. Wood, R. Chang, D. Ryan, P. Thomas, H. Yagi, D. Thakker, K. Vyas, C.

282 375. 376.

377. 378.

379.

Arene Oxides-Oxepins Boyd, S.-Y. Chu, A. Conney, and D. Jerina, DrugMetabolism Reviews, 13,555 (1982). M. K. Buening, P. G . Wislocki, W. Levin, H. Yagi, D. Thakker, H. Akagi, M . Koreeda, D. M. Jerina, and A. H. Conney,F’roc. Natl. Acad. Sci. U.S.A., 75,5358 (1978). D. M. Jerina, R. E. Lehr, H. Yagi, 0. Hernandez, P. M. Dansette, P. G. Wislocki, A. W. Wood, R. L. Chang, W. Levin, and A. H. Conney, in Vitro Metabolic Activation In Mutagenesis Testing, Elsevier/North-Holland Biomedical Press, Amsterdam, 1976, pp. 159-177. D. M. jerina and R. E. Lehr, Microsomes and Drug Oxidations, Pergamon, Oxford, England, 1977, pp. 709-720. D. M. Jerina, R. Lehr, M. Schaefer-Ridder, H. Yagi, J . M. Karle, D. R. Thakker, A. W. Wood, A. Y. H . Lu, D. Ryan, S. West, W. Levin, and A. H. Conney, Origins of Human Cancer, Cold Spring Harbor Laboratory, Cold Spring Harbor, New York, 1977, pp. 639-65 8. M. Nordqvist, D. R. Thakker, H. Yagi, R. E. Lehr, A. W. Wood, W. Levin, A. H. Conney, and D. M. Jerina, Molecular Basis of Environmental Toxicity, Ann Arbor Science Publishers Inc., Ann Arbor, Michigan, 1980, pp. 329-357.

Chemistry of Heterocyclic Compounds, Volume42 Edited by Alfred Hassner Copyright 0 1985 by John Wiley & Sons, Ltd.

CHAPTER I11

Oxaziridines MAKHLUF J . HADDADIN

Department of Chemistry. American University of Beirut. Beirut. Lebanon

JEREMIAH P . FREEMAN

Department of Chemistry. University of Notre Dame. Notre Dame. Indiana

I.

I1 .

111.

IV .

Introduction . . . . . . . . . . . . . . Preparation of Oxaziridines . . . . . . . . 1. Oxidation of Imines with Pcroxy Acids . . . 2 . Reaction o f Ketones with Aminating Agents . . 3 . Photolysis of Nitrones . . . . . . . . 4 . Other Photolyses . . . . . . . . . . 5 . Miscellaneous Methods . . . . . . . . Stereochernistry . . . . . . . . . . . . 1. Asymmetric Induction Using Chiral Peracids . . 2. Oxidation o f Chiral Imines with Achiral Peracids . 3 . Asymmetric Synthesis in Chiral Media . . . . 4 . Interconversion of Oxaziridine Stereoisomers . . Reactions . . . . . . . . . . . . . . . Reactions with Basic Nucleophiles . . . . . 1. A . P-Elimination . . . . . . . . . B. Attack at Oxygen . . . . . . . . C. Attack at Nitrogen . . . . . . . . 2 . Acid-Catalyzed Reactions . . . . . . . 3 . Thermal and Photochemical Reactions . . . . 4 . Metal-Ion-Catalyzed Reactions . . . . . . 5 . Cycloaddition Reactions . . . . . . . .

283

. . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . .

. . . . . . . . .

. . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . .

284 284 284 307 309 312 313 313 314 316 319 320 322 322 322 325 321 329 333 340 341

Oxaziridines

2 84

I.

INTRODUCTION

Since the announcement of their discovery in 1956-1 957, oxaziridines have been widely investigated, principally for two reasons. The presence of an inherently weak N-0 bond in a strained ring promised a group of compounds of unusually high reactivity. In addition, this system possesses the structural elements that seem to be required to observe stereochemical isomerism at nitrogen: ring strain and an atom with unshared electron pairs attached to nitrogen. Since the discovery of oxaziridines, several reviews have Our intention in this review is t o present a broad picture of the current state of knowledge of this heterocyclic system with particular attention to methods of syntheses, structure and stereochemistry, and its reactions, both photochemical and nonphotochemical. The investigations of the past 15 years are emphasized t o bring Emmons' original review3 in this series up-to-date. Originally called oxaziranes and/or isonitrones, these compounds are now almost universally referred to as oxaziridines, Chemical Abstracts preferred nomenclature. The numbering system has been consistent since their discovery: 1

PREPARATION OF OXAZIRIDINES

11. 1.

Oxidation of Imines with Peroxy Acids

The first method used in the preparation of oxaziridines was the treatment of imines (Schiff bases) with peracids, especially peracetic acid. Although other methods have been occasionally employed in the preparation of oxaziridines, the reaction of peracids with imines has proven to be quite versatile and, invariably, the method of choice. This method was discovered by three independent groups in 1956- 1958.8-'0

R R >N\R The procedure consists of the addition of peracetic acid to a solution of the imine. The reaction temperature varies between room temperature and - 78°C. The selectivity of the reaction increases with the lowering of the reaction temperature." Ether and dichloromethane have often been used as solvents in the reaction, with oxaziridine yields ranging between 35-90%. Tables of some oxaziridines prepared by this method are included in two review^,^?' and these will not be listed in Table 1 except where new physical constants, better yields, and/or different methods of preparation have been reported,

CH3

CH3

-

95 85 53 46

(7 8-7 9/8) (35/0.3) (43-45/1.2)

46

36

46 MCPBA

+RGN

38

t-my1 hydroperoxide

H,O,

38

44 45 PBA t-my1 hydroperoxide

43

41

41,42

40

40

Ref.

PAA or MCPBA

MCPBA

55 48

MCPBA

86

(40-41/0.5)

(5 8-60/10)

(35-40/20)

PCA

-9.0

(69-71/11-12)

Methoda PCA

[alD - 3.3

Yield

(67-69138)

Melting Point (Boiling Point/mm Hg)

OXAZIRIDINES BY PERACID OXIDATION OF IMINES

L“+CH,

Oxaziridine

TABLE 1.

'?

00

6

W

m

W M

W

m

W M

I

I

I

I

0

3

d

m

cn

10

. . . . z 2

0

h

M

9

N

9

0

m

m m

vl

r-

W

I

m,

W W

d

I

m

m w

cn

vl

w m m w

6 3

OI

P 0

cn

3

I 0 10

d

Q 2 86

r-

I

M

3

I

o m

3 3

d

. . !5z h h

mvl W d 0 -

m d

m d

m d

0

m

bma

3

m

d

d

Q

d

Lo

E

z Q

m

'?

I

I

d

r-

W rn

W" W

W W

0 d

rn

V

v

I

I

0

v)

m

W

vr

W

0

I

I

m

r3 h

0

0

N

m

I

I

. . . . 2. s . . z 3 h

m

0 N

m

r?

r3

I

0 r 4

r3

3

0 VI

v

m N

V v

h

3

'0

N

V v

d h

N

r-

0

z W

m

v

W

W

m rm

T

u

281

0 N

W

d

r-

r-

d

d

hl

m

N

m

hl

m

m

Z5W - N

I

I

I

91

rn m

I

. 3

W

.d &

0

28 8

m m

3

. i;i 0

m,

rj

0

d

d

N

o

m d

d

d

e

m d

1

I

I

I

I

I

I

m

0

r-

d

O

1

W

m

r

w

r

.

-

n

r

N

-

.

h

h

m p'

'D,

e

t.

m r-

m

d

N

?

1

I

I

e

*

I

.

m

I

'c!

s

r-

v

n

",

07

L,

I

"l

3

c,

289

I

m

.r

. . .

i

r-

rn I

m

'c!

e

e

m

h

'c!

h

m d

N N

h

h

2

0

0

m

3

P, m 3

m rI

z

m

W N I

rN

vl

d

4 d

to

m

d

m m

o m

0

N

N

I

I

I

I

I

I

I

m

2 m

m

i

I

I

3

W

m

N

0

2 . 0

2

m rrr-

v)

d

-

9 0

mI

W

r

n

N

v

l

o

vl

vl

N 0

. .. . . 8 . n

n

h

0

n

rn

N

z

290

2

d

z

n

vl

9 0

'0 n

d

m

W

r-

m

z

d d

v

n '0

9 0

' I ]

vl

mI

vl

v

W

Lo

d

W

N

v,

W

r-

v,

v,

4

4

4

Lo

2V

r-

r-

r-

r-

9 rn

f

W

+

t-3

Lo

vr

Lo

E

W

m

r-

I

I

I

I

I

I

r3

i

c

0

I

y!

W

Lo

r3

3

3

s u I

o=& I

0%I

U

291

v)

m

+

L? 3 3

+

r-

r-

r-

B

4

2

vl

2

b. vl

0 N

+

I

I

10

r-

vl

wl

9

P?

2m

*

2m

I

I

I

a

m

m

m N

I

1

e

vl

E

E

V

r-

r-

10

+

+

I

m

'0

N vl

I

m

v1

E

...e 292

r-

d

o!

r-

d

W

m

N 3

N 3

I

I

W

Vl

W W

W

vl

W Lo

I

I

0

N

P

0 3

I

m

r-

I 0

t

0

m

Lo

r-

. . . * 1

m

3

0 N

h

h

00 d

0 N

4

0 N

0

0

h

0

2

W

2

vl

8I

s u I

vl

W

b 2

6

m

Y

293

I

0 00 10

0

m

10

4

8E I

I

m

vl UJ

m

d

m

rn

m m

r-

d 0

m

Q 0

0

4 'z

O0

s u

294

g-2'

m

-

0

W

10

0

0

m

m

m

v)

0

W

In

U

W

10

I

0

r-

0

v)

d

d

W

N

d W

0

In

,-I

d

rcn

N

i

295

W I

W

v)

i

cn

3

CONTINUED Melting Point (Boiling Point/mm HE;

0

-0

C6H5A ' N --CHzCHzC6Hs

CsH5 C6Hs@N

MCPBA

33

-

50 PCA -

(1 10-112/0.05)

50 PCA -

(90-91/0.1)

50 PCA

-192

85-86

46

50,53

PCA

-258

117.5-1 18.5

60

59

PCA

-

MCPBA

-- 194

110

-

-

101-104

59

MCPBA

-

46

MCPBA

-

Ref.

Methoda

Lff1D

-

67

Yield

97-100

33 C~H,-L\NCH~CH~C~H~

0

Oxaziridine

TABLE 1.

d

d W

0-

d

W 4

W

N

W

m m

w w

m

d.

w

0-

W W

W W

W

dW

d

0” d

d v,

m

0

I

m 0 W

m

m 00

m W

I

1

01

d

;

d

0

W

r-

0

I

0

m

cc

r-

r-

I

d

d

4

m

I

d

m t-

m t-

W I

O W

m d I

N d

W

0

I

m

z

g 2 u-0

I

297

rd

V

n

d

0 3

I N 0 d

~w

vlw

0”

4

b w

c? r3 3

I

d

I

00 0

I t-

d

.t

r3

m

w

;

%

w w

I

I

I

1

vl vl

0 d

rn d

3

W

3

I

I

I

m

m

CO

c-

rn

3 3

d

I

I

3

d

m

0

r3

5-5 I

298

10

m

m

rn

d

d

2

d

m

0

d

CI

L(

0

a

2 m

4

4 10 m

I

I

I

1

p!

2m

1

W W

m

m

d W I N W

4

0

t-

m

W

rn

mI

0

?!

0’

o_ T u

t;

299

2 3

I

4

00

0

m

0 N

0

0 N

r4

0 N

? 0

I

N

CO

0

3

*

0 3

.\

U,

g*': 300

r3

r-

W

W

E

4

f

\4 m

9

I

I

I

W

4

d

2

0

z

z

z

4

10

W W

W

W W

W

W

W W

P 4

d

d

I

I

I

I

I

m W

00 10

d

r-

m

301

10

W

W

m W

W W

m

m

' I ) 4

I

0

d

2

I

I

m

N 3

m

10

I

W 'I)

' I )

a,

I

d

m

3 02

z m

I

W 0

*

d W

m W

4

2

iD N

m W

0

r-

m W

m W

4

V

a

I

+

N

.l

I

* 3 3

I

m

3

d

r-

m

W d

00

W

0

m

v

303

0

vr

I

rW

CONTINUED

PB A

PBA

PBA PBA

-

-

36

63 72 80

Methoda

160

[alD

Yield

Melting Point (Boiling Point/mm Hg)

70

70

70

70

Ref.

aPAA = Peracetic acid; PBA = Perbenzoic acid; MCPBA = rn-chloroperbenzoic acid; PCA = Percamphoric acid; PNPBA = p-Nitroperbenzoic acid.

Oxaziridine

TABLE 1.

Preparation of Oxaziridines

305

Peracetic acid was later replaced by m-chloroperbenzoic acid (MCPBA), which is easier to handle and relatively more stable than peracetic acid." Other solid peracids including chiral peracids have been used in the synthesis of chiral oxaziridines (see Section 111.1). Recently, MCPBA has been found t o be effective in the preparation of oxaziridines with no substituent on the ring nitrogen, a class of oxaziridines that are rather unstable (Ref. 13 and references cited therein). Phasetransfer catalysis has been employed in an improved synthesis of N-sulfonyloxaz i r i d i n e ~ . ' p-Nitroperbenzoic ~~ acid was used to oxidize an epoxy imine to an epoxyoxa~iridine.'~~ In some cases, the reaction of peracids with imines has produced nitrones along with oxaziridines. It has been found that product selectivity depends on the structure of the imines and the reaction conditions, especially acidity.14 The formation of oxaziridines is predominant in the presence of alcohols or carboxylic acids, whereas the yield of nitrones is increased in aprotic media.

1 a,R=H b, R = CH,

2

3

Oxaziridine 2a was unstable and 2b was difficult to purify. Another example of the formation of a mixture of nitrones and oxaziridines is that of nitrone 5 and oxaziridine 6 in 40% and 10% yields,15 respectively, from imine 4.

4

5

6

Although speculative mechanisms for the reaction of imines with peracids to form oxaziridines have been suggested,*,16 only two kinetic studies of this reaction have been undertaken. The first concluded that the reaction proceeded by a onestep mechanism where the n-electrons of C=N perform a nucleophilic attack on the sterically less-hindered hydroxylic oxygen in a manner analogous to epoxidation of olefins. The peroxy acid undergoes a synchronous hydrogen exchange process with HY, where HY is the solvent, benzoic acid (a product), or another molecule of peroxy acid. The molecule HY (if solvent) must be a protic solvent, capable of proton exchange. The transition state is composed of the peroxy acid, the Schiff base, and a molecule of HY (Scheme I).17

3 06

Oxaziridines 0

R-c

II ‘0-0

I

I

H

+ lmine

Scheme 1

In the second study, the above one-step mechanism was discounted and a twostep mechanism (a Baeyer-Villiger type) was advanced. “Although the rates are summarized as v = kobs [C=N] [perbenzoic acid], the reaction exhibits complex kinetics because of the two adverse effects, acceleration by carboxylic acids and protic solvents, and retardation by basic solvents including ethers and alcohols” (Scheme II).’*

)C=N

\

+

RC03H

‘C--N

’I

0-0

I

RC02H

+

%-IN-

/

I

H

i SN

Scheme 2

It is interesting to note that a-hydroperoxyamines have been isolated in high yields from the reaction of hydrogen peroxide with imines. Subsequent heating of these a-hydroperoxyamines gave oxaziridines.”

307

Preparation of Oxaziridines

H-0

I

Recent related stereochemical investigations that attempted to settle the issue of a one-step mechanism vs. a two-step mechanism were not conclusive; nevertheless, these studies favored a two-step mechanism.20~'1 A recent ab initio MO investigation supports a two-step mechanism.2' The number of stable N-phenyl substituted oxaziridines is rather sma11.7~32380~118 Most of the attempts to prepare such oxaziridines were performed in acidic media in which these oxaziridines are apparently unstable. An attempt to prepare an oxazabicyclobutane by peroxidation of an azirine yielded only an N-acylimine, but that product may have been derived from the heterobicycle.166 fN l\

PhC-CHCH3f (CH3)3C-OOH

2.

Triton

7

PhC -N =CHCH

Reaction of Ketones with Amhating Agents

Schmitz prepared a variety of oxaziridines, unsubstituted at nitrogen, by the reaction of chloramines or hydroxylamine-0-sulfonic acid with ketones.' Such 5 generoxaziridines, first reported in 196lZ3and developed somewhat l a t e r ~ 4 3 2are ally not stable in the neat state.26 Although 3,3-diphenyloxaziridine is converted into benzophenone at room temperature, 3,3-di-t-butyl-oxaziridinewas recently isolated in 90% purity by high-vacuum distillation, and could be stored for several hours as a colorless oil without significant further decomposition to the principal contaminant, di-r-butyl ketone.13

3 08

Oxaziridines

TABLE 2. 2-ACYCLOXAZIRIDINES27a~z6

Melting Point (Boiling Point/mm Hg)

% Yield

70

40

80-81

57

0

N -C

II

C6HS

0

N - C -CH3

O

C,H5--L\N

C6H5 0

<\N

l

0

C,H, 0 <\N

f

- C - NH2 II

- C -NHC,H,

[51-53 (0.3)]

70

190-94 (0.04)]

30

116-117

60

107-108

86

67-68

40

127

74

58

75

82-84

61

96-98

70

0

II

- C -NH(n-C,,H,,)

0 e

o

\

N

-

! -NH(nC4H,)

309

Preparation of Oxaziridines 0

Oxaziridines with no substituent on the ring nitrogen may be stabilized as the N-acyl derivatives. Indeed, the presence of an acylating agent, that is, benzoyl chloride, is necessary for the trapping of such oxaziridines derived from aliphatic aldehydes (Table 2)?7a

B

R-C-R'

+

NH20S03H

R + C,H5C-C1

-

x

O, :>LN-C-C,H,

The stabilizing effect also can be achieved in the reaction of these oxaziridines with isocyanates (Table 2).28

3.

Photolysis of Nitrones

The photolysis of nitrones has been used as a method of preparing oxaziridines. A table of fairly stable oxaziridines prepared from the photolysis of the corresponding nitrones has been included in an extensive re vie^.^ The photochemical method, though limited in its scope, often serves as an alternative to the peroxidation of imines. The synthetic usefulness of this method is demonstrated by the conversion of nitrones 7 and 9 into oxaziridines 8 and 10 in yields of 78% and 74%, respect i ~ e l y . ~(Apparently, '~~~ the phototoxicity of benzodiazepine N-oxides, e.g., 7 , 9, is due t o this isornerization.z08) Similarly nitrones 1l a , b, c yielded oxaziridines 12a, b, c (25-30%).j1

Oxaziridines

310

8,R-H CH3

7,R=H 9 , R = CH3

10, R

C H c6H5

1la, b, c a,

R

b, R

' Y N - K 12a, b, c

Q= =Q

Additional examples of oxaziridines prepared by irradiation of nitrones are listed in Table 3. A 3-acyl oxaziridine, a rare stable derivative of its kind, was made photochemically from the isomeric nitrone to which it reverted upon standing. Further irradiation led both to rearrangement with acyl migration and t o nitrene elimination (see Section IV.3).170

311

Preparation of Oxaziridines TABLE 3.

OXAZIRIDINES FROM PHOTOLYSIS OF NITRONES Melting Point

% Yield

Ref.

25

31

134-136

30

31

182-183

30

31

136

78

30

99-100

74

29

155-156

100

100-101

5

35

167-167.5

-

198

Ph

@? \

131

Ph Ph

Oxaziridines

312

The photochemical isomerization reaction has been shown"g to be stereospecific following the disrotatory photochemically allowed cyclization path. Thus the stereochemistry of the nitrone is preserved in the oxaziridine. However, since some nitrones undergo trans-cis isomerization under the conditions of photolysis, mixtures of oxaziridines often result. The nitrone-oxaziridine ring-chain isomerization has attracted theoretical at ten ti or^.'^^-'^^ The quantum yield for the reaction has been measured'82 and the reaction has been examined in a rigid polymer matrix.lE3

4.

Other Photolyses

A single example of the formation of an oxaziridine by nitrene addition to a carbonyl group was found in the photolysis of ethyl azidoformate in the presence of excess acetone (for about 40 hr), producing oxaziridine 13. The reaction failed to give the corresponding oxaziridine when acetone was substituted by cyclohe~anone.~,

CH,'

::

C 'CH,

+ N3C02C2HS

60% hv

* CH3 cH3$N-8-Cl~2E& 13

Oxaziridines have been detected iodometrically, but not isolated, in the photolysis of a$-unsaturated oximes.%

It has been suggested that oxaziridines are products of the photochemical autoxidation of aliphatic a m i n e ~ . ' ~ ~ The photolysis of diphenyldiazomethane in nitroso nonafluoroisobutane was reported to yield an ~xaziridine.'~'

(CF,),CN = O

+ Ph2CN2 A

(CF,),C-N-O

' b

/"\

Ph Ph

Stereochemistry

5.

313

Miscellaneous Methods

The following methods can be considered variations of the peroxidation of imines, yet they offer a novelty of approach and sometimes give oxaziridines (reaction 4) that are inaccessible by the usual methods that have been already discussed. 1.

X = CO or SO2

111.

STEREOCHEMISTRY

The stereochemistry of the oxaziridine ring has received considerable attention mainly due t o the chirality of the nitrogen atom and the appreciable barrier to its inversion; thus, the separation o f enantiomers became possible. Optically active oxaziridines have been prepared b y the following methods:

Oxaziridines

3 14

1.

Asymmetric Induction Using Chiral Peracids

Although partial resolution of 2-n-propyl-3-methyl-3-isobutyloxaziridine (14, [ a ] g = - 3.94") was reported in 1957,* the first direct preparation of optically active oxaziridines was achieved in 1968.40 Treatment of a number of imines (Table 1 - entries 1, 2, 95, 96, 98, 100, 102) with (S)-(+)-monopercamphoric acid at 3°C in dichloromethane gave optically active oxaziridines in 47-80% yields. The optical purity of these oxaziridines was not established, but oxaziridine 14 was obtained with higher optical activity ([aID= - 9.0") than the sample obtained from partial resolution ([a],, = - 3.94").

In the same year, an optically active oxaziridine with nitrogen as the only chiral center was prepared by the treatment of N-diphenylmethylenemethylamine 15 with (S)-(+)-monopercamphoric acid, (S)-(+)-2-(a-naphthyl)peroxypropionic acid, (R) (-)-2-phenylperoxypropionic acid, and (S)-(+)-2-methylperoxybutyric acid to give 2-methyl-3,3-diphenyloxaziridinewith optical rotations of [a]&, = - 49.2", - 8.5", + 12.5", and - 5.7", respectively."

15

Further studies of asymmetric induction in the synthesis of optically active oxaziridines via oxidation of imines with chiral acids and the degree of stereoselectivity of these reactions have been r e p ~ r t e d . ~ ' ~It' ,was ~ ~ found that the degree of stereoselectivity in the conversion of aldimines and ketimines to oxaziridines by (+)-monopercamphoric acid (MPCA) is dependent on the solvent and the reaction temperature (Tables 4 and 5 ) . The stereoselectivity of the reaction does not seem to depend on the nature of the alkyl group attached to n i t r ~ g e n . ~ ' Although a number of peroxy acids have been used in the preparation of optically active oxaziridines, for example, (R)-(-)-2-phenylperoxypropionic acid, (S)-(+)-2-(a-naphthyl)peroxypropionic acid, and (S)-(+)-2-methylperoxybutyric acid, the peroxy acid of choice seems to be (S)-(+)-monopercamphoric acid (PCA). Recently, the purity of this acid used in earlier studies has been questioned and a procedure for the preparation of PCA in crystalline form has been described.72 The purer form of PCA gives 50-100% greater optical yields than previously reported. Unpurified PCA consists of a mixture of isomers (16 and 17) that gave opposite stereochemical senses of asymmetric induction.

Stereochemistry TABLE 4.

315

SOLVENT DEPENDENCE OF ASYMMETRIC INDUCTION

Solvent

[&ID

[a]::,

CHCI, ClI c1

17.1 - 12.7 - 10.9 + 1.5 + 6.5

-

-

- 23.4

-

, ,

6'

(C,H ) ,O C,H,OH

cc1,

C,HQ :C,H;,(7:3) CHCI, (C, H ,), 0 CH,CN CH,OH (CH,),CHOH

~

-

-

-

-

-

-

- 79.0 - 12.5 - 65.0 -31.2 - 3.3 0 f 2.7

- 22.0 - 21.2 9.9 - 2.1 0 - 0.7

~

~

-

-

~

-

Ref.

[aI::o

67 67 67 67 67 50 50 50 50 50 50 50

-

Crystalline PCA 16 gave oxaziridine 18 in 60% optical yield. /C(CH3)3

-N 7\

p-BrPh

PCA

-7 8 O

p-BrPh 18

Moreover, PCA has been found t o react with chiral imines (vide infra) t o yield oxaziridines with higher preference for the S configuration at nitrogen than that produced by achiral peroxy Among the methods discussed in this section, the preparation of optically active oxaziridines using chiral peroxy acids has been employed extensively.21 ,51,52,54,60,63~66,72,73 TABLE 5.

TEMPERATURE DEPENDENCE OF ASYMMETRIC INDUCTION

Tcrnperature P C )

+ 29

+ 3 - 18 -40 - 72 -60 -60 - 20 - 20 0 0

I01D - 3.2

11.3 - 13.2 36.5 -62.7 -

-

~

[01%

-

-

-

-

~

-

~

-

55.8

-

-

- 42.2 -

~

~

0

-

~

-

[ 012

- 21.2 -

-

% Optical Purity

Ref.

3.4 11.9 13.9 38.5 66.0

67 67 67 67 67 50 50 50 50 50 50

-

145.0

~

20.1 ~

- 77.0 -

-65.0

10.9 -

9.3

Oxaziridines

316

2.

Oxidation of Chiral Imines with Achiral Peracids

The oxidation of imines 19, 20, and 21 with rn-chloroperbenzoic acid in dichloromethane at 0-5°C gave oxaziridines 22a, b, 23a, b, and 24a, b, respectively, in high yields (75-85%).57,74 In each of these cases, one diastereomer was predominant to the extent of 82, 87, and 97%, respectively. The diastereomeric ratio was determined by Hnmr. For example, the diastereotopic methyl groups in 22a, b gave signals at 6 1.32 and 1.40 for 22a, and 1.43 and 1.61 for 22b. The methyl group in C6H&HCH3 gave a doublet at 1.47 for 22a and another at 1.32 for 23b. This c6H5

RLN>,T3 R r

-

R

19, R = R CH3 20, R, R = (CH2)4 21, R, R = (CH2)s

22a, b 23a, b 24a, b

R

CH3

work was extended to include aldimines 25 which gave rise to four diastereomers: 26, 61.1%; 27, 22.2%; 28, 11.1%; 29, 5.5%. The separation of diastereomers was effected by column chromatography or high-performance liquid chromatography, and the purity of the reaction products was determined by TLC and Hnmr.57

25

26

21

More definitive studies were carried out of analogous reactions inchding x-ray analysis and, therefore, the absolute configurations of the new chiral centers in the resulting oxaziridines 30-33 were determined.

317

Stereochemistry

31, 20%

30,58%

33,5%

32, 16%

X-ray analysis showed that oxaziridine 30 is (2R,3R)-2-(S)-l-phenylethy1-3-pbromophenyloxaziridine. Furthermore, thermal isomerization at 120°C converted oxaziridine 33 into 30 and oxaziridine 32 into 31. Hence the absolute configurations Moreover, a rule analogous of the chiral centers in 30-33 were to Freudenberg's rule of shift7' was proposed that relates the value of the optical rotation of oxaziridines t o the absolute configuration, and therefore predicts the latter in a number of oxaziridines. An interesting stereochemical aspect of the reaction of achiral acids (for example, rn-chloroperbenzoic acid) with chiral imines has been the finding that the absolute configuration of the nitrogen in the resulting oxaziridine is the opposite of the absolute configuration of the chiral substituent attached to the nitrogen or carbon of the i ~ n i n e . ' ~A' ~case ~ in point is the formation of oxaziridines 30 and 33 which possess an R configuration at the ring carbon in 63% yield. Other studies have confirmed the above findings with respect to the high stereospecificity of the oxidation of chiral imines with achiral peroxy acids. Sources of evidence included x-ray analysis and the application of chiral solvating agents.52354i63b The absolute configuration of the nitrogen of the major oxaziridine 34 (87%) was established to be S.63b

-t

35, 13% 34,81%

(-1-

(2S,aR)-

(+)-(2R,aR) -

Oxaziridines

318

Ar+OH H

a, Ar b, Ar c, Ar d, Ar

36 = 9-anthryl; Rf = CF, = 9-(10-methylanthryl); Rf = CF, = 9 4 10-bromoanthryl); Rf = CF3 = phenyl, Rf = CF,

The use of chiral solvating alcohols 36 as a tool in the determination of absolute configuration of o x a z i r i d i n e ~depends ~ ~ ~ ~ ~upon formation of short-lived, chelatelike, diastereomeric solvates in which the stereochemical disposition of the oxaziridine substituents with respect to the anthryl group of the chiral alcohol causes an anisochronicity of the enantiotopic groups that could be observed by Hnmr. The determination of enantiomeric composition and the absolute configuration of chiral oxaziridines were achieved simultaneously. This method for assigning absolute configurations to oxaziridines does have limitations in that oxaziridines having additional basic sites may depart from the “normal” model, and it does not determine the absolute configuration of a chiral carbon in the oxaziridine ring. For example, when (-) enriched 2-tert-butyl-3-methyloxaziridine 37 was examined in the presence of (R)-(-)-36b, separate tert-butyl singlets, methyl doublets, and carbinyl quartets were observed in each enantiomer. The tert-butyl signal of the major enantiomer is downfield from that of the minor enantiomer, whereas the remaining doublet and quartet signals show the reverse sense of nonequivalence. Enantiomeric composition could be judged from the relative intensities of the doublet sets of signals. Clearly, the major issue in assigning absolute configurations of oxaziridines by this technique is to establish the site of primary hydrogen bonding (for example, 38 vs. 39) and to avoid the presence of extra basic sites that might interfere in the process of chelation. A pattern for solvation models of chelation has been established on the basis of a comparison of the absolute configuration of oxaziridines determined by this method (CSA) with those of known configurations from x-ray studies. Liquid crystals have also been used to determine the absolute configuration of oxa~iridines.”~

31

38

39

319

Stereochemistry

C6H5’

‘c

=N- CHCH ‘GH,

-

40

I

The influ w e of reaction conditions on the stereochemistry of the oxidation of optically act. qe or racemic N-diphenylmethylene a-rnethylbenzylamines 40 with chiral or achiral peroxy acids to oxaziridines was investigated.*’ It was found that asymmetric induction at the ring nitrogen in the resulting oxaziridine from optically active imine 40 does not depend on the nature of the peroxy acid or the solvent. However, the diastereoselectivity seems to be dependent only on the reaction. temperature. The ratio of the resulting oxaziridine diastereomers changed by 10% when the reaction temperature was raised from - 30°C to 40°C. On the other hand, the enantioselectivity was found to depend on the chirality of the peroxy acid, the temperature, and the solvent. For example, the optical yield of the major oxaziridine diastereomer decreased from 3.4 to 1.3 when the solvent was changed from chloroform t o methanol in the oxidation of racemic 40.

+

3.

Asymmetric Synthesis in Chiral Media

A number of optically active oxaziridines have been synthesized by the photolysis of the corresponding nitrones in (+) or (-)2,2,2-trifluoro-l -phenylethanol/ fluorotrichloromethane as solvents (Table 6).76 A similar study using m-chloroperbenzoic acid to oxidize imines in chiral alcohols gave optically active oxaziridines though in low optical purity (Table 7).” It appears that the optical yield is dependent on the nature of the chiral solvent, the highest yield being in chiral alcohols with aromatic substituents. Recently, greater success has been achieved.’78 A recent study of the irradiation of nitrones critically evaluated asymmetric induction in cholesteric media7? and concluded that asymmetric transformation in cholesteric phases, as in ordinary chiral solvents, can generally result in only low optical yields, although exceptions may be found in special cases where strong and TABLE 6.

PHOTOLYSBS IN (+) AND (-)C,H,-CHCF,

I

OH

42

R,

R2

R3

Solvent

[a111

Optical Purity %

a

Ph Ph Ph Ph

Ph Ph Ph Ph H CH

t-Bu

(+)

+ 15.9

t-Bu t-Bu iPr t-Bu t-Bu

(-)

29 31

b c

d

e f

C 6H ,,NO 2-p C6H4N02-p

(+) (+)

(+I

(+)

-80.9 + 12.1 + 38.8 -5.6 - 2.1

5

2n 6 3

Oxaziridines

320 TABLE 7.

CHIRAL SOLVENT EFFECTS ON IMINE OXIDATION

44b: R

44b

44a

[ffB + 3.20

[.I8

Chiral Medium (R)-(-)-Menthol (R)-(-)-Oc tan-2-01 (S)-(+)-Octan-2-01 (S)-(-)-l -Phcnylethanol (S)-(+)-2,2,2-Trifluoro-l -phcnylethanol

= t-Bu

+ 0.9 + 0.9

+ 4.5

- 0.7

- 4.1

- 1.5

- 23.6

+ 20.9

+ 49.6

Optical Purity % 1.2 1.7 1.6 9.1 19.2

specific interactions between solute and solvent exists. Photolysis of nitrone 45 in a mixture of cholesteryl nonanoate, cholesteryl oleate, and cholesteryl propionate (cholesteric J mixture) gave oxaziridine 46 with [ a ] g = + 0.18 ? 0.04, a negligible enantiomeric excess. c6H5 0 C H

=.:

Cholesteric hu

C ( ~ ~ 3 ) 3J mixture,

H

28OC

45

*

, *5

H 46

C(CH313

A recent study of such irradiations in the presence of P-cyclodextrin and various L-amino acids also revealed asymmetric induction, but the optical yields were In one case of asymmetric induction, brief heating of 2-tert-butyloxaziridine in a medium of cholesteryl benzoate at 148°C yielded a (-)-enriched enantiomer in up to 20% enantiomeric excess.78 It seems that this experiment requires special attention to the experimental details.77

4.

Interconversion of Oxaziridine Stereoisomers

The interest in the stereochemistry of the oxaziridine ring stems from the relatively high barrier to inversion of the chiral nitrogen atom. In a recent the rates of the thermal epimerization of diastereomers (-)-(47) + (+)-(48) were determined in tetrachloroethylene at 35 1.4"K. The barrier to inversion of 47 + 48 was found to be AGS = 31.9+-0.2kcal/mole, while that of 48 + 47 is 30.6 k0.2 kcal/mole. Such values are in agreement with ab initio SCF-LCAO-MO calcul a t i o n ~of ~ ~32.4kcal/mole. When oxaziridines 47 and 48 were separated and purified by column chromatography, after the completion of thermal isomerization, they showed a very high retention of optical activity. These findings confirm earlier r e s ~ l t s that ~ ~ indicate ~ ~ ~ , that ~ ~ the isomerizations of oxaziridines do not involve any measurable degree of bond cleavage or racemization processes, but only a nitrogen inversion mechanism.

321

Stereochemistry

(-)-(47)

47 48

+ +

48 = 0.14 0.03 x 10-6 s-' 47 = 1 .O k 0.2 x 10-6 s-' +_

Similar studies determined the barrier of inversion at 330°K to be A c t = 25.40 2 0.25 kcal/mole for trans-49 + cis-49 and 25.85 k 0.15 kcal/mole for cis-49 + ~ a n s - 4 9 Other . ~ ~ values for t h e barriers of inversions are 26.2 kcal/mole and 24.5 kcal/mole for oxaziridines 50 and 51,r e s p e c t i ~ e l y . ~ ~

cis-49

trans-49

51

It is interesting to note that the rate of isomerization of 50 exceeds that of 2methyl-3,3-diphenyloxaziridine b y a factor of 8000 at 100°C.53 Inversion of the chiral nitrogen in some oxaziridines has been effected b y photolysis; in most of the examined cases the isomerization is accompanied by racemization and proceeds via nitrones as intermediate^.^^ y

cis

2

racemic

0xa ziri dines

322

The factors that may contribute to the unusual configurational stability of the nitrogen in oxaziridines have been related to those in aziridines.@ These factors include (a) ring size since smaller rings are known to invert much more slowly than larger ones; (b) the electronegative oxygen in the oxaziridine ring may increase the s character of the unshared nitrogen electron-pair producing a molecule whose geometry is further from the planar transition state associated with “Umbrella inversion”; (c) large substituents on nitrogen lead to increased inversion rates due to nonbonded interactions. This factor was supported by the finding (vide supra) that a tertiary alkyl group on nitrogen in oxaziridines increases the rate of nitrogen ~ inversion dramatically in comparison with a methyl group on that n i t r ~ g e n ; ’(d) an increase in electron repulsion between unshared electron pairs on adjacent atoms in passing from ground state to the transition state. N-Aryl substitutents also lower the inversion barrier as expected of n-systems.80 The barrier in N-acyloxaziridines has not been examined. A theoretical study of the chiroptical properties of oxaziridines has appeared.”’

IV.

REACTIONS

Since the original investigations of the chemistry of the oxaziridine function, our knowledge of this system has been greatly expanded in detail, but the new work has remained largely within the boundaries originally delineated. The characteristic reactions of this ring system are associated with the presence of a weak N-0 bond in a strained ring. Thus, in addition to thermal and acid- and base-catalyzed ringopening reactions, there are a variety of electron-transfer processes leading to reductive ring-opening. The discovery that certain oxaziridines can function as aminating agents in reactions that resemble nitrenoid processes is one of the important new developments of the past decade. Finally, there are a host of photochemical reactions in which oxaziridines are proposed intermediates. 1.

Reactions with Basic Nucleophiles

Three-membered ring heterocycles such as oxiranes and aziridines undergo SN2-type attack by basic nucleophiles at carbon with cleavage of a carbon-heteroatom bond. Because of the presence of the weak N-0 bond in oxaziridines, such nucleophilic attack on this ring system in principle could also be expected at either oxygen or nitrogen. In addition, base-catalyzed elimination reactions involving exocyclic C-H bonds are much more important with these heterocycles.

A.

13-Elimination

For the most part Emmons’ original suggestion3 about the base-catalyzed decomposition, as pictured below, has been confirmed in most of its details:

Reactions

R’

Go

RC-j-I’JA: I

I

H \’

-

323

OH R\ ‘/C=N-C, I / R R R

I

B:

R R”

‘C=O

+ NH3

Using a rigid steroidal framework to stabilize inermediates in this process, Lusinchi and co-workersXlbhave shown that the first stage of the reaction is a concerted Ez elimination of the anti-oriented a-hydrogen and oxaziridine oxygen to yield an iminal 52.

52

53

The fate of the iminal depends upon the reaction conditions. It may cleave in the manner observed by Emmons to yield ammonia and dicarbonyl compounds that aldolize under the alkaline reaction conditions, or it may undergo an SN2’-like substitution t o produce the isomeric iminal ether 53. When the a-hydrogen and oxaziridine ring are constrained t o a cis relationship, no reaction occurs under these conditions. This mechanism has received further study and has been generally ~0nfirmed.l~~ Ordinarily, the imines that result from dissociation of the iminals are not isolable, but by using hindered bases such as 1,4-diazabicyclo[2.2.2]octane (DABCO) or 1,s-diazabicyclo[4.3.0]-non-S-ene (DBN) in carbon tetrachloride or toluene, it was possible t o isolate these heretofore little known c o r n p o ~ n d s, l.X~5~ This reaction has been used as a method of converting amines t o ketones. By carrying out the elimination with potassium hydroxide in aqueous acetone (to trap the aldehyde coproduct) containing methanol or dimethylformamide, Dinizo and Wattx3 were able to obtain ketones in yields of 40-80%. The scheme may be summarized as follows:

Oxaziridines

3 24

R\ CHO

~

1

C '

/H \N=CH

MCPBA,

A recent study examines this conversion further .lg6 In a variant of this type of reaction in the diazepine system,84 the oxaziridine ring-opening was followed by reaction of the iminal that led to the destruction of the heterocyclic ring:

1

i"i" 12%

16%

Reactions

325

When the amide nitrogen was unsubstituted, the ring-opening occurred simply upon stirring the oxaziridine derivative in ethanolw :

H

+ HOCZHS c1

Ph OH

I

.c1

N-CH2OCzH.j Ph

OH

Emmons3 reported that oxaziridines lacking an a-hydrogen in the N-alkyl group were stable to base,85 but it was later shown that sufficiently strong bases could cleave the ring by abstracting a hydrogen from the ring carbon; the products were amides." A similar reaction was observed upon treatment of 2-@-nitrobenzoyl)-3phenyloxaziridines with cyclohexylamine.27a

This reaction has now been studied in greater detail using lithium amide bases in t e t r a h y d r o f ~ r a n .Deoxygenation ~~ predominated (3-4: 1) over ring-opening and became more important at higher base concentrations. It was concluded that, as previously suggested,@' amide formation occurred by concerted hydrogen abstraction and ring opening. A similar rearrangement, initiated by base-catalyzed deacylation, has been reported for 2-cyclohexyl-3-benzoyl-3-phenyloxaziridine.'39 B.

Attack at Oxygen

The deoxygenation reaction is of interest because of the possibility that flavin oxaziridines may function as oxygen transfer agents at monooxygenase active sites.% The original kinetic resolution of an oxaziridine was accomplished by the reaction of brucine with a racemic oxaziridine.8 Since brucine N-oxide was identified as a product of the reaction, it was assumed originally that nucleophilic deoxygenation, similar to that known for epoxides, had occurred. However, reinvestigation of this reaction, while confirming the partial resolution, has led to the conclusion that the reaction involves a base-catalyzed elimination and not a

Oxaziridines

326

deoxygenation.gOThe reaction of enamines with oxaziridines, leading ultimately to pyridines, appears to involve first deoxygenation of the oxaziridine followed by condensation of the Schiff base and enamines." In the investigation cited above using amide bases,89 the authors concluded that deoxygenation was a result of successive electron transfers, as in the following scheme:

Ph

f'OLi

H

>c<(NC(CH,), 0

PhCH=NC(CH3I3 + LizO

A long-lived intermediate, possibly 54, was detected but not identified. Direct attack of the base on the oxygen atom was regarded as unlikely since little or no hydroxylamine was obtained. Direct attack on oxygen was postulated in the reaction of Grignard and lithium reagents with [El -2-benzenesulfonyl-3-phenyloxaziridine55.92 The principal organic products were alcohols and phenols (50-95% yields), derived from the organometallic reagent, and amines derived from addition of the organometallic to the intermediate N-sulfonyl imine (60-95%). /0\ PhS02N-CHPh

+ RLi -[PhSO,N-

@ I'

eR CHPh]

55

ROH

+ PhSO,N=CHPh

On the other hand, an ordinary oxaziridine, such as 2-t-butyl-3-phenyloxaziridine, produc d a phenol only with phenyllithium. The main pathway led to the isomeric amide and coupling of the organornetallic, apparently by electron-transfer processes. The strongly electron-withdrawing sulfonyl group probably biases the reaction course by providing an excellent leaving group for the direct substitution at oxygen. Oxaziridines oxidize sulfides to s u l f ~ x i d e s . 'Again, ~~ the N-sulfonyl derivatives seem to be the best oxidizing agents. They react with sulfides at room temperature to produce sulfoxides uncontaminated with ~ u l f o n e s ; ~ chiral ~ , ' ~ oxaziridines produce chiral ~ u l f o x i d e s . 'In ~ ~addition, chiral thiolsulfinates can be obtained from

Reactions

327

di~ulfides.”~Alkenes can be converted to e p o x i d e ~ , thiols ’ ~ ~ to disulfides,lgOand silylsulfinates to sulfinate esters.lgl One of the most exciting applications of the chiral N-sulfonyloxaziridines was the oxidation of an enolate to a chiral ahydr~xyketone.’~~ Germenes, R2Ge, are reported to deoxygenate o~aziridines.”~

C.

Attack a t Nitrogen

Nucleophilic attack at nitrogen also has been proposed by Hata and Watanabe to with amines, explain the reactions of cis-2 and trans-2-methyl-3-phenyloxaziridines phosphines, and thi01s.’~ These reactions were pictured as nitrenoidlike in that benzaldehyde is produced as the nitrogen group is transferred to the nucleophile. For example, diethylamine was converted to N,N-diethyl-N’-methylhydrazine and methylamine to azomethane (by further oxidation of the first-formed 1,2dimethylhydrazine). Triphenylphosphine, which early had been reported to deoxygenate oxaziridines,’ may first react at either carbon or nitrogen depending upon the size of the N-alkyl group. With 56, it appeared to react first at nitrogen t o form a phosphine imine and aldehyde, which in turn reacted to form N(benzy1idene)methylamine and triphenylphosphine oxide.

0 Ph9N/CH3 H

+ Ph3P

-

0 II

PhCH

+ Ph3P=NCH3 I

56

C6H5CH=NCH3f P h 3 P + 0 When an N-t-butyl group was present, attack occurred at carbon forming the usual four-membered oxapho~phorane.’~Analogously, sulfenamides were the firstformed products from thiols but they reacted with additional thiol and benzaldehyde to finally produce imines and disulfides. However, more complex sulfur nucleophiles, such as thiourea, thiocyanate ion, and xanthate salts appeared to accomplish deoxygenation of the oxaziridines by ring-opening attack at carbon followed by the usual reactions leading to thiaziridines, which lost elemental sulfur.41 The most important and well-defined reactions involving attack at nitrogen are those discovered by Schmitz and co-workers.” N-Unsubstituted oxaziridines react with a variety of nucleophiles to effect transfer of the NH group from the oxaziridine to the nucleophile. Many of these reactions resemble nitrene or nitrenoid reactions; although little mechanistic work has been reported, it seems better to classify them as involving nucleophilic substitution followed by elimination:

Oxaziridines

328

Secondary amines reacted to form hydrazines in yields of 90% and better. Aniline can be converted to phenylhydrazine. Sometimes the addition was followed by the elimination of water rather than the aminated nucleophile. For example, treatment of 3,3-pentamethyleneoxaziridine with methoxide ion produced cyclohexanone oxime O-methyl ether. Formanilide reacted with 3-phenyloxaziridine in Of the presence of sodium ethoxide to produce benzaldehyde phenylhydra~one.’~ considerable interest is the reaction of Schiff bases with these oxaziridines to produce diaziridines. Other examples are given in Schmitz’ recent review.’ One intramolecular version of this kind of amination is known: oxaziridine 57 was converted to benzophenone and 5,6-dihydro-4H-l,2-thiazine58 upon heating9*

58

Recently, Schmitz has reported aminations of weak nucleophiles such as alkenes to produce aziridines directly.” Although simple aliphatic olefins do not react, styrene, indene, acrylonitrile, and norbornene were converted to aziridines. The reaction of 3-ethyl-3-methyloxaziridine with diphenylcyclopropenone may be a reaction of this type.’”

9

Some intramolecular versions of nucleophilic attack at nitrogen have been reported. Oxaziridine 90 is converted to an aziridine 91 by acids and bases’87:

0

H0

or OH@

c1

c1

90

*

c1

OH

91

Reactions

"'a

329

Treatment of nitrone 92 with anhydrides in pyridine produced oxaziridines 93188.

0

4

(pyridine KCO),O+

92

93

It has been reported that episulfides can be desulfurated t o alkenes by oxaziridines but how the attack occurs is ~ n k n o w n . ' ~ ' Although N-acyloxaziridines are known, a systematic examination of their reactions with basic reagents has not been made. In the case of N-(N'-phenylcarbamy1)oxaziridines, nucleophiles appear t o attack at nitrogen either intermolecularlyZ8 or intramolecularly by way of diaziridinone formation." This work has recently been summarized.' Brief reports have been made about two unusual oxaziridine derivatives. A quaternary oxaziridinium salt apparently reacts with nucleophiles at oxygen; in any case, this salt suffered deoxygenation by some process."' Finally, the perfluorinated oxaziridine 59, undergoes attack exclusively at nitrogen to produce amide derivatives"' :

The nucleophiles ranged from fluoride ion to alcohols, thiols, acids, and cyanide ion. This oxaziridine is unique in having a good leaving group on carbon. Clearly, it is difficult at this point to generalize too extensively about the reactions between nucleophiles and oxaziridines. Steric factors may divert reactions from one center t o another and the relative nucleophilic character of the attacking reagent also must be considered. Attack at any of the ring atoms must be considered and eliminated before a true mechanistic picture can be established.

2.

Acid-Catalyzed Reactions

Emmons3 reported two kinds of acid-catalyzed hydrolyses of oxaziridines, which depended upon the nature of the substituent groups. Both paths were proposed t o proceed via the 0-conjugate acid with subsequent fission of either the C-0 (path 1) or the N - 0 bond (path 2). Simple isornerization to the nitrone was also observed.

Oxaziridines

330

R' 0 \/\ C-NCH2R3 /

R'

o@

\/I C-NCH2R3

+ H@

R2

IrII

/

Ri

R'

R'

\@

' R2

C -NCH2R3 I OH

R'

\

C=O

/

R2

+ R3CH2NHOH

Y

OH

I"\

R2 N=CHR3

R'

\

C=O + R3CH0 R2' +NH3

Careful and extensive work by Milliet and Lusinchi81b and Challis and COhas confirmed the broad outlines of this proposal. However, the latter investigators found that the extent of acid catalysis was determined overwhelmingly by the structure of the N-substituent, particularly when that substituent was a bulky tertiary group and much less so when a primary group was present. Since the products of hydrolysis by path 2 were the same as those of base-catalyzed ahydrogen abstraction, it was concluded that the latter method is more effective for hydrolysis of N-primary alkyl derivatives. A complicating feature of the process is that both 0- and N-protonation can take place and that apparently N-protonation, which only leads to ring cleavage when R' or R2 is aryl, becomes more competitive as the size of the N-substituent decreases.'03 Emmons3 reported that oxaziridines were isomerized to nitrones by boron trifluoride through complexation at oxygen. Silver ion complexes have been characterized as having Ag-N bonds,'" although the reactions of these compounds may be due to prior isomerization to 0-complexes. Theoretical studies suggested that nitrogen was the more basic site,'" but more recent calculations favor oxygen. ' 0 6 The hydrolysis by path 1 to produce hydroxylamines has been used often for synthetic purposes. Amino-acid esters may be converted to N-hydroxy derivatives in this way.'07

Reactions

33 1

NH2'HCl p-AnCH-NCHRC02R1

\/ 0

Hf

RCHC02H I NHOH

The anisyl group was used since the phenyl oxaziridines simply isomerized t o nitrones upon acid treatment. The yields were modest (30-40%), but the products were optically pure. A similar method was used to make 6-N-hydroxy-L-arginine and 6-N-hydroxy-L-ornithine,s6 and the optically active hydroxylamine precursor of dopastin.lo8 Since path 1 would be expected to be favored by cation-stabilizing groups on carbon, it is not surprising that 3-methoxyoxaziridines hydrolyze exclusively by this path.49 The acid-catalyzed isomerization to nitrones has been used as a route to precursors of doxy1 spin labels.109 This method provides a route whereby imines can be converted to nitrones, a route not generally available previously. Lewis acids seem to be best for catalyzing the i s o m e r i ~ a t i o n . ~Indirectly ~"~ this route also leads to hydroxylamines by addition of organometallics to the nitrone. Hydrolysis by E m m o n ~path ' ~ 2 has been suggestedM as a method for converting amines t o ketones, the acid counterpart of a base-catalyzed procedure cited prev i o ~ s l y The . ~ ~ oxaziridines were obtained by oxidation of the product from amines and acetone, and hydrolyzed with 2M hydrochloric acid at room temperature for 4 0 hours. The only aliphatic aldehyde produced was not stable under these conditions. This reaction has received further study.'99 In the diazepinone series, the hydrolysis by path 2, catalyzed in this instance by both ferrous and ferric salts, is followed in part by an SN2'-like substitution"' :

The ether product is analogous to the amines obtained in a base-catalyzed process.84 The path 2 mechanism suggests that N-aryloxaziridines might undergo various rearrangements such as the Schmidt rearrangement to amides or Wallach-type rearrangements leading to attack on the aromatic ring. Such mechanistic paths may be found in the l i t e r a t ~ r e , " ~ - "but ~ one must be very careful in assessing these results since only in rare instances have the N-aryloxaziridines actually been isolated and characterized. (In some of these cases, it appears that oxazepines rather than oxaziridines are the actual intermediates.6)

Oxaziridines

332

Two examples may be cited. In the indole series, nucleophilic substitution akin to the substitutions observed by Gassman and his co-workers with arylnitrenium ions1I6 has been observed113:

Similar attack of methanol on the presumed oxaziridine intermediate in the photolysis of C,N-diphenylnitrone led to the formation of 2- and 4-methoxyazoben~ e n e s . " ~The reaction converting dibenz [b,f] [ 1,4] oxazepine 60 to 2-(2-hydroxypheny1)benzoxazole 6 2 seems better explained by a nucleophilic substitution on protonated 61 than by the electrophilic process suggested by the a ~ t h o r s . " ~

UP \

N-

60

RC03H*

61

OH 62

Oxaziridines can be oxidized by peroxy acids to cleave the ring t o produce oximino ketone^."^

This sequence has been used to convert a pyrroline ring to useful functional groups with control of stereochemistry. (This reaction is a variation of the oxidation of oxaziridines to nitroso compound^.^)

Reactions

3.

333

Thermal and Photochemical Reactions

Emmons3 described two isomerizations when oxaziridines were heated to appropriate temperatures: nitrone formation and amide formation. The former reaction appears t o be restricted t o oxaziridines bearing cation-stabilizing groups on the carbon atom. Thus 3-aryl oxaziridines, particularly those containing electronreleasing groups,"' are most prone to this simple ring-opening. This isomerization, which involves cleavage of the C-0 bond, apparently involves development of some cationic character at carbon in the transition state, whether the cleavage is heterolytic or homolytic. It is also nonstereoselective, cis- or trans-oxaziridines giving 1 : 1 mixtures of cis- and trans-nitrones."' This result has been interpreted to confirm theoretical calculations to the effect that the Woodward-Hoffmann rules cannot be applied simply t o many heteropericyclic reactions.12' It has previously been observed that certain C-aryloxaziridines isomerize with racemization upon irradiation; nitrones were implicated as intermediate^^^ (Section 111.4). An excited singlet state appeared to be involved. Theoretical treatments are in agreement with this It is of some interest that it has been established that this isomerization does not take place in the inlet system of the mass spectrometer and thus the mass spectra of nitrones and oxaziridines differ significantly.121 There had previously been suggestions that such isomerizations complicated the spectra of these two classes of compounds. The reaction leading to amides is more complex. It was early proposed3 that thermal gas-phase reactions involved biradical intermediates formed by cleavage of the weak N-0 bond. In solution, a spectrum of transition states have been suggested ranging from radical to concerted to ionic. An extensive and detailed exposition of the merits of various mechanisms has been made by Lamchen,'22 who favors dipolar intermediates or transition states. This oxaziridine-amide rearrangement also can be accomplished photochemically, a method that in many cases leads to cleaner reactions and greater regioselectivity. For example, photolysis of 2-benzyl-3,3-(a-methylpentamethylene)oxaziridine 63, yielded 2-methyl-N-benzylcaprolactam64 and 5-methyl-N-benzylcaprolactam 65 in a total yield of 80% and in a ratio of 95:5, r e ~ p e c t i v e l y . 'The ~~ corresponding thermal reaction at 375°C gave the products in 60% yield in a ratio of 65:35, r e s p e ~ t i v e 1 y . IThis ~ ~ regioselectivity in both processes is not that expected of 0-cleavage of a first-formed oxy radical to yield the more stable secondary radical. It has been suggested that, at least in these spirooxaziridines, the regioselectivity is controlled by stereoelectronic factors in that the C-C bond that lies quasiantiperiplanar t o the nitrogen lone pair (and to one of the oxygen lone pairs) is the one favored t o fragment Quantum-mechanical calculations indicate a substantial barrier to migration of a group syn to the nitrogen lone pair, but also favor a stepwise rather than a concerted migration.'26 These calculations on the parent oxaziridine, using double 5 plus diffuse basis sets and extensive CI, are consistent with the assumption that the lowest singlet excited state of the oxaziridine ring results from an nt9, + a;j, excitation and undergoes .1253205

Oxaziridines

334

63

64

65

the breaking of the NO bond. The H(C) migration does not occur simultaneously, but should proceed on a ground-state surface after deexcitation in the open geometry. Briefly, the photochemical reaction of the parent oxaziridine is proposed to proceed through a three-events mechanism: (a) The photochemical breaking of the NO bond; (b) deexcitation to the ground-state surface; (c) hydrogen migration to nitrogen on the So surface.

That completely "free" radical intermediates are probably not involved was indicated by the synthetic utility of this reaction for the formation of medium to large lac tam^'^^ in yields of 30-50%. Yet in hydrogen-donor solvents such as isopropyl alcohol, open-chain arnides can be obtained in significant amounts. For example,'23 oxaziridine 63 gave a 85 : 10 mixture of lactam 64 and amide 66. (The same ratio was observed in the photolysis in the same solvent of spirooxaziridines that have no substituents in the alicyclic ring.) Amide 66 resulted from the cleavage of the most substituted alkyl group, which arises first from a triplet excited state of the oxaziridine followed by a diradical intermediate that abstracts a hydrogen from the solvent as shown below:

0"" (CH,),CHOH hv

63

(CH,),CHOH

I

*

QN:R 64 85%

66 15%

t

(CH,),CHOH

Reactions

335

Earlier, irradiation of 3,3-~entamethyleneoxaziridine 67 was reported to give cyclohexanol and n-caproamide, via an excited triplet state, and c-caprolactam, dicyclohexylideneazine, and cyclohexanone via a singlet excited state. The lowest triplet energy of 67 was estimated to be 60 k ~ a l / m o l . " ~

OH

67

A potentially important industrial application of this reaction involves the thermal rearrangement of 3,3-pentamethylene-oxaziridine67 to ecaprolactam, a reaction that is strongly catalyzed by transition-metal ions."'

This catalysis seems to be related to that of ferrous ion which has been more widely investigated (see below). Other bicyclic oxaziridines give rise to some interesting products either through ring contraction o r more complex cleavage. For example, when oxaziridine 68 is heated to 150°C, it rearranges to an azetidine 69 in 44% ~ i e 1 d . l ~(This ' reaction is also observed photochemically and appears to be more general under these conditions.)

CH3 CH3

CH 15ooc +

0 N\O 68 C H 3

CHJ-j

N-CCH3 69

8

In the indole and isoindole series rather more unusual kinds of mechanisms have been invoked. Oxaziridine 70 rearranged quantitatively at 170-1 80°C to the keto anil 71.13' This involves a reaction not often observed when the nitrogen is substituted, that is, cleavage of the C-N bond as well as the N - 0 bond. This is like a

336

Oxaziridines

___)

A

I

Ph 70

71

nitrene-forming reaction but probably one of the bond-breaking reactions is synchronous with the phenyl migration. (It has been reported that oxaziridines can be formed by the intramolecular addition of a nitrene to a carbonyl group, the reverse of the reaction above, under photochemical condition^.^^) A speculative reaction path involving a similar reaction under thermal conditions has been proposed for A similar path the rearrangement of 3-P-styryl- and 3-arylazo-2,1-benzisoxazoles.'3z was suggested for the formation of an oxaziridine intermediate in the thermal isomerization of 3-benzoyl-2,l-benzisoxazole to 2-phenyl-3,l -benzoxazin-4-0ne.'~~ Peracid oxidation of 7-t-butyl-3,3-dimethyl-3H-indole 72, which was expected to give oxaziridine 73, gave a mixture of the oxindole 74 and isocyanate 75,presumably by spontaneous decomposition of 73.'34 In this reaction C-C bond cleavage is observed along with N-0 cleavage. The influence of the 7-t-butyl group which strongly favors the cleavage reaction is unexplained. 7

I-

MCPBA O0

I

73

I

Nitrenes have been proposed as fragments of the photochemical decomposition of N-aryl ~ x a z i r i d i n e s , ~but ~ ~only ' ~ ~abbreviated ~ ' ~ ~ ~ ~studies ~ have been reported. The 2- and 3-acyloxaziridines deserve special comment. The 2-acyl derivatives rearrange thermally to 1,3,4-dio~azoles.*~

COR"

A

RI, ,O-C-R" R' C '0-N II

Reactions

337

Such a rearrangement is consistent with a dipolar intermediate (or transition state):

Though no detailed mechanistic studies have been reported these rearrangements are analogous to those of N - a c y l a z i r i d i n e ~ . ~ ~ ~

77

3-Acylaziridines are thermally and photochemically very labile and only three authenticated examples are known, although their intermediacy has been assumed. Oxaziridine 77 was isolated from short irradiation of 2-phenyl-5,5-dimethyl-3-oxo1-pyrroline 1-oxide 76. Further irradiation of 77 or extended irradiation of 76 produced a mixture of 78 and 79. In the case where R = t-butyl, 79 was obtained e~clusively.'~ (The ~ third example was cited in Section 11.2.) The high migratory aptitude of acyl over other groups was observed in early investigation^'^' and confirmed by these recent results: the thermal conversion of 2-cyclohexyl-3-phenyl-3benzoyloxaziridine exclusively to N-cyclohe~yldibenzamide,~~~ the photochemical conversion of 2-phenylisatogen 80 to 2-phenyl-4H-3, I -benzoxazin-4-one 81 ,140 and the thermal transformation of 2,4,5-triphenyl-(3H)-pyrrol-3-one82 to 2,4,5triphenyl-(6H)oxazin-6-one 83.141 The migration t o oxygen rather than nitrogen in several of these cases has only been observed with the bicyclic oxaziridines. 0

i,

so

Ph

82

Ph 83

Oxaziridines

338

The remarkable stability for 2-phenyl-3,3-dibenzoyloxaziridinein the face of Padwa's inability to isolate oxaziridines but only amides upon oxidation of N-phenylacylimine derivative^'^' and the lability of nitrones 80 and 82 has recently been shown to be in error.'" The product from the thermal or photois the expected rearrangechemical isomerization of N-phenyl-C,C-dibenzoylnitrone ment product, N-benzoylphenylglyoxanilide. PhC,fi0 N O ,C=N PhC, 0 'Ph

*

]

fi00 PhC, I \ ,C-N-Ph

[PhC+o

0 0 0 PhC-C-N-CPh I

Ph

(The reported synthesis and properties of an oxaziridine by the thermal isomerization of the 0-trityl ester of 3 - a ~ i n i t r o c a m p h o r bears '~ reinvestigation, particularly in view of the recent report that irradiation of nitronate salts yields hydroxamic acids14' but that oxaziridine intermediates could not be detected.) N-Sulfonyloxaziridines also rearrange, thermally to nitrones that further decompose to products,s8a but photochemically they yield a m i d e ~ . ' ~ ~ There are a number of thermal and photochemical reactions for which oxaziridine intermediates have been proposed but never isolated. These include, among others, the photochemical Beckmann rearrangement of oximes, many photochemical reactions of aromatic N-oxides, and the thermal rearrangement of nitrones to amides. A brief discussion of the first two seems warranted in this review because they have been studied extensively and some strong inferential evidence for oxaziridine intermediates has been obtained. The first photochemical Beckmann rearrangement of aromatic aldoximes was reported in 1963.147 Subsequently, cyclohexanone oxime was shown to rearrange, upon photolysis, to c a p r ~ l a c t a m . ' Although ~~ the presence of oxaziridines in the no oxaziridines solutions of photolyzed oximes was have been isolated from these reaction mixtures presumably because of the general instability of oxaziridines that have no substituents on the ring nitrogen.' The qualitative results are consistent with the intermediacy of oxaziridinesZo3 in the photolysis of oximes to amides, yet the possibility of the reactions following other pathways cannot be ruled Mechanisms of the photo-Beckmann rearrangement have been advanced to involve the transformation of an excited singlet state of the oxime into an oxaziridine followed by the reorganization of the singlet excited intermediate to a lactam or amide.'49y153 Other mechanisms have been suggested in which a nitronelike intermediate is the precursor of the oxaziridine rather than the oxime

CH,OH

>C=N

O 'H

>C=N 0'0 0

0

Reactions

339

All attempts to supply physical evidence for the formation of oxaziridines as intermediates in the photolysis of aromatic N-oxides have met with scanty success, so investigators have relied on indirect evidence. Theoretical calculations seem to agree that, in aromatic N-oxides, oxaziridines do not arise from the ground state but very likely from the first excited singlet state. A comprehensive critical review of this subject has appeared.6 Recently, nanosecond and low-temperature matrix stabilization techniques were used in the study of the photolysis of 6-cyanophenanthridine 5-oxide 84 in ethanol solution.'s4

& ' 84

N

i 0

CN

cmrr h u b s ;

-

\

N, 85

0

CN -

OC ZH Fluorescence and absorption spectra were measured for 84 after irradiation at 77°K and later at room temperature. The data are interpreted to involve an intermediate to which structure 85 was assigned. In the photolysis of 4,6-diphenylpyridine 1-oxide, both ring-expansion and ringcontraction products were obtained and the proposed oxaziridine intermediate could be detected.'" Other reactions also give evidence of oxaziridines.'02p'04 Although there seems to be some growing acceptance of the intermediacy of oxaziridines in these reactions,2m it has recently been suggested that even these more recent studies can be rationalized better by open intermediates (biradicals) rather than by oxaziridine formation.'" In a somewhat different kind of reaction 2-butyl-3-propyl-oxaziridine has been reported to be converted to 3,5-diethyl-4-propylpyridine by heat;'74 a similar result had been reported p r e v i o ~ s l y . ~Oxaziridines ' have been implicated as the precursors of lactams and amides in the photolysis of aliphatic nitro compounds in hydrocarbon~.~~~ A mechanism to account for the previously reported'68 formation of nitroxides upon irradiation of nitrones and oxaziridines has been put f 0 r ~ a r d . l ~ '

Oxaziridines

340

-

0

R

0. I 1 PhCH-N-C(CH3)3

t R - + PhCH=N-C(CH&

4.

-

R OH I I PhCH-NC(CH,),

Metal-IonCatalyzed Reactions

Emmons investigated in some detail the ring-opening reactions of oxaziridines that were catalyzed dramatically by ferrous ion.3 He pictured these as involving an electron transfer as a first step leading to an aminoalkoxy radical which then followed different reaction paths depending upon the substituents. This reaction has been further examined by Minisci and his c o - ~ o r k e r s , 'who ~ ~ have used it to generate alkyl radicals for studies of their reactions. They prefer to generate the radical character on nitrogen rather than oxygen (a-hydroxyamino radicals) and have obtained some inferential evidence for this ~tructure.'~'For the most part, however, the fate of the radicals is independent of the structure of the first-formed radicals. Spirooxaziridines undergo primarily 0-cleavage of the ring-opened radical to produce 5-carbamoylalkyl radicals that may undergo a variety of typical alkyl radical reactions including intramolecular hydrogen abstraction to give a rearranged As~ noted above, Schmitz found that vanadyl chelates 1-carbamoyl r a d i ~ a 1 . l ~ catalyzed rearrangement of 3,3-pentamethyleneoxaziridine to ecaprolactam apparently by metal-complexing of the radical intermediates. It is possible, however, that this mechanism changes to an ionic one in the presence of this Lewis-acid ion. Black and his co-workers have used ferrous ion to catalyze the conversion of bicyclic oxaziridines to pyrrolidine and pyrroline derivatives. When a good leaving group (i.e., stable radical) was attached to the oxaziridine carbon, 0-cleavage of the intermediate radical (oxygen or nitrogen) produced the corresponding in~ good yield. However, when a good leaving p y r r ~ l i d o n e ' or ~ ~p y r r ~ l i n o n e s ' ~ group was not present, 0-cleavage was suppressed and, in the presence of stoichiometric amounts of ferrous salts, the supposed intermediate aminals were dehydrated to pyrr~lines.'~'By introducing a C-cyano group, this latter reaction was avoided by the competing loss of hydrogen cyanide from the aminal to again produce pyrrolinones and p y r r ~ l i d o n e s . ' ~ ~

Reactions

34 1

Although radical intermediates have been invoked often in the ring-opening reactions of oxaziridines, there has been no systematic study of the reactions of this heterocycle with radicals generated from other sources. One such report is that germyl radicals, generated from trialkylgermanes, add readily to oxaziridines by preferential attack at oxygen to produce unstable a-aminoalkoxygermanes, which in turn decompose to germanium oxides and imines.lm

5.

Cycloaddition Reactions

Agawa and his co-workers have reported a series of investigations of the reactions of cumulenes with oxaziridines. Reaction with isocyanates led to oxadiazolidinones 86,45370 the same product obtained from nitrones and isocyanates. Detailed mechanistic information is not available and the classification of these reactions as cyclo-

R: R2,C-N-R3 \ / 0

-

+ C,H,N=C=O

C H

0

’\N--d/

R,!

I

86

\

I R3

additions is arbitrary. Ketenimines reacted similarly, but the first-formed heterocycle 87 was thermally labile and rearranged or decomposed depending upon its structure.161

CH3’ CH3\C=C=N-Ar

80°C 50 hr

+ t-Bu-N--CHPh \/ 0

*

/“\

Ph

H

Carbodiimides reacted rather differently to yield hexahydrotriazine derivatives or guanidines, depending upon substitution at carbon.45

Oxaziridines

342

Ph;C-N-C"(CH3)2 H \I 0

+ PhN=C=NPh

-

YNHPh

PhN=C

'NHPh

Diphenylketene reacted somewhat similarly, giving o x a z ~ l i d i n o n e s16' .~~~

t-Butylcyanoketene and oxaziridine 88 gave simple adducts 89.163

89

The mechanisms of these reactions are highly speculative because several steps must be involved, but it can generally be said that the Japanese workers propose a scheme similar to that of Hata and Watanabe for reactions of oxaziridines with n ~ c l e o p h i l e sin~ ~ which the transition state for the initial reaction has a nitrenoid character and leads to an ylide intermediate. On the other hand, Abou-Gharbia and J ~ u l l i e 'propose ~~ cycloaddition of a zwitterionic ring-opened oxaziridine leading to a heterocycle that subsequently decomposes. With carbon disulfide N-n-alkyl or sec-alkyloxaziridines yield alkyl isothiocyanates in excellent yields.'@'

R, ,C-N-R2 R1 \ / 0

+ CS2

-

R2N=C=S + RR'C=O

+S

R2 = CH3, n-Bu, cyclohexyl

Thiocyanates themselves also react with oxaziridines. The products are similar to those from carbon disulfide at 110°C but principally resemble those from isocyanates at lower temperatures.'@

343

References

S

S

CF3-N-0

\ /

+

CF,=CFCl

-

CF,

59

CF3N-CF2 \ F\ I /c\ /O c1 CF2

Some cycloaddition reactions of oxaziridine 59 with halogenated alkenes have been reported along with reactions with trimethylsilyl cyanide and antimony pentafluoride.209 A related cycloaddition of oxaziridine 94 with hexafluoroacetone has been r e p ~ r t e d . ’ ~ ’

0

(CF&-N,-,O

f

/C\

Ph

It

CF3CCF3

-

Ph

(CF,),C-T;J

NO,

(CF3)2C-O

CPh, I

94

REFERENCES 1.

2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12.

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189. 190. 191. 192. 193. 194. 195. 196. 197. 198. 199. 200. 201.

349

0. Kikuchi, K . Morihashi, and K. Suzuki,Bull. Chem. SOC.Jpn., 1133-1136 (1982). F. C. Schaefer and W. D. Zimmermann,J. Org. Chem., 35, 2165-2174 (1970). D. P. Del’tsova, N. P. Gambaryan, and E. P. Lur’e, Bull. Acad. Sci. USSR,Div. Chem. Sci. (Engl.), 28, 1648-1651 (1980). M. Bogucka-Lcd6chowska, A. Konetz, A. Hempel, Z. Dantor, and E. Borowski, Z. Kristallogr., 149,49-56 (1979). W. H. Pirkle and P. L. Rinaldi,J. Org. Chem., 45, 1379-1382 (1980). M. Bucciarelli, A . Forni, I. Moretti, and G. Torre, J. Chem. Soc. Perkin 1 , 2152-2161 (1980). 1. Nakamura, T. Sugimoto, J.-I. Oda, and Y. Inouye, Agr. Biol. Chern., 45, 309-310 (1981). D. R. Boyd, K. M. McCombe, and W. B. Jennings, Tetrahedron Lett., 1557-1558 (1980). A. Rauk,J. A m . Chem. SOC., 103,1023-1030 (1981). K. Koyano, H. Suzuki, Y. Mori, and I. Tanaka, Bull. Chem. Soc. Jpn., 3582-3587 (1 970). G. Smets and S. Matsumoto,J. Polym. Sci. Polym. Chem. Ed., 14, 2983 (1976). I. G. Tishchenko and V. G. Grinbevich, Khim. Geterosikl Soedin., 707 (1980); Chem. Abstr., 93, 1 8 6 2 1 2 ~(1980). D. R. Boyd, K. M. McCombe, and N. D. Sharma, Tetrahedron Lett., 2907-2908 ( 1982). J. E. Arrowsmith, M. .I.Cook, and D. J . Hardstonc, J. Chem. Soc. Perkin I , 23642368 (1979). E. J . Trybulski, E. Reeder, J. F. Blount, A. Waiser, and R. I. Fryer, J. Org. Chem., 47, 2441-2447 (1982). (a) H. Suginome, N. Sato, and T. Masamune, Tetrahedron, 27, 4863-4881 (1971); (b) H. Suginome, T. Mizuguchi, and T. Masdmunc, Bull. Chern. Soc. Jpn., 50,987-990 (1 977). F. A . Davis, N. I’. Abdul-Malik, S. B. Awad, and M. E. llarakal, Tetrahedron Lett., 917-920 (1981). F. A . Davis and R. 11. Jenkins, Jr., J. A m . Chem. SOC.,102, 7967-7969 (1980). F. A. Davis, S. Q. A . Rizvi, R. Ardecy, D. J . Gosciniak, A . J. Friedman, and S. G. Yocklovich,J. Org. Chem., 45, 1650-1653 (1980). M. N. Akhtar, D. R. Boyd, J . D. Neil], and D. M. Jerina, J. Chem. SOC. Perkin I , 1693-1699 (1980). F. A. Davis, R. H. Jenkins, Jr., S. B. Awad, 0. D. Stringer, W. H. Watson, and J . Galloy, J. A m . Chem. Soc., 104,5412-5418 (1982). D. Doschelli, A. B. Smith, 111, 0. D. Stringer, R . H. Jenkins, Jr., and F. A . Davis, Tetrahedron Lett., 4385-4388 (1 981). Y. Hata a n d M. Watanabe,J. Org. Chem., 45, 1691-1692 (1980). P. Rivicre, J. Sat@, A. Castel, and A. Cages, J. Organornet. Chem., 177, 171-180 (1979). W. €1. Rastetter, W. R. Wagner, and M. A . Findeis,J. Org. Chem., 47,419-422 (1982). J. B. Hester, Jr., A . D. Rudzik, and P. F. Van Voightlander, J. Med. Chem., 23, 643647 (1980). G. Bhattacharjec,lnd. J. Chem., 19B, 377-381 (1980). M. Nastase and J . Streith, in Rearrangements in Ground and Excited States, Vol. 3, 1’. d e Mayo, Ed., Academic, New York, 1980, pp. 468-490. F. Roeterdink and H. C. van der Plas, J. Chem. SOC.Perkin 1 , 1202-1204 (1976).

350 202. 203. 204. 205.

206. 207. 208. 209. 210. 211.

Oxaziridines K. Tokumura, H. Goto, H. Kashiwabara, C. Kaneko, and M. Itoh, J. Am. Chem. SOC., 102,5643-5647 (1980). T. Oine and T. Mukai, Tetrahedron Lett., 157-160 (1969); (b) G. Just, M. Cunninghdm, Tetrahedron Lett., 1151-1153 (1972). G. J. Gainsford and A. D. Woolhouse, Aust. J. Chem., 33, 2447-2454 (1980). A. Lattes, E. Oliveros, M. Rivierc, C. Belzecki, D. Mostowicz, W. Abramsky, C. I'iccinniLeopardi, G. Gcrmain, and M. Van Mcersscke, J. Am. Chem. SOC., 104, 3979-3934 (1 9 82). A. R. Forrestcr, M. M. Ogiloy, and R. H. Thomson, J. Chem. Soc. Perkin I , 20232026, 2027-2034 (1982). S. T. Reid, J . N. Tucker, and E. J . Wilcox,J. Chem. SOC.Perkin I , 1359-1363 (1974). P. J. G. Cornclissen, G. M. J . Berjersbcrger van Henegouwen, and G. R. Mohn, Photochem. Photobiol., 32,653-659 (1980). W. Y. Lam and D. D. Dcs Marteau,J. Am. Chem. Soc., 104,4034-4035 (1982). A. Albini, E. €'asmi, and 0. Buchardt, Tetrahedron Lett., 4849-4852 (1982). M. J. Haddadin, A. M. Kattan, and J . P. Frceman,J. Org. Chem., 47,723-725 (1982).

Chemistry of Heterocyclic Compounds, Volume42 Edited by Alfred Hassner Copyright 0 1985 by John Wiley & Sons, Ltd.

CHAPTER IV

1.2.Dioxetanes and a-Peroxylactones WALDEMAR ADAM*

Institute of Organic Chemistry. University of Wurzburg. Wiirzburg. West Germany and Department of Chemistry. University of Puerto Rico. Rio Piedras. Puerto Rico

FARIS YANY

Department of Natural Sciences. Interamerican University.Hato Rey. Puerto Rico

I. I1 .

I11 .

IV .

*

Historical Perspective. . . . . . . . . . . Synthesis . . . . . . . . . . . . . . . 1. 1.2.Dioxetanes . . . . . . . . . . . A . The Kopccky Method . . . . . . . Singlet Oxygenation . . . . . . . . B. C. Miscellaneous . . . . . . . . . . 2 . a-Peroxylactones . . . . . . . . . . A . Dicyclohcxylcarbodiimide (DCC) Cyclization B . Ketcne Singlet Oxygenation . . . . . Purification and Identification . . . . . . . . 1. Physical Methods . . . . . . . . . . 2 . Chemical Methods . . . . . . . . . . 3 . Spectroscopic Methods . . . . . . . . . A . Nuclear Magnetic Resonance . . . . . B . Infrared Spectra . . . . . . . . . C . Electronic Spectra . . . . . . . . D . Massspectra . . . . . . . . . . Chemiluminescencc . . . . . . . . . . . 1. Dircct and Energy Transfer . . . . . . . A . Energy Balance . . . . . . . . . B . Activation Parameters . . . . . . . C. Excitation Parameters . . . . . . . a. Photophysical Methods . . . . .

Dircct all correspondence to the Wurzburg a d d r c s .

35 1

.

. . . . . . . . . . . . . . . . . . . . . .

.

. . . . . . . . . . . . . . . . . . . . . .

.

. . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . .

. . . . . . .

. . . . . . . . . . . . . . . .

. . . . . . .

. . . . . . . . . . . . . . . . . . . . . .

352 370 371 371 372 374 375 375 377 378 379 380 380

380 381 381 382 382 382 382 386 393 394

352

V.

VI. VII. VIII.

1,2-Dioxetanes and a-Peroxylactones i. Direct Chemiluminescence. . . . ii. Energy-Transfer Chemiluminescence . b. Photochemical Methods . . . . . . i. Intramolecular Transformations . . ii. Intermolecular Transformations . . c. Empirical Trends . . . . . . . . i. Nature of Excited States . . . . ii. Excited-State Energy . . . . . iii. Substitution Patterns . . . . . iv. Heteroatom Substitution . . . . v. Heavy Atom Substitution . . . . D. Mechanism . . . . . . . . . . . a. Diradical and Concerted Retrocyclizations . b. Theoretical Work . . . . . . . . c. Experimental Results . . . . . . . 2. Electron Exchange . . . . . . . . . . . A. Intermolecular Systems . . . . . . . . B. Intramolecular Systems . . . . . . . . C. Bioluminescence. . . . . . . . . . Chemical Transformations . . . . . . . . . . 1 . Reactions with Nucleophiles . . . . . . . . 2. Reactions with Electrophiles . . . . . . . . Biological Implications . . . . . . . . . . . Concluding Remarks . . . . . . . . . . . . Acknowledgments. . . . . . . . . . . . . References. . . . . . . . . . . . . . .

I.

. . . . . .

. . . . . . . . . . . . . . . .

. . . . . . . .

. . . . . . . . . . . . . . . . . . . .

. . . . . . .

. . . . . . . .

. . . . . . .

. . . . . . . .

. . . . . . .

. . . . . . . .

. . . . . . .

. . . . . . . .

. . . . . . .

. . . . . . . .

. . . . .

394 396 399 399 402 404 405 407 408 409 409 410 410 411 412 414 414 415 417 417 418 420 420 421 422 422

HISTORICAL PERSPECTIVE

The four-membered ring cyclic peroxides, that is, the 1,2-dioxetanes and their carbonyl derivatives the 1,2-dioxetanones or a-peroxylactones and the 1,2dioxetandiones, are all members of the 1,2-dioxacyclobutane ring system and have received a great deal of attention during the last decade. This tremendous surge of research activity, as witnessed by the numerous recent reviews in this field,’ derives from the unique property of these “energy-rich’’ molecules to generate electronically excited carbonyl products during thermolysis2 (Eq. 1) and is therefore mechanistically relevant to the phenomenon of biolumine~cence.~

R R

I

I R- C -C -R I

I

0-0

R

O

1 4

R-C-C I I 0-0

0

*c -c//

0

I I 0-0

Historical Perspective

353

The earliest mention4 of the existence of 1,2-dioxetanes reaches back about 80 years. The most plausible claim is in the autoxidation of the stable enol of 1,2,3,3tetraphenyl-1-propanone (Eq. 2). The benzoic acid and benzhydryl phenyl ketone products were postulated t o arise from the cleavage of the unstable 1,2-dioxetane (1). Recent studies' on related systems give credence to these pioneering interpretations, except that the isolated peroxide must have been the a-hydroperoxyketone that decomposes into the carbonyl fragments with prior cyclization to a 1,2-dioxetane. Around the 1930s, the elusive 1,2-dioxetanes were postulated as stable autoxidation products in the reaction of olefins with molecular oxygen6; however, a thorough mechanistic investigation revealed7 that the true products of these autoxidations were allylic hydroperoxides (Eq. 3). Similarly, the claimga that photooxygenation of ergosterol (Eq. 4) gave a steroidal 1,2-dioxetane was refuted by showinggb that the endoperoxide was formed instead. However, in the 1960s, plausible evidence for the intervention of 1,2-dioxetanes as intermediates in numerous chemiluminescent reactions involving the autoxidation of electronrich olefins was documented." Ph Ph I I Ph2CH-C =C-OH-Ph2CH-C0 2

Ph 0 I It C-Ph-

Ph Ph

I

t

I

OOH -Ph,CH-C-Ph

II 0

HO

+ Ph-C-OH I1 0

(1)

(2)

1,2-Dioxetanes and a-Peroxylactones

354

Serendipity, insight, and keen observation power were the ingredients of success in the preparation, isolation, and characterization of the first stable 1,2-dioxetane,* namely, the trimethyl derivative (2) obtained in the base-catalyzed dehydrobromination of 3-bromo-2-hydroperoxy-2-methylbutane(Eq. 5). Since then, well over a hundred 1,2-dioxetanes have been documented in the organic literature, most as transient intermediates and a good number (Table 1) as stable, isolable substances. CH3CH3 I I

CH3-C-C-H

I

I HOO Br

KOH CCI,

CHjCH3

I

I

I

I

(5)

CH3-C-C-H 0-0

The chemical history of the a-peroxylactones is almost as long. Derivatives (3a, b) were postulated"a as labile reaction intermediates in the autoxidation of ketenes (Eq. 6) to explain the formation of ketones and carbon dioxide. Indeed, very recent confirmed these claims, except that singlet oxygenation of ketenes is preparatively more effective. However, the first stable a-peroxylactone that was isolated and characterized was the tert-butyl derivative (4), obtained from the corresponding a-hydroperoxy acid via dicyclohexylcarbodiimide (DCC) dehydration (Eq. 7).12 In the meantime, a number of stable a-peroxylactones have been reported (Table 2).

R

R, R'

II

0-0

0

3a ( R = M e ) 3b ( R = Ph)

H

O

H

a-Peroxylactones were first postulated in the late 1960s in the bioluminescence literature as intermediates responsible for the light emission in fireflies (Eq. 8).13 Early '*O-labeling experiment^'^^ refuted this claim; however, careful, recent ~ t u d i e s ' ~ substantiate ~-~ that a-peroxylactone (5) is an authentic intermediate in firefly bioluminescence.

wl

wl

W

R'

Molecular formula

21. C,H,,O,

20. C,H,,O,

19. C,H,O,

1. C311,04 2. C,H,O, 3. C,H,O, 4. C,H,O, 5 . C,H,O, 6. C,HlOO, 7. C,H,,Br,O, 8. C,H,,Br,O, 9. C,HIOO* 10. C 6 H l o 0 3 11. C,H,,BrO, 12. C,H,,O, 13. C,H,,O, 14. C,H,,O, 15. C,H,,O, 16. C,H,,O, 17. C,H,,O, 18. C,H13N0,

1,2DIOXETANES

TABLE 1.

R2

0-0

0

0-0

R4 R 3 RL~+R*

R3

H

R4

Liquid

A

- 11

20

B C

Solid Solid -9to-8

C

C

C

Liquid Liquid 76-77

C

Liquid 5-7 Liquid Liquid

C

Liquid Liquid

C

Melting point ("C)

C B B A A A A

D

A A B B B B D C B B

Method'

107

62

158

5.18-5.45; 6.1 5 -6.35 ; 81.96;90.73 5.1

4.9

89.4 5.0 5.04 5.87 5.67

4.92

156 127,156 38,157 18b 18b 22b 31,96 31,96 62 51 31,96 22b, 30b 18b 18b 39b 39b 39c, 127 41

Ref.

6.68 6.22 4.90 5.1-5.2 4.7 5.7 -

'H nmr 6 (ppm)b I3C nmr 6 (ppm)

cd

W

3

hl P N

m

9 vl

3 3

I

m

8

cn

3 0

GN

0

w

m w

4

2m m

m 3 vl

P

o

3

:I

N

w

d

3 W

m

I

I

2 0

6

. I

40

0

C m

n m

0

u

d d

V

C

6

zm

V Z

a

m

6

U

a V

m

0

8a

m hl

-

4 N

. .

. .

m m

v l YN) N

N N

356

0 m

3 ' 4 m

m

m

m

v)

N

3

N N

w w 3

3

ION

? ? w .^w .^ r-m

om.

m

m

4 v)

N 3

.^ .^

I W

m a m I

.-

I

m - 0

P

m

v)

3

w

U

m

W

W

I

10

W

m

* m

v)

rvl

.-U

U

d

2

1

I

rn

u u

;rj

4

4 4

d

V

i m

mrn

< rn

m

. .

0 3

v)

3 3

v)w

r-

'?-?A

s

3

N

O O N

wv)

N N

N D

rn

351

u!

s

el

3

d

0

N 10

;j: rn

g oo m w w

.-m

rn

5 m rn

rn 4 W

3 W

CO

rn

v)

10

d:

09

I

*

I 4

?

2 m

c

In

3:

Y,

3:

a

3:

I

4

3

u

c

c

0

0

m

d

i W

._ m

d

W i

0

m P

0 W

rn

i

m

‘ I )

‘I) i

W

09

‘I)

m

d

‘ I )

d

09

‘?

9

a 3

0-

.C

cl

r A

0

4

U

4

8

z

x

4

4

(ci

5?

z

4 ‘I)

‘I) ‘I)

359

\d

‘I)

m

%.-

4 m

‘I)

0

d

00

r 3 l

10

P-

3

N

w

v)

N

3

m -Id m..t-

mmvl m

'd

m

m

vl

3 w

0 %-I 0

...

N

3

w m

vl

N

P-

I

0 P-

u

O

c

v

<

9

.2N"

u c l

vvv

m

v)

W v,

4

w

5:

8

n z v"

m

m

W

360

4 V ; w w w w

G

W

O

d

al

m

m

0

In

W W 3

W

3

N 3

1-

r-

3 W

4 W

m

r 4

v; .^ m

m .^ m

Tt

v1

3

N

o!

\9

m

I

I

W

r-

4

I

N 3

5

I

rn 0

m

r?

N

r-

I

u

Fp

T

&

Q z

m

/

\

W

0 t-

Pi

i

r-

r-

36 1

0 5:

0

T

m

i r-

z

0;

T

r-

N

N N N

m m m "

~

w m m m w m m m d

" rl

m

d

u

m

t-nmwmmm"

m

m

N W

4

m u m 4 4 4

4

U

d

m

r

m

m n m4o 3 w3 w m

I 0

ti

m W

u 4 4 4

4

U

m

z

u

73

m

z

U

s

a

\ /

viwr-w r-r-r-t-

m m

3

M

N

d

m

m

m

0 W

m

rj

m w

i

W

9 vr

rj

w m

P

d

2

I

9 u

4

4

4

0 I

g 3:

c

.c-l

4

U

v

'r

0:I

m

m

m

o

363

\

Q

w \

0

m

J2

m

4 W

-a m

m

m

T

[: W 0

,+

00

d

m rl

m

p.

W

I

tW

i

d

I td

rl

4

p' 4

o

4

4

4

i

&

4

i

o

U

3:

w

m

0

364

0

2

c

rn m

rn

rn m

W

W

QI

\4

rn 0

3

rn

N

i 0 4

i

t-

i

? m

.^

2m

09 d

3 0

3

4

d,

c

n

vl 0 i

tm m

c

W

m

0 4

4

0

365

’u

m

m

c a

-

L.

m

m N ,+

N W

m

8;

% 5

\

/

\

c

a

z

I

5

xs V 0;

0

3

4

0

3 3 3

3

366

3

’

c

L.

m rn

m

m

N

3 r-

D PI

rm

m

00

i

m

3

4

4

a

4

d

Y

.K

m

i i

s

a

c a

m 3 3

367

W

i 3

r: a

ti

i

l x

o\

w

Ph

RZ R3

R4

A

A

A

Methoda

117

205

150

Melting point ("C)

-

-

'H nmr 6 (ppm)b I3C nmr 6 (ppm)

174

173

173

Ref.

a Method A, singlet oxygenation; Method B, basecatalyzed dehydrobromination; Method C, silver-ioncatalyzed dehydrobromination; Method D, miscellaneous. Dioxetanylring proton or carbon. Not isolated, but spectrally identified by 'H nmr.

120. C,,H3,N,02

119. C,,H,,O,

R'

CONTINUED

118. C3,H,,03

TABLE 1. Molecular formula

SBNV13XOIa-Z'I-ONIKI-E a N V SINOJJVTAXOX3d-D

' Z 378Vl

1,2-Dioxetanes and a-Peroxylactones

370

0

(luciferin)

(oxyluciferin)

I

The existence of 1,2-dioxetandione (6) is still arguable. It was postulated" as an intermediate in the chemiluminescent decomposition of oxalates with basic peroxide (Eq. 9), a reaction first discovered for oxalic ch1oride.l6 Although its isolation was claimed in this r e a ~ t i o n , ' no ~ characteristic spectral data could be documented." The reportlg that this carbon dioxide dimer was detected by mass spectrometry was shown to be erroneous.'' Consequently, this elusive species has so far defied synthesis and detection, and it seems urgent and timely to reinvestigate this challenging problem.

X = CI, OAr, NR2

11.

(6)

SYNTHESIS

The synthetic difficulties of preparing four-membered rings are further accentuated for the 12-dioxetanes in view of the weak peroxide bond in the strained ring system. Indeed, the methods of preparing these thermally labile and energyrich molecules are very limited. Only two procedures have general applicability, that is, hydroperoxide cyclization and singlet oxygen cycloaddition (Eq. 10).

Synthesis

37 1

For the 1,2-dioxetanes the first route can be executed by catalysis with bases (HOO, M e O a ) or by metal cations (Ag+, Hg”); for the more labile a-peroxylactones, neutral reagents such as the mild carbodiimide are essential. In both cases t h e yields are usually very low (< 30%). Thermal decomposition of the fourmembered ring peroxide or destruction by the catalyst are prominent side reactions, responsible for the low yields. The singlet oxygenations can give much higher yields provided the olefinic substrates (alkenes for dioxetanes and ketenes for a-peroxylactones) are sufficiently reactive. Even then, ene-reaction (substrates with allylic hydrogens) and (2+4)-cycloaddition (substrates with aromatic substituents) can be menacing side reactions (Eq. 11).’l Even if some dioxetane is formed, the separation problems (to isolate pure product) can be formidable.

For the dioxetanes, except recrystallization and chromatography (silica gel or Florisil and subambient temperatures), other purification methods are usually not applicable. The more labile a-peroxylactones cannot usually be isolated in pure form and are handled as solutions. 1.

A.

1,2-Dioxetanes

The Kopecky Method

The dehydrohalogenation of P-bromohydroperoxides (Eq. 5) is of historical significance8 because it constitutes the preparation of the very first stable 1,2dioxetane (2). We refer t o this as the Kopecky method,” as illustrated in general terms in Eq. 12. Bromide ion is normally the leaving group, but in isolated cases chlorides and iodides have also been used.” The bromohydroperoxides are prepared b y electrophilic addition of bromine, usually using 1,3-dibromo-S,5-dimethylhydantoin (DDH) as a carrier of Bra in the presence of concentrated (85-95%) hydrogen peroxide. Other bromine carriers, for example, N-bromosuccinimide (NBS) can also be used.

372

1,2-Dioxetanes and a-Peroxylactones

k C / R

II

R/'\R

DDH

H202

R

R

-.

I I R-C-0 I

I

R-C-Br

R-C-0

OH

I

R-C-OOH

I

I

(12)

R

R

For primary and secondary bromides base-catalysis is required, while for tertiary bromides silver acetate or silver oxide are more effective cyclization catalysts. For tertiary substrates dehydrobromination leading to allylic hydroperoxides is a serious side reaction when base-catalysis is employed and, thus, silver ion catalysis is essential. Furthermore, the silver salts must be freshly prepared because metallic silver that might be present due to exposure to light causes decomposition of the (7) was the first example prepared in this dioxetane. The tetramethyl-l,2-dioxetane way22b (Eq. 13). For primary substrates, abstraction of the base-sensitive dioxetanyl hydrogens are probably responsible for the low yields.23 For secondary substrates, both side reactions might operate.

In view of the labile nature of the weak peroxide bond, the cyclization methods must be executed at low temperatures (- 30 to lO"C), but in the case of the thermally more stable derivatives, room temperature (up to 30°C) can be tolerated. In the silver ion-catalyzed cyclizations, solvents such as alkanes (pentane, hexane, cyclohexane) and haloalkanes (carbon tetrachloride, methylene chloride, dichlorodifluoromethane) are advantageous. In the base-catalyzed reactions, protic solvents are employed, that is, water and/or methanol and ethanol; but heterogeneous solvent systems, for example, aqueous methanol and pentane, are useful. The latter conditions are designed to minimize base-catalyzed destruction of the dioxetane product by extraction into the alkane phase. The preparations of 1,2dioxetanes via the Kopecky method are collected in Table 1.

+

B.

+

Singlet Oxygenation

Electron-rich olefins, especially vinyl ethers,24 ketene a ~ e t a l s , ~ thioalkyl' substituted olefins,26 and e n a r n i n e ~ ,react ~ ~ readily with singlet oxygen to give dioxetane cleavage products. Under carefully controlled temperature conditions, the intermediary 1,2-dioxetanes can be isolated. The first 1,2-dioxetanes prepared in this manner were the cis and trans isomers (8a) and (8b), respectively (Eq. 14).

313

A @a)

The singlet oxygen can be generated either through photosensitization or chemically. The former is the more convenient procedure. The sensitizer-solvent systems that are frequently used are tetraphenylporphine (TPP) in methylene chloride, Rose Bengal in acetone, and methylene blue in methanol." Excellent chemical sources are triphenylphosphite ozonatez8 and 1,4-dimethyInaphthalene endoperoxidez9 (Eq. 15). These singlet oxygen precursors liberate the singlet oxygen at sufficiently low temperatures for the dioxetane product to survive.

Me

Me

The most serious side reactions are ene-reaction and (2+4)-cycloaddition (Eq. 11) when allylic hydrogen and aryl substituents are present in the olefin, respectively. For example, 2,3-dimethyl-2-butene gives exclusively allylic hydroperoxide on singlet oxygenation (Eq. 16). Thus, alkyl-substituted olefins, which are otherwise rather reactive towards singlet oxygen, cannot be used in the formation of 1,2-dioxetanes via singlet oxygenation in view of the ene-reaction. However, when the allylic hydrogens are positioned at bridgeheads as in diadamantylidene (Eq. 17), the ene-reaction is suppressed since a Bredt-type olefin would result and the dioxetane (9) is formed in high yield.30 The 1,2-dioxetanes that have been prepared via singlet oxygenation are summarized in Table 1.

3 14

1,2-Dioxetanes and a-Peroxylactones

C.

Miscellaneous Methods

Besides the Kopecky route and singlet oxygenation, very few other methods have been reported for the preparation of 1,2-dioxetanes. This is not surprising in view of the sensitive nature of these unusual compounds. Some isolated reports deserve mention and can probably be extended into more general routes for the preparation of 1,2-dioxetanes. Intramolecular peroxymercuration (Eq. 18) followed by brominolysis afforded Since the allylic hydroperoxides are readily available” via the dioxetane ene-reaction of a suitably alkyl-substituted olefin (Eq. 16), this method has synthetic potential, especially if electrophiles other than bromine can be employed to provide dioxetanes with other substituents.

~~ Certain endoperoxides rearrange on silica gel to afford 1 , 2 - d i o x e t a n e ~ .For example, singlet oxygenation of the dioxene (Eq. 19) produced the endoperoxide instead of the desired dioxetane (11) via the (2+4)-cycloaddition side reaction that was pointed out in Eq. 1 1. On silica-gel column chromatography, the endoperoxide rearranged into the desired 1,a-dioxetane (11). Although of limited scope, this novel rearrangement might be of potential use for such aryl-substituted dioxetanes.

315

Synthesis

SiMe,

OSiMe3

(20) CH3 (12)

Finally we mention the interesting o b ~ e r v a t i o nthat ~ ~ vinyl silanes afford dioxetanes on ozonization (Eq. 20). In this unusual manner, dioxetane (12) was obtained in the ozonization of 2-methyl-3-trimethylsilyl-2-butene. The general scope of this potentially convenient method merits investigation, especially since the conditions are mild and convenient. The 1,2-dioxetanes that have been prepared via these miscellaneous methods are shown in Table 1.

2.

a-Peroxylactones

A. Dicyclohexylcarbodiirnide (DCC) Qclization This general synthetic sequence" is illustrated in Eq. 21. The choice of the neutral and mild dehydrating agent, that is, dicyclohexylcarbodiimide (DCC) is particularly critical.'2b It is now known that in view of the delicate nature of the a-peroxylactones as well as the a-hydroperoxy acids (1 3), the dehydrating agent has t o be nonacidic, nonbasic, nonnucleophilic, nonelectrophilic, and nonparamagnetic since a reagent without these properties would cause decomposition of the a-peroxylactone and/or its precursor, that is, the a-hydroperoxy acid. In addition, the reagent has t o possess subambient reactivity so that the cyclization can be executed at low temperaures in order to avoid decarboxylation of the a-peroxylactone product. Moreover, the reagent should be readily available, preferably purchasable, and allow easy isolation and purification of the a-peroxylactone. Of the many dehydrating agents that have been successful in the preparation of the sensitive peptides,lZb the dicyclohexylcarbodiimide stands out as the best compromise. For example, it is relatively inert both to the a-hydroperoxy acid starting material and a-peroxylactone product, it has a high reactivity even at - 50°C, and it forms the

1,2-Dioxetanes and a-Peroxylactones

376

relatively inert dicyclohexylurea as a dehydration side-product. The latter fortunately precipitates essentially quantitatively when methylene chloride is used as solvent, thereby enabling ready isolation and purification of the a-peroxylactone product. This is done by simple low-temperature decantation from the urea sideproduct, washing with cold methylene chloride, and in those cases in which the a-peroxylactones are sufficiently volatile, flash distilling the combined decantates to give reasonably pure a-peroxylactone solutions. In the case of nonvolatile a-peroxylactone derivatives, the decantates are used directly without further attempts of purification. Table 2 lists the a-peroxylactones that have been prepared with the DCC dehydration method.

A problem of considerabIe difficulty in this synthetic sequence (Eq. 21) has been the preparation of the exceedingly sensitive a-hydroperoxy acids (13) that serve as precursors to the a-peroxylactones. Unfortunately these substances undergo readily base- and acid-catalyzed Grob-type fragmentation^^^ (Eq. 22) and must, therefore, be prepared under mild, preferably neutral, conditions. The successful routes’2b are summarized in Eq. 23.

R,c=C=o R, B

0

R, R’

II

/‘I0 C I C ‘0 .

II

0

Synthesis

311

The first method (Route A ; Eq. 23) utilizes the ketene bis(trimethylsily1)acetal as a starting point. Its singlet oxygenation leads to the trimethylsilyl a-trimethylsilylperoxyester, that on desilylation with methanol at < 0°C affords the desired a-hydroperoxy acid (13) in high yield. This amazing singlet oxygenation fulfills several important functions. First of all and most important, through a silatropic shift, a peroxy functionality is introduced next to the ester carbonyl. Second and from the practical point of view equally important, the peroxy and carboxy functionalities are protected against fragmentation with readily removable trimethylsilyl groups. This allows isolation, purification, and storage of the labile a-hydroperoxy acids. When the latter are required, desilylation with methanol releases the essential a-hydroperoxy acid (13) at will. Most important, all operations are perfectly neutral! The limitations of this method are those of singlet oxygenation, that is, ene-reaction when allylic hydrogens are present and (2+4)-cycloaddition when aromatic substituents are present (Eq. 1 I ) , that compete effectively with the silatropic shift. Recently even 1,2-dioxetane formation has been reported (Eq. 24).35

tBuCH=C

, OAr 'OSiMe,

OAr I LtBu-CH-C -OSiMe3 '0

I

0-0

I

0

+

II

tBu-CH-C-OAr

I (24) OLOSiMc,

The second method (Route B; Eq. 23) took advantage of the fact that a-lactones add protic nucleophiles at the a-carbon. Thus, hydrogen peroxide adds to a-lactones to give the desired a-hydroperoxy acids (13) in essentially quantitative yields.'2b However, the big limitation in this route is the availability of the elusive a-lactones. Sterically hindered a-lactones that are sufficiently stable at low temperatures for preparative purposes can be made by ozonization of the respective ketenes, e.g. d i - t e r t - b ~ t y l k e t e n eThe . ~ ~ unstable ones, which necessarily must be prepared in situ, are now quite readily available through photodecarboxylation of malonyl pero x i d e ~ .Again, ~ ~ the synthesis of a-hydroperoxy acids via a-lactones takes place under perfectly neutral conditions! The third method (Route C ; Eq. 23) engages the autoxidation of a-enolate carboxylates. Since the latter are prepared from the corresponding carboxylic acids by deprotonation with lithium diisopropylamide (LDA) or n-butyllithium (BuLi), obviously very strong basic conditions, the autoxidation step and the subsequent protonation must be executed under strictly controlled low temperature (< - 78°C) conditions.'2b Otherwise, the base- and acid-sensitive a-hydroperoxy acids are destroyed during their preparation. Undoubtedly, this method is the most convenient and most general of the three listed in Eq. 23. B.

Ketene Singlet Oxygenation

The most direct method for the preparation of a-peroxylactones is via singlet oxygenation of ketenes (Eq. 25). A few a-peroxylactones have been prepared in this way,"b including dimethyl, diphenyl, phenyl, and methyl phenyl derivatives,

318

1,2-Dioxetanes and a-Peroxylactones 0 -

II

C II C

R' 'R

lo,

0 NC-0

1

R-C-0 I R

1

(25)

which are given in Table 2. Apparently ene-reaction and (2+4)-cycloaddition (Eq. 11) are not serious side-reactions since ketenes bearing methyl and/or phenyl substituents afford the desired a-peroxylactones on singlet oxygenation. Since ketenes are prone to autoxidationlla (Eq. 5), this complication can in principle be minimized by using chemically generated28929 singlet oxygen (Eq. 15). An additional shortcoming of this method is that sterically hindered ketenes, for example, di-tertbutylketene, and electron-poor ketenes, for example, bis(trifluoromethyl)ketene, are quite inert towards singlet oxygenation.

111. PURIFICATION AND IDENTIFICATION 1,2-Dioxetanesand a-peroxylactones are unusual molecules, in view of their high energy content. To claim them as products, it is essential to identify them rigorously. Thus, the standard criteria such as a positive potassium iodide test, fragmentation into carbonyl products, and emission of light are indicative, but not necessarily proof that a four-membered ring peroxide is on hand. For example, allylic hydroperoxide (Eq. 26) gives obviously a positive potassium iodide test and on acid treatment it affords acetone (Hock cleavage) accompanied with weak light emission.31 Of course, even a simple infrared spectrum would distinguish the allylic hydroperoxide from a 1,2-dioxetane beyond argument.

Their purification is equally problematic. In view of the thermal ability and ease of catalytic decomposition of the four-membered ring peroxides, many of the usual methods of purification are not applicable. This problem is more severe for the more labile a-peroxylactones than the 1,2-dioxetanes. To the best of our knowledge, no analytically pure a-peroxylactones have been prepared to date.12b If the dioxetane is a solid, recrystallization is obviously the method of choice. It is critical to use metal-free solvents since traces of metal ions can lead to extensive decomposition. In the case of volatile crystalline dioxetanes, prepurification via sublimation can be advantageous. In some systems low temperature column chromatography is effective. In the case of liquid 1,2-dioxetanes, unless they are sufficiently volatile for low-temperature distillation such as 3,3-dimethyl-l,2d i ~ x e t a n e , ~repeated ' low-temperature column chromatography is the only means of purification.

Purification and Identification

319

Silylated silica gel or low-activity (Grade 111) silica gel are effective adsorbants, but even these can frequently cause decomposition of the very sensitive dioxetanes, even at - 50°C. In such cases Florisil can sometimes be useful. Eluant mixtures of halogenated hydrocarbons, for example, methylene chloride, carbon tetrachloride, fluorotrichloromethane (Freon-I l), and alkanes, for example, n-pentane, n-hexane, and cyclohexane, are quite effective and convenient, but their purity is critical, especially the absence of metal impurities. To spot the dioxetanes, monitoring the eluate by TLC, utilizing their peroxidic and/or chemiluminescent properties. is quite convenient. In most instances, a TLC plate soaked with an aqueous KI solution will do; but for very resistant cases such as diadamantylidene-l,2-dioxetane(9),30ferrous sulfate-ammonium thiocyanate and concentrated hydrochloric acid will not fail. In the case of detection via chemiluminescence, the TLC plate is sprayed with a 9,lO-dibromoanthracene (DBA) or 9,lO-diphenylanthracene (DPA) solution and heated in the dark. The dioxetane spot glows bright blue. We have made the interesting observation that most dioxetanes bleach iodine when the latter is used as a spotting agent. Thus, a bright white spot remains where dioxetane is located, while the rest of the TLC plate turns yellowish on exposure to iodine vapors. The combination of potassium iodide detection (brown spot) and iodine detection (white spot) can be quite definitive for the presence of dioxetanes. The lack of such tests, however, does not mean that dioxetanes are not present. Once a four-membered ring peroxide is reasonably pure (2 90%), a number of physical, chemical, and spectroscopic methods can be employed for their identification. These methods will be taken up in order. 1.

Physical Methods

To differentiate monomeric, dimeric, and polymeric products, a molecular weight determination is essential. The usual cryoscopic and osmometric techniques are applicable.'8b,22b,30339 In fact, these methods have been used for impure dioxetanesZ7 and at low temperature^.^^'^^' Furthermore, the dioxetane derived from the acridine (14) by singlet oxygenation (Eq. 2 7 ) was shown to be the dimeric peroxide (15) by cryoscopy.w

380

1,2-Dioxetanes and a-Peroxylactones

Melting points of crystalline and stable dioxetanes have served for identification purposes. However, the melting points are frequently decomposition temperatures, which limit their use.

Of course, the most rigorous identification is by x-ray structure analysis. The difficulty is in growing suitable crystals. More seriously, on extended exposure to x-rays, the crystals deteriorate and do not permit a definitive structure elucidation. Nevertheless, a few x-ray structures of the very stable dioxetane (9) in Eq. 1763a,b and the unusual cyclobutadiene-l,2-dioxetane(16)63ahave been reported. 2.

Chemical Methods

Whenever feasible, a combustion analysis is an essential method of characterization because it establishes the elemental composition. All precautions should be exercised in view of the explosive nature of 1,2-dioxetanes. As already mentioned in connection with the determination of purity, iodometric titration is useful in the identification of dioxetanes.zzb Unfortunately this simple and convenient method is not specific since most peroxides release iodine from acidic potassium iodide. If the necessary care is taken, iodometry is quantitative and thus an excellent purity criterion. However, the sterically hindered dioxetanes (9)30 do not titrate well. Catalytic reductions over platinum or palladium, which are usually quantitative methods for the identification of organic peroxides, are problematic. Little of the expected 1,2-diol is obtained because the dioxetane fragments into its carbonyl products due to metal ~atalysis.4~ However, lithium aluminium hydride reduction under subambient conditionszzbaffords the expected 1,2-diol quantitatively. Again, the sterically hindered dioxetane (9) is an exception. Here zinc in acetic acid proved s u c c e s ~ f u l . ~ ~ A convenient and quantitative method is thermal decomposition into the carbonyl fragments. These can be easily characterized by ir and nmr. 3.

A.

Spectroscopic Methods

Nuclear Magnetic Resonance

'H and 13C nmr are the most important tools for the identification of 1,2dioxetanes and a-peroxylactones. The dioxetanyl ring protons have characteristic

Purification and Identification

381

chemical shifts at 6 (TMS) 4.9-5.2 ppm. The specific values are listed in Table 1 for the particular derivatives. Alkoxy substituents tend to shift the ring protons to lower fields, that is, 6(TMS) 5.6-6.8 ppm. For aryl and olefinic substitution, the dioxetanyl protons are located at 6 (TMS) 5.6-5.9 ppm. The dioxetanyl ring carbons, if not substituted by heteroatoms, are located characteristically at 6 (TMS) 88-90 ppm. Heteroatom substitution shifts this resonance in expected amounts to lower fields. The specific values are listed for the individual derivatives in Table 1.

B.

Infrared Spectra

Except for the a-peroxylactones, which have characteristic carbonyl stretching frequencies at 1850-1 875 cm-' (for specific values, see Table 2),"," infrared spectra are of no great help for the identification of 1,2-dioxetanes. The weak and controversial 0-0 stretching frequency of peroxides is not sufficiently characteristic for structural confirmation.44

C.

Electronic Spectra

-

Most 1,2-dioxetanes are yellow-colored, except the diadamantylidene-l,2dioxetane (9) that is a colorless solid. The h,,, occurs at about 280 nm ( E 20),22b with weak tail-end absorption all the way out to 450 nni (which is responsible for the yellow color). Theoretical and photoelectron spectra46 attribute the excitation of the 0-0 bond. For the tetracharacteristic yellow color t o i~; + methyl-l,2-dioxetane (7) the vertical ionization potentials were determined to be 8.98, 10.94, 11.41, and 12.09 eV from their photoelectron Undoubtedly, the most characteristic property of 1,2-dioxetanes and a-peroxylactones is the fact that they ernit light on thermal decomposition. Since in liquid media in the presence of molecular oxygen triplet excited states are efficiently quenched, the observed direct chemiluminescence is ascribed to the fluorescence of the carbonyl product. This fluorescence occurs usually at 4 2 0 t lOnm and corresponds to n + i ~ excitation.'a,s,22b * Th e shortest wavelength emission has probably been observed for the indole-l,2-dioxetane (17) that occurs at 320 nm.47

CH,

1,2-Dioxetanes and a-Peroxylactones

382

The emission of transient 1,2-dioxetanes in the gas phase has recently been actively investigated and matches the n,n* fluorescence of the carbonyl fragments.24b Recently n,n* fluorescence has also been documented for the 1,2-dioxetane (18).48

M

e

2

N

n G

w

e

CH3 CH,

N M

e

2

CH,-H-C-CH, II

0-0

0-0

(18)

(19)

0

Emission of phosphorescence by 1,2-dioxetanes and a-peroxylactones has also been observed, but is quite rare. Thus, in degassed acetonitrile the 430 nrn emission exhibited by the tetramethyl-l,2-dioxetane (7) has been assigned to acetone phosp h o r e ~ c e n c e .Similarly, ~~ this acetone phosphorescence has been detected for the dimethyl-a-peroxylactone.so For the acetyl derivative (19), both the n,n* fluorescence and phosphorescence of 2,3-butanedione have been reported.’l Thus, if the photoexcited luminescence spectrum of the carbonyl product is known or can be readily measured, the chemiluminescence spectrum can be used as corroborative structure confirmation of the 1,2-dioxetane or a-peroxylactone.

D.

Muss Spectra

This potentially powerful structural tool is of limited use because the dioxetanes are too prone to catalytic decomposition by metal surfaces. It has, however, been possible in optimal cases to detect the parent ions of 1,2-dio~etanes.’~ b330,39e

IV. 1.

CHEMILUMINESCENCE Direct and Energy Transfer

A.

Energy Balance

As pointed out in Section II1.3.C, the emission of light by 1,2-dioxetanes and a-peroxylactones on thermolysis is a most characteristic property of these unique substances. More important, such chemiluminescent transformations represent one of the most unusual chemical reactions.’ The chemical energy that is stored in these hyperenergetic molecules is converted into electronic energy and is released in the form of light. The fundamental steps of this process are detailed in Eq. 28. Thus, the ground-state reactant Ro (the four-membered ring peroxide) acquires sufficient thermal energy on heating to form the activated complex ($). This activated complex dissociates into the electronically excited product P* (the carbonyl fragment). It is this fundamental step that is so unusual, at least for reactions in condensed

Chemiluminescence

383 P* -

R* -

R"-

(*I

RO

I

A H0

i"

R" P" -

RO PO

.1 I

-

-

(a)

media, since a crossover from a ground-state energy surface t o an excited-state surface, that is, a nonadiabatic path, has taken place. Subsequently, the electronically excited product state rids itself of the excess energy by exhibiting luminescence, that is, fluorescence in the case of singlet excited product 'P* and phosphorescence in the case of triplet excited product TP*. The reaction profile for the chemiluminescent reaction is schematized in Figure l(a).

In contrast, in a typical exothermic thermal decomposition reaction, whose fundamental steps are given in Eq. 29, the ground-state reactant Ro leads again to the activated complex ( 3 ) on heating, but the activated complex ( 3 ) affords a vibrationally excited product molecule Ps that disposes of its excess energy b y evolving heat [Figure 1(b)]. As in the chemiluminescence process, the absorbed heat is utilized to change bonds in the molecules involved, but unlike the chemiluminescent process, the excess energy is degraded into heat rather than light. Thermal reactions o f the type shown in Figure l ( b ) are common, those of the type shown in Figure 1(b) are rare.

3 84

1,2-Dioxetanes and a-Peroxylactones Photoenergization process

Chemienergization process

P"

1 Photophysical transformations (fluorescence, phosphorescence, energy transfer, etc.)

Photochemical transformations (fragmentation, isomerization, rearrangement, cycloaddition, etc.) Figure 2

For purposes of comparison, a typical photochemical reaction is given in Eq. 30 and illustrated in Figure l(c). The ground-state reactant molecule Ro absorbs a photon of the appropriate wavelength to produce an electronically excited reactant molecule R * . The acquired electronic energy is utilized to promote a chemical reaction, leading to the vibrationally excited product molecule Pz . The latter evolves heat. Consequently, the chemiluminescent process shows traits that are common to both modes of promoting chemical reactions, that is, by heat or light. Specifically, in the chemienergized mode, heat is utilized to produce the electronically excited state, while in the photoenergized mode, light is used. Irrespective of its past history, the excited-state intermediate manifests its presence either through photophysical changes (luminescence, energy transfer, etc.) or photochemical changes (fragmentations, isomerizations, rearrangements, cycloaddition, etc.), as is illustrated in Figure 2.

Ro+hu-+R*

R* + P f P f -+Po

+A

(30)

Clearly (Figure I), it is the favorable exothermicity of the chemienergized process that leads to the electronically excited product P* rather than the vibrationally excited product P f . Consequently, one of the most important criteria that a molecule decomposes on heating into electronically excited product, is that of energy sufficiency. The sum of its activation enthalpy ( A H f ) and reaction enthalpy ( A H o )must be greater than the excitation energy ( E * )of the electronically excited product (Eq. 31). A substance that conforms to this energy balance we designate

385

Chemiluminescence

*

f

q g

sco,*

+

+

KO

KO

0 0

f

AHf

as hyperenergetic. Recently, this oversimplified criterion of chemienergization has been justly criticized because free energies should be employed instead of enthalpies in order to deal properly with the entropic factor.”

AH$

+ (-

AHO) Z E*

(31)

The energy-sufficiency criterion for the two hyperenergetic molecules under discussion, that is, the 1,2-dioxetanes and a-peroxylactones, is convincingly demonstrated in Figure 3, which summarizes the energetics of their thermal decomposition in the form of a heat of formation ( A H f ) diagram. Typically, the activation energies, determined from isothermal kinetic methods range between 20-30 kcal/mole and the heats of reaction, estimated from thermochemical calculation^,^^ vary around 60-90 kcal/mole. Since the lowest excited states ( n , r * ) of simple carbonyl compounds such as aldehydes and ketones range between about 75-85 kcal/mole for singlet excitation and about 70-80 kcal/mole for triplet e ~ c i t a t i o n , ’the ~ energy sufficiency criterion (Eq. 3 1) demands that at least 70-85 kcal/mole of energy must be made available at the transition state of dioxetane decomposition t o create one of the carbonyl fragments in its n,r* excited state. For the specific case of tetramethyl-l,2-dioxetane, the heat of reaction was determined experimentally by differential scanning calorimetry (DSC) to be AH, = - 61 k c a l / m ~ l e Its . ~ activation ~~ enthalpy is about 25 kcal/mole.22bThus, a total of

386

1,2-Dioxetanes and a-Peroxylactones

about 86 kcal/mole of energy is available in the activated complex of tetramethyl1,2-dioxetane. This is sufficient to produce one of the acetone molecules in its n,n* excited state, since the singlet and triplet energies are, respectively, 84 and 78 k ~ a l / m o l e . Note, ~~ however, that the corresponding n,n* states of acetone since these excited states cannot be chemienergized by tetramethyl-l,2-dioxetane lie well above 86 kcal/mole. Thus, on the basis of energy balance, we can expect to observe fluorescence or phosphorescence from the n,n* excited carbonyl fragment that is generated in the thermolysis of four-membered ring peroxides.

B.

Activation Parameters

The kinetics ofthe thermal decomposition of 1,2-dioxetanes and a-peroxylactones are first order and are usually unimolecular. A variety of experimental methods can be used to monitor the rates. These include direct chemiluminescence of the excited carbonyl p r o d ~ c t , ~ energy-transfer ',~~ chemiluminescence of the chemienergized excited carbonyl product to an efficient f l ~ o r e s c e r , ~dioxetane ~ ~ ~ ~ ~ consumption ,~' or carbonyl product formation by nmr s p e c t r o ~ c o p y iodometry , ~ ~ ~ ~ ~ of ~ ~the cyclic peroxide,22bi57a and infrared spectroscopy of a-peroxylactone c o n ~ u m p t i o n , ' ~ ~ ~ ~ ~ ~ or appearance of the carbonyl product.30b Of these kinetic methods, the chemiluminescence techniques are by far the most convenient and most sensitive. Besides the isothermal kinetic methods mentioned above, by which activation parameters are determined by measuring the rate of dioxetane disappearance at several constant temperatures, a number of nonisothermal techniques have been developed. These include the temperature jump method,58e in which the kinetic the temperature is run is initiated at a particular constant initial temperature (Ti), suddenly raised or dropped by about 15"C, and is then held constant at the final temperature (Tf), under conditions at which dioxetane consumption is negligible. Of course, for such nonisothermal kinetics only the chemiluminescence techniques are sufficiently sensitive to determine the rates. Since the intensities Iiat Tiand If at Tf correspond to the instantaneous rates at constant dioxetane concentration, the rate constants ki and kf are known directly. From the temperature dependence (Eq. 32), the activation energies are readily calculated. This convenient method has been modified to allow a step-function analysis at various temperatures58cand a continuous temperature variation .57f Finally, differential thermal analysis has been employed to assess the activation parameters6'; in contrast to the above nonisothermal kinetic methods, in the latter the dioxetane is completely consumed and, thus, instead of initial rates, one measures total rates.

In Table 3 the activation energies of tetramethyl-l,2-dioxetaneby a variety of isothermal and nonisothermal kinetic methods are compared. The values range

Chemiluminescence TABLE 3.

387

ACTIVATION ENERGIES OF lETRAMETHYL-1,2-DIOXETANEBY VARIETY OF KINETIC METHODS

A

AH$

Mcthod

Solvent

1. Isothermal kinetics

(direct CL) 2. Isothermal kinetics (direct CL) 3. Isothermal kinetics (direct CL) 4. Isothermal kinetics (iodometry) 5. Isothermal kinetics (DPA or DBA energy-transfer CL) and temperature drop (direct CL) 6. Step-function analysis (fluorescence) I. Step -fu nc tio n analysis (phosphorescence) 8. Differential thermal analysis (direct CL) 9. Continuous temperature variation (direct CL) 10. Continuous temperature variation (direct CL) 1 1 . Continuous temperature variation (DBA-enhanced CL) 12. Continuous tcrnperature variation (DPA-enhanccd CL)

' Error is about

f

1 kcal/rnole.

Eu for DBA fluorescence is about

-4

(kcal/mole)'

Ref.

C 6 H 6 ,C-C6HI2

26

58a

CII, CN

31

58a

C61I6

25

51c

CCI,

26

22b

C6H6, CI1,CN

28

86

CI1, CN

28

58c

CH,CN

25

5 8c

Decalin

21

6 Oa

Decalin

21

6 Oa

C6H6

28

Slf

C6H6

23b

57f

CC1,

21

5 7f

kcal/mole

between 25-30 kcal/tnole, but the large majority lies around 26 f 1 kcal/mole. Although the results of the activation energies determined b y the isothermal and nonisothermal techniques are in close agreement, some caution should be exercised in using the temperature-jump method. For example, it was reported that under isothermal conditions (total rates), the activation enery of dimethyl a-peroxylactone 40°C, while under was about 22kcal/mole in the temperature range + 15 to nonisothermal conditions (initial rates), the activation energy was about 25 kcal/ 14°C.61 However, it was recently shown mole in t h e temperature range - 1 to for the dirnethyl a-peroxylactone that under nonisotherrnal conditions, the activation energy depends on the temperature range at which the temperature-jump kinetics is run.59 Representative activation parameters of 30 four-membered ring peroxides are collected in Table 4. Since such data are amply covered in numerous reviews,' we have limited ourselves to the tnore interesting and unusual cases. In want of a better reason, the examples in Table 4 have been arranged according t o their thermal stability from highest first-order rate constant, that is, k z o o c is about

+

+

ACTIVATION PARAMETERS AND EXCITATION PARAMETERS OF SOME SELECTED DIOXETANES Activation Parameters

17

6

(e.uJC

(kcal/mole)b

AsS

AHS

k%c (sec-')

+3

Excitation Parameters @T+S

0.003

700

0-0

Me -

2

Q-Me

0.1

17

21

+1

+8

8

f

1

f

0-0

lo-=

22

19

+8

-7

0.3

70

22

m

10

D-

N

3

23

W

3

N

r-

N

3

0 0 0

N

W

m

3 v)

0

0

d

0

N

0 N 0

0

3

N

m

N D N

3 v)

3

t-

W

3

3

0

0 3

N

0 0

3 3

W

r-

3

m

3

W

d

d

0

d

3

3

N

m

N

N d

m N

N

N

m

W N

W N

N v)

*

n

n

v)

0

0

0

0

N

3

X N

1

I

I

+

+

0

0

v)

v)

0

0

0

0

0

X

X

X

X

N

v)

N

N

X N

0;

0

3

t-’

3

m

3

3

3

389

3

3 3

3

hi

3

3

m

3

vl

m *.+ L

CO P

tvl

d

N \D

r0

i N

* rn

0

0

0 N N

N i

N

0

0

3

3

0

3

W

P"

N

0

0 3

i 3

N

3

10 N

vl N

W N

W N

N

c

c

c

I I-

c

2

0

0

0

0

X

X

X

vl

vl

d

X rn

X rn

m

w

P

w

I

3

3

i

390

PI

d

+

i

3

rn

+

i

i

r-

3

W

m

3

m

0

N W

0

m

N

N

m

0 N

0

0

0 0

0

3

Lo

r-

3

W

vl

3

0 N

rn N

3

m 0 bo

3

9 0

0

0

+

N

m

N

r-

c

rn

m

rn

Yt

0 W

aa

Lo

3 3

Lo

+

W

W N

W N

m N

c1 W

3

m

N

(0

m

m

m

0

0

0

I

-c

I

m

m

0

0

0

0

3

3

X

X

X

X

X

r3

N

0

N

3

3

m

d

m

3

N N

N

N

m

391

4

4

r-

3

X Yt

N

N

I

+

10

N

N W

h)

10 w

0-0

0-0

OPh ' B u ~ O P h

0-0

M e 0 OMe M e O w O M e

10-l2

7 x 10-1°

9 x 10-1°

34

28

29

AsS

+3

-5

-1

+4

(e.uJC

17

0.1

11

18

@T+S

Excitation

8

2

10

90

30b

92

127

107

Ref.

a

Calculated from the activation parameters arbitrarily at 20°C for sakes of comparing their relative thermal stabilities. The errors are at least 1kcal/mole, even if stated more precisely in the publications. The errors are at least 2 e.u., even if stated more precisely in the publications. The errors are usually 30 to 50% so that we have rounded the values up or off. Most of these excitation yields have been determined by energy-transfer chemiluminescence using 9,lO-diphenylanthracene (DPA) and 9,lOdibromoanthracene (DBA) as fluorescers. f Could not be determined because energy-transfer chemiluminescence failed with DPA and DBA. g Could not be determined because it is CIEEL-active.

30.

29.

28.

30

2 x 10-9

27.

AH$

(kcal/mole)b

Activation Parameters k%c (sec-')

CONTINUED

Dioxetane

TABLE 4.

Chemiluminescence

3 93

6sec-' for the iminodioxetane (Entry 1 in Table 4) to the lowest, that is, kzooc is about lo-'' sec-' for the diadamantylidenedioxetane (Entry 30 in Table 4). This wide range in thermal stability, that is, relative rate constants covering 13 orders of magnitude or a difference in activation energies of 17kcal/mole, is impressive. In more tangible terms, the half-life of the iminodioxetane (Entry 1 in Table 4) is about 0.1 sec at 20°C; for the diadamantylidenedioxetane (Entry 30 in Table 4), it is about 20,000 years at this temperature. This is truly a remarkable variation in the thermal stability of these unusual substances. Unfortunately no clear-cut trends can be read out of this thermal stability data in terms of structural features and substitution patterns. For example, that the iminodioxetane (Entry 1 in Table 4) and the a-peroxylactone (Entry 6 in Table 4) should be considerably less stable than the simple tetramethyldioxetane (Entry 19 in Table 4) is readily reconciled in terms of additional ring strain by incorporating an sp' carbon into the ring. But why should the vinyl substituted dioxetane (Entry 4 in Table 4) or the cycloheptatrienedioxetane (Entry 3 in Table 4) be as unstable as the a-peroxylactone? Still more puzzling, why should the tetraethyldioxetane (Entry 25 in Table 4) be so much more stable than the tetramethyldioxetane (Entry 19 in Table 4)? Furthermore, what factors are responsible for the fact that fusion of the dioxetane ring to six-membered rings, as in Entries 8 and 9 in Table 4, lowers the thermal stability of the system; although this effect is by no means general (see Entries 16 and 17 in Table 4)? On the other hand, spirocyclization of six-membered rings, for example, Entries 22 and 30 in Table 4 , enhance the thermal stability of the dioxetane enormously. No convincing rationalization of these stability trends in terms of structural variations has been offered so far. It has been suggested6' that the more easily the dioxetane ring can be puckered, the lower its thermal Stability. This could be the reason for the high activation energies of cyclobutadienedioxetane (Entry 23 in Table 4) and diadamantylidenedioxetane (Entry 30 in Table 4).63 However, why should the tetraethyldioxetane (Entry 25 in Table 4) be more planar and more rigid than tetramethyldioxetane (Entry 19 in Table 4)? Clearly, we do not as yet understand the thermal stability of 1,2-dioxetanes and much has yet to be learned. X-ray structure data would seem important on this problem. C.

Excitation Parameters

As already pointed out o n several occasions, the unique property of dioxetanes is to generate electronically excited states on thermolysis, which then manifest themselves by light emission (Eq. 28). The total yield of excited states (Eq. 33), triplet excitation yield (GT), that is, the sum of the singlet excitation yield (d), and the spin-state selectivity (Eq. 34), that is, the ratio of the triplet and singlet excitation yields, are excitation parameters that characterize a particular dioxetane. Total Excitation Yield Spin-State Selectivity

@Tts

(33)

$T/@

(34)

3 94

1,2-Dioxetanes and a-Peroxylactones

Unlike activation parameters, the determination of which well-defined experimental kinetic methods exist, the state of the art for the determination of the excitation parameters leaves much room for improvement. However, a great deal of progress has been made in recent years. For the sake of simplicity and clarity, the methods for the determination of the excitation yields are classified into photophysical and photochemical techniques. This is warranted in view of the distinct experimental methodologies involved. a.

PHOTOPHYSICAL METHODS

In the photophysical techniques for determining excitation yields ($*) of chemienergized processes, the physical properties of the electronically excited state are utilized, specifically their luminescent properties. Thus, the observed chemiluminescence, that is, fluorescence in the case of singlet states and phosphorescence in the case of triplet states, of the chemienergized process is related to the photoluminescence of the electronically excited product. For convenience we distinguish between direct chemilurninescence (DC), in which the chemienergized product K* directly exhibits chemiluminescence (fluorescence and/or phosphorescence), and energytransfer chemiluminescence or enhanced chemiluminescence (EC), in which the chernienergized product K* first transfers its excitation energy to a suitable luminescer Lu (fluorescer and/or phosphorescer) and the electronically excited luminescer Lu* emits, giving rise to the observed enhanced chemiluminescence. The two events are illustrated in terms of an energy diagram in Figure 4. i. DIRECT CHEMILUMINESCENCE. In this method, the luminescence of the chemienergized carbonyl product K* is directly detected and quantified. It is essential that the electronically excited product K* be known and characterized,

1

h up,'

Direct

Figure 4

o:

I

h ufi'Lu

'

LUO

Energy transfer

Chemiluminescence

395

which is usually confirmed through photoluminescence with the authentic material, fluorescence in the case of singlet state ‘K* and phosphorescence in the case of triplet state ‘K*. Since phosphorescence is usually difficult to detect in solution at ambient conditions in the presence of molecular oxygen, the direct chemiluminescence technique is essentially restricted to the determination of singlet excitation yields (4’). Our discussion focuses on the latter; however, it should be clear that in principle the same methodology applies to the determination of triplet excitation yields (GT), except that instead of the fluorescence the phcsphorescence is quantified. Excellent reviews@ on the instrumentation and calibration of light emissions required to measure chemiluminescence quantum yields have appeared recently. The direct chemiluminescence quantum yield (GDC) is given by Eq. 35, where @‘ is the singlet excitation quantum yield and q+& is the fluorescence quantum yield of the singlet excited carbonyl product ‘ K * . The latter is directly responsible for the observed chemiluminescence. If 4: is known from photoluminescence work, determination of GDC allows us to calculate the desired @-parameter. Frequently 4% is not known and it is necessary to measure it, using routine fluorescence techn i q u e ~ . ~ ~ ~ ~ ~ ~ @IlC =

s fl @ @K

(35)

For the experimental determination of the @DC, it is necessary t o quantify the light output of the direct chemiluminescent process. The experimental definition of the direct chemiluminescence quantum yield is given in Eq. 36, that is, the initial rate of photon production (Ik)“) per initial rate of dioxetane decomposition ( k , [Ill0). Alternatively, the total or integrated light intensity per total dioxetane decomposed can be used. The k,[Dlo term is readily assessed by following the kinetics of the chemiluminescence decay, which is usually first order. Thus, from a semilogarithmic plot of the emission intensity vs. time, the dioxetane decomposition rate constant kD is obtained and the initial dioxetane concentration [Ill0 is known,57d especially if the dioxetanes have been isolated and purified. In those cases in which the dioxetanes are too labile for isolation and purification, [Ill0 is determined by quantitative spectroscopic measurements or iodometric titration.

With a suitable photometer,64a the initial or total light intensity is measured and quantified. The detailed experimental techniques are p ~ b l i s h e d . ’ ~It ~is, ~ ~ ~ critical t o standarize the photomultiplier tube against suitable light standards and t o calibrate for wavelength response if the emission intensities of the chemiluminescent process and the light standard occur at different wavelength. In recent years the l ~ m i n o land ~ ~ the “scintillation cocktail”66 have found wide acceptance for standardizing light intensities in dioxetane work.lg Once the standardized and calibrated direct chemiluminescence quantum yield (q5DC) has been acquired experimentally, the singlet excitation yield (@‘) can be calculated for the chemienergized process from Eq. 35. However, as already stated, this requires that the fluorescence quantum yield (4%) be known under the same experimental conditions at which @’)‘ was determined. This is not always the case

3 96

1,2-Dioxetanes and a-Peroxylactones

and the disadvantage of the direct chemiluminescence method is that 4% may have to be determined. For very weakly chemiluminescing systems that can be a difficult task because the chemienergized emitter might not be defined. ii. ENERGY-TRANSFER CHEMILUMINESCENCE. By far the most popular photophysical technique to count chemienergized singlets and triplets is via energy transfer to suitable luminescent acceptors (Figure 4). Usually the fluorescence of the acceptor is chemienergized, but in principle the phosphorescence could also be stimulated, provided the acceptor exhibits measurable phosphorescence under the conditions of dioxetane decomposition, that is, in solution, at ambient temperatures and in the presence of molecular oxygen, as in the case of b i a ~ e t y l We . ~ ~limit ourselves to the case of chemienergized fluorescence by energy transfer, although the same treatment applies to phosphorescence. In the case of fluorescence, that is, chemienergized by energy transfer, an energy acceptor is chosen that exhibits efficient fluorescence, for example, polycyclic aromatic hydrocarbons and, particularly, 9,lO-disubstituted anthracene derivatives.68 Consequently, in the presence of such fluorescers (FI), the feeble direct chemiluminescence emission intensity is significantly enhanced. Such a phenomenon is commonly referred to as enhanced chemiluminescence (EC). We distinguish between enhanced chemiluminescence chemienergized by singletsinglet (SS) energy transfer and triplet-singlet (TS) energy transfer. The former permits us to determine singlet excitation yields (& the latter triplet excitation yields ( @ T ) . In the singlet-singlet energy-transfer process, the fluorescer of choice is 9,lO-diphenylanthracene (DPA) since it is readily available commercially, easily purified, and has a high quantum yield of f l u o r e ~ c e n c e . ~ ~ By means of steady-state kinetics, the relationship in Eq. 37 for the DPAenhanced chemiluminescence quantum yield is derived in terms of the singlet excitation yield (@'), the efficiency of singlet-singlet energy transfer (@;%), and the DPA fluorescence quantum yield The 4' parameter can be readily assessed once the remaining terms are known. s ss fl (37)

(@flDpA).

=

@

GETGDPA

The DPA fluorescence quantum yield is essentially unity and relatively insensitive to temperature and solvent.58e However, if the DPA-enhanced chemiluminescence is run under drastically different conditions, it would be essential to determine the DPA fluorescence yield under such conditions. T h i s can be readily achieved by measuring the relative quantum yields under the two sets of conditionsHb and making the necessary corrections. The energy-transfer term @%is unity under conditions of infinite DPA concentration. What is typically done is that one measures the DPA-enhanced chemiluminescence intensity as a function of DPA concentrations and constructs a plot of 1/Z;GA vs. I/[DPA]. The intercept of such a double reciprocal plot represents the DPA-enhanced chemiluminescence intensity at infinite DPA concenThe DPA-enhanced chemiluminescence quantum yield tration, that is, Zf&A1,. represents complete that is calculated from this emission intensity, that is, $; is unity. singlet-singlet energy transfer, that is, @

@fgPA]_,

Chemiluminescence

397

is quite analogous to that disThe experimental procedure to determine cussed for GDC. The experimental definition is given by Eq. 38, in which all the terms have been already defined. Again the dioxetane decomposition rate constant k , is determined by following the first-order kinetics of the DPA-enhanced chemiluminescence decay. The initial or total DPA fluorescence intensity is standardized with a suitable light standard, usually with lumino16’ or the “scintillation cockThe photomultiplier tube should be corrected for wavelength response.64b

To avoid reabsorption problems and thus low-emission intensities, the fluorescer M. Typically the fluorescer concentration concentration should not exceed Mfor the double reciprocal plot. Should it be range is taken between lo-’ to necessary to work at much higher fluorescer concentration, correction for reabsorption is essential. This is readily done by measuring the fluorescer emission intensity as a function,of ~ a t h l e n g t h . ~From ’ a plot of fluorescer emission intensity vs. pathlength one extrapolates I:? at zero pathlength and applies the necessary correction. Another potential complication with fluorescer-enhanced chemiluminescence concerns electronexchange chemiluminescence.” which will be the subject of the next section. While this is usually of little importance for simple 1,2-dioxetanes, it can be the dominant mechanism for the a-peroxylactones. Furthermore, for readily oxidized fluorescers such as rubrene (Ru), electron exchange is considerably more likely than for DPA. It is therefore essential, especially for new dioxetanes, to test for electron-exchange chemiluminescence. A simple and convenient diagnosis is to measure under identical conditions the relative enhanced chemiluminescence intensities of DPA vs. rubrene, chemienergized by the dioxetane in q ~ e s t i o n . ~ ’ Since the fluorescence quantum yields of DPA and rubrene are both essentially unity, the enhanced intensities should be approximately equal. If rubrene gives rise to a much larger enhanced intensity (usually at least by magnitudes), then the electron-exchange mechanism probably operates. Under such circumstances the singlet excitation yield derived from fluorescer-enhanced chemiluminescence will be erroneous and a different counting technique must be sought. Finally, although DPA is a most favored fluorescer for enhanced chemiluminescence, one of its inherent disadvantages is its high singlet state energy, Es = 70.1 k ~ a l / m o l e . ~As ’ should be evident from Figure 4, chemienergized carbonyl products with singlet state energies lower than 70 kcal/mole will go undetected by DPA. While this is no problem for simple aliphatic carbonyl products, since their singlet state energies are normally in considerable excess of 70 kcal/mole, already for aromatic carbonyl products such as fluorenone (E, = 63.2 kcal/mole) DPA is ineffective. In such cases rhbrene could be used, for which E, = 55 k ~ a l / m o l e . ~ ’ For excited states with Es values below SOkcal/mole, it would be difficult to employ the enhanced chemiluminescence technique to determine the singlet excitation yields. In view of the fact that triplet excited states do not generally phosphoresce, neither the direct chemiluminescence nor the enhanced chemiluminescence (via triplet-triplet energy transfer) techniques are of much help in counting chemi-

398

1,2-Dioxetanes and a-Peroxylactones

energized triplets. In fact, usually it is quite difficult to determine triplet excitation yields by photophysical methods. Fortunately, molecules with heavy atoms such as the 9,lO-dibromoanthracene (DBA)73 or the europium tris(thenoy1trifluoroacetonate)-1 ,10-phenanthroline'8b are capable of accepting the excitation energy of a chemienergized triplet carbonyl product i T K * ) and release it in the form of fluorescence. The mechanism of this overall triplet-singlet energy transfer appears to be first spin-allowed triplet-triplet energy transfer from the first excited triplet state of the ketone to the T , state of the fluorescer. Subsequently the second excited triplet state of the fluorescer undergoes spin-forbidden internal conversion to the first excited singlet state of the fluorescer, which is promoted via spin-orbital coupling by the heavy atom sub~ t i t u e n t Although .~~ the mechanistic details of this energy transfer appear to be complex, for our purposes we will consider it as an overall triplet-singlet energy transfer, leading to the observed fluorescence. The fluorescer of choice for counting chemienergized triplet states via tripletsinglet energy-transfer chemiluminescence has been 9,lO-dibromoanthracene (DBA). Like DPA, it is readily available and easily purified; unlike DPA it has a relatively low fluorescence quantum yield, that is, @flDBA is about 0.10 and is temperature- and s o l ~ e n t - d e p e n d e n t .For ~ ~ reliable triplet yields, the fluorescence quantum yields of DBA should be measured under the conditions at which the chemienergized carbonyl product TK* is generated. Steady-state kinetics affords the expression given in Eq. 39 for the DBA-enhanced which desigchemiluminescence quantum yield (@$A). The critical term is 4; nates the efficiency of triplet-singlet energy transfer from TK* affording 'DBA", which is defined in Eq. 40, where k;; and k;; are, respectively, triplet-singlet and triplet-triplet energy transfer steps. In the latter case, DBA molecules in their first triplet excited state are energized and do not luminesce. &$A

=

4

@TS = k T S ET ET

T TS fl GETGDBA

/ {k;?

$-

k'E? 1

(39) (40)

As in the case of DPA-enhanced chemiluminescence, to ensure that all chemienergized carbonyl triplets TK* are intercepted by DBA via triplet-singlet and triplet-singlet energy transfer, the DBA-enhanced chemiluminescence intensity is determined at infinite DBA concentration. Thus, the initial or total Z ~ $ A values are measured as a function of DBA concentration and the $FBAI_ quantity extrapolated as the intercept of a double reciprocal plot of l / Z g B A vs. l/[DBA]. Under these conditions of 100% energy transfer, the energy transfer parameter @ A :; takes values between 0.20 to 0.30. These values have been determined by a variety of techniques, including triplet-singlet energy transfer by chemienergized triplet state cyclohexanone (from autoxidation) to DBA,73 by photoenergized triplet state acetophenone to DBA,'g,76 and by chemienergized triplet acetone However, a recent investigation has shown77 (from tetramethyl-1,2-dio~etane).~~ ; for DBA (Eq. 40) is depenthat the triplet-singlet energy transfer parameter; @ dent on the solvent and the excited ketone donor. If these findings are general, the value of the DBA photoluminescence method is severely limited.

Chemiluminescence

399

-

In practical terms, the enhanced chemiluminescence intensity of DBA (I:$,) fl is only about 1/40 that of DPA (IE",,,) because one has: ;4 4 x @$; and @DPA 10 x However, it must again be emphasized and cautioned that Eq. 39 is < 10, because this expression for the DBA-enhanced chemionly valid when luminescence quantum yield was derived neglecting the formation of TK* by intersystem-crossing from chemienergized sK*. When @=/GS < 10, it is essential to assess the relative contribution to the DBA-enhanced chemiluminescence intensity from triplet-singlet energy transfer via chemienergized TK* vs. singletsinglet energy transfer via chemienergized ' K * . This can be attempted by measuring in the presence and absence of triplet quenchers, for example, piperylene. 1 the interpolated values (from a double reciprocal However, for GT/@' plot) for the piperylene quenched and unquenched DBA-enhanced chemiluminescence are indistinguishable within the experimental error. Under such circumstances the determination of triplet yields by the DBA-enhanced chemiluminescence technique is problematic.

-

@flDBA.

ZEBA],

-

@fZBA],

= z~~BA],/kDIDIO

(41)

The experimental procedure to measure the DBA chemiluminescence yield follows that outlined for DPA, using Eq. 41. Again, the DBA-enhanced chemiluminescence intensity must be standardized against a reliable light standard and calibrated for wavelength response. Precautions must be taken against reabsorption problems at high fluorescer concentrations. Contributions from electronexchange chemiluminescence are usually not important in view of the relatively large oxidation potential of DBA. As already stated, the DBA fluorescence quantum yield is low and temperature- and ~olvent-dependent,~~ and corrections should be applied for changes in reaction conditions. Even with all these shortcomings, DBA-enhanced chemiluminescence is to date still the most used technique for counting chemienergized triplets derived from 1,2-dioxetanes. (@fjBA,,)

b.

PHOTOCHEMICAL METHODS

Mechanistic photochemistry has been sufficiently intensively developeds6 over the last two decades so that a large body of valuable photochemical data has been accumulated for the chemical t i t r a t i ~ nof~ ~chemienergized singlet and triplet excited carbonyl products. For convenience we distinguish between intramolecular and intermolecular chemienergized photochemical transformations. In the intramolecular chemienergization, the electronically excited carbonyl product K* directly undergoes a given photochemical change. In contrast, in the intermolecular case, the chemienergized product K* first transfers its excitation energy to a suitable photochemically active acceptor. The electronically excited acceptor subsequently undergoes a given photochemical transformation. i. INTRAMOLECULAR TRANSFORMATIONS. The basic relationship, derivable by steady-state kinetics, which allows us to determine the excitation yield, is given by Eq. 42. GCHEM represents the chemienergized photochemical quantum yield, @PHOTO is the photoenergized photochemical quantum yield, and @ * the excitation yield of the 1,2-dioxetane. The latter may represent the singlet

400

1,2-Dioxetanes and a-Peroxylactones &HEM

(42)

= @*@PHOTO

(4)or triplet (@) excitation yields, depending on whether the singlet ('K*) or triplet (TK*) excited carbonyl products are photochemically active. This must be assessed previously via the usual photomechanistic techniquess6 by photoenergizing the carbonyl product KO.If both the singlet and triplet excited carbonyl product are photochemically active, then @* represents the total excitation yield (@T'S). If @PHOTO is not known under the conditions of the chemienergization, then it will be necessary to measure it. Again, the usual photomechanistic methodss6 are used for that purpose. Frequently, it suffices to measure a relative @PHOTO value between the established and new conditions and to apply the necessary correction. The chemienergized quantum yield @CHEM is experimentally defined in Eq. 43 as the concentration of photochemical product P formed per concentration of dioxetane D decomposed in a given time interval. Thus, to determine @ C H ~ Ma, known amount of dioxetane is thermally decomposed until complete consumption under the same conditions as @PHOTO and the same amount of photochemical product P determined by the usual spectroscopic and/or chromatographic methods. With and GPHOTO available, the excitation yield @ * is readily calculated. The intramolecular chemical titration is conceptually and experimentally simple and convenient, but it requires that a particular dioxetane must be made that chemienergizes the photochemically active carbonyl product K " . This is usually a formidable and challenging synthetic problem. Representative intramolecularly chemienergized photochemical transformations include Norrish Type I cleavage78 (Eq. 44), Norrish Type I1 (Eq. 45a, b, c) cleavages,s9279cyclohexadienone rearrangement8' (Eq. 46), and cyclopentenyl ketone rearrangement" (Eq. 47).

(44) I

I

0 Ph-CH,-C-

II

*CH2- Ph

Chemilurninescence

401

CH3 CH3 CH, -CH,-CH,-CH,

~~CH2-CH2-CH,-CH3

-

0-0 1-MeCOBu]

A

1

r

OH

CH3-CH2-CH2-CH2+f

Ph 0-0

N-Bu'

A

L

-

(45b)

$: Ph-CC-CH, + CH,=CH-CH3

402

1,2-Dioxetanes and a-Peroxylactones

0-0

["*I

~

4 --+\ 0 0

(47)

ii. INTERMOLECULAR TRANSFORMATIONS. The more widely employed chemical titration technique for chemienergized products is via intermolecular photochemical transformations. The expression in Eq. 48 can be derived from steady-state kinetics. As in the intramolecular case, $* may represent the singlet ($') or triplet ( @ T ) excitation yields if the acceptor A undergoes photochemical transformation from its singlet state 'A* or triplet state TA*.This must be assessed previously from photomechanistic work. If both the 'A* and TA* give rise to the same photoproduct P, then @ * represents again the total excitation yield (GT"). Furthermore, the photoenergized quantum yield ($PHOTO) must be known for the photochemical transformation under the conditions of the chemienergization. @CHEM =

@*GET @PHOTO

(48)

To assure complete energy transfer, that is, interception of all the chemienergized excited carbonyl product K * by the acceptor A , the GCHEM term is determined at the infinite acceptor concentration. Experimentally what is done is to determine the chemical yield of chemienergized photoproduct P at constant dioxetane concentration, but varying acceptor concentration. From a double reciprocal plot of the chemical yield vs. acceptor concentration, one interpolates the yield of photoproduct at infinite acceptor concentration as the intercept. Under these conditions $ET is unity since all K* molecules have been intercepted by A. From $&EM and $PHOTO the excitation yield $* is calculated, provided the chemi- and photoenergized transformations of the acceptor have been run under similar experimental conditions. Compared to the intramolecular process, the intermolecular process is considerably more convenient and valuable because any dioxetane can serve as the chemienergization source and not that a specific dioxetane has to be tailor-made to release a particular photochemical transformation. Of course, an obvious requirement is that the chemienergized carbonyl product K * possesses a high enough excitation energy so that energy transfer to the photochemically active acceptor

403

Chemiluminescence Me

Me

(50) 0-0 A

Me

*

Me

7' Me

+

Ph

(51)

Me Ph

A is exothermic. An additional advantage is that one has a wider margin to select spin-state specific photochemical transformations. Representative examples include ~ ~ ~50), oxetane cis-trans-olefin i s ~ m e r i z a t i o n(Eq. ~ ~ 49), olefin d i m e r i ~ a t i o n(Eq. formation" (Eq. 5 l), dienone r e a ~ a n g e m e n t ~(Eq. ~ " 52), di-r-methane rearrangement83 (Eq. 53), azoalkane denitrogenationW (Eq. 54a, b), and photocyclizationB5 (Eq. 55).

&

Me

0-0

A

*

404

1,2-Dioxetanes and a-Peroxylactones Me Me

c.

EMPIRICAL TRENDS

In Table 4 we compiled the excitation parameters @ T + S and for a large number of 1,2-dioxetanesand their derivatives, as well as the activation parameters. The counting methods discussed in the previous sections have been employed either directly or in modified form in these determinations. For this reason we dispense with the details. While in general it is still harder to draw definitive conclusions concerning the dependence between these excitation parameters and structural variations than for the activation parameters, some interesting empirical trends emerge that are worth bringing out.

R R R--+tR

R' R' R++R

R Q - R

R R-H-R'

R'

0-0

0-0

0-0

0-0

21a

21b

21c

21d

R$Tx X = 0 , N-R

0-0 ~-

0-0

21e

21f

For symmetrically substituted dioxetanes (21a, b) or cyclic doxetanes (21c) only one electronically excited product fragment is possible; there is no question about the identity of the excited state that is chemienergized. However, in unsymmetrically substituted dioxetanes (21d) and (21e) or spirocyclic systems (21f), two different electronically excited product fragments are possible and the identification of the excited states can be a major problem. This is particularly true when the two possible product fragments are very similar, for example, trimethyl-n-butyl-l,2dioxetane (Eq. 56), which may generate chemienergized acetone and/or 2-pentanone. In their photophysical properties these two ketones are indistinguishable via direct or energy-transfer chemiluminescence techniques. Application of such methods necessarily affords the excitation yields of both excited products. However, in the

Chemiluminescence

405

particular case of trimethyl-n-butyl-l,2-dioxetane, the chemienergized acetone and 2-pentanone can be distinguished photochemically since electronically excited 2pentanone can undergo Norrish Type I1 fragmentation (as illustrated in Eq. 56) while acetone cannot. O* CH3 CH3

CH,-c

I

I

-c -CH2-CH,-CH,-CH3 I I

0-0

/c,

J

,"ICH,

H3C

CH3

/CH2 CH, (56)

+ CH,=CH-CH3

When the two possible chemienergized products are sufficiently distinct in structure, for example, acetone and glyoxal derived from 3-acetyl-4,4-dimethyl-l,2dioxetane (19), as illustrated in Eq. 57, the characterization of the excited product and the quantification of the individual excitation yield are feasible.51 For example, rubrene-enhanced chemiluminescence allowed determination of the singlet-excited glyoxal yield, and DBA-enhanced chemiluminescence allowed the triplet-excited acetone yield, while glyoxal direct phosphorescence gave the triplet-excited glyoxal yield. Normally such detailed information about excitation yields for unsymmetrical dioxetanes is scarce. Whenever it can be done, it is strongly recommended, because only from such unsymmetrical dioxetanes do we stand to learn about the mechanism of energy partitioning among the possible product fragments. Such excitation yield data are presently badly lacking. A few specific molecular properties of the excited carbonyl fragment and their influence on the excitation parameters will now be considered.

0-0 0 I I II CH,-C-C-C-CH,

I

I

A

O*

/C\'I H,C CH,

0

+

o*

II I I

H-C-C-CH,

(57)

i. NATURE OF THE EXCITED STATE. For dioxetanes that chemienergize n , x * excited states of carbonyl products, typical examples are given in Eq. 58; the triplet yields are high (@T> lo%), the singlet yields low (@'<1%). Consequently, the total excitation yields @ T c s are > 10% and the spin-state selectivities are in the hundreds (@T/@s> 100). These dioxetanes are efficient sources for triplet excitation, but ineffective for singlet excitation. Furthermore, it has been noted7' that for such dioxetanes, the triplet excitation yield is linearly proportional

1,2-Dioxetanes and a-Peroxylactones

406

Me H M

e

q

H

P

h

w

0-0

0-0

13 240 78

14 14578

Me Me H

M e H M e

0-0

(58) Me Q

M

I H P H

e

0-0

0-0

23 2.50’’

20 (2000)86

to the activation energy (Eq. 59). Thus, the higher the activation energy for decomposing the dioxetane, the larger the triplet excitation yield.

”/.GT

=

7.24 E,

-

156

(59)

On the other hand, in the case of dioxetanes that chemienergize T , T * or chargetransfer excited states of carbonyl products, typical examples are given (Eq. 60); the singlet excitation yields are very high (@>10%) compared to the n,r* chemienergizers. Although the triplet yields are generally not reported for these systems (triplet yields are difficult to measure when the singlet yields are high), it is clear from the large 4’ values that the $T values must be quite low and thus, the tripletsinglet ratios are also low (q5T/@S < 1). This has been confirmed for dioxetane (22), for which such excitation data are available (Eq. 61).

407

Chemiluminescence

O*

+ I

Me I

Q I

Ph

O*

Ph

hv

The interesting feature about these dioxetanes is that they possess easily oxidized groups, for example, 3 - i n d o l ~ 1 ,p-dimethylanilinyl,48 ~~ and acridinyls7 groups. Consequently, it has been proposed that these types of dioxetanes chemienergize n-n* singlet excited states b y the intramolecular electron exchange mechanism." This topic will be discussed in detail in Section V.2. However, for dioxetanes ( 2 0 ) that are structurally similar t o ( 2 2 ) , as shown in Eq. 46, but d o not bear easily oxidized groups, that is, R = methyl, phenyl, 0naphthyl, and so o n , the n,n* triplet state of the cyclohexadienone is efficiently (GT > 14-20%) chemienergized.80 Particularly revealing is the case in which the R,C=O fragment in dioxetane (20) is the methyl P-naphthyl ketone. This ketone has a n,n*triplet state significantly lower in energy (about 10 kcal) than the n,n* triplet state of the cyclohexadienone; yet, only the latter is chemienergized." Therefore, o n t h e basis of this limited data, one is tempted t o conclude that n,n* triplet states are preferentially chemienergized. However, when oxidizable groups are present, then n,n* singlet states are preferentially chemienergized. ii. EXCITED-STATE ENERGY. Provided the dioxetane is energy-sufficient t o chemienergize a particular carbonyl product, empirically n o correlation between excited state energy of the product and excitation yield can be discerned. For example, in the case of the n,n* chemienergizing dioxetanes listed in Eq. 62, the triplet excited-state energies vary at least by about 20 kcal, yet the total excitation yields ($T's), which are essentially complete triplet excitation, are approximately t h e same within the experimental error. The effect appears t o be t o o small and is buried in the experimental errors. In addition, it should be kept in mind, as is discussed in Section IV.l .C.c.i., that n,n* triplet states are preferred over n,n* triplet states, even if the latter are of lower excitation energy, for example, dioxetane ( 2 0 ) (Eq. 46).80This trend does not apply to the n,n*singlet state chemienergizers, for example, dioxetanes ( 2 2 ) (Eq. 60),87since they operate via intramolecular electron exchange involving t h e oxidizable group and the dioxetane ring.

1,2-Dioxetanes and a-Peroxylactones

408

H H I I

Me Me I I Ph-C-C-Ph I I 0-0

Me Me

I I Me-C-C-Me I 1 0-0

Ph-C-C-Ph I I 0-0

% @T+S

H H I I EtO-C -C -0Et

MeO-C -C -0Me

0-0

0-0

I

Me0 OMe

I I

I

I I

In the case of unsymmetrical dioxetanes (21d), which can chemienergize two different carbonyl products, an attempt has been made to correlate the energy partitioning between the two possible fragments.82 From the excitation yields of the n,n* chemienergizing dioxetanes that were used, it was concluded that the available energy is Boltzmann-distributed between the two fragments. In other words, the n,n* triplet state of lower energy is chemienergized preferentially. An obvious (19).'l A difference of about exception is the 3-acetyl-4,4-dimethyl-l,2-dioxetane 25 kcal in n,n* triplet excitation energies between methylglyoxal and acetone should have had as consequence exclusive chemienergization of n,n* triplet methylglyoxal if Boltzmann statistics were to apply. However, the n,n* triplet yields of acetone and methylglyoxal are 0.5 and 15%, respectively. iii. SUBSTITUTION PATTERNS. It appears that symmetrically substituted dioxetanes are more efficient (@T+S> 10%) in generating excited states than unsymmetrically substituted ones (@T+S< 1%). Representative examples are given in Eq. 63. Although obvious exceptions are evident in Table 4, the effect of substitution patterns, that is, symmetrical vs. unsymmetrical, is dramatic. The reasons for this are as yet not understood, but might be connected with the problem of energy partitioning since two different carbonyl fragments can be excited in unsymmetrical dioxetanes.

Me Me % dT+S

25

Me Me

llie hie

0S6'

30"

0-0

0-0

P h - wPh Ph H

P h - W P h OMe OMe

0.582

1393

0-0 tB

u

w OPh

H OPh 0.19~

Chemiluminescence

409

iv. HETEROATOM SUBSTITUTION. An impressive series is made up of tetramethyl-l,2-dioxetane,dimethyl a-peroxylactone and 3-N-t-butylimino-4,4dimethyl-l,2-dioxetane (Eq. 64), all of which produce excited acetone. However, the total efficiency of excited state production (@T'S) drops from 30% to 0.001%, that is, over four powers-of-ten. Such heteroatom substitution is clearly very effective in extinguishing the ability of dioxetanes to generate excited states. On comparison of the singlet (@') and triplet ( d T ) excitation yields of the tetramethyldioxetane with the a-peroxylactone (Eq. 64), we note that the about 20fold reduction is exclusively in the triplet yields since the singlet excitation yields are the same within the experimental error. Me Me M e w Me

0-0

MeV('

M e V (

0-0

0-0

76 @T+S

31 770

% @S

0.04

1.6 30 0.05

31 5'7C,83

1.557d,61a.83

@TI@s

70 GT

N-tBu

0.003 700 5.2 x 3.4 1 0 - ~94

It is tempting to search for an explanation in the energetics (Figure 3) of these two hyperenergetic molecules. However, even a casual inspection of Figure 3 reveals that the contrary should be expected. For example, the decomposition of aperoxylactone is about 22 kcal/mole more exothermic than the tetramethyldioxetane and both have more than sufficient energy to chemienergize singlet or tripletexcited acetone. This differentiation in exothermicities becomes still more pronounced if the respective diradical intermediates or even the respective activated complexes are considered. In short, the more energetic a-peroxylactone is the less efficient system to chemienergize excited acetone and the discrimination is in favor of the lower energy triplet-excited acetone. Consequently, the energetics of these decomposition reactions (Figure 3) do not account for the chemienergization efficiency (@T'S), nor spin-state selectivity (@T/@s) of these molecules. v. HEAVY ATOM SUBSTITUTION. The series of bromine-substituted 1,2dioxetanes, shown in Eq. 65, were studied96 to assess whether such a heavy atom influences the excitation parameters through its spin-orbit coupling property .97 Clearly, the effect is dramatic on both the total efficiency (@") and the spinstate selectivity (@T's). Before a heavy atom effect is claimed, it would be prudent to investigate the respective chloro- and fluoro-substituted 1,2-dioxetanes.

Me Me M e w , M e

0-0

Me Me M e w C H , B r

0-0

Me Me BrH,CwCH,Br

0-0 0.01

196

(65 1

410

1,2-Dioxetanes and a-Peroxylactones

D. a.

Mechanism

DIRADICAL AND CONCERTED RETROCYCLIZATIONS

Two mechanisms have been argued over the years concerning the thermal decomposition of 1,2-dioxetanes leading to electronically excited (n,n*)carbonyl products. These are the diradical mechanism (Eq. 66) suggested by Richardsons3 and the concerted mechanism (Eq. 67) suggested by T ~ r r o . 'In ~ ~the diradical mechanism, the dissociation of the dioxetane ring proceeds stepwise by first stretching the 0-0 bond (step k, in Eq. 66), leading to the singlet-state diradical ('OR).

This singlet diradical has three options: (a) recyclize via step k-, to the dioxetane, (b) disengage C-C bond via step ks into ground-state carbonyl product and singlet excited ('n,n*) carbonyl product, or (c) intersystem-cross via step ki, to the tripletstate diradical (TOR).The latter can either reverse intersystem-cross via step k - i , or fragment via kT state carbonyl product and triplet excited (Tn ,n*)carbonyl prod~ * Tn,?l* carbonyl products by the usual uct. Finally, deexcitation of the s ~ , and photo physical and photochemical ways, for example, fluorescence via step kfl and phosphorescence via step kph, respectively, affords ground-state carbonyl product. To account for the high spin-state selectivity for triplet product (qhT/qhs > 100) that is observed experimentally (Table 4), all one would need to impose is the condition that kT > k-isc > k s , which is not unreasonable.

Cherniluminescence

41 1

In contrast, for the concerted retrocyclic path (Eq. 67), the 0-0 and C-C bonds are disengaged simultaneously. Vibrational deformation leading to a puckered four-membered ring transition state aligns the orbitals (hatched) optimally to create an n,n* excited state of the carbonyl product. It is arguedssb that during this puckering electron density is displaced in such a way as to promote spin-orbit coupling at the oxygen atom and thereby generate preferentially T n , ~ *carbonyl product. Both mechanisms have in common a spin-multiplicity change; however, the fundamental difference between them is that in the diradical mechanism (Eq. 66), the intersystem-crossing step is reversible, while in the concerted mechanism (Eq. 67) it is irreversible. Thus, the classical mechanistic dilemma of distinguishing between normal spin-conserved diradical and concerted reactions, particularly [ 2 + 2 ] - c y ~ l o a d d i t i o nis , ~still ~ further complicated by the fact that in the dioxetane retrocyclization distinct spin-multiplicity changes are involved. The theoretical and experimental work o n this challenging problem will be briefly discussed. b.

THEORETICAL WORK

The earliest theoretical thoughts on the chemiluminescent decomposition of 1,2dioxetanes were based on orbital symmetry arguments.13bIt was predicted that the suprafacial [2+2]-retrocyclization must lead to electronically excited carbonyl product. However, such a retrocyclic process should chemienergize the r,n* state that is inaccessible on grounds of energy balance (see Section V.1.A.). A more thorough orbital and state symmetry analysis of the concerted decomposition revealed'"" that an n,n* excited carbonyl product should be formed. More important, this intuitive study predicted well before it was confirmed e ~ p e r i r n e n t a l l y ~ ~ that a triplet excited n p* product should be formed preferentially. Specifically, it was noticed that the energy surface for the less energetic T n , ~ *carbonyl product ) fragment along the out-of-plane bendintersects the singlet excited ( n , ~ *carbonyl ing vibrational mode. Numerous semiempirical calculations have been carried out on the dioxetane decomposition, including CND0/2 calculations with and without configuration with configuration i n t e r a ~ t i o n . 'These ~ ~ differ in i n t e r a ~ t i o n ~and ~ ~MINDO/3 '~~ their opinions of whether first 0-0 bond homolysis occurs leading to a diradical intermediate, followed by fast C-C bond cleavage. However, on the basis of qualitative considerations it was argued'" that a crossover of the diradical path to the triplet excited product path, prior to reaching a bona fide stable diradical

1,2-Dioxetanes and a-Peroxylactones

412

intermediate, is feasible. This attractive alternative represents a merger between the two extreme mechanistic views, that is, the diradical (Eq. 66) and the concerted (Eq. 67) decomposition routes. The most ambitious theoretical investigation of this problem has employed the It was concluded that a lP-diradical is an internonempirical GVB mediate, resulting from 0-0 bond cleavage but leaving the C-C bond intact. The eight possible singlet and triplet-state electronic configurations of the diradical lie all within a narrow band of 3 kcal/mole and correlate with singlet and tripletexcited carbonyl product and ground-state carbonyl product. What specific spin state of a particular excited state is chemienergized depends on its energy relative to the 1,4-diradical intermediate. For example, for the unsubstituted 1,2-dioxetane the energy of the surface crossing point of the (Tn,n*)state of formaldehyde lies about 8 kcallmole lower than its (‘n,n*) state relative to the lP-diradical. Consequently, triplet-excited formaldehyde is preferentially chemienergized, as observed e ~ p e r i m e n t a l l y . ’The ~ ~ quantitative results on diradical stability obtained from the ab initio GVB calculations match well those derived from thermochemical estim a t i o n ~ ’ ~ ,(see ’ ~ ~Figure 3 ) . c.

EXPERIMENTAL RESULTS

Most of the experimental evidence also points to the diradical mechanism as the preferred decomposition mode. Thus, the very earliest experimental evidence in support of the diradical mechanism53i57arests on the fact that alkyl and phenyl substitution does not significantly alter the activation parameters for dioxetane decompositon.Io6 It was argued that if C-C bond cleavage occurs simultaneously with 0-0 bond cleavage, the incipient carbonyl group in the activated complex (23) should be stabilized in the relative order phenyl > alkyl >hydrogen. Thus, the activation energies should obey the relative order E,(Ph) < EJR) < E,(H), that is, lowest for phenyl-substituted dioxetanes. Since this expectation was not borne out by the experimental data,lo6 the diradical (24) was proposed as an intermediate.

r

0

I!

R- C I R

l #

0. 01

1

R-C -C -R I I R R

As additional support for the diradical mechanism, it was shown that the 3,4diethoxy-l,2-dioxetane (8) and the p-dioxene-l,2-dioxetane had identical activation energies,86 implying that the C-C bond is not significantly stretched in the activated complex. That these notions on substituent effects in dioxetane decomposition are grossly oversimplified has come clearly into focus in recent years (Table 4). The fact that little yet is understood about the correspondence between activation parameters and dioxetane structure has already been amply expounded in Section V.1.B. Nevertheless, a few additional comments seem appropriate on this subject in

Chemiluminescence

413

regard to the diradical mechanism. For example, how can the variation in activation energies of the bicyclic dioxetanes (Entries 12,17,and 27 in Table 4)'07 be explained in terms of a simple diradical mechanism? Whatever mechanistic explanation is advanced, it must incorporate involvement of the dioxetane C-C bond cleavage in the rate-determining step. A similar argument was already voiced6* for monocyclic dioxetanes (Entries 9, 16, and 21 in Table 4). But the most impressive failure of the diradical theory is the unusual stability of tetraethyldioxetane (Entry 25 in Table 4). Thermochemical calculations assuming a diradical intermediate afford an activation energy that is much lower (about 7 kcal/mole) than the experimental value.g0b Moreover, a pressure dependence (1-1000 atm) study of the energytransfer chemiluminescence of DBA, chemienergized by tetramethyl-l,2-dioxetane, gave activation volumes that are more readily reconciled with a concerted rather than diradical mechanism.108 Consequently, while the diradical mechanism succeeds quite well for the simple dioxetanes, it fails badly for the more complex dioxetanes. A dramatic solvent effect58 in the thermolysis of tetramethyldioxetane, which followed the isokinetic relationship A H = BAS for a variety of solvents, formed the basis for the postulation of the concerted mechanism. However, it was shortly thereafter r e p ~ r t e d ' ' ~that the dramatic solvent effect in methanol was the result of catalysis by transition-metal ion impurities. In the presence of metal-ion complexing agents such as EDTA or Chelex 100, the menacing catalysis could be suppressed. That utmost care must be taken in measuring reliable kinetic parameters in 1,2dioxetane decomposition cannot be overemphasized. Probably the strongest support in favor of the diradical mechanism is the lack of a deuterium isotope effect in the thermal decomposition of trans-3,4-diphenyl-l,2d i ~ x e t a n e . ~In' the concerted mechanism, the ring carbon of the dioxetane changes its hybridization state from s p 3 to sp2 jn the activated complex (23) and an inverse ) be expected."' Consequently, a diradical secondary isotope effect ( k H / k D would mechanism was argued to accommodate these results. Similarly, in the thermal decarboxylation of the dimethyl a-peroxylactone, a negligible ( k w / k D= 1.06 0.04) secondary isotope effect was Presumably, in the a-peroxylactone decomposition, a diradical mechanism similar to that of dioxetanes (Eq. 66) upholds. Trapping experiments would constitute the most unequivocal proof for the intervention of diradical intermediates in the decomposition of 1,2-dioxetanes. Although such experiments have not been reported to date, the interesting observation that tri-t-butylphenol extinguished the trimethyldioxetane chemiluminescence more efficiently than piperylene, was construed as evidence that the phenol scavenged a relatively long-lived precursor, presumably a diradical to the electronically excited product."' Direct spectroscopic observation of the postulated diradical intermediates has not been possible so far. Thus, multiphoton infrared laser excitation of tetramethyldioxetane in the gas phase failed to detect diradical intermediates with lifetimes greater than about 5 nsec."' Picosecond spectroscopy limited the lifetime of a diradical intermediate, if formed, to less than about 10psec in the 264-nm pulsed photolysis of tetramethyldioxetane in acetonitrile, using a mode-locked neodymium

*

414

1,2-Dioxetanes and a-Peroxylactones

phosphate laser.'13 Thus, we must conclude that the mechanism of dioxetane decomposition is uncertain. It may very well turn out, as we have pointed out in an earlier review," that the merged mechanism of Turro and DevaquetlW is much closer to the truth than the two extreme views. In that case, the answers to the dependence of the activation and excitation parameters should be sought in the excited states rather than in the ground states because the former lie more closely to the surface-crossing points.

2. A.

Electron Exchange Intermolecular Systems

The fact that hyperenergetic molecules such as the 1,2-dioxetanes should be prone by catalytic decomposition is not surprising, Early examples include the protecting effect of molecular oxygen on the thermal decomposition of 3,4diethoxydioxetane,58e the efficient catalytic decomposition of this dioxetane by a m i n e ~ , " and ~ of alkyl-substituted dioxetanes by transition-metal ion imp~rities.'~' However, all of these catalytic decompositions are competing dark reactions that greatly diminish the chemiluminescence efficiency of the dioxetanes. An unusual observation was made by in connection with the energytransfer chemiluminescence of a-peroxylactones with aromatic fluorescers such as rubrene. Under similar conditions rubrene produced about a 50fold greater light intensity than DPA with dimethyl a-peroxylactone; however, the rate of the aperoxylactone decarboxylation was significantly greater for rubrene than for DPA. Rubrene was not consumed during the reaction and served, therefore, as a catalyst in the decomposition of the a-peroxylactone, by enhancing the efficiency of light emission of the system. In other words, the rubrene; a-peroxylactone reaction represented one of the few examples of a catalytic chemiluminescent reaction of dioxetanes. Another such reaction, known even much longer," was that of aryl oxalates with hydrogen peroxide and aromatic fluorescers.'lS As soon as the phenomenon of chemically induced electron-exchange chemiluminescence (CIEEL), exhibited by peroxides and easily oxidized fluorescers had been recognized," it was obvious that the peroxylactone-rubrene case belonged to this category of chemiluminescence reactions. The electron-exchange mechanism shown in Eq. 68 was proposed116 to account for the facts (a) that the easily oxidized fluorescers catalyze the decomposition of the a-peroxylactones and (b) that the rate of catalysis is proportional to the ease of oxidation of the fluorescer. During the slow step an electron is transferred from the fluorescer to the a-peroxylactone, producing a fluorescer-radical-cation-peroxide radical-anion pair. Decarboxylat ion affords a fluorescer-radical-cation-ketyl-radical-anionpair that can either diffuse to free ion radicals or back-exchange the electron to generate electronically excited fluorescer. The latter emits light. In other words, this process constitutes a chemical equivalent of the well-known phenomenon of electrochemiluminescence.1'7

415

Chemiluminescence

I

I

'yR+Fl*0

F].@

1

00

diffusion

dark reactions

F1+ hv R e ~ e n t l y , " ~the electron-transfer was extended in order t o incorporate the slow and reversible chemically induced electron-exchange reactions, as observed for the fluorescer-catalyzed chemiluminescent decomposition of aperoxylactones.'16 It was argued that electron transfer is complete in the transition state for such a slow and irreversible endergonic electron-transfer reaction, but that the typically small slopes (- a/RT where a is about 0.3) of the In (intensity) vs. oxidation potential plot was due to the fact that only a fraction (a) of the total free-energy change manifests itself in the activation While other "high-energy" peroxides exhibit such electron-exchange chemiit is noteworthy that no simple 1 ,a-dioxetaneshave been reported to display efficient intermolecular CIEEL. Apparently, the reduction potentials are too high for the electron-exchange process t o be energetically feasible. However, we have noticed recentlylZ3 that the epoxycyclobutadienedioxetane (Entry 26 in Table 4) exhibits the electron-exchange chemiluminescence with rubrene, perylene, and DPA. The fact that the chemiluminescence yield with rubrene was much larger than for DPA hinted that a CIEEL mechanism was involved, which was then confirmed by the characteristic linear In I vs. E,, plot. It is interesting to mention that the related cyclobutadienedioxetane (Entry 23 in Table 4) does not display intermolecular electron-exchange chemiluminescence.

B.

Intramolecular Systems

The behaviour of 1,2-dioxetanes with easily oxidized substituents, for example, N-methyldihydroacridinylidenyl (Entry 2 in Table 4),lZ9 i n d ~ l y l ,or ~ ~N,Nd i m e t h y l a m i n ~ p h e n y l(Entry ~~ 5 in Table 4), is quite distinct from the simple (Entry 19 in Table 4). First of derivatives, for example, tetramethyl-l,2-dioxetane

416

1,2-Dioxetanes and a-Peroxylactones

all, they are thermally among the least stable ( A H < 20 kcal/mole) and the singlet excitation yield (4') is comparatively high, so that the spin-state selectivities are typically low, that is, $JT/$JS<10. Among the first examples of this type are the dioxetanes (22) (Eq. 61).87 The intramolecular electron-exchange chemiluminescence mechanism (Eq. 69) was proposed"387b for these systems.

y-r

y y'.;. 0

x

*

00 ___)

I

/c\

0

II

0

c -x-

/

An unusual chemiluminescent catalysis has been observed by silica gel and Fo r example, hydroxylic solvents on the dianthryldioxenedioxetane (Eq. 70).32b148b silica gel increased the light intensity by as much as about 104-fold and the rate about 150-fold; while in 2,2,2-trifluoroethanol the light enhancement was about 190-fold (the singlet excitation yield about 10%) with a rate increase of about 240-fold. In fact, the catalytic rate constant correlated reasonably well with the p K A of the hydroxylic solvent in the form of a Bronsted plot. As shown in Eq. 70, the silica gel and alcohol catalyses are interpreted in terms of electron-exchange chemiluminescence in which the acidic silica gel and alcohol coordinate to the dioxetane site, thereby lowering its reduction potential and thus promoting electron transfer from the easily oxidized anthryl substituent to the dioxetane ring. Subsequent cleavage of the dioxetane ring and internal electron reorganization afford electronically excited singlet state products very efficiently.

Chemical Transformations C.

417

Bioluminescence

Prior t o the recognition of the CIEEL mechanism," the high yield of singlet excitation that was observed in bioluminescent systems, especially the firefly,13' was a great mystery. In fact, a key feature that escaped the mechanistic chemist for a long while was the fact that methylation of the phenol group of the firefly ~ luciferin (Eq. 8) almost completely extinguished the b i ~ l u m i n e s c e n c e . ' ~Presumably the phenolate moiety is essential for efficient light production. Consequently, as shown in Eq. 7 1, the mechanism of efficient bioluminescence requires intramolecular electron transfer from the electron-rich phenolate moiety to the a-peroxylactone ring.87b,116,'32After decarboxylation and electron back-transfer an electronically excited singlet state oxyluciferin is formed, which then emits the greenish-yellow bioluminescence. In this context, it is of interest to mention that a detailed theoretical analysis133 suggests that the fluorescence of the oxyluciferin enolate is derived from a low-lying n,n* singlet state with substantial charge transfer from the benzenethiazolyl group to the oxythiazoline chromophore. Subsequent charge annihilation leads to the observed emission.

00

V.

CHEMICAL TRANSFORMATIONS

Besides their thermal decompositions into carbonyl fragments, the chemistry of 1,2-dioxetanes is quite limited. Obviously one of the reasons for this is the great lability of the dioxetane ring system. However, a number of reactions with nucleophiles and electrophiles have been performed and will be briefly reviewed here.

1,2-Dioxetanes and a-Peroxylactones

418

1.

Reactions with Nucleophiles

One of the earliest chemical transformations of 1,2-dioxetanes was their reaction with phosphines (Eq. 72).22,'34 It was shown that the trivalent phosphorus first inserts into the peroxide bond to afford a relatively stable phosphorane. On warming the phosphorane eliminates phosphine oxide to yield the epoxide product. In this elimination, there is inversion of the stereochemistry at one of the carbon centers.'34c

Recently, this reaction was extended t o include triphenylarsine and triphenyla n t i m ~ n y . ' ~The ' fact that the relative reactivity was Ph3P 2 Ph3Sb > Ph3As confirms that the mechanism involves biphilic insertion into the peroxide bond rather than nucleophilic displacement, leading first to the pentacovalent intermediate. The reaction with trivalent phosphorus nucleophiles has been utilized for the characterization of four-membered ring peroxides. For example, the reaction of the iminodioxetane (Eq. 7 3 ) with triphenylphosphine gave the expected fragmentation products.% However, the reaction of a-peroxylactones with triphenylphosphine gave polyester and triphenylphosphine oxide (Eq. 74).'36 Presumably the a-lactone intermediate was formed, which is known to p ~ l y m e r i z e In . ~ an ~ effort to characterize the indoledioxetane (Eq. 75),'37 the reaction with methyl phosphite gave the indolinone (25).

0-0

,i

Ph'

A

[ -Ph, PO I

i

'Ph Ph

0

/c,II

CH3

CH3

(73)

+ t-BUN-C

419

Chemical Transformations

+Ph3P 0-0

@$b \

-

-

c H 3 p < o O\ /O P Ph/ I 'Ph Ph

[-Ph,PO]

Me O\P(OMe),

Me tBu

(MeO),P

N

I

Me

tBu

\

N

I

Me

tBu

-(MeO), PO ___)

\ N @ 0 I

CH 3

(25) (75)

Reaction with sulfur nucleophiles has also been investigated. For example, dioxene-dioxetane (Eq. 76) gave on reaction with diphenylsulfide, the dioxenel ~ ~the other hand, the reaction of dimethylepoxide and the acetal of b e n ~ i 1 . On 1,2-dioxetane with dimethyl sulfoxylate gave the sulfurane (Eq. 77).38

+

(76)

1,2-Dioxetanes and a-Peroxylactones

420

2.

Reactions with Electrophiles

The reaction of divalent metals, such as copper, nickel, and so on, with dioxetanes in methanol leads to clean catalytic decomposition into carbonyl fragment^.'^' The reaction rates increase with increasing Lewis acidity of the divalent metal and indicate, therefore, typical electrophilic cleavage of the dioxetane. On the other hand, univalent rhodium and iridium complexes catalyze the decomposition of dioxetanes into carbonyl fragments via oxidative a d d i t i ~ n . ' ~ ' Simple Lewis acids such as boron trifluoride or protons, which only have a single site for coordination, promote completely different chemi~try.'~'For example, the reaction of tetramethyldioxetane with BF3 gave acetone, pinacolone, and the 1,2,4,5-tetroxane (Eq. 78). Similar results have been obtained when this dioxetane is treated with aqueous sulfuric acid.14*

$I;

3_ BF

Me

0

'0-BF, ~

Me

Me

Me ~~

tBu

X0

Meyo + c: I Me

0

Me

Me

VI.

O 0

Me

BIOLOGICAL IMPLICATIONS

The fact that biological systems are capable of generating electronically excited states is amply demonstrated in the phenomenon of biolumine~cence.~ The light emission that is observed is a manifestation of the singlet excited states that are created in these enzymatic reactions. If biological organisms are capable of producing singlet excitation via labile a-peroxylactone intermediate^,'^ whose fluorescence is readily perceived, then the question must be raised if in the living cell triplet excitation can be generated through enzymatic oxygenation, which through their

Concluding Remarks

42 1

nonemissive nature go undetected and unleash dark photochemical transformations. In other words, it would indeed be surprising if dioxetanes were not implicated in such cell reactions, particularly in metabolic processes involving molecular oxygen. Moreover, all sorts of labile peroxide intermediates are produced in the enzymatic oxygenation of cell constituents, as amply d ~ c u m e n t e d . ’Cir~~ cumstantial evidence confirms that 1,2-dioxetanes play a central role in the enzymatic action of dioxygenases.’44 One of the most efficient enzymatic systems that generates triplet state acetone is the horse radish peroxidase(HRP)-catalyzed oxygenation of isobutyraldehyde (Eq. 79).14’ Related enzymatic processes include the autoxidation of linear carboxaldehydes,’46 m a l ~ n a l d e h y d e , ’ ~a-formylphenylacetic ~ acid,’48 indole-3-acetaldehyde,14’ indole-3-pyruvic acid,’” and ind0le-3-acetaldehyde.~’~Consequently, there is no question about the existence of enzymatically generated electronic excitation in the cell; however, what do these excited states do in the biological system?

CH,OH

CH,

Some of the interesting “dark” biological transformations brought about with enzymatically generated triplet-excited acetone include chlorpromazine o x i d a t i ~ n ~ ’ ~ phytochrome p h o t o t r a n s f ~ r m a t i o n ,thymidine ~~~ d i m e r i ~ a t i o n , ”DNA ~ damage,”’ and photoreactivation of pyrimidine dimers in DNA.’54 Clearly, some of these photobiological processes are benign and essential, while others are malignant. Particularly worrisome are those that lead to DNA damage through dimerization of pyrimidine bases, which might have as consequence mutagenesis and ultimately carcinogenesis akin to the damage of cells on irradiation with UV light. It seems, therefore, important to understand the physical, chemical, and biological behavior of four-membered ring peroxides such as the 1,2-dioxetanesand a-peroxylactones.

VII.

CONCLUDING REMARKS

High-energy molecules such as the 1,2-dioxetanes and a-peroxylactones are fascinating target molecules for the synthetic as well as mechanistic chemists alike. The best witness to this fact is the large number (several hundred) of publications that have appeared on these compounds since their discovery about fifteen years ago. Not counting those cases in which 1,2-dioxetanes and a-peroxylactones have been postulated as intermediates (these have not been included in this review) in the reaction of organic matter with molecular oxygen (singlet as well as triplet states), well over 100 derivatives have been prepared and characterized. Of these, approximately half have been the subject of mechanistic investigation, particularly the

422

1,2-Dioxetanes and a-Peroxylactones

determination of the activation and excitation parameters. Much has been learned during the last decade about these intriguing substances, but more remains yet to be understood concerning their most characteristic property, namely, their chemiluminescence. To assert that we can rationalize the dependence between structure, stability, and chemiluminescence on the basis of what we know to date experimentally and theoretically about four-membered ring peroxides is simply being unrealistic. We have tried precisely to emphasize what is not understood about these molecules in order to attract and engage the expert and novice alike in helping solve the many existing synthetic, analytic, and mechanistic problems. The most significant and challenging advances are expected to be made on the biological front.

(26)

(27)

Finally, we would like to sound out with one specific query that must have been on the minds of most readers. Do the related 1,3-dioxetanes ( 2 6 ) and 1,3dioxetanones (27) behave similarly as the 1,2-dioxetanes and a-peroxylactones respectively? It is embarassing to have to admit that essentially nothing is known about these novel structures. Besides a few unconvincing claims for “stable” 1,3dioxetanes in the recent patent literature, these so far elusive molecules have been postulated as transient intermediates in a few reaction^.'^^ Clearly, the 1,3dioxetanes should be challenging target molecules for investigation to both the synthetic and mechanistic chemists during this decade.

VIII.

ACKNOWLEDGEMENTS

Generous financial support of our work in this area of chemistry has been made available by the Donors of the Petroleum Research Fund, administered by the American Chemical Society, the National Institutes of Health, the National Science Foundation, the Deutsche Forschungsgemeinschaft, and the Fonds der Chemischen Industrie.

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N . J. Turro and H. Dcvaquet,J. Am. Chem. Soc., 97,3859 (1975). L. B. Harding and W. A. Goddard 111, J. Am. Chem. Soc., 99,4520 (1977). (a) W. 8 . Richardson, M. B. Yclvington, and H. E. O’Neal, J. Am. Chem. Soc., 94, 1619 (1972); (b) W. H. Richardson, J. H. Anderegg, M. E. Price, W. A. Tappcn, and H. E. O’Neal, J. Org. Chem., 43, 2236 (1978); (c) W. H. Richardson, J . H . Andercgg, M. E. Price, and R. Crawford, J. Org. Chem., 43,4045 (1978).

107.

K. R. Kopecky, P. A . Lockwood, R. R. Gomez, and J.-Y. Ding, Can. J. Chem., 59, 851 (1981). R. Schmidt, H . C . Stcinmetzcr, H.-D. Brauer, and H. Kelm, J. A m . Chem. SOC., 98, -8181 (1976). (a) T. Wilson, M. E. Landis, A . L. Baumstark, and P. D. Bartlett, J. A m . Chem. Soc., 95, 4765 (1973); (b) W. H. Richardson, F. C. Montgomery, P. Slusser, and M. B. Yelvington,J. A m . Chem. Soc., 97,2819 (1975). E. K. Thornton and E. R. Thornton, in Isotope Effects in Chemical Reactions, C. J. Collins and M. S. Bournan, Eds., Van Nostrand-Reinhold, New York, 1970, p. 213. (a) I. Simo and J. Stauff, Chem. Phys. Lett., 34, 326 (1975); (b) C. Neidl and I. Stauff, Z. Naturfursch., 33B, 1 6 3 (1978). (a) Y. Haas and G. Yahav, J. Am. Chem. Soc., 100, 4885 (1978); (b) Y. Haas and G. Yahav, Chem. Phys. Lett., 48, 63 (1977); (c) W. E. Farneth, G. Flynn, R. Slater, and N. I. Turro, J. A m . Chem. Soc., 98,7877 (1976). K. K. Smith, J.-Y. Koo, G. B. Schuster, and K. J . Kaufmann, Chem. Phys. Lett., 48, 267 (1977). D. C.-S. Lee and T. Wilson, in Cherniluminescence and Bioluminescence, M. J . Cormicr, D. M. Hercules, and I. Lee, Eds., Plenum Press, New York, 1973, p. 265. P. Lechtken and N. J. Turro,Mol. Photochem., 6,95 (1974). (a) W. Adam, 0. Cucto, and F. Yany, J. Am. Chem. Soc., 100, 2587 (1978); (b) S. P. Schmidt and G. B. Schuster, J. Am. Chem. Soc., 102,306 (1980). A. Weller and K. A . Zacharidsse, in Cherniluminescence and Bioluminescence, M. Cormier, D. M. Hercules, and J. Lee, Eds., Plenum Press, New York, 1973, p. 193. G. B. Schuster,J. Am. Chem. Soc., 101,5851 (1979). R. A. Marcus, J. Chem. Phys., 24,966 (1956). F. Scandolaand V. Balzani,J. Am. Chem. SOC.,101,6141 (1979). C. Walling,J. A m . Chem. Soc., 102,6854 (1980). (a) W. Adam and I. Erdcn, J. Am. Chem. Soc., 101, 5692 (1979); (b) W. Adam, C. Cadilla, 0. Cucto, and L. 0. Kodriguez,J. Am. Chem. Soc., 102,4802 (1980).

108. 109.

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135. 136. 137. 138, 139. 140. 141. 142. 143. 144. 145. 146. 147. 148. 149. 150. 151.

1,2-Dioxetanes a n d a - P e r o x y l a c t o n e s W. Adam, K. Zinner, A. Krebs, and H. Schmalstieg, Tetrahedron Lett., 22, 4567 (1981). W. Adam, M. Balci, 0. Cueto, and B. Pietrzak, Tetrahedron Lett., 4137 (1979). W. Adam, 0. Cueto, E. Schmidt, and K. Takayama, (unpublished results). W. Adam, C.-C. Cheng, 0. Cueto, I . Erden, and K. Zinner, J. Am. Chem. Soc., 101, 4735 (1979). T. Wilson, D. E. Goban, M. S. Harris, and A. L. Baumstark, J. Am. Chem. SOC.,98, 1086 (1976). K. R. Kopecky and J. A. Lopez Sastre, Can. J. Chem., 58, 2089 (1980). K.-W. Lee, L. A . Singer, and K. D. Legg, J. Org. Chem., 41, 2685 (1976). H. H. Seligerand W. D. McElroy, Arch. Biochem. Biophys., 8 8 , 1 3 6 (1960). (a) E. H. White, H. Worther, H. H. Seliger, and W. D. McElroy, J. Am. Chem. SOC.,88, 2015 (1966); (b) E. H. White, E. R a p p o r t , H. H. Seliger, and T. A. Hopkins, Bioorg. Chem., 1 , 9 2 (1971). J.-Y. Koo, S. P. Schmidt, and G. B. Schuster, Roc. Nutl. Acad. Sci. USA, 75, 30 (1978). J. Jung, C.-A. Chin, and P.-S. Song,J. Am. Chem. Soc., 98,3949 (1976). (a) P. D. Bartlett, A. L. Baumstark, and M. E. Landis, J. Am. Chern. Soc., 95, 6486 (1973); (b) P. D. Bartlett, A. L. Baumstark, M. E. Landis, and C. L. Lcrnian, J. Am. Chem. Soc., 96, 5267 (1974); ( c ) P. D. Bartlett, M. E. Landis, and M. J. Shapiro, J. Org. Chern., 42, 1661 (1977); (d) A. L. Baumstark, C. J. McCloskey, T. E. Williams, and D. R. Chrisope, J. Org. Chem., 45, 3593 (1980); (e) B. S. Campbell, N. J. De’Ath, D. B. Denney, D. Z. Denney, I. S . Kipnis, and T. B. Min, J. Am. Chem. Soc., 98,2924 (1976); (f) B. C. Campbell, D. B. Denney, D. Z. Denney, and L. S . Shih,J. Chem. Soc. Chem. Commun., 854 (1978). A. L. Baumstark, M. E. Landis, and P. J. Brooks, J. Org. Chem., 44,4251 (1979). N. J. Turro and Y . Ito, unpublished results; cf. Ref. 94, footnote e. I. Saito, S. Matsugo, and T. Matsuura,J. Am. Chem. Soc., 101,4757 (1979). H. H. Wasscrman and I. Saito, J. Am. Chem. Soc., 97, 905 (1975). P. D. Bartlett, A. L. Baumstark, and M. E. Landis,J. Am. Chem. Soc., 96,5557 (1974). P. D. Bartlett and J . S. McKennis,J. Am. Chem. Soc., 99, 5334 (1977). P. D. Bartlett, A. L. Baumstark, and M. E. Landis,J. Am. Chem. Soc., 99, 1890(1977). W. Adam and K. Sakanishi, (unpublished results). W. Adam and A. J. Bloodworth, Ann. Revs. (B),342 (1 978). (a) G. Cilcnto, Ace. Chem. Res., 13, 225 (1980); (b) G. Cilento, Photochem. Photohiol. Revs.,5, 199 (1980). E. J. H. Bechara, 0. M . M. Faria Olivcira, N. Duran, R. Casadei de Baptista, and G. Cilento,Photochem. Phofohiol., 30, 101 (1979). M. Haun, N. Duran, 0. Augusto, and G. Cilento, Arch. Biochem. Biophys., 200, 245 (1980). C. Vidigal-Martinelli, K. Zinner, B. Kachar, N. Duran, and G. Cilento, FEBS L e f f . , 108, 266 (1979). V . S. Kalyanaraman, S. Mahdevan, and S. A. Kumar, Biochem. J., 149,565 (1975). C. C. C. Vidigal, A. Faljoni-Alario, N. Duran, K. Zinner, Y . Shimizu, and G. Cilento, Photochem. Photobiol., 30,195 (1979). K. Zinner, C. Vidigal-Martinelli, N. Duran, A . J . Marsaioli, and G. Cilento, Biochem. Biophys. Res. C o m m u ~ .92, , 32 (1980). N. Duran, K . Zinner, C. C. C. Vidigal, and G. Cilento, Biochem. Biophys. Res. Commun., 74, 1146 (1977).

References 152. 153. 154. 155.

156. 157. 158. 159. 160. 161. 162. 163. 164. 165. 166. 167. 168. 169.

170. 171 172. 173a. 173b. 174. 175. 176.

177.

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N. Duran, M. Haun, A. Faljoni, and G. Cilento, Biochem. Biophys. Res. Commun., 81, 785 (1978). 0. Augusto, G. Cilento, J. Jung, and P.-S. Song, Biochem. Biophys. Res. Commun., 83, 963 ( I 978). G. Cilento, (unpublished results). (a) A. Faljoni, M. Haun, M. E. Hoffmann, R. Meneghini, N. Duran, and G. Cilento, Biochem. Biophys. Res. Commun., 8 0 , 4 9 0 (1978); (b) R. Meneghini, M. E. Hoffmann, N. Duran, A. Faljoni, and G. Cilento, Biochim. Biophys. Acta, 518, 1 7 7 (1978). A. P. Schaap, Tetrahedron Lett., 1757 (1971). W. H. Richardson and V. F. Hodge, J. Am. Chem. Soc., 9 3 , 3 9 9 6 (1971). W. Adam and 11. Rebollo, (unpublished results). (a) C. W. Jefford and C. G. Rimbault, J. Am. Chem. Soc., 100, 295 (1978); (b) C. W. Jefford and C. G. Rimbault, J. Am. Chem. Soc., 100,6437 (1978). E. W. H. Asveld and R. M. Kcllogg,J. A m . Chem. Soc., 102,3644 (1980). J. Basselier, J. C. Cherton, and J. Caille, C. R. Acad. Sci. Ser. C, 273, 514 (1971). A. P. Schaap and N. Tontapanish, J. Chem. SOC. Chem. Commun., 490 (1972). G. Rosscau, P. Le Pcrchec, and J . M. Conia, Synthesis, 6 7 (1978). E. W. Meijer and H. Wynberg, Tetrahedron Lett., 3997 (1979). I. Saito, S . Matsugo, and T. Matsuura,J. Am. Chem. Soc., 101,4757 (1979). A. L. Baumstark, T. Wilson, M . E. Landis, and P. D. Bartlctt, Tetrahedron Lett., 2397 (1976). (a) E. Wong and J. M. Wilson, Phytochem., 15, 1325 (1976); (b) J. M. Wilson and E. Wong, Phytochem., 15, 1333 (1976). G. Rio and J . Berthclot, Bull. Soc. Chim. Fr., 3555 (1971). (a) G. Maier, Angew. Chem. Int. Ed. Engl., 13, 425 (1974); (b) H. Irngartinger, N. Riegler, K.-D. Malsch, K.-A. Schneider, and G. Maier, Angew. Chem. Int. Ed. Engl., 19, 211 (1980). (a) F. McCapra and I. Beheshti, J . Chem. SOC. Chem. Commun., 517 (1977); (b) P. B. Hitchcock and I . Beheshti,J. Chem. SOC.Perkin Trans. II, 126 (1979). (a) H. Wynberg and H. Numan, J. A m . Chem. Soc., 99, 603 (1977); (b) H. Wynberg, H. Numan, and H. P. J. N. Dekkers, J. Am. Chem. Soc., 99, 3870 (1977). M. Muramatsu, N. Obata, and T. Takizawa, Tetrahedron Lett., 2133 (1973). J. J . Basselier and J . P. Le Roux, Bull. Soc. Chim. Fr., 4443 (1971). J. P. Le Roux, G. Letertc, P.-L. Desbene, and J. J . Basselier, Bull. Soc. Chim. Fr., 4059 (1971). G. Rio and B . Serkiz, J. Chem. Soc. Chem. Commun., 849 (1975). S. A. M a t h and P. G. Sammes, J. Chem. SOC. Perk. Trans. I , 5248 (1978). (a) M. S. De Groot, C. A . Emeis, I. A. M. Hesselman, E. Drent, and E. Farenhorst, Chem. Phys. Lett., 17, 332 (1972); (b) M. Larchevcquc and T. Cuvigny, Tetrahedron Lett., 3851 (1975); (c) J. F. Le Borgne, Th. Cuvigny, M . Larcheveque, a n d H . Normant, Tetrahedron Lett., 1379 (1976); (d) N. C. Yang, W. Eisenhardt, and J . Libman,J. A m . Chem. Soc., 9 4 , 4 0 3 0 (1972). The literature inclusive of 1980 was reviewed here at the time of writing. For recent reviews: (a) W. Adam and G. Cilento, Angew. Chem. Int. Ed. Engl., 22, 529 (1983); (b) W. Adam, in “The Chemistry of the Peroxide Bond,” S. Patai (Ed.), John Wiley and Sons, New York (1983), pp. 829-920; (c) W. Adam and G. Cilento (Eds.), “Chemical and Biological Generation of Excited States,” Academic Press, New York (1982).

Chemistry of Heterocyclic Compounds, Volume42 Edited by Alfred Hassner Copyright 0 1985 by John Wiley & Sons, Ltd.

CHAPTER V

Four-Membered Sulfur Heterocycles D . C . DITTMER AND T. C . SEDERGRAN Department of Chemktry. Symcuse University. Symcuse. New York

I. 11.

Introduction . . . . . . . . . . . . . . . . . Thietanes (Thiacyclobutanes. Trimethylene Sulfides) (C. S) . . . . 1. Occurrence . . . . . . . . . . . . . . . . 2 . Uses . . . . . . . . . . . . . . . . . . . 3 . Properties . . . . . . . . . . . . . A . Structure andConformations . . . . . B . NMRSpectra . . . . . . . . . . . . . . C . Raman and IR Spectra . . . . . . . . . . . D . UVSpectra . . . . . . . . . . . . . . . E. Basicity . . . . . . . . . . . . . . . . F . Thermodynamic Quantities . . . . . . . . . . G . Mass Spectrometry;IonizationPotentials . . . . . . H . Dipole Moments . . . . . . . . . . . . . I. Miscellaneous Properties . . . . . . . . . . . 4 . Synthesis . . . . . . . . . . . . . . . . . A . From 1 ,3-Disubstituted Propanes . . . . . . . . B. From Chloromethyloxiranes (Epichlorohydrins) and Chloromethylthiiranes (Thioepichlorohydrins) C. From Cyclic Carbonates and Related Intermediates . . . D . From 1 ,2.Dithiolanes via Ring Contraction . . . . . . E . From Thietane 1.1.Dioxides by Reduction . . . . . . F . From Thiocarbonyl Compounds via Cycloaddition to Alkenes . . . . . . . . . . . . . . . . C . Miscellaneous Methods . . . . . . . . . . . 5 . Reactions of Thietanes . . . . . . . . . . . . . A . Reactions with Carbon Electrophiles . . . . . . . B. Reactions with Nitrogen Electrophiles . . . . . . . C. Reactions with Oxygen Electrophiles (Oxidation) . . . . D . Reactions with Halogen Electrophiles . . . . . . . E . Reactions with Sulfur Electrophiles . . . . . . . .

43 1

431 438 438 438 439 439 439 440 440 441 441 441 442 443 443 443 449 450 451 452 452 455 456 456 461 462 463 464

Four-Membered Sulfur Heterocycles

432

Reactions with Protons . . . . . . . . . . . Reactions with Metal Ions . . . . . . . . . . Reactions with Nucleophiles and Bases . . . . . . . Desulfurization by Chemical, Photochemical. and Thermal Methods . . . . . . . . . . . . . . . . J. Reactions with Free Radicals . . . . . . . . . . K . Ring-Expansions . . . . . . . . . . . . . L . Polymerizations . . . . . . . . . . . . . M . Reactions Involving Substituents on Thietanes . . . . . Thietane 1-Oxides(Thixycl0butane 1-Oxides) . . . . . . . . 1. Uses . . . . . . . . . . . . . . . . . . 2 . Properties . . . . . . . . . . . . . . . . . A . X-Ray and Microwave Structure Determinations . . . . B . NMR . . . . . . . . . . . . . . . . . C . Dipole Moments . . . . . . . . . . . . . D . Mass Spectra . . . . . . . . . . . . . . E . Basicity . . . . . . . . . . . . . . . . F . Thermochemistry; Electrochemistry . . . . . . . . . . . . . . . . . . . G . Solvent Characteristics 3. Synthesis . . . . . . . . . . . . . . . . . A . Oxidation of Thietanes . . . . . . . . . . . B . Miscellaneous Methods . . . . . . . . . . . 4 . Reactions of Thietane 1-Oxides . . . . . . . . . . . A . Isomerization; Resolution; Polymerization . . . . . . B . Oxidation . . . . . . . . . . . . . . . C . Reduction . . . . . . . . . . . . . . . D . 0-Alkylation . . . . . . . . . . . . . . E . Metal Complexes . . . . . . . . . . . . . F . Thermolysis, Photolysis . . . . . . . . . . . G . Keactions with Free Radicals . . . . . . . . . H . Reactions with Grignard Reagents and Potassium t-Butoxide Thietane Sulfilimines . . . . . . . . . . . . . . . Thietane 1.1-Dioxides (Thietane Sulfones) . . . . . . . . . 1. Uses . . . . . . . . . . . . . . . . . . 2 . Properties . . . . . . . . . . . . . . . . . A . Structure and Conformation . . . . . . . . . . B . NMR . . . . . . . . . . . . . . . . . C . Acidity . . . . . . . . . . . . . . . . D . Mass Spectra . . . . . . . . . . . . . . E . Dipole Moments . . . . . . . . . . . . . 3 . Synthesis . . . . . . . . . . . . . . . . . A . Oxidation of Thietanes . . . . . . . . . . . B . Cycloadditions of Sulfenes . . . . . . . . . . C . From Thiete 1.1-Dioxides . . . . . . . . . . D . Miscellaneous Methods . . . . . . . . . . . 4 . Reactions . . . . . . . . . . . . . . . . . A . Reduction to Thietanes . . . . . . . . . . . B . Thermo- and Photochemical Extrusion of Sulfur Dioxide . . C . Other Ring-Opening Reactions; Ring-Expansions and Contractions . . . . . . . . . . . . . . . . D . Anionic Reactions of Thietane 1.1-Dioxides . . . . . E . Halogenation . . . . . . . . . . . . . . F . Reactions Involving Substituents on Thietane 1. 1-Dioxides . Thietane Sulfoximines and Sulfodiimides . . . . . . . . . F. G. H. I.

111.

IV . V.

VI .

464 465 466 468 410 472 412 414 416 416 476 416 417 479 479 480 480 480 480 480 481 482 482 483 483 484 484 484 485 486 481 488 488 489 489 489 490 491 491 491 491 492 491 498 498 498 499 501 504 505 5 05 508

Four-Membered Sulfur Heterocycles VII . VIII .

1X .

X.

XI . XI1.

XI11.

Thietanium Salts . . . . . . . . . . . . . 1. Synthesis . . . . . . . . . . . . . . . . . 2 . Reactions and Properties . . . . . . . . . . . . . Sulfuranes and Persulfuranes of Thietanes . . . . . . . . . Thietes (Thiacyclobutenes) . . . . . . . . . . . . . 1. uses . . . . . . . . . . . . . . . . . . 2 . Properties . . . . . . . . . . . . . . . . . A . Structure . . . . . . . . . . . . . . . B . Theoretical . . . . . . . . . . . . . . . C. Spectroscopic Properties . . . . . . . . . . . 3 . Synthesis . . . . . . . . . . . . . . . . . 4 . Thietes as Intermediates . . . . . . . . . . . . . 5 . Reactions of Thietes . . . . . . . . . . . . . . A . Oxidation . . . . . . . . . . . . . . . B . S-Alkylation . . . . . . . . . . . . . . C . Hydrolysis . . . . . . . . . . . . . . . D . Reactions with Bases and Nucleophiles . . . . . . . E. Ring-Opening to Enethials or Enethiones . . . . . F . Miscellaneous Ring-Opening or Expansion Reactions; Isomerizations . . . . . . . . . . . . . . . . G . Donor-Acceptor Complexes . . . . . . . . . . Thiacyclobutene Sulfonium Ions . . . . . . . . . . . . Thiete 1-Oxides (Thiete Sulfoxides) . . . . . . . . . . . Thiete 1 , 1-Dioxides (Thiete Sulfones) . . . . . . . . . . 1. Uses . . . . . . . . . . . . . . . . . . . 2 . Properties . . . . . . . . . . . . . . . . . 3. Synthesis . . . . . . . . . . . . . . . . . A . Oxidation of Thietesor Thiete 1-Oxides . . . . . . B . Elimination Reactions of Thietane 1,1-Dioxides . . . . C . CycloadditionsofSulfenestoYnamines . . . . . . D . Miscellaneous Methods . . . . . . . . . . . E . Thiete 1,1.Dioxides with Exocyclic Double Bonds . . . I: . Thiete 1 ,1-Dioxides Fused to Aromatic Systems . . . . 4 . Reactions of Thiete 1.1-Dioxides . . . . . . . . . . A . Reduction . . . . . . . . . . . . . . . B . Isonierization; I-1-D Exchange . . . . . . . . . C . Additions t o the Carbon-Carbon Double Bond . . . . D . Ring-Openings and Expansions: Chemical, Thermal, Photochemical . . . . . . . . . . . . . . . . E . Miscellaneous Reactions . . . . . . . . . . . 2-Thietanones ('J-Thiolactones) . . . . . . . . . . . . 1. Uses . . . . . . . . . . . . . . . . . . 2 . Properties . . . . . . . . . . . . . . . . . 3 . Synthesis . . . . . . . . . . . . . . . . . A . Intramolecular Cyclizations . . . . . . . . . . B . Cycloadditions of Thiocarbonyl Compounds to Ketenes and Carbon Oxysulfide to Alkenes . . . . . . . . . C . Hydrolysis of 2, 2.Dichlorothietanes . . . . . . . . D . Miscellaneous Methods . . . . . . . . . . . 4 . Reactions . . . . . . . . . . . . . . . . . A . Addition of Nucleophiles;Polymerization . . . . . . B . Thermolysis; Photolysis . . . . . . . . . . . C. Anions of p-Thiolactones . . . . . . . . . . . D . Desulfurization . . . . . . . . . . . . . .

433 508 509 510 512 512 512 513 513 513 515 516 519 520 520 521 521 522 522 525 526 526 529 530 530 530 531 531 531 534 534 536 536 538 538 540 541 544 546 541 548 548 548 548 551 552 552 554 554 556 551 558

Four-Membered Sulfur Heterocycles

434

XIV . XV .

XVI .

XVII . XVIII .

XIX . XX .

E . Oxidation. Reduction . . . . . . . . . . . . F . Miscellaneous Reactions . . . . . . . . . . . 2-Thietanethiones @-Dithiolactones). . . . . . . . . . . 2-Iminothietanes . . . . . . . . . . . . . . . . 1 . Properties . . . . . . . . . . . . . . . . . 2 . Synthesis . . . . . . . . . . . . . . . . . A . Cycloadditions to ThiocarbonylGroups . . . . . . B . Intramolecular Cyclization . . . . . . . . . . 3 . Reactions . . . . . . . . . . . . . . . . . A . Thermal and Photochemical Ring-Opening; Fragmentation . B . Ring-Opening and Ring-Expansion by Nucleophiles . . . C. Miscellaneous Reactions . . . . . . . . . . . 3-Thietanones . . . . . . . . . . . . . . . . . 1 . Occurrence . . . . . . . . . . . . . . . . 2 . Properties . . . . . . . . . . . . . . . . . 3 . Synthesis . . . . . . . . . . . . . . . . . A . Intramolecular Cyclization . . . . . . . . . . B . Oxidation of 3-Hydroxythietanes . . . . . . . . C. Hydrolysis of Ketals of 3-Thietanone . . . . . . . D . Cycloadditions of Thiocarbonyl Compounds to Ketenes . . E . Miscellaneous Methods . . . . . . . . . . . 4 . Reactions . . . . . . . . . . . . . . . . . A. Reactions with Nucleophiles . . . . . . . . . . B . Reduction and Oxidation . . . . . . . . . . . C . Aldol Condensations . . . . . . . . . . . . D. Thermal and Photochemical Reactions . . . . . . . E . Miscellaneous Reactions . . . . . . . . . . . 3-Iminothietanes . . . . . . . . . . . . . . . . 1. Synthesis . . . . . . . . . . . . . . . . . 2 . Reactions . . . . . . . . . . . . . . . . . Methylene Thietanes . . . . . . . . . . . . . . . 1 . Occurrence . . . . . . . . . . . . . . . . 2 . Properties . . . . . . . . . . . . . . . . . 3 . Synthesis . . . . . . . . . . . . . . . . . A . Intramolecular Cyclization . . . . . . . . . . B . Intermolecular Cyclization . . . . . . . . . . C. AldolCondensations with 2-Thietanones . . . . . . D. Wittig Reactions . . . . . . . . . . . . . E . From 1,3Cyclobutanediones and Thiones . . . . . . F. Miscellaneous Methods . . . . . . . . . . . 4 . Reactions . . . . . . . . . . . . . . . . . A . WithNucleophiles . . . . . . . . . . . . . B . Oxidation . . . . . . . . . . . . . . . C. Photochemical Reactions . . . . . . . . . . . D . Diels-Alder Reactions . . . . . . . . . . . . E . Isomerization to Thietes . . . . . . . . . . . F . Miscellaneous Reactions . . . . . . . . . . . Thietanone 1-Oxides . . . . . . . . . . . . . . . Thietanone and Thietanthione 1 , 1.Dioxides . . . . . . . . 1 . Uses . . . . . . . . . . . . . . . . . . 2 . Synthesis . . . . . . . . . . . . . . . . . A . Hydrolysis of Ketals and 3.(N,N.Dialkylamino).2 H.Thiete 1,1.Dioxides . . . . . . . . . . . . . . B . Oxidation of 3-Thietanones . . . . . . . . . .

558 559 561 562 562 563 563 565 566 566 567 568 569 569 569 569 569 570 571 571 571 572 572 574 574 574 575 575 575 571 577 577 577 578 578 578 579 579 579 580 580 580 581 581 581 582 582 582 583 583 583 583 583

Four-Membered Sulfur Heterocycles C . Miscellaneous Methods . . . . . . . . . . . Reactions . . . . . . . . . . . . . . . . . A . With Nucleophiles . . . . . . . . . . . . . B . Reduction . . . . . . . . . . . . . . . C . Thermal and Photochemical Reactions . . . . . . . D. 0-Alkylation . . . . . . . . . . . . . . E . Miscellaneous Reactions . . . . . . . . . . . Methylenethietane 1-Oxides and 1,1.Dioxides . . . . . . . . 1. Synthesis . . . . . . . . . . . . . . . . . A . Oxidation of Methylene Thietanes . . . . . . . . B . Miscellaneous Methods . . . . . . . . . . . 2 . Reactions . . . . . . . . . . . . . . . . . 1,2.Thiazetidines (1-Thia-2-azacyclobutanes) . . . . . . . . 1.2.Thiazetidine 1-Oxides and 1-Imines (Sulfilimines) . . . . . . 1. Uses . . . . . . . . . . . . . . . . . . 2 . Properties . . . . . . . . . . . . . . . . . 3 . Synthesis . . . . . . . . . . . . . . . . . 4 . Reactions . . . . . . . . . . . . . . . . . 1,2 Thiazetidine 1,1.Dioxides (p-Sultams) and 3-Keto Derivatives . . 1. Uses . . . . . . . . . . . . . . . . . . 2. Properties . . . . . . . . . . . . . . . . . 3 . Synthesis . . . . . . . . . . . . . . . . . A . Intramolecular Cyclization . . . . . . . . . . B . Cycloadditions . . . . . . . . . . . . . . C . Miscellaneous Methods . . . . . . . . . . . 4 . Reactions . . . . . . . . . . . . . . . . . A . Tautomerism; 0-Alkylation of 3-Keto Derivatives; Isomerism B . N-Alkylation . . . . . . . . . . . . . . C . Reactions with Nucleophiles and Bases . . . . . . . D . Reduction . . . . . . . . . . . . . . . E . Thermal Reactions . . . . . . . . . . . . . 1,2.Thiazete Derivatives . . . . . . . . . . . . . . 1,3.Thiazetidines . . . . . . . . . . . . . . . . 1. Uses . . . . . . . . . . . . . . . . . . 2. Properties . . . . . . . . . . . . . . . . . 3 . Synthesis . . . . . . . . . . . . . . . . . 1,3.Thiazetidine. 2.ones and -2-Thiones . . . . . . . . . . 1. Uses . . . . . . . . . . . . . . . . . . 2 . Synthesis . . . . . . . . . . . . . . . . . 3. Reactions . . . . . . . . . . . . . . . . . 2-Imino- and 2,4.Bis.imino.l, 3.Thiazetidines . . . . . . . . 1. Uses . . . . . . . . . . . . . . . . . . 2 . Properties . . . . . . . . . . . . . . . . . 3 . Synthesis . . . . . . . . . . . . . . . . . 4 . Reactions . . . . . . . . . . . . . . . . . 1,3.Thiazetes . . . . . . . . . . . . . . . . . 1,2.Oxathietanes. 1,2.Oxathietane 2-Oxides (p-Sultines); 1,2.Oxathietane 2, 2.Dioxides (p-Sultones) . . . . . . . . . . . . . . 1. Uses . . . . . . . . . . . . . . . . . . 2 . Properties . . . . . . . . . . . . . . . . . 3. Synthesis . . . . . . . . . . . . . . . . . 4 . Reactions . . . . . . . . . . . . . . . . . A . Nucleophilic Ring-Opening . . . . . . . . . . B . Retrocycloadditions . . . . . . . . . . . . 3.

XXI .

XXII . XXIII .

XXIV .

xxv .

XXVI .

XXVII

XXVIII .

XXIX .

xxx .

43 5 584 584 584 584 584 585 585 586 586 586 586 587 588 589 589 589 589 591 592 592 593 593 593 594 595 595 5 95 596 596 597 597 598 601 601 601 601 602 602 603 604 604 605 605 605 607 609 610 611 611 612 615 615 617

Four-Membered Sulfur Heterocycles

436 XXXI . XXXII . XXXIII. XXXIV.

xxxv.

XXXVI.

XXXVII.

XXXVIII.

XXXIX.

C. Miscellaneous . . . . . . . . . 1,2-Oxathiete Derivatives . . . . . . . . . 1,3-0xathietane Derivatives . . . . . . . . 1,2 and 1,3-Thiaphosphetane Derivatives . . . . Thiasilacyclobutanes and Thiagermacyclobutanes . . 1,2-Dithietanes and 1,2-Dithietes . . . . . . . 1. 1,2-Dithietanes . . . . . . . . . . 2. 1,2-Dithietes . . . . . . . . . . . A . Properties . . . . . . . . . . B. Synthesis . . . . . . . . . . C. Reactions . . . . . . . . . . 1,3-Dithietanes . . . . . . . . . . . . 1. Uses . . . . . . . . . . . . . 2. Properties . . . . . . . . . . . . 3. Synthesis . . . . . . . . . . . . A. Dimerization of Thiocarbonyl Compounds . B. Miscellaneous Methods . . . . . . 4. Reactions . . . . . . . . . . . . A . Ring-Opening . . . . . . . . . B. Reactions at Sulfur . . . . . . . C. Miscellaneous Reactions . . . . . . 5. Sulfoxides and Sulfones . . . . . . . . 1,3-Dithietane-2-ones and 2-Thiones . . . . . . 1. Uses . . . . . . . . . . . . . 2. Structure . . . . . . . . . . . . 3. Synthesis . . . . . . . . . . . . 4. Reactions . . . . . . . . . . . . Imino-l,3-dithietanes . . . . . . . . . . 1. Uses . . . . . . . . . . . . . 2. Structure . . . . . . . . . . . . 3. Synthesis . . . . . . . . . . . . 4. Reactions . . . . . . . . . . . .

Methylene-l,3-Dithietanes. . 1. Uses . . . . . .

XXXXI.

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . .

. . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . .

. . . . .

. . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Properties . . . . . Synthesis . . . . . Reactions . . . . . A . Thermolysis . . B. Desulfurization and Reduction . . . . C. Oxidation . . . . . . . . . . D. Reactions with Nucleophiles . . . . . E. Miscellaneous Reactions . . . . . . Four-Membered Sulfur Heterocycles with One Carbon Atom 1. C S N O . . . . . . . . . . . . . . . 2. C S N P . . . . . . . . . . . . . . . 3. C S N , . . . . . . . . . . . . . . . A . Synthesis and Properties . . . . . . . . B. Reactions . . . . . . . . . . . . 4. C S O P . . . . . . . . . . . . . . . 5. c s o , . . . . . . . . . . . . . . . 6. C S , N . . . . . . . . . . . . . . . 7. c s , o . . . . . . . . . . . . . . . 8. CS,. . . . . . . . . . . . . . . . Four-Membered Sulfur Heterocycles with One Sulfur Atom and Three

2. 3. 4.

XXXX.

. . . . . .

. . . . . . . . . . . . . . . .

617 619 621 621 623 6 24 624 625 6 25 626 628 6 29 629 629 630 630 631 632 632 633 635 635 638 638 638 638 638 639 639 639 640 640 641 641 641 642 646 646 646 641 641 649 650 650 651 65 1 651 652 653 653 655 655 656

Introduction

XXXXII .

XXXXIII . XXXXIV .

XXXXV . XXXXVI .

Heteroatoms . . . . . . . . . . . . . . . . . 1. SNP.. SOP.. SNOP . . . . . . . . . . . . . . 2 . SN.0. SN.P. SN.Si. SN. B . . . . . . . . . . . . 3 . SN.. SP. . . . . . . . . . . . . . . . . . Four-Membered Sulfur Heterocycles with Two Sulfur Atoms and T W O . . . . . . . . . . . . . . . . . Ileteroatoms 1. S.NO . . . . . . . . . . . . . . . . . . 2 . S.N. . . . . . . . . . . . . . . . . . . 3 . S.P. . . . . . . . . . . . . . . . . . . A . Uses . . . . . . . . . . . . . . . . B . Properties . . . . . . . . . . . . . . . C . Synthesis . . . . . . . . . . . . . . . D . Reactions . . . . . . . . . . . . . . . a . With Nucleophilic Reagents . . . . . . . . . b . With Carbonyl Compounds and Phosphine Oxides . . c . Miscellaneous . . . . . . . . . . . . . 4 . S.Si.. S.Ge.. S.B. . . . . . . . . . . . . . . . A . Properties . . . . . . . . . . . . . . . B . Synthesis . . . . . . . . . . . . . . . C . Reactions . . . . . . . . . . . . . . . Four-Membered Sulfur Heterocycles with Three Sulfur Atoms and One Heteroatom or Four Sulfur Atoms . . . . . . . . . . . Pour-Membered Heterocycles Containing Selenium o r Tellurium . . . 1 . C.Se.C,Te . . . . . . . . . . . . . . . . . 2 . C.Se..C.Te.. C.SeS.CSeN. . . . . . . . . . . . . 3 . Four-Membered Heterocycles of Selenium or Tellurium Containing No Carbon Atoms . . . . . . . . . . . . . . Tables . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . .

437 656 656 651 658 658 658 658 661 661 661 661 663 663 664 665 667 667 661 668 669 670 670 612 612 675 714

I . INTRODUCTION This chapter will review the properties. syntheses. and reactions of four-membered cyclic sulfur-containing compounds up to the end of 1981 with some coverage of the literature published in early to mid.1982 . Compounds containing three carbon atoms in the ring will be taken up first. followed by ring systems having two. one. and no carbon atoms. respectively . Saturated derivatives will be treated before unsaturated (ex0 or endo) derivatives and sulfides will take precedence over sulfoxides and sulfones . Rings containing selenium or tellurium will be discussed last . Three earlier reviews cover thietanes and other derivatives up to the mid 1950s or 1960s.'> zb Organic Compounds of Sulphur. Selenium and Tellurium. a Specialist Periodical Report of The Royal Society of Chemistry. includes reviews of smallring compounds (April 1969-March 1980 in six volumes) . One chapter in Comprehensive Heterocyclic Chemistry gives a survey of four-membered sulfur heterocycles.2c A useful review on (2 + 2) cycloreversions covers some chemistry of relevance .2d

438

Four-Membered Sulfur Heterocycles

Because of the strain existing in four-membered rings, the relative weakness of a carbon-sulfur bond and the relatively high nucleophilicity or oxidizability of divalent sulfur, the ring systems to be discussed are rather reactive.

11. THIETANES (THIACYCLOBUTANES, TRIMETHYLENE SULFIDES) (C,S) 1.

Occurrence

2,2-Dimethylthietane is a component of the secretion from the anal gland of the mink (Mustela v i s i ~ n ) . ~ the~ ~European -~ polecat (M p u t ~ r i u s )and , ~ ~ferret.3b The ferret also produces cis- and trans-2,3-dimethylthietane, 2-n-propylthietane, and 2 - ~ - p e n t y l t h i e t a n e2-n-propylthietane .~~ is the major malodorous substance secreted by the anal gland of the male stoat (M. emzinea).5a.5bThe female stoat secretes 2-eth~lthietane.'~ Thietane, itself, is said to be a component of shale

2.

Uses

3-Hydroxythietane and a complex 0-3-thietanylhydroxylamineare said to be effective in controlling Staphylococcus aureus? and prostane derivatives of thietane have anti-ulcer activity.7a Thromboxane analogs (e.g., (9,l l)epithia(l 1,12)methanothromboxane) induce aggregation of human blood platelets and cause contractions in an isolated rat a ~ r t a . Quinazoline ~ ~ - ~ ~ derivatives of thietane carboxylic acid may be useful in combatting hypertension,7' and a 2(1 H)pyrimidone derivative is said t o inhibit the metaphase of cell division of L1210 cells (leukemia) in ~ i t r - 0 . ~ ~ Aminothietanes are inhibitors of monoamine oxidase? and 7-phenyl-2-thia-6,8dioxaspiro(3S)nonane is reported to be a pharmacological excitant.8b 2-Hydroxythietanes are flavoring substancesg and phosphate esters of 3-hydroxythietane and 3-(P-hydroxyethylthio) thietane have been investigated as pesticides.lOa-lOd 2,2-Dimethylthietane, when applied t o carrots, is said to rebel rabbits and other game.'& Thietane is a superior inhibitor of corrosion of iron in 10% hydrochloric acid and its effectiveness is said to be due to partial polymerization on the surface of the iron. Addition of chloride ion reduces the inhibition, possibly by inducing ringopening with the formation of sulfhydryl groups." The cyclic sulfide also has been considered as an odorant for natural gas and its absorption by organic soil and clay have been determined.12 Stabilization of methylchloroform and trichloroethylene by thietane, 2 -meth ylt hietane, 3 -hydroxythietane, and two spirothietane derivatives has been ~ 1 a i m e d . Phosphorus l~ and tin derivatives of 3,3-bis-hydroxy-methyIthietane are reported to be light stabilizers for poly(viny1 chloride),14 and the dibutyltin derivative is a catalyst for the polymerization of aliphatic i s o c y a n a t e ~ . Mercury '~~ and zinc compounds derived from phenylmercury or phenylzinc hydroxide and 3-

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) ((23s)

439

hydroxymethyl-3-methylthietane are catalysts in the formation of urethane polymers as well as being bactericides and fungicides for use in paints.'sc Polymers and copolymers of thietanes have received considerable attention and oriented fibers of poly(thietane) have tensile strengths up t o 41,000 Protective coatings are obtained from cross-linked copolymers of methyl methacrylate and the methacrylate ester of 3-hydro~ythietane."~(Polyolefins are claimed to be stabilized by thietane.lsh Spirothietane derivatives of cyclic carbonates are homo- or copolymerized through the carbonate group to give high-molecular-weight solids useful in the laminating arts."j Polymers of thietanes are discussed further in Section II.5.L. 3.

A.

Properties

Structure and Conformations

Electron diffraction data16 on thietane show that it is puckered; the dihedral angle of the C2-S-C4 plane with the C2-C3-C4 plane is 154 ? 2" (saddle angle). The C-S bond lengths are somewhat longer than the normal 1.8128.17 The following bond lengths were determined: C-S, 1.847 8; C-C, 1.547 8 ; C,-H, 1.09 .02 8 ; Cp-H, 1.12 ? .04& The C-S-C bond angle is 76.8'. An x-ray analysis of cis-2,3dichloro-4,4-diphenylthietane indicates a dihedral angle of 15 1.1' with one long (1.898) and one normal (1.81 8) C-S bond.17a Structural analysis of trans-2,3dichloro-4,4-diphenylthietane shows a shorter Cz-C3 bond than in the cis isomer. A dihedral angle of about 150" was determined.'7b Bond angles in the cis isomer are as follows: C-S-C, 79.3'; C-C-S, 87.8", C-C-C, 98.1°.'7a The thietane ring formed by the cycloaddition of a-methylacrylonitrile and 4-thiouracil also is nonplanar with a dihedral angle of 162" and one long (1.8448) and one normal (1.8178) C-S bond." Electron diffraction studies on 5-thiabicyclo[2.1.1.] hexane also show somewhat long C-S bonds (1 .8658).19 Theoretical analyses of the conformations of thietanes are in agreement with the observed r i n g - p ~ c k e r i n g . ~More ~ - ' ~ ~data concerning the conformations of thietanes and m i c r o w a ~ e , ~ 1~~ ,~2 6,d ,~3 0~- 4 -1 ~ ~ ~ are derived from dipole Raman,26d.40-43 UV,44,4sand nmr The total barrier t o planarity of thietane is 274 cm-' (784 c a l / m ~ l e ) *so ~ ,that ~~~ at room temperature only about 25% of the molecules occupy vibrational levels above the barrier. The barrier is greater than that in oxetane but less than that in cyclobutane. Ring-strain favors planarity whereas eclipsing of methylene protons favors torsion and nonplanarity. a-methylthietan possesses equatorial and axial conformers observable at room temperature with an inversion barrier of 341 cm-' (975 cal/mole). 3,3-dimethylthietane has a barrier of 300 cin-' (857 ~ a l / m o l e ) . ~ ~ B.

NMR Spectra

The carbon nmr spectrum of thietane has been obtained and analyzed:54b~54e~ss-s7

Four-Membered Sulfur Heterocycles

440 TABLE 1.

13C N M R SPECTRA OF SOME 3-SUBSTITUTED THIETANES

Substituent(s1

6 (C,)

6 (Cp)

€I CH, Pha Ph, CH, -CH,S-CH,-‘ -CH,SO-CH,-‘ -CH,SO,CH,-a Cla (CH,),NC (CH,),SiOa HOa CH,COO-“

26.1,“ 26.2,” 27.0b 33.1 32.0 38.2 39.7 38.6 37.8 38.9 32.0 39.1 38.7 35.0

28.0: 36.1 44.1 47.4 52.1 38.4 33.7 51.0 64.7 66.9 67.3 68.2

Ref.

28.2:

29.2b

55a, 55b, 56b 56c 56b 56c 56d 56d 56d 56b 56b 56b 56b 56b

Solvents: a , CDC1,; b , neat; c , (CD,),CO.

S Zrs 27.5, 26.1, S z M S 29.7, 28.0; J&H 146.5, J ~ - H134.6; Jc-c 3 1.5 Hz. The one-bodcarbon proton coupling constants are about 3 Hz greater =

=

=

=

=

than in oxetane.56 The carbon spectra of several 3-substituted thietanes and spiro derivatives have been obtained. Analysis of both carbon and proton nrnr spectra of partially oriented thietane indicates ring-puckering, but the one-dimensional model used does not explain differences between observed and calculated coupling constants.54b Chemical shifts are tabulated in Table 1. Proton and, occasionally, carbon nmr spectra of thietanes are reported routinely in descriptions of the synthesis of various derivatives. Although an early proton nmr spectrum indicated identical chemical shifts for the a- and 0-protons of thietane,57b more recently the spectrum has been analyzed as an A4B2 s y ~ t e m ’ ~and ’~~ additional chemical shifts = 3.43, SF?$ = 3.17)48360i62 and coupling constant s48 56763 have been reported. Studies of the proton nrnr spectrum of thietane in nematic liquid crystal solvents have provided intermolecular distances and evidence for r i n g - p u ~ k e r . 4 ’ - ~ ~Th , ~e~proton ~ , ~ ~ nmr spectra of 3-chl0rothietane~~’~’ and 3-acetoxythietane6’ show relatively large cross-ring coupling constants.

(Szg;,

C.

Raman and IR Spectra

IR ~ p e ~ t r a of~ thietane - ~ ~ ~and , ~Raman ~ ~ spectra40-43’66-69of thietane and a-methylthietane have been recorded. The IR and UV spectra of several spirothietane derivatives that have one or more sulfur atoms in the second ring7’ or that involve a dioxane ring71have been discussed.

D.

UVSpectra

The electronic spectrum of thietane shows that it is nonplanar in the ground

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) (C3S)

44 1

Other electronic transitions state, but planar in the first excited state (226 lead to excited states that are nonplanar. The electronic transitions are of the n + u* and u + u* type. The position of the weak absorption band in the spectrum of cyclic sulfides is at highest wavelength for thietane (about 277 or 272 nm):1b341c the ring-size effect being 4 > 3 > 5 > 6.72 This was interpreted as indicating more electron density on sulfur in thietane. The vacuum UV spectrum of thietane has been recorded with that of other sulfides and mercaptans and the electronic transitions were assigned.73 The electronic absorption spectra of thietane and 59 other divalent sulfur compounds have been reported.74 Two theoretical calculations of the UV spectrum of thietane disagree as to the importance of d-orbitals in low-lying excited states.75776An extended Hiickel treatment of thietane and other 3- to 5 membered heterocycles demonstrates that the highest occupied molecular orbital is the lone-pair orbital.77

E.

Basicity

Association complexes of pheno141a'78a-78eand chloroform79 have been used to investigate the basicity of thietane by means of IR41">78a,78b or proton nmr79$80 techniques. The basicity of cyclic sulfides is a maximum at the five-membered ring followed by thietane (5 > 4 > 6 > 3), whereas for cyclic ethers, the four-membered ring is most basic (4 > 5 > 6 > 3).78-80 The nmr spectrum of protonated thietane (-- 60°, FS03H-SbF5-S02) shows the S-H proton as a multiplet at 67.40 and the ring protons at 6 3.2-4.4.81a Earlier attempts to determine the acidity constant of protonated thietane in aqueous sulfuric acid were plagued by decomposition:1b,81c although it seemed that thietane was less basic than the five- and six-membered cyclic sulfides.'lc Shifts in electron-spin-resonance parameters reveal a 1 : 1 Lewis acid-lewis base adduct of copper(I1) acetoacetate and thietane.82

F.

Thermodynamic Quantities

Thermodynamic quantities (heat of formation and combustion, free energy, heat capacity, entropies, heats of fusion and vaporization) for thietane have been ~ - ~the ~ strain energy has been assessed (18.9obtained or c a l c ~ l a t e d ~and 19.6 kcal/mo1).83'88790a,90b Thietane is about as strained as thiirane and is much more strained than thiacyclopentane (about 1.O-2.0 kcal/mole) and less strained than cyclobutane (26.1 kcal/mole).88 The heat of formation in the liquid state, AH;",is 5.77 or 6.04 k ~ a l / m o l e . ~ ~ , ~ ~ , ~ ~

G.

Mass Spectrometry; Ionization Potentials

The vertical ionization energy from the highest filled orbital of thietane is 8.65 eV,453walthough a slightly higher value (8.9 eV) was reported earlier.95396 The

Four-Membered Sulfur Heterocycles

442

ionization potential was compared with the potentials of 49 other thiols and sulfides.97 The electronic ground-state of the thietane cation-radical is said to be nonplanar.4' The photoelectron spectrum of thietane shows vibrational fine spacings probably corresponding to the symmetric stretch of the C-S bond and the wagging of the methylene groups.% The orbital shapes for thietane and other fourmembered heterocycles have been discussed, and ionization energies, both calculated and observed, from all orbitals have been given.94 The mass spectrum of thietane shows the base peak at m/e 46, derived from the molecular ion by four-center f r a g m e n t a t i ~ n . ~96398 ' ~ ' Molecular ions are fairly abundant, and there are a number of minor fragmentation pathways, several of which are shown. CH, = ,? m l e 46

%

p,

+.

+ CH,

= CH,

z = 44.9

2 ps+ de73

%,Y = 1.4

CH2-S.

-H.

CH, - CH;

-I

CH=S CH,CH,

+

-

+ HC E S m/e 45 % 9.3

+ CH,=CI-L,

z

The electron-impact mass spectrum of thietane calculated by quasiequilibrium theory agrees well with the observed spectrum.99 The chemical ionization (CH,) mass spectrum of thietane has been obtained along with that of thiols, disulfides, and other sulfides."' The ( M + 1) peak is prominent but is surpassed in intensity by an ( M + S) peak. The ( 2 M + 1) peak is more intense than the peak for the molecular ion (M). 2,4-Dimethylthietane yields an ion, CzH4S+', believed to be the ion-radical of thi~acetaldehyde.'~ 91013102a The mass spectrum of 3-hydroxythietane shows the loss of vinyl alcohol from the parent ion t o give CHzS+'.102b

H.

Dipole Moments

The dipole moment of thietane in benzene solvent is 1.781°3 or 1.72 D.24 It is slightly less than the moment for oxetane (1.92D).lo3 The dipole moments of 3-hydroxythietane (1.92 D, CC14)26d-26f 3-chlorothietane (0.72 D, CC14;26f 1.01, 3-phenoxythietane (1.30 D, CC14)?6f 3-( p-nitrophenoxy) thietane

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) ( C 3 S )

443

(3.33 D, CC14),26fand 3-acetoxy- and 3-(a-methylacrylyloxy) thietanesZbbhave been measured and compared with values calculated for various conformations. Calculated moments for a series of 2,2-diphenyl-3- and 3,4-chloro or cyano-substituted thietanes have been compared with observed moments to determine conformat i o n ~ The . ~ ~ substituents prefer a pseudoequatorial conformation when possible. The two C-Cl bond moments in cis- and truns-2,2-diphenyl-3,4-dichlorothietane differ [p(C3-C1) = 1.40D, p(C4-C1) = 2.10D], which is said to be caused by differing interactions between the lone-pair electrons on sulfur and chlorine.24 2-Methylthietane has a moment of 1.79 D,2' 3,3-dimethylthietane, 1.76 D'04 or 1.87 D'', and the spiro-derivative, 2.6-dithiaspiro[3.3] heptane, 1.12 D.lW

I.

Miscellaneous Properties

Other physical data for thietane that have been collected are the boiling point, melting point, density, cryoscopic constant, viscosity, surface tension, refractive index, parachor, molar refraction, molar volume, specific dispersion, and molar refraction coefficient!lb> Similar data have been compiled for 3-methylthietane.'06 The magnetic susceptibility of thietane has been m e a ~ u r e d . " ~The molecular Zeeman splittings have been reported for thietane; and the magnetic susceptibility anisotropies, both out-of-plane and in-plane, are given.losa The in-plane anisotropy is positive for thietane but negative for thiirane, oxirane, and oxetane. The quadrupole moment Q,, is more negative for thietane than for oxetane, indicating that the sulfur-containing ring has greater electron density above and below the plane of the ring. The molecular stopping cross-section of thietane for fast helium ions has been determined.'Osb Data on the separation of thietane by gas chromatography have been reported along with data on other sulfur c~mpounds."~-"' Thin-layer chromatographic separation of thietane from 1,2-dithiolane and 1,2.3-trithiane works well on silica gel."2a Thietane forms a hydrate (dec 11.7") with water. Its clathrate structure was investigated by use of the nmr line shapes of the deuterium oxide hydrate."2b 4.

Synthesis

The more general methods of thietane synthesis have been reviewed.'32a-2c,lSe Table 5 in Section XXXXV gives some examples of the various thietanes prepared.*

A.

From 1,3-Disubstituted Propanes

Treatment of 1,3-dihalopropanes with sulfide or hydrosulfide ion has been used extensively to prepare thietanes."7b-7e~'5h'70'"3-136e Y'ields reported vary from

* Tables 5

through 22 can be found in Section XXXXV.

Four-Membered Sulfur Heterocycles

444

11-90%. The yields of 3,3-disubstituted thietanes70,'16~117~126~129-136b,136d,136e are generally better than those for less-substituted thietanes, perhaps because elimination is not possible in the 2,2-disubstituted 1,3-dihalopropane precursors and because of the so-called Thorpe-Ingold effect;'37 for example, thietane 2 is obtained from 1 in 85% ~ i e 1 d . l A ' ~ number of spirothietanes have been prepared in fair-to-good yields.~,129-'36b~'36e

I

I

dry Na,S lloo, N,

(ICH2)ZC -CHzC=CCH2C(CH,I),

+

ethvl cellosolve

2

Both anhydrous and hydrated sodium or potassium sulfide in ethanol have been used in the synthesis of thietanes. A common procedure is to use a solution of sodium or potassium hydroxide saturated with hydrogen sulfide. Liquid ammonia has been used as a solvent for the preparation of thietane (32%) from sodium sulfide and 1,3-dibr0mopropane."~Phase-transfer catalysis has been used to good effect.'36d A variation in which 1,3-dichloro-3-methylbutane 3 is treated with aluminium chloride and hydrogen sulfide followed by aqueous sodium hydroxide gave 2,2-dimethylthietane 4 in 90% ~ i e 1 d . l 'An ~ intermediate aluminium chloridealkene complex, 5 or 6 , was proposed.

3

4

AlC13

(CH3),C

$ CHCH,Cl

AlC13

CH,

4 CCH2CH2CI I CH3

5

6

When a five-membered ring can be formed in preference to a four-membered ring, it does so as exemplified by the treatment of 7 with sodium ~ulfide.'~'Only 8 is formed, none of thietane 9 being reported. If excess sulfur is present (formation

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) (C, S)

445

of Si- and higher molecular weight sulfur containing anions), five-membered rings and other sulfur-rich derivatives are obtained.130i135 Treatment of 1,3-dibromide 10 with sodium sulfide and sulfur gave the spiro compound 11 instead of 12, which was prepared in 71% yield by use of potassium hydroxide and hydrogen ~ u 1 f i d e . l ~ ~

Na,S

+Br 0

S , , H,O-EtOH refl. 2 h

L

-

10

S

11

KOH, H 2 S 4h,

KT;

15 min, 100'

71%

12

Thietanes such as 13 are intermediates in the synthesis of thioctic acid.120-122The formation of a five-membered tetrahydrothiophene derivative 16 as well as thietane 17 from 14 is explained by invoking an intermediate epoxide 15.'24A mixture of threo- and erythro-l,4-dichloro-3-pentanol(threo:erythro, 1.6 : 1) gave similar results (45.4% 16, cis:trans, 1.25: 1; 17.6% 17, threo:erythro, 1.3: 1). Benzenesulfonate or p-toluenesulfonate esters of 1,3 glycols frequently give better yields of thietanes than the 1 , 3 - d i h a l i d e ~ . ~ Sodium ~ ~ ~ ~ ~ sulfide -'~ in dimethyl s u l f ~ x i d e , ' ~diethylene ~ aqueous n-butyl alcohol,8b 1,2-

OHCl I I CH3CHCH CHzCH2C1 threo:erythro (1.9 : 1 ) 14

1CH

1

CHzCHzCl

3

15

S-2 ___)

Four-Membered Sulfur Heterocycles

446

OH I

threo:erythro(2.3: 1)

cis:trans(l.8:1)

17 (16%)

16 (37%)

d i m e t h ~ x y e t h a n e , or ’ ~ ~ethanol’@ and sodium hydrosulfide in methyl cellosolvelW have been used. 2-thiaspiro[3.5]nonane 19 is obtained in 75% yield via the benzenesulfonate ester 18,’39 but in lower yields from the d i b r ~ r n i d e . ’ ~ ~

OSOzPh OSOzPh

Na2S.9H,0

DMSO, 9 0 ° , Zh 7S%

19

18

3-Halomercaptans are converted to thietanes by treatment with a 1452146a3 146b as exemplified by the formation of 3-hydroxythietane 21 from 3-chloro-1-mercapto-2-propanol 20;14’ 4-thiocyano-2-pentanol 22 is converted to a mixture of cis- and trans-2,4-dimethylthietane 23 by treatment with sodium hydride.”> 147 The latter reaction involves displacement of cyanate ion by the mercaptide ion. 2,2,4-Trimethylthietane was also prepared by this method. OH I ClCHzCHCH2SH

lO%(aq) NaHCO,

Ho,

60°,3 h , 90%

20

21

Frequently, a “masked” thiol group is allowed to become “unmasked” during the r e a ~ t i o n , ~one~ example - ~ ~ ~ being ~ ~ ~the~ conversion ~ ~ of 22 to 23.52,147Thiol-

OH I CH3CHCHzCHCH3 SCN

I

NaH

triglyme 20%

[

’

SCN

0-

I CH3CH-CHZCHCH3 A ~-

23

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) (C3 S )

44 I

acetates or benzoates of y-halo, y-mesyl, or y-tosyl derivatives have been used.7C - 7e,148-156 Yields range from 94% to 8%. The starting materials are prepared conveniently by addition of a thiol acid to an ally1 halide.148-1s0~152 The method has been used to obtain a good yield of 3-methylthietane 25 from 3-chloro-2-methylpropene 24.148“Deprotection” of a thiol group also has been accomplished by a reverse Michael reaction of a P-thioether of methyl p r ~ p a n o a t e .Treatment ~~ of a 1,3-dihalopropane with thiourea gives the S-alkylated thiourea, which is a mono-yhaloalkylthiouronium salt; the salt reacts with hydroxide ion to give thietanes 27 in yields of 15-50%,’36b31s7-160 as exemplified by the sequence beginning with the 2-alkyl-l,3-dibromobutanes 26.160The oxetane ring of 28 is attacked in preference to the halomethyl groups to ultimately give 29.16’ Pyridothiones, for example, 30 may be S-alkylated by 1,3-dibromopropane derivatives, and the resulting pyridinium salt 31 yields the thietane 32 on treatment with aqueous sodium hydroxide.’62 CH3

CH3

I CH, = CCH,CI 24

I

CH3C0SH

100 W bulb l h 87.8%

CH,COSCH,CHCH,Cl

+

t?

Cl13 NaOH ____)

H,O 80%

25

R Br

I 1 BICHZCHCHCH, R

=

S II

+

NHZCNH,

CH3, C z H 5 , n-C3H7 26

-

+ NH2

R Br

I I NH, - C - S PCH2CHCHCH3 Br-

R

I/

R Br

+

OH

___)

I ’ HSCH,CHCHCH,

27

28

R T , overnight

29

Four-Membered Sulfur Heterocycles

448

Q

Br

SCH2CI

!

I+

CH,

32

31

Treatment derivatives of [2.2.0]hexane penam 3 ~ .

of monothiolcarbonate esters, for example, 33 with bases yields 3-hydroxythietane 34.16,-16' The bactericidal 2-thia-6-azabicyclo36 is obtained by cleavage of a carbon-sulfur bond in the ' ~ ~ 0 II

H2NC-0

34

0 33

OH I CHCH, Br ~

~

0

b

Ph,P, EtO,CN=NCO,Et q (

C02CHzPh

*

~

~

THE', R T 20-30%

35

NHC0,Et

Br -Ph,PO --EtO,CNHNHCO,Et

*

36

~

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) (C3S) B.

449

From Chloromethyloxiranes (Epichlorohydrins) and Chloromethylthiiranes (Thioepichlor0 hydrins)

3-Hydroxythietanes are obtained by treating epichlorohydrins with hydrosulfide ion,15f,51,124,167-171 as illustrated by the preparation of 3-hydroxythietane it~e1f.l~' Work reporting that an hydroxymethylthiirane is formed171 was reinvestigated and the thietane structure was ~ 0 n f i r m e d . l ~ ~

When the potassium salts of thiolacetic acid or 0,O-diethyldithiophosphoric acid are used, the 3-0-acetate or 3-0,O-diethyldithiophosphate derivative is ~ b t a i n e d . ' ~ Thioepichlorohydrin ~,'~~ was believed to be an intermediate, and, in fact, treatment of thioepichlorohydrin with the above-mentioned salts in aqueous media gives similar r e s ~ l t s . ' ~ ~In- 'absolute ~~ ethanol or in 1-propanol, the reaction with the dithiophosphate salt gives mainly the thiirane derivative 38 instead of the thietane, 37. 17' Reactions of thioepichlorohydrin with oxygen nucleophiles (H20,145,178 Ace- ,172 178,179a, 179b PhC0;,'77 C1CH2C0;,177 CH2=C(R)C0;,'80 3

Ar0-,181 -lg3

9

S II (Et0)2PO-184a) and other sulfur nucleophiles (SCN,lwa-lwd A c S - . ' ~ ~

(EtO)PS-184a) give 3-0- or 3-S- substituted thietanes, respectively. Thiirane structures reported as the products of several reactions171 have been shown to be thietane~.'~'The acrylate adducts undergo Diels-Alder cycloadditions with butadiene, isoprene, and cyclopentadiene.180

S II

(EtO), PF

S

II

T L

(EtO),PSK, H,O

+ 37

C

IS

s

dry (EtO),PSK /I

EtOH

38

The kinetics of the reaction with acetate have been investigated and the following mechanism was proposed: 179,185

Four-Membered Sulfur Heterocycles

450

AcO, HOAc, 55'

The rate was retarded by added chloride ion (common-ion effect) but no 3-chlorothietane was identified among the products. No reaction occurred in the absence of a~etate.'~'The possible intermediacy of a sulfurane, proposed in reactions of episulfonium was not considered.

C. From Cyclic Carbonates and Related Intermediates The transformation of 22 to 2352,147 probably involves the cyclic intermediate 39. A similar intermediate is likely in the conversion of 40 to 41."'

39

(1) NH,SCN, H,O, reflux (2) Ac,O, C , H , N , R T 14 h

H

46%

~

Sv"' OAc

40

41

yRydroxy- or y-mercaptothiuronium salts yield thietanes on treatment with base;'2031893190 a cyclic intermediate may be involved as shown for the preparation of 42 in an overall yield of 15.7%.'" 0- or S-esters of 3-mercapto-1-propanol are converted to thietane with b a ~ e , ' ~ ' - ' ' ~a cyclic intermediate 43 being proposed.'" 8-keto S-esters of 0,Odiethyl hydrogen phosphorodithioate are converted to 1,3-diarylthietanes (7994%) by reduction of the carbonyl group by sodium borohydride followed by treatment with sodium h ~ d r i d e . A ' ~ cyclic ~ ~ 5-valent phosphorus intermediate was suggested. Cyclic carbonates of 1,3-propanediols yield thietanes when treated with thiocyanate ion and heated until carbon dioxide is evolved.'32c~158b~194-196e Yields vary from 3 to 6376, the yield being greater for 3,3-disubstituted thietanes, as illustrated in the synthesis of the spirothietane, 44.13*' Oxetanes are formed as byproducts in

45 1

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) (C, S) Br

I HOCH2CH,CH(CH,),CO,CH3

(NH,),CS, EtOH reflux 3 h

w

+NH2 II

C-NH,

Br-

S' NaOH ____)

reflux 6 h

L

-3LG

(CH,),COOH

LtCH 0 /I

EtOCSCH,CH,CII,OH

-

-

42

1

r

NaOH

13mm

J I

I

-co2 -OEt

*

Q

9 1% crude

43

- ocs -0CN

44 (57%)

several cases. Cyclic carbonates with a 54"N-dimethylarnino substituent do not yield thietanes under these ~ 0 n d i t i o n s . lThe ~ ~ chiral (2S)-2+propylthietane has been prepared from a cyclic ~ a r b 0 n a t e . l ~ ~ ~

D.

From 1,2-Dithiolanes via Ring Contraction

The conversion of a-lipoamide 45 to thietane 46198-200 has been used analytically in the determination of the concentration of lipoamide by gas chromatography .,O0

Four-Membered Sulfur Heterocycles

452

c;

(CHz hCONH2

-

-

(2) HCI (1) KCN, EtOH, refl. c 89%

f H 2 ) 4 c 0 N H 2

45

46

Similar ring-contractions have been accomplished by treatment of a dithiolane with tris(&N-diethylamino) p h o ~ p h i n e . ~ ~ ~1,2-Dithiolane-4-one, '~'~'~~ however, gave only polymeric material.'O1 The reaction proceeds by thiophilic attack by the nucleophilic cyanide or phosphine:

Thermolysis of 4-benzoyl-3-phenyl-l,2-dithiolane 2,2-dioxide at 230" in a sealed tube gives 3-benzoyl-2-phenylthietanein 55% yield.202aPhotolysis of 1,2-dithiolanes gives low yields of thietanes.'OZb

E.

From Thietane 1,l-Dioxides by Reduction

Thietane sulfones are reduced to thietanes in moderate yields by lithiurr aluminum hydride~~8a~'39~'41b,203-209 as exemplified by the conversion of 47 t o 48.'" Since many thietane sulfones can be prepared by the cycloaddition of (see Section V.3 .B) this method is useful for sulfenes to e n a r n i n e ~ ' ~2W1206,207b '~' preparing 3-amino substituted thietanes.

N(CH3)2 (1) LiAIH,, E t , O , 0 '

( 2 ) H,O, 53%

47

F.

*

ph+ 48

From Thiocarbonyl Compounds via Cycloaddition to Alkenes

Good yields of thietanes have been obtained by photolysis of a thiocarbonyl compound and an alkene. The thione is excited initially to one of two singlet states, S1 (n + n*) or S2(n+ n*).*" Thietane formation via the SIstate proceeds through

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) (C3 S)

453

a triplet ( T , ) state; the additions to alkenes are nonstereospecific, but regiospecific, which is expected if a diradical intermediate were formed. Cyclization involving the S2 state appears to be nonregiospecific, but stereospecific. Most studies have been with aryl thiones243211-226because of the instability of aliphatic thiones in the ground state. However, the sterically hindered a d a ~ n a n t a t h i o n e ~ ~and ' - ~ ~di-t~ b ~ t y l t h i o n ehave ~ ~ ~ been successfully added to alkenes. T h i ~ a m i d e s , ' ~ ,thio~~'~ e ~ have ~ ~ ~been ~~~ imides,231b-231d,232-2% thiono esters ,235-238 and t h i o p h o ~ g e n also used. A thietane intermediate has been proposed for the photolysis of o-vinyl thioa n i l i d e ~ . ~The ~ ' ~ difference in the behavior of the cycloaddition of reactions proceeding through the n -+ n* triplet and the i-r + i-r* singlet is exemplified by the Reactions proceeding through the n + n* triplet often give reactions of 49.214,215 and other products derived from a diradical intermediate.218 Support for such an intermediate is the observation that the rates of addition of the methylthio radical to alkenes are similar to those for addition of ~ a n t h i o n e . ~ ~ , Molecular orbital interaction diagrams have been used to explain the preference for electron-deficient alkenes to react by the S2 state and electron-rich alkenes by the T1 state224 and to explain the greater preference of aliphatic thiones for reaction with electron-rich a l k e n e ~ . ~ ~ '

I

60%

30%

50%

13%

Ph,CS 49

The photochemical cycloaddition method provides good yields of spirothietanes, as illustrated in the preparation of The (-)3-menthyl ester of methacrylic acid gives thietane 51 in 17% optical purity via the diradical mechanism (S, + T,), but in only 6% optical purity via the S2 state.226 Nonphotochemical cycloadditions of hexafluorothioacetone to alkenes (vinyl cyclohexene,2Mand dimethyl maleate2M) have been ethers,242'243 vinyl observed, as illustrated for methyl vinyl ether.243 The formal addition of thiocarbonyl fluoride to tetrafluorethylene to give hexafluorothietane occurs on mm) of a copolymer of the two components.245a thermolysis at 600-700" 0,U-Dimethyldithiooxalate undergoes a thermal cycloaddition to quadricyclane to give thietane 51a.245c,245d

454

Four-Membered Sulfur Heterocycles

Ph I

50

CH,O I II + CH, = C --OR*

R*OC --loo%

R * = (-)3-menthyl

ratioHA/HB = 5 9 : 4 1

(1) OH-, H,O

(2) C H , N ,

HB 5 1 (47%)

ss

+ MeOCCOMe

CCI,

e

72%

'OMe

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) (C3S)

G.

455

Miscellaneous Methods

Addition of sulfur dichloride to bicyclo[2.2.l]heptadienes gives tricyclic thietanes such as 52246and 53.2473248 In a related reaction, the episulfide 54 yields 52 on treatment with chlorine.249Several spirothietanes 56 have been obtained by treatment of the methone derivatives 55 with sulfur d i c h l ~ r i d e . ~ ~ ~

52

-

c1

SCI,

hexane

-40"

S3%

C1,

54

CH,CI, -20" 100%

I

55 SCI,

EtOAc ice bath 7S-80R

56

53

52

CH,Cl

Four-Membered Sulfur Heterocycles

456

Photolysis of the bicyclic enone 57 gives a modest yield of thietane 58;2s1,252 thermolysis of 5-cyano-2,2,4,4-tetraphenyl- 1,3-dithiane gives 3-cyano-2,2-diphenylthietane by loss of thiobenz~phenone.~~~’~~’ Photolysis of 3,3,6,6-tetramethyl-Sacetoxy-I-thiacycloheptan-4-one gives a small amount of 3,3-dimethyl-2-acetoxythietane which also can be obtained in 30% yield by treatment of 3,3-dimethylthietane with lead tetraacetate in p ~ r i d i n e . ’ ~ ~ ~

dOH

58

51

Cyclization of 8-mercaptoaldehydes has been reported to give 2-hydroxythietanes (which are thioacetals) in 16-84% yield.2s3 They are said to be useful as flavoring substances. However, cyclization of 4-mercaptopropene gave only 0.1% of 2 - m e t h ~ l t h i e t a n e . 2 The ~ ~ ~ major product was thiolane. Photolysis of the a-diazoketone of 2,2,5,5-tetramethylthiolane-3,4-dione in methanol gave a 28% yield of 2,2,4,4-tetramethyl-3-carbomethoxythietane~s4d Several dispirothietanes have been obtained from the bis-hydrazone of 3 - t h i e t a n 0 n e . ~ ~ ~

5.

Reactions of Thietanes

The reaction of thietanes are subdivided as follows: reactions with electrophiles with sulfur acting as a nucleophile or Lewis base, reactions involving ring-opening (including expansion or contraction of the ring), polymerization and miscellaneous reactions involving transformations of functional groups attached to the thietane ring. Some overlap between categories is unavoidable; for instance, reactions with electrophilic reagents may lead to ring-opening. Polymerizations also usually involve ring-opening but are discussed separately because of their commercial interest.

A.

Reactions with Chrbon Electrophiles

Thietanes 59 react with trimethyloxonium tetrafluoroborate to give the S-methyl salts, 60.s2~147~2ss These salts are unstable and decompose on warming (see section II.5.L on polymerization), but one salt 60c has been successfully recrystallized at - 40°C from acetone-methanol.2ss Alkylations with alkyl halides occur readily but yield ring-opened products because of the relatively

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) (C3S)

+ (CH,),O+BF;

-

457

BF, 'CH,

high carbon nucleophilicity of the halide anion coupled with the ring-strain of the intermediate sulfonium salt. Reports of nonring-opening of thietanes on treatment with alkyl halides'32a should be treated skeptically. A monomethiodide salt of a hindered thietane gave a satisfactory elemental analysis and an immediate precipitate with alcoholic silver nitrate.205 Methyl iodide is most commonly Used.113a,116,129,131,132,136b,145,149,161,168,191~192,231a,256-258 It usually alkylates the ring-opened methyl sulfide to yield the sulfonium salt, as exemplified by the reaction of the thietane 61 ,145,168 but there is one case (that of 6 2 ) in which the methyl sulfide 63 is obtained.231a3-Diakylaminothietanes are alkylated at nitrogen instead of at An N-acetylaziridine 64 alkylates thietane under acidic conditions.260The thietanium salt in turn alkylates another mole of thietane. This type of reaction is involved in polymerization of thietanes by electrophiles ( 4 . v . ) .

OH

HO

I

acetone

ICHzCHCH2k C H 3)z I-

61

H

H

acetone CH3

62

COOCH,

CH3 COOCH,

Four-Membered Sulfur Heterocycles

458

Nu:

*

L!

Nu = OAC-,

64

OAc

OAc

;zh I3 Nu

AcN AcO

Ac{-&

OAc-

OAc

SCH3 OAc

Nu=

)3

c+ *

S (CH

)3

0Ac

OAc

SCH3 OAc

\

Alkylation of the sulfur atom of thietane with allyl bromides (or chlorides) gives allyl 3-bromopropyl sulfides, useful intermediates in the synthesis of larger rings, as illustrated by the conversion of thietane to 2 - v i n y l t h i 0 l a n e .261b ~~~~~~~~~

+ CH,=CHCH,Br 7 CH2=CHCH2SCH,CH2CH2Br CH,CN, RT

(1) LiN(iFr),,

~

70’

b

(2) HCI, (3)NaHCO,

(85%)

Treatment of thietane with allyl chloride and silver hexafluorophosphate at room temperature for three days gives a polymer.262a-chloroethers react with thietane and 2-methylthietane to give ring-opened products, for example, 65.263 Alkylation also occurs on treatment of thietane with tribenzylsulfonium perchlorate but a polymer is obtained.78e The formation of polymer where nonnucleophilic anions (PFi, C104) are involved probably is due to unreacted thietane acting as a nucleophile. The acetyl cation affords ring-opening of thietane or 2-methyl-thietane, which gives y-chlorothiolester.264a With 3,3-dimethylthietane, a polymer is obtained.’& The trityl cation gives also ring-opened products?64d What may be considered an intramolecular alkylation of the sulfur atom of thietanes can occur when there is a good leaving group at the 3-position. Reactions of such substituted thietanes may proceed via the bicyclic sulfonium ion 6 6 . The

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) (C3S)

45 9

65

major product is 67 rather than 68. In a series of P-chlorosulfides, the rate of hydrolysis of 3-chlorothietane was g r e a t e ~ t . ' ~ ' -Although ~~~ a special salt effect was observed for its hydrolysis, which indicates return from 66265(via the k - , step), no " 0 scrambling was observed with the carbonyl 180-labeled 3,5-dinitrobenzoate ester, which indicates that this substrate is not undergoing significant return, that is, k z> k-1?66

66

67

68

The intermediate ion may be considered a hybrid 69 of resonance structures a-c analogous to those written for the cyclobutyl cation. Alternatively, the ion may

be considered a complex of a sulfur atom with an ally1 carbenium ion. Nucleophiles may attack 69 to give 6 7 , 6 8 , and 70, the latter the result of thiophilic attack. Thiophilic attack is shown by the formation of disulfide 71 on treatment of 3-chlorothietane with thiophenoxide ion?66,268Although the reaction of 3-chlorothietane with thiocyanate ion gives both 3-thietanyl thiocyanate and 3-thietanyl isothiocyanate (the former isomerizing to the latter at room temperature), in dioxane solvent the disulfides 72 or 73 are said to be obtained.'84c A possible scheme involving ion 69 is given. Reactions of 3-chlorothietane with piperidine266 and O-Oand anions such as thioacetate,268 O-O-diethyldithi~phosphate,'~~~~~~ diethylmonothiophosphate (formation of C-S bond).'84c have also been reported. An intermediate ion analogous to 66 was suggested to explain why treatment of 2-phenyl-3-hydroxythietane with thionyl chloride gives 3-chloro-1-phenylpr~pene.'~' Intramolecular alkylation of the sulfur atom of thietanes also is invoked in reactions of c~-haloalkylthietanes,''~~'~~for example, the formation of 75 in reactions of alcohol 74.lz3 The salt 75 has been isolated. The ion 76 is attacked at carbon by acetate ion, but at sulfur by hydride ion.z69The reactions of sulfur dichloride with 5-ex0-methylene-2-norbornene to give 53 is believed to involve an intramolecularly S-alkylated t h i e t a ~ ~ e . ' ~ ~ The investigation of the reaction of carbenes or carbenoid species with thietanes

460

L

Four-Membered Sulfur Heterocycles

a

b

+

C

J

L

69

Nu

+ CH,=CHCH,SNu 67

68

C1

70

PhS

+ PhSSCH,CH=CH,

PhSH, KOH 70-80”, 1 h

71 (32%)

(30%)

CH, =CHCH, SSCH~CHCH,Y 72 X = - S C N o r - N C S , Y=C1 7 3 X = C1; Y = -SCN o r -NCS

OH I CHCH,

C1

reflux 1 5 rnin. 87.5%

(333

75

74

z

Aco&foAc

76

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) (C3S)

46 1

has been limited. A trace of ylide 78 is said to be obtained from thietane and 77, but characterization was confined to an infrared spectrum.270Diethyldiazomalonate reacts with thietane at 110" in the presence of copper(I1) sulfate to give a ringexpanded product, 2,2-(bi~-methoxycarbonyl)thiolane 80, probably via the ylide 79.271 Polymeric material is obtained when the azo ester is photolyzed with thietane. Intramolecular thietane ylide formation occurs via the carbene derived from 1-phenyl-3-thioalkyl (or 3-thiophenyl)-l-propanonet o ~ y l h y d r a z o n e . ~ ~ ~ ~ - ~ ~ ~

a

CN l C S CHCI + (PhCH2I2Se= CCOOCH3 2 , RT, 24 h

77

(PhCH,),Se

+ 78

vC(CN)COOCH3

8 0 (26%)

B.

Reactions with Nitrogen Electrophiles

0-Mesitylenesulfonylhydroxylamine (MSH) reacts with thietane to give the S-amino salt 81 .272-274 An attempt to prepare a sulfilimine by treatment of 81 with a basic ion exchange resin was not successful.272 Chloramine-T gives the N-@tolylsulfony1)sulfilimine 82.27s Several substituted thietanes yield the N-tosylsulfilimines in 56-1000/0 The S-NTs bond prefers an equatorial conformation.276 Of cyclic (four-sevenmembered rings) and acyclic sulfides, thietane reacted slowest with c h l ~ r a m i n e - T .The ~ ~ ~chloramine-T reactions really proceed via an electrophilic attack by chlorine on sulfur.

Four-Membered Sulfur Heterocycles

462

81 (77%)

C.

Reactions with Oxygen Electrophiles (Oxidation)

Thietanes may be converted to S-oxides or S,S-dioxides (sulfoxides and sulfones, respectively) by treatment with oxidizing agents. Hydrogen peroxide (30%) is most in acetic acid,10a,25,51,116,129-135,139,161 168,179b,l81,188,207b, conlmon~y used 211,212,214,242,246,257,258,277,278 but also in formic acid,53,146a,146b acetone,125a,207b, 276,279,280a ethano1,277 o1 wa~er~26a,151,163,165,180,213,216,280b Add'ition of a small amount of tungstate ion is helpful in the oxidation of 3-hydroxythietane to the su1f0ne.l~~ The rate of oxidation of thietane by hydrogen peroxide is slower than ~ ~ difficulty with the the oxidation of five- or seven-membered cyclic ~ u 1 f i d e s . lOne use of hydrogen peroxide to prepare sulfoxides is overoxidation to the sulfone. Avoiding an excess of hydrogen peroxide and working at low temperatures optimizes sulfoxide formation. Use of acetone as a solvent gives predominantly sulfoxides, but sulfones have been obtained with excess o ~ i d a n t . ~ ~ ~ , ~ ~ ~ ~ l f o Potassium or sodium permanganate yields thietane ~ and treatment of thietane with concentrated nitric acid gives polymeric material.257 Less concentrated nitric acid gives the ~ u l f o n e sor, ~ ~in~ the ~ case of a spirodithietane, a trace of the sulf~xide-sulfone.'~~ Peracids such as m-chloroperbenzoic,sa~'41b'158b'170,202a,207b222a,250 ,281a perben~ o i ~or , ~ ~ ~ , ~acids ~ may ~ give ~ sulfoxides (especially m-chloroperbenzoic acid at 0" in methylene chloride207b),but oxidation to the sulfone stage is not UnCOmmOn~8a,52,125b,130,136d,141b,158b,170,202a,207b,222a Sodium and potassium metaperiodate at 0" converts thietanes to sulfoxides in moderate to good yie~ds,51,141b,207b,249 ,276,281a,282 as exemplified by the formation of the isomeric sulfoxides 83 and 84 from 3-liydro~y-3-methylthietane.~' Other reagents of utility in the synthesis of thietane sulfoxides are sodium I

'

n

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) (C3S)

463

HO H,O, O o * NalO,

C I I&s=o ,

+Ho&s=o 84 (30%)

8 3 (26%)

hyp~chlorite'~' or t-butyl h y p o ~ h l o r i t e ,N-chlorotriazole,207b~283 ~~~~ chromium 280c singlet oxygen,284 trioxide-acetic acid,'29 chromic acid,207b dinitrogen t e t r o ~ i d e ? ' ~N,N-dimethylaniline ~ N - o ~ i d e s ? ~and ' oxaziridines such as 85 ?86a Azaaromatic N-oxides photochemically transfer oxygen to the sulfur atom of thietanes but the yield of sulfoxides is low.286b CHCI,

iP

Ph

N ,

2 5'

SO,Ar

*

ps+ P h C H = N S O , A r \\

60-63%

0

8 5 (Ar = Ph, pCIl,C,H,)

The stereochemistry of oxidation of 3-substituted thietanes has been discussed.207b Both thermodynamic and kinetic determination of products are observed. For example, oxidation of 3-t-butylthietane with dinitrogen tetroxide gives a cis:trans ratio of 82: 18 (the cis isomer is more thermodynamically stable than the trans, provided the sulfinyl oxygen prefers an equatorial configuration) whereas oxidation with hydrogen peroxide-acetic acid gives a cis: trans ratio of 43 : 57.207b

D.

Reactions with Halogen Electrophiles

The reaction of sulfides, such as thietane with chloramine-T previously mentioned, proceeds by initial formation of a sulfur-chlorine bond.275The intermediate sulfonium salt may yield the sulfilimine or the sulfoxide:

1

ArSO NHCl

A

ps+ ArS02NH

C1

NS0,Ar

Four-Membered Sulfur Heterocycles

464

Treatment of thietane with ~ h l o r i n e , "bromine,287 ~ or sulfuryl chloride'57 yields ring-opened materials. Trifluoromethyl hypofluorite gives tetravalent and hexavalent sulfur-fluorine compounds 86 (a sulfurane) and 87 (a persulfurane) from Ionization of 86 (R = H) at -20" to -40°C thietane and 3-methylthietane.288'289 was indicated by the collapse of the two doublets observed in the I9F nmr spectrum.288

I

F 87

86

Dibromosulfuranes of thietanes are not but diiodosulfuranes have been These dihalosulfuranes may ionize, as does 86, to the S-halothietanium halides, although this is more likely for the bromo- than the iodo derivatives. The bromine adduct of thietane is said to lose hydrogen bromide at 15°?57 The equilibrium constant ( K f z87, CC14, 25") for the formation of the thietane-iodine complex has been determined by nrnrz9O and spectrophotometric technique^.^^^'^^^ The thietane complex is less stable than the complexes of the five- or six-membered cyclic sulfides. The basicity of eight 3-substituted thietanes toward iodine has been determined.IMbThe enthalpy of formation (- 7.5 kcal/mole) and the wavelength (305 nm) of the charge-transfer band of the thietane-iodine complex have been determined."j E.

Reactions with Sulfur Electrophiles

The cation radical 88 is obtained in low yield by the reaction of thietane with hydroxy radicals. A three-electron bond between the two sulfur atoms was proposed.294 The ring-expansion of thietanes to 1,2-dithianes by treatment with elemental sulfur will be discussed in Section II.5.K.

88

F.

Reactions with Protons

The basicity of thietanes has been discussed in Section II.3.E. The conjugate acid of thietane has been observed by nmr spectroscopy in fluorosulfonic acid-antimony and in the mass Treatpentafluoride-sulfur dioxide at - 60"

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) (C3S)

465

ment of thietanes with gaseous hydrogen chloride gives an unidentified, low-melting solid treatment with aqueous acid gives polymeric materia1.81c’257’263 Sulfuric acid treatment gives sulfur dioxide and a polymer.150 a-alkoxythietanes undergo ring-opening in acidic media, as is expected for their monothioacetal structures.243

G.

Reactions with Metal Ions

Mercuric &loride ,113a,i 16,129-131,148,207b,257 mercuric b r ~ r n i d e , ‘ ~ ~ ’and ’~~ mercuric acetate15’ 7296a form stable, solid complexes with thietanes which melt with decomposition. They are useful in the characterization of thietanes. No difficulty was experienced in the formation of complexes of 3-substituted thietanes even when the substituent was t - b ~ t y l ? ~but ’ ~ the 2,3-disubstituted thietane 89 did not give an isolable mercuric chloride complex.205 The superior complexing ability (relative to acyclic sulfides) of thietane was determined by partitioning thietane between heptane and saturated aqueous mercuric a ~ e t a t e . 2 ~ ~ ~

89

and p a l l a d i ~ m ~complexes ~ ~ , ~ ~ of ~ thietane297-299 and 3,3d i m e t h ~ l t h i e t a n e ~have ’ ~ been prepared as illustrated for 90.298The platinum complexes exist in cis and trans c o n f i g ~ r a t i o n s , 2but ~ ~no cis-trans isomerization of the palladium complexes in the solid state was ~ b s e r v e d . ~ ”Stability constants of thietane with Mn(II), Co(II), and Ni(I1) chelates have been determined.296bProton nmr studies show that the absorption of the a-methylene protons, which are syn to the metal, is shifted downfield (about 0.7 ppm) more than the absorption of the ’~ of activation for protons anti to the metal (about 0.4 ppm d ~ w n f i e l d ) . ~Energies pyramidal inversion were determined.298Bis-ruthenium complexes of di-, tri- and tetraspirothietanes (e.g., 90a) show rapid electron transfer between the ruthenium ions; long-range electron tunneling was proposed.299c3d

90

90a

Four-Membered Sulfur Heterocycles

466

Other Lewis acids that complex with thietane are titanium tetrachloride or boron trifluoride?'' trimethylaluminum,302 and tin t e t r a c h l ~ r i d e . ~ ' ~ The enthalpies of formation of the aluminum complex (- 16.04 k c a l / m ~ l e )and ~~~ the tin complex (- 14.2 k ~ a l l m o l e )and ~ ~ ~the wavelength of the charge transfer band of the tin complex (270 nm) have been determined. The titanium tetrahalides form both a 1 : 1 and a 1 :2 adduct (titanium halide :thietane).300 Treatment of 3methyl-thietane with aluminum chloride or tin tetrachloride yields a rubbery white S

O

I

~

~

.

~

~

H.

~

~

Reactions with Nucleophiles and Bases

Nucleophiles may attack either the sulfur atom or a carbon atom of thietanes to give ring-opened products. Bases may effect an elimination with rupture of the ring. Nu:.

n S-NU

-

Although the thietane ring is relatively stable to hydride ion (see Section II.4.E.),'55 in one case it can be cleaved, as is shown by the reaction of 91.269A similar result is obtained by treating the dichloride analog (52) of 91 with ethanolic potassium cyanide.249 n - b ~ t y l l i t h i u m , 2e t~h~y~l l~i ~t h i ~ m ,and ~ ~ phenyllithi~m~'~ attack the sulfur atom of thietanes to give ring-opened products, exemplified by the reaction of thietane with n - b u t y l l i t h i ~ m .Sulfur ~~ nucleophiles ( ~ - B u S K , ~ " PhSK268) and p h o ~ p h i n e s[PhSP, ~ ~ ~ (PhO),P] ~ attack the sulfur atoms of 3-chlorothietane with ringopening as shown. The phosphines effect desulfurization but their reaction with thietane and 3-hydroxythietane is poor, possibly suggesting that a different mechanism is involved for these substrates. Lithium phenylphosphide reacts with thietane to give the lithium salt of 3-phenylpho~phinopropanethiol.~~~ Thietane is reported to react with ammonia to give 3-aminopropanethi01,"~~but a later report was n e g a t i ~ e . 3 'Ammonia ~~ does react at both @-carbon atoms of 2-(2-phenylethyl)thietane in the presence of zeolite sieves.307bWater also was said to give 3-rner~aptopropanol,"~~ No reaction occurred with NN-di-n-butylamine (even in a sealed tube at 100-1 15°C264a) or aniline.' Nor was any reaction reported with potassium hydrosulfide?@a Photochemical addition of a-methylacrylonitrile to 3-methyl-4-thiouracil in the presence of methanol is said to yield 93 via a thietane

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) (C3 S)

LIAIH,, AICI,

461

-

*

17%

THF', reflux 24 h

91

33%

+

n - C , H ,SK

P-

b

C1

L

xylene [

C

6 ',%

H - C ~ H ~ S S C H ~ C H = C KC1 H~

H

2

= CH-CH2iPPh3 C1-]

C H z = CHCHzCI

+ Ph3PS 93%

reflux 7 0 h

intermediate 92 ;231d the reaction probably does not proceed via direct nucleophilic attack of methanol on the thietane, but rather through a diradical since thietanes are photochemically labile (see Section 11.5.1). HSCH2

I

H 92

93

Treatment of 2,4-diphenylthietane 94 with potassium t-butoxide yields a variety of products for which a cyclopropane mercaptide precursor was suggested, although it seems equally likely that the ring might be directly cleaved by an elimination reaction.308 A ring-cleaving elimination of 91 via an organocuprate derivative 95 also has been reported.269

468

Four-Membered Sulfur Heterocycles

flph KOtBu DMF

S

II

[Ph6HCH2CPh

-

80'. N ,

Ph 94

0

Ph

I/

+

+ PhCH2CHzCPh

s

Ph

Ph

Ph

Ph

Ph

Ph

CH3:kY (1) CH,Li

cs

(2) CH, Br

SCH3

95

I.

Desulfurization by Chemical, Photochemical, and Thermal Methods

Desulfurization of thietanes by Raney nickel in ethanol or methanol yields either ring-opened products,117,132C,145,166,188,206,246 a synthetically useful procedure illustrated by the conversion of 2 to the bis-neopentylethylene 96,117 or c y c l o p r ~ p a n e s ~ " as ~ ~in' ~the ~ ~formation ~~ of 98 from thietane 97.'11 Cyclo-

S CH2 C

CCH2

Ka-Ni

CH,OH, N ,

(C€13)3CCH,CH = CHCHZC(CH,), (cis and trans) 96

CH3 Ka-Ni,

C,H,DH

reflux,

lh

7 7%

CH(CH3 )2 98

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) ( C , S)

469

propane formation has been observed only with thietanes substituted in the 2-position with at least one phenyl group or two alkyl groups. Molybdenum atoms3" and singlet carbon atoms310 remove sulfur to give cyclopropanes and/or alkenes. Phosphines also may effect desulfurization, but yields are poor for thietane.306a Thietanes are photochemically unstable and should be protected from light if they are to be stored for any length of time.311 Short-lived (hot) biradical intermediates, for example, 98a, appear to be formed and can undergo a variety of reactions, as shown for thietane.312-317 Mercury-sensitized photolysis gives triplet biradicals that are longer lived than the singlet biradicals formed on direct excitation.317-319a Some cyclopropane product is produced in the sensitized photolysis. The second excited singlet state of thietane decomposes either to ethylene and thioformaldehyde via a 1,4-biradical or to elemental sulfur and c y c l ~ p r o p a n e . ~ ~ ~ ~ 3-Ethyl-2-n-propylthietane photochemically gives products of retained stereochemistry.319bDecomposition of the biradical to an alkene and a thiocarbonyl compound is COmmOn~202a,218 ,221,231C,231d,232,233,237,238,320,321 Electron-spin resonance reveals the presence of sulfur radicals, probably dimers of 98a, when thietane is photolyzed at 77°K.322 Thioformaldehyde from thietane has been trapped as the Diels-Alder adduct (98b) of cyclopentadiene which also apparently traps the b i r a d i ~ a l .The ~~~ dependence of the products on whether a singlet or triplet biradical The intermediate thietane is a precursor is shown by the photolysis of 99 to 101, proposed in the photochemical reaction of cytosine with 4-thiouracil, was suggested to open to a thiol intermediate that loses hydrogen sulfide to give the observed product.323 Dissociative photoionization of thietane yields the ion CHS' .319c Thietane is apparently shattered to atoms, radicals, and ions on irradiation by a pulsed, l00mW ruby laser.5c Sulfur is lost and scavenged by molecular oxygen to

. .

-CH ,=CH

98a

\P

*/ polymer-

Ci

* CH2=S -polymer

[c! or

S

or

&

98b

Four-Membered Sulfur Heterocycles

410

hv (> 400 n m )

CHCOOCH, 100 (87%)

hu (300 n m )

99

bl00(44%)

+

(24%)

101

give sulfur dioxide. Carbon xide and water are also produced in the presence of oxygen. At higher oxygen pressures, the sulfur atom appears as hydrogen sulfide, carbon oxysulfide, and carbon disulfide. ' ~ ~ ~ ~ yields principally ethylene and thioThermolysis of t h i e t a r ~ e31533243325 formaldehyde, a vibrational analysis being done on the latter derived from both protio- and p e r d e u t e r i ~ t h i e t a n eThe .~~~ kinetics has been Thermolysis of 2-phenylthietane proceeds similarly.'36c A number of other products such as methane, ethane, propane, thiophene, and ally1 mercaptan have been observed. 136c731

J. Reactions with Free Radicals The reaction of thietane with N-chlorosuccinimide to give 102 may proceed via attack of a nitrogen radical on sulfur, but an ionic mechanism via an S-halosulfonium salt intermediate is also possible.326 Alkoxy radicals attack the sulfur atom of thietanes to give ring-opened alkyl radicals 103 whose electron-spin resonance spectra have been obtained.3273328a Trifluoromethylthio and other sulfur

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) (C3 S)

47 1

radicals react with the sulfur atom of thietane to give an adduct that is nonplanar at the 3-coordinate sulfur atom.328b The unpaired electron occupies an S-So* orbital. The adduct undergoes rapid ring-opening. Treatment of thietane with chlorine287 or sulfuryl chloride’57 gives the ring-opened 3-chloropropane sulfenyl chloride that may react with excess thietane to give bis-(3-chloropropyl) d i s ~ l f i d e . ’ ~In~ aqueous acetic acid chlorine and thietane give 3-chloropropanesulfonyl chloride (72% yield).287 The formation of 2-acetoxy-3,3-dimethylthietane by treatment of 3,3-dimethylthietane with lead tetraacetate in pyridine may involve radical intermediate^."^^

C,H, or CCI,

P

R

0

+

R’O.

($N-sr.c..;3cl

-

0

102

R’OS(CH,),CHR 103

R = H, CH3 R’ = t-Bu, (CH3)3Si, Et

The excited state (diradical) of thiobenzophenone gives 3-cyano-2,2-diphenylthietane and the disulfide 104.,18Treatment of 91 with tri-n-butyltin hydride or chromium(I1) acetate gives the tricyclic thiol 105 via radical intermediate^.'^'

CN

CN tFfr:’th2CS 104 r

91

nBu,SnH or Cr(OAc),

r

*

4 -& SH

105

SH

Four-Membered Sulfur Heterocycles

472

K.

Ring-Expansions

Ionic ring-expansions of 2-substituted thietanes in many cases probably proceed via the ion 106, which can open to a five-membered cyclic cation. The ringexpansion of 74 by such a mechanism has already been discussed in Section 11.5 The conversion of 2-methylthietane to thiophene and di- and tetrahydro, ~and ~ ~ aluminum ~~ thiophenes with triphenylmethyl cation^,^^^^^ 329 c h l ~ r a n i l329 OXide264,330a-33& so may occur via similar ions. 2-Methylthietane also yields 3-butenethiol when heated with alumina.330a-330fThe isomerization of hydroxybenzodihydrothiophenes by aluminium chloride is believed to involve common thietane intermediates that subsequently undergo ring expansion.330g

r ~ ~ yields ~ ~ 1,2-dithiolanes ~ ~ ~ Heating several thietanes with s ~ l f or~ selenium141a and a 2-selenathiolane, for example, 107 from 19, respectively. The reaction of 108 with sulfur provides a synthesis of thioctic acid.'" A somewhat similar reaction involves heating thietane with aluminum oxide whereby 1,2-dithiolane and A photohydrogen sulfide are produced, but the dithiolane yield is very chemical ring-expansion of 99 has been described in Section 11.5.I?' Treatment of thietane with hexafluoroacetone gives a six-membered cyclic sulfenate.331c

gray Se, KCN (trace) diethylene glycol 180-190°, 16 h

7 5%

19

107

dCH2)4c00H 5f (CH 2 )4 C OOH

s*

160-180°, 30 min. 64%

S.

108

4

L.

Polymerizations

Early reports and patents mentioned the formation of oligomers and polymers from t h i e t a n e ~ . ' J ' ~ ~ , Possible ~~~ polymers of 3-hydroxythietane obtained from 9333

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) (C3 s)

473

epichlorohydrin and sodium sulfide were said to be elastomer^.^^,^^^ The instability of thietanes to protons has been mentioned in Section II.S.F., polymeric . ~ ~ ~ ,mp ~ 200~ ~ material being obtained in several c ~ s ~ sPoly(3-thietanol), 240°C, is obtained by treatment of aqueous 3-thietanol with a small amount of 5% sulfuric The cationic polymerization of heterocyclic monomers has been reviewed?36c and the polymerization of thietanes has been effected by the use of Lewis acids ( B F .~~ ~ , 0 ) , 1 3 6 a , 1 9 6 ~ , 3 3 7 - 3 4 2 BF3(gas),339 BF3.Et20-epichlorohydrin ,78b- 78d,337 Et3AI-H20-epichlorohydrin,78h,342 PF 5 , NbF5,%l TaF5,341 alkyl ~~~ sulhalides and silver(1) ion,26233431344 acetyl h e ~ a f l u o r o a n t i m o n a t e , 2dimethyl ~ ~ - ~ ~ ~ ~ ~ ~ ~tetra-~~~ fate,337h triethyloxonium t e t r a f l ~ o r o b o r a t e , ~ trimethyloxonium f l u o r o b ~ r a t e and , ~ ~tribenzylsulfonium ~~~~~ p e r ~ h l o r a t eA. ~variety ~ ~ of 2,2- and 3,3disubstituted thietanes and thietane itself have been polymerized with these initiators, but 6-thiabicyclo[3.1.l]heptane did not give a high-molecular-weight polymer.342 A block copolymer was obtained from 3,3-dimethylthietane and poly(ethy1ene oxide): the sulfhydryl groups of the thietane polymer (prepared via BF3.Et20 catalysis) were reacted with one of the isothiocyanate groups of toluene2,4-diisothiocyanate, the remaining isothiocyanate group being allowed to react with poly(ethy1ene oxide).340 This polymer absorbs iodine and silver ions. A block copolymer with poly(tetrahydr0furan) and thietane or 3,3-dimethylthietane has been prepared.345 Graft copolymers with poly(viny1 chloride)344 or poly (chloroprene)262 have been obtained via the silver salt-alkyl halide method. 3,3Dimethyl- and 3,3-diethylthietane have been copolymerized with 3-ethyl-3(methy!eneallyloxy) thietane.341 Rate constants have been obtained for propagation and termination steps in the polymerization of thietane, 3,3-dimethylthietane, and 3,3-diethylthietane catalyzed by triethyloxonium tetrafluoroborate and for the cross-propagation reaction in which the propagating species from one thietane is ' ~ steric effect of the 3-substituents is treated with a different t h i e t a r ~ e . ~The apparent. The cationic polymerization is propagated by nucleophilic attack of the thietane on the thietanium salt. 78h-78d,13493419342

Treatment of thietane with electron acceptors, such as tetracyanoquinodimethane (TCNQ),353tetracyanoethylene (TCNE),354maleic anhydride ,355 or tetran i t r ~ m e t h a n einduces , ~ ~ ~ polymerization, believed to occur through an intermediate charge-transfer complex. The reaction with tetranitromethane is unusual because nitric oxide, nitrogen dioxide, carbon monoxide, ethylene, ethane, and propane are

~

~

Four-Membered Sulfur Heterocycles

414

formed in addition to the polymer that is believed to contain some disulfide links on the basis of the sulfur content.354 Anionic polymerization of thietane and various 2-, 3- and polysubstituted thietanes has been achieved with alkali metals (Li, Na, K, Cs, Rb),356 naphthyl sodium,357-359 n - b ~ t y l l i t h i u m , 3 ~ 1,4-dilithi0-1,1,4,4-tetraphenylbutane,~~~~~~ ~-~~~ and a thiolate anion.359Treatment of 3-chlorothietane with aqueous sodium thiocyanate is said to give polymeric rnaterial.lMc Polymerization of thietane has been effected with Grignard reagents.337b,337cThietane and substituted thietanes have been polymerized with dialkyl zinc reagents.365 A copolymer has been obtained by treating 2-methylthietane and styrene with n - b ~ t y l l i t h i u m a; ~block ~ ~ copolymer has been derived from thietane and i ~ o p r e n e .Co ~ polymers ~ ~ ' ~ ~ of ~ thietane and 3,3dimethylthietane with pivalolactone have been reported.366 Polymerizations also have been effected with heat'" and light.245a7271a3367 Photolysis of thietane in the presence of catalytic amounts of diaryliodonium salts gives a 14%yield of polymer.367Poly(hexafluorothietane) is obtained on photolysis of the monomer for four days.245a 6-Thiabicyclo[3.1.1]heptaneis said to give positive indications for free-radical formation in a ~ r y l o n i t r i l e . ' ~ ~ Polymers of thietanes have been converted to the corresponding polysulfand p o l y s ~ l f o n e s3383341 . ~ ~ ~ 342,360 ~~ A bl end of preformed polyalkene [e.g., polypropylene] and poly(thietane) has been milled and molded and is used for making fibers, films, bottles, and pipes.368 Polymerizations via the hydroxyl group of 3,3-bis(hydroxymethyl) thietane have been used to prepare and pol yet her^.^^' Tin derivatives are stabilizers for poly(viny1 ~ h l o r i d e ) ' as ~ well as being used in polyurethane formation.370Cyclic carbonate derivatives are homo- or copolymerized to high-molecular-weight solids.15j The methacrylate ester of 3-hydroxythietane has been copolymerized with methyl m e t h a ~ r y l a t e . ' ~ ~ Raman spectral-band frequencies for poly (thietane) as a crystallized melt annealed at 62" satisfy the rules for a longitudinal acoustic-mode frequency for deducing thickness.372The morphology and physical properties of isoprene thietane block copolymers have been Potential energies have been calculated for helical- and glide-type conformations of ~ o l y ( t h i e t a n e ) and , ~ ~ the ~ ~ conformations of the homopolymer have been calculated.374b

M.

Reactions Involving Substituents on Thietunes

2,2-Dichlorothietanes (e.g., 109), prepared by the photochemical addition of thiophosgene to alkenes, can be hydrolyzed to 0-propiothiolactones; the chlorine atoms can be replaced with hydrogen by treatment with lithium aluminium hydride.239,240aThietanes investigated were highly substituted at other positions. The 2-alkoxythietane 110 undergoes an acid-catalyzed exchange of the alkoxy group .243 3-Hydroxythietane may be converted to esters of carboxylic acids by treatment ~~ of 3-hydroxythietane with an acid chloride15f'1772178 or a n h ~ d r i d e . 'Treatment

Thietanes (Thiacyclobutanes, Trimethylene Sulfides) (C3S)

47 5

H2O

silica gel, 7 1 %

110

with aminophosphines (1 11) yields 0-3-thietanyl phosphines, some of which show insecticidal proper tie^.^^'-^^^^ These derivatives may be converted to thiophosphate esters by reaction with elemental sulfur. The urethane of 3-hydroxythietane is obtained by treatment with sodium cyanate and trifluoracetic acid.'63 Acrylic esters of 3-thietane undergo Diels-Alder additions with cyclopentadiene, butadiene, and isoprene.'*' 3-Chlorothietane is obtained from 3-thietanol by treatment with thionyl ~ h l o r i d e . ~ ~ " , ~ *Ph' ~osphorous ,~~* pentachloride gave three products of unknown structure, one of which was believed to be 3-chorothietane-1,ld i 0 ~ i d e . I ~3-chlorothie ' tane reacts with various nucleophiles (CH3COSK,268PhS-,268 (E tO),PS,K , 1 7 7 3 (E t 0)2P0S-,184c SCN- 84") to give 3-substitu ted thie tanes (see also Section II.5.A). Thietane carboxylic acid derivatives react normally with [3.1.3.2]undecane, a m i n e ~The . ~ ~dispiro compound, 2,5,8-trithia-lO,ll-diazadispiro can be dehydrogenated to the azo derivative that thermally loses nitrogen to give 2,7,9-trithia[3.0.3.ljdispirononanc, which is desulfurized by triphenylphosphine to 3-(3- thie t anylidene) thie t ane .254d Functional groups not directly attached to the thietane ring react normally. Alcohols can be converted to e s t e r ~ , ~ g , "j, log,1237156116' ethers,'61 urethanes,161 loci

111

Four-Membered Sulfur Heterocycles

476

and s t a n n o ~ a n e s . ~ ~Acetals , ~ ' ~ , ~are~ hydrolyzed in dilute acidEb and carboxylic acids can be converted to esters120"21 and amides.'*' 3,3-bis(halomethyl) thietanes can be converted by displacement reactions into ethers379 and a dithiophosphate ester.380aThe chlorine atoms of the dichloride 52 may be replaced by h y d r o ~ y l ? ~ ' acetate,269or bromine269without a rupture of the thietane ring. The carbonyl group of 2-acetylthietane can be reduced with sodium borohydride without loss of the thietane function.'z4b Further cycloaddition may occur to the double bond of thietane 51a?45C

111. THIETANE-1-OXIDES (THIACYCLOBUTANE-1-OXIDES) 1.

Uses

Thietane 1-oxide may absorb carcinogens.3EmThe cyclic carbonate derived from bis(3,3-hydroxymethyl)thietane 1-oxide can be homo- or copolymerized to give high-molecular-weight solids."J The sulfoxide of compound 52 is said to be useful in the preparation of pesticides, pharmaceuticals, and high-melting plastics.27E 3-aryloxythietane 1-oxides are claimed to be useful as herbicides, fungicides, insecticides, acaricides, antioxidants, stabilizers for plasticizers, and dye interm e d i a t e ~ .Quinazoline ~~~ derivatives of thietane 1-oxide carboxylic acids may be antihypertensive.7f

2.

A.

Properties

X-Ray and Microwave Structure Determinations

X-ray analysis of cis- and trans-3pbromophenylthietane l - ~ x i d e , ~trans-3'~ carboxythie tane 1 cis-2,4-diphenylthietane-trans1 and the tris(dipivalomethanato)europium, Eu(dpm)3, complex of 3,3-dimethylthietane 1 - o ~ i d shows e ~ ~that ~ ~(in~ the ~ ~solid state) the ring is puckered with dihedral angles (CzSC4 vs. C2-C3-C4) ranging from 153" to 138.1". The sulfoxide oxygen atom is equatorial in all cases; hydrogen bonding occurs intermolecularly in the 3-carboxy derivative.3E2Bond distances in are as follows: S-0, 1.482 (cis-pb r ~ m o p h e n y l ) , 1.492 ~ ~ ~ ( t r a n s - p - b r o r n ~ p h e n y l ) 1, ~.53,382 ~ ~ 1.466,3E3 1 . 4 8 y S-C, 1.84,381 1.83,3E1, 1.83,jE2 1.85,3E21.847,3E31.85,3E51.84;385C-C, 1.54,3E11.52,381 1.50,38z 1.55,3Ez 1.565,3E3 1 ~ 6 , ~1.55.3E5 " Bond angles are as follows: C-S-C, 76.6" ,3E2 76.5" ,J's 75.8" ;3E5 C-C-C, 96.6" ,3Ez 93.9" ,383 93.6°;3E5S-C-C, 89.9" ,382 90.6" ,382 86.9" ,3E3 89.1" ,3E5 89.9" .3E5 In the 3-carboxy compound, the lengthening of the S-0 bond may be due to hydrogen bonding. In the europium complex, the sulfoxide oxygen occupies one of four equivalent positions of lowest symmetry in a wedged octahedron.384i3E5The crystal structure of rel-( lR,2S,3R,4R)-3-hexyl-2hydroxymethyl-4-methylthietan-1-oxidehas been determined; bond lengths and angles are similar to those in the other thietane l - o x i d e ~ . ~ ' ~ ~

a

Thietane I-Oxides (Thiacyclobutane-1- Oxides)

477

The structure of thietane 1-oxide has been investigated by microwave spectroscopy: dihedral angle 145.1', C-S, 1 . 8 3 6 8 ; C-C, 1 . 5 4 2 8 ; C-S-C 75.7', C-C-C, 95.9'; S-C-C, 89.6°.3869387a The sulfoxide oxygen prefers the equatorial position. The ring-puckering has also been studied by infrared spectroscopy; the barrier to interconversion between a stable equatorial form and an axial conformer is about 3440 ~ a l / m o l e . ~ ~ ~ " The conformations of thietane 1-oxide and 3-chlorothietane 1-oxide have been calculated by the CND0/2 method.'l The barrier to inversion at sulfur in thietane I-oxide is 47 kcal/mole in the gas phase and 58 kcallmole in solution. The most stable calculated conformation of trans 3-chlorothietane 1-oxide has oxygen axial and chlorine equatorial and cis has both groups equatorial. However, in trans-3phenylthietane 1-oxide, the oxygen is equatorial while the phenyl group is An ab initio SCF calculation was used to predict the geometry of 0-equatorial thietane l - o ~ i d e . ~Bonding ' ~ ~ C-C orbitals have centers of charge in the C-C-C plane; C-S orbitals, outside the C-S-C plane. The calculated value of the ringpuckering angle is close to the observed value. B.

Nmr

13C nmr spectra of several thietane I-oxides have been recorded.55b,56b-56d~141b The a-carbon atoms are deshielded from 21.2 to 26.6ppm and the 0-carbons are shielded 2-18 ppm, both relative to the sulfide. Cis-sulfoxides show larger upfield shifts, relative to the trans isomers, for the 0-carbon atoms. The chemical shift data are given in Table 2. 'H nmr data have been used in attempts to differentiate between the axial and 53b, 139, 141b3207b32761 equatorial conformations of the sulfoxide oxygen atom.51153a, 281a,381,388 -390b Th ere is general agreement that in 3-substituted thietane 1-oxides, the oxygen and substituent are equatoiial in the cis isomers. In the trans isomers, it was argued that the oxygen is predominantly axial and the substituent is equatoria1;27613s9but this view has been challenged.141b>381 Typical proton chemical shift differences in ppm between cis and trans isomers are illustrated for 112a and l12b.141b Similar differences are seen in other derivatives (R=CH3, tBu, Ph). In the trans isomers, the equatorial oxygen conformation is estimated t o be predominant when lanthanide shift reagents [Eu(dpm)3, Yb(fod)3] are present, the percent varying from 100 to 68.141bOther lanthanide shift reagent studies on thietane 1-oxide itself indicate both planar and Oequatorial conformations are favored over an 0axial confomiation.390c When a 3-methyl group is trans, four-bond proton-proton coupling (about 0.8Hz) is observed between the axial methyl group and Hc.s13139,141bThe shift reagent studies corroborate the stereochemical assignm e n t ~ . ' ~Benzene '~ solvent-induced shifts also have been used to differentiate axial and equatorial configurations, the equatorial or trans a-methylene protons being most affected.'393389,397bIn 113a and 113b, the 0-equatorial and 0-axial positions are fixed and the 'H nmr shifts are The puckered conformation for thietane 1-oxides is supported by the nmr data

Four-Membered Sulfur Heterocycles

478 TABLE 2.

13C

NMR CHEMICAL SHIFTS OF THIETANE 1-OXIDES'

Compound

s x s o

6a,ppm

6 p , ppm

Ref.

52.69,52.80

10.43, 10.40

55b, 56b

57.84b 59.72'

22.94b 21.77'

56c

57.00b, 56.24' 59.53', 58.63'

34.25b, 33.39' 28.Olc, 27.1lC

56b, c

62.8Sd, 62.7 63.24e, 63.3

37.17d, 37.1 34.44e, 34.4

56c, 141b

63, 63.8

28.56, 28.6

56c, 141b

64.38

45.13, 21.65

5 6d

64.58

38.36

5 6d

64.36

45.13

141b

68.01

27.35

141b

59.9b 62.5'

63.8b 54.9c

56b

57.60' 59.90'

66.01b 57.1oC

56b

60.41b 63.29c

48Xb 38.73c

56b

67;0

(trans)

(cis)

'In CI)CI,. bTrans. cCis. dPh, 0 trans. 'Ph. 0 cis.

cited above. Computer-analyzed coupling constants have yielded the dihedral angle for &-2,4-diphenylthietane trans-I-oxide (159°).50 Proton nmr studies of thietane I-oxide in a nematic solvent (4-n-butyl-4-methoxyazoxybenzene)indicate a dihedral angle of 142°.3"a

Thietane 1-Oxides (Thiacyclobutane-1-Oxides)

479

3.2 H

R

3.6 H,

R

112a

3.2 H,

= p-BrC, H,

2.00 H

112b

4.44 H

@ I

H =O 3.61 113b

113a

C.

Dipole Moments

Dipole moments of thietane 1-oxide derivatives have been used to differentiate cis and trans isomers and to indicate a puckered conformation for the ring.24,26ai26f, 51,207b,276,389 Comparison of the moments calculated for planar and nonplanar conformations of trans 3-chlorothietane 1-oxide with the observed moment (1.73 D) leads to the conclusion that the molecule is nonplanar (dihedral angle 143") with an axial S-0 bond and an equatorial C-Cl bond.26a The cis structure was excluded because the observed moment was too low for any cis contrans-1-oxide ( p = 3.29 D), on fomiation.26a Cis-2,3-dichloro-4,4-diphenylthietane the other hand, is claimed to have an axial 3-chlorine atom and an equatorial 1-oxide are distinguished oxygen atom.24Cis- and trans-3-hydroxy-3-methylthietane readily by their dipole moments (cis OH, 3.60D; trans OH, 4.30D)which also indicate considerable ring-p~ckering.'~ The relatively high melting point of the cis hydroxy isomer (mp 106") compared to the trans (mp 76") is probably the result of intermolecular hydrogen bonding which is facilitated in the cis isomer where both hydroxy and sulfoxide oxygen are equatorial.

D.

Mass Spectra

The mass spectra of both isomers of 3-methyl-3-phenylthietane 1-oxide are similar, the base peak at m/e 131 being due to the loss of HSO from the parent ion.'39 The mass spectrum of thietane 1-oxide shows up as the most abundant fragment, C3H:, m/e 41.98,391Other fragments are observed at m/e 73 (C3H5S+), 62 (CH,SO+), and 28 (C2Hi).

Four-Membered Sulfur Heterocycles

480

E.

Basicity

The basicity of the sulfoxide oxygen has been investigated by observing infrared shifts in protic ~ o 1 ~ e n t In~this? way, ~ ~it was ~ ~shown ~ ~that~ thietane ~ - ~1-oxide ~ ~ ~ is more basic than cyclobutanone, but less basic than tetramethylene sulfoxide (thiolane 1-oxide) or pentamethylene sulfoxide (thiane l-oxide).280aToward phenol, the order of basicity is as follows: thiolane 1-oxide > diethyl sulfoxide > thiepan 1-oxide > dimethyl sulfoxide > thiane 1-oxide > 9-thiabicyclo[3.3.1]nonane 9-oxide > 7-thiabicyclo[2.2. llheptane 7-oxide > thietane 1 - 0 x i d e . ~ ~The ' ~ pKa of the conjugate acid of thietane 1-oxide is - 1.92, as determined in aqueous sulfuric acid.81c

F.

Thermochemistiy; Electrochemistry

The heat of oxidation (heat evolution) of trans-3-t-butylthietane 1-oxide by perlauric acid is 1.5 ? .9 kcal/rnole, greater than that for the cis isomer as expected on the basis of the puckered ring.393 In 1N sulfuric acid, no catalytic wave corresponding to hydrogen evolution was observed in the electrolysis of thietane 1-oxide, although some acyclic sulfoxides did give

G.

Solvent Characteristics

The distribution coefficients for benzene and toluene with thietane 1-oxide was compared with those of other sulfoxides; aqueous thietane 1-oxide has a greater extraction capacity than dimethyl ~ u l f o x i d e . ~ ~ ~

3.

Synthesis

Table 6 (in Section XXXXV) lists some typical thietane 1-oxides that have been prepared.

A.

Oxidation of Thietanes

The principal method of synthesis of thietane 1-oxides is by oxidation of thietanes, a reaction discussed in Section II.5.C. Reagents used for oxidation are hydrogen peroxide-acetic acid,'oa,116,129,131,135 hydrogen peroxide,24,26a,151,280a 179b3,1819207b,246,277 hydrogen peroxide-formic acid,53a,146ahydrogen peroxideacetone,125a,207b,2m,396 m-chloroperbenzoic acid,141b,207b,250~281a,381 perbenzoic acid,280b 0 ~ 0 n e , 2 ~ singlet ~ ~ ,oxygen:84 ~ ~ ~ ~ sodium or potassium metaperiod,te,51,141b,207b,249 ,276,281a,282,389,391 sodium hypochlorite,139 t-butyl hypochlor*13'7

48 1

Thietane 1-Oxides (Thiacyclobutane-1- Oxides)

ite,207b N-chlorotriazole,207b~ 283 d'mitrogen t e t r ~ x i d e , ~ 389' ~ ~ chromic ~ chromium t r i ~ x i d e , 'N-arylsulfonyl ~~ oxaziridines,286a azaaromatic Noxides:86b and aryldimethylamine o ~ i d e s . ~Overoxidation " to the sulfone, which is a complication with hydrogen peroxide and the peracids, may be minimized by use of only one equivalent of oxidant and low temperatures. Sodium metaperiodate, rn-chloroperbenzoic acid, and hydrogen peroxide in acetone are often the oxidants of choice when the convenient hydrogen peroxide-acetic acid method is unsatisfactory. When particularly mild conditions (CHC13, 25") are desired, the oxaziridines may be useful (no acids or bases are present). An extensive study has been made of the stereochemistry of oxidation of substituted thietanes by a variety of reagents.207bThe cis: trans ratios for 3-methylthietane 1-oxide decrease as follows: N204, 0" (75: 25); NaI04-H20-CH30H, 0" (59: 41); (CH3)3COC1-CH30H, 0", (55: 45); HzCr04-pyridine, 25" (54: 46); 3% H202-CH3COOH, 0" (46 : 54); 30% H20z-acetone, 0" (46 : 54); rn-C1C6H4CO3HCH2C12, 0" (45 : 55); 03-CH2Cl2, 25" (41: 59); N-chlorotriazole-CH30H, - 78" (33:67). The ratios for 3-t-butylthietane are generally similar. The cis form is thermodynamically more stable but the trans form may be favored kinetically. The cis and trans isomers have been separated in some cases by chromatography on silica gel.207bOxidation of the tricyclic sulfide 114, obtained by reduction of the ex0 sulfoxide with sodium metaperiodate is reported to give the endo sulfoxide 115 and considerable s ~ l f o n e . ' ~ ' ~

cb

&7

2 days, Na'04,R T

+ &7

/

,

114

'\\\

'0

0 2

115

B.

Miscellaneous Methods

Thermolysis of 4-t-butylsulfinyl-1-butene (1 16) and similar compounds gives a mixture of cis- and trans-2-methylthietane l - o ~ i d e . The ~ ~ ~assignment ~ - ~ ~ ~of ~

0 ti

CHz=CHCHZCH,SC(CH3)3

Xylene N 1 _ refl. 3.5 h

116

trans 7%

[CH2= CHCH,CH,SOH]

Four-Membered Sulfur Heterocycles

482

stereochemistry was based on the 'H nmr shifts in chloroform and benzene, the trans methyl group being relatively more shielded in benzene. Thietane 1-oxides are formed by hydrolysis of the intermediate 117275and other S-halo derivative^'^^^^^^^ such as the sulfurane 86.2s8 The tricyclic thietane 52 is hydrolyzed to 118.'41b,249

ArS0,NH\

117

&

c1 NaHCO

A \

H,O

F

86

NaHCO,, H,O 90-100°

e

52

118 (13-3976)

4. A.

Reactions of Thietane 1-Oxides

Isomerization; Resolution; Polymerization

Cis- and trans-3-t-butyl (or 3-p-chlorophenyl) thietane 1-oxides are isomerized on treatment with hydrogen chloride in dioxane. Mixtures of varying isomer composition yield equilibrium mixtures consisting of 85-1 00% of the cis isomer.389 A similar result is obtained by heating the sulfoxides at 170-175" in decalin. Likewise, 3-methyl-3-phenylthietane 1-oxide may be isomerized to an equilibrium mixture consisting mainly (74%) of the equatorial, cis-3-phenyl isomer.139 Thermal isomerization of either cis- or trans-2-methylthietane 1-oxide gives an equilibrium mixture containing 6 1-68% of the cis isomer.397a Trans-2,4-diphenylthietane 1-oxide is isomerized to the cis isomer by treatment with methoxide ion.53a The sulfoxide 118 is isomerized to 115 via the ethoxysulfonium salt.246 The spiro-bis-sulfoxide 119 has been resolved via a cobalt(I1)d-camphorsulgnate The chloroplatinate of one enantiomer had a specific rotation [.]DO of - 1.7". No polymerization of thietane I-oxide could be effected by either cationic or anionic

Thietane 1-Oxides (Thiacyclobutane-I-Oxides)

483

& ..8s ,“o 115

118

o s x s o 119

B.

Oxidation

Oxidation of thietane I-oxides to thietane 1,l-dioxides is easy, but not particularly important except as a structure proof, since most sulfones can be made directly from the sulfides. Oxidation reagents that have been used on the sulfoxides hydrogen peroxide-formic acid,53a are hydrogen peroxide-acetic acid,lZ9 perbenzoic acid,399 peroxydodecanoic and perlauric acid.393 The relative rates of oxidation of four-, five, and six-membered sulfoxides with perbenzoic acid in 40% dioxane at 25” were similar.399Oxidations were more rapid at high pH. J~~~~~~

C.

Reduction

Thietane 1-oxides may be reduced to thietanes by iodide ion in acidic media,392ci399by hydrogen and by zinc-hydrochloric acid.lZ9Thietane 1-oxide is reduced by iodide about four times more rapidly than dimethyl sulfoxide;399 the rate of reduction as a function of ring-size decreases as follows: 5 > 4 > 6.392c9399 The mechanism of reduction by iodide involves slow formation of an iodosulfonium salt 120. The thietane product is unstable in the acidic medium and was not identified.

The mechanism proposed for the reduction of thietane 1-oxide by hydrogen sulfide is complex; the order of reactivity is ethyl methyl sulfoxide > thiolane 1-oxide > diethyl sulfoxide > dimethyl sulfoxide > thietane 1-oxide.400

4 84

Four-Membered Sulfur Heterocycles

D.

0-Alkylation

0-Alkylation of several thietane 1-oxides has been accomplished by treatment of the sulfoxide with trimethyl- or triethyloxonium tetrafluoroborate. 1391246 or hexachloroantimonate282 or with methyl iodide-silver t e t r a f l u ~ r o b o r a t e . ~ Non~~ nucleophilic anions are preferred to avoid ring opening.

E.

Metal Complexes

Mercuric chloride complexes of thietane 1-oxides (1 : 1) are easily prepared, and, because of their sharp melting points, they are useful derivatives.1167'297131'207bi 2s8 Chloroplatinic acidzs8 or potassium chloroplatinateml is reported to yield stable complexes containing one or more thietane 1-oxide ligands. Complexes of the spiro disulfoxide 119 with CaC12, MnC12, CoCl2, NiC12, CuC12 and CdC12 have been described.258The structure of the europium tris(dipivalomethanant0) complex with 3,3-dimethyl-thietane 1-oxide has been determined by x-ray analysis.384i385The oxygen atom is equatorial and is attached to europium at one of four positions in the equatorial plane of the metal. The usual assumption of axial symmetry about the europium-ligand bond is not valid in this case for predicting nmr chemical shifts induced by the lanthanide reagents. F.

Thermolysis;Photolysis

Flash-vacuum thermolysis of thietane 1-oxide affords the reactive intermediate, sulfine, CH2=S=0.m2 Field-ionization mass spectrometry of the thermolysis products also indicates the formation of thietane, propenal, ethylene, C3H60, C3H6, and hydrogen sulfide.m2b A 1,2-0xathiolane intermediate was suggested. The ex0 sulfoxide 118 is thermally stable, but the endo derivative 115 decomposes around 200°C, probably because of the ease of 0-elimination: 246 Photodissociation of thietane 1-oxide in the gas phase yields cyclopropane and ethylene.m2cIt is suggested that singlet sulfur monoxide is produced except in the mercury-atom-sensitized decomposition that is supposed to yield triplet sulfur

Thietane 1-Oxides (Thiacyclobutane-1-Oxides)

485

A ..

115

monoxide. Photolysis of the sulfoxides 121 in either Pyrex or quartz apparatus results in the extrusion of sulfur monoxide to give the cyclopropanes 122.250Yields were somewhat better in Pyrex (50-100%) than in quartz (50-70%).

R

= H, CH3, iPr

121

R

=

H: 100% (Pyrex), 70% (quartz)

122

G.

Reactions with Free Radicals

Thietane 1-oxide underwent ring-opening faster than thiolane 1-oxide or thiane 1-oxide when treated with the t-butoxy or trimethylsiloxy radical^.^^ Relief of angle strain is given as the reason for the more rapid ring-scission of thietane 1-oxide. The radicals formed were identified by their electron-spin resonance spectra.

Four-Membered Sulfur Heterocycles

486

0

H.

Reactions with Grignard Reagents and Potassium t-Butoxide

Treatment of 2,4-diphenylthietane 1-oxide with methylmagnesium iodide or phenylmagnesium bromide is reported to give a variety of products, which depend on the stereochemistry of the sulfoxide and the structure of the Grignard reagentw Mechanisms were proposed involving addition of the Grignard reagent to the S-0 bond with subsequent loss of a sulfenate ion or formation of an ylide followed by rearrangement.

Ph

JfPh v

0

CH MgI

,IfPh v

3

PhO‘

0

A +tfPh /

Ph

(Cis:trans

cis or trans

Ph

=

Ph‘

0.44)

I

Yields of 2-substituted tetrahydrothiophenes (thiolanes) obtained by treating thietane I-oxide with a two-molar excess of Grignard reagent, RCH2MgX, vary from 18-5 1% (R=H, CH,, Ph, o-CH3C6H)4.160h’405The best yields came from the benzylmagnesium halides. Treatment of either cis- or trans-2,4-diphenylthietane-loxide (stereochemical notation refers to arrangement of phenyl groups) with potassium t-butoxide in dimethylformamide gives mainly the cis-I ,2-diphenylcyclopropane derivatives, 124 and 125, via the anion 123!06a Stereospecific cyclopropane formation occurs on treatment of 3-n-hexylthietane 1-oxide with lithium cyclohexylisopropyl amide.406h

Thietane Sulfilimines (Table 7 )

487

JPh H

r

1

123 _____)

Ph&Ph ,

+

P

h

\

‘SH

H‘

H’

124

IV.

a

I

\

h

‘S02H

125

THIETANE SULFILIMINES (Table 7)

Treatment of thietanes with chloramine T gives N-t~sylsulfilimines,’~~~~~~~~ for example, 126. Acyclic and five-, six-, and seven-membered cyclic sulfides all react more rapidly than thietane.275 The mechanism has been i n ~ e s t i g a t e d . 2The ~ ~ IR stretching vibrations of the S-N-S02 system are at 948 and 759 ~ m - ’ , 2 ~and ’ the ‘H nmr spectrum of 3,3-dimethylthietane 1-tosylsulfilimine in benzene and chloroform suggests an equatorial conformation for the ~ u l f i l i r n i n e .Oxidation ~~~ of this sulfilimine gives the sulfoximine derivative, 127 .276 The two diastereomeric tosylsulfilimines of 3-methyl-3-phenylthietanecomplex at nitrogen with silver ion.’39 pCH,C,H,SO,NClNa

CH,OH, R T , I h

[

tyro2A]

*

[ -

~+,~rso2RH]

-

-Ha

uNS0,Ar

126 (50%)

(cH3)2b KMnO, 6 8%

~

( c H 3 ) 2 ~ /p s

%NSO,Ar

Ar = p-CH3C6H,

\\

N S 0 2Ar

127

An attempt to trap the sulfilimine 128 by reaction with p-toluenesulfonyl chloride resulted in S-N bond cleavage before the tosyl derivative could be formed.272

Four-Membered Sulfur Heterocycles

488

Amberli!e I R 140A resin

(OH-)

128

V.

THIETANE 1,l-DIOXIDES (THIETANE SULFONES) 1.

Uses

Various amino derivatives of thietane 1,I-dioxides have been investigated as analgetics of the methadone as monoamine oxidase (MAO) inhibitors,8a as antiinflammatory d r ~ g s , as ~ ~ ~ ~ ' ~ as antihypertensive^^^ as bacteriostatic and bactericidal d r ~ g s , ~and ~ ' as~ fungicides.412 ' ~ 3-aryloxythietane sulfones are said to be useful as herbicides, fungicides, insecticides, antioxidants, stabilizers for plasticizers, and as dye intermediate^.'^^ Phosphate esters of 3-hydroxy- or 3-mercaptothietane sulfones have been investigated as insecticides.'Oa The sulfone 129 is claimed to be a pesticide2783413 and useful in the preparation of high melting plastics278 and pharmacological Thietanoprostanoids in the sulfone modification show thromboxane-like activity and some are mild PGEz a g o n i s t ~ . ~ ' ~ ~

129

A spirothietane sulfone-oxetane is a comonomer in the preparation of polyethers. A polymer obtained from this sulfone in a solution of bis(3,3chloromethyl) oxetane with phosphorus pentafluoride can be spun to drawable filaments.134 Thietane sulfone spirocyclic carbonates may be polymerized via the carbonate group to high-molecular-weight solids said to be useful in laminating.'5j Thietane 1,l-dioxide improves the dye receptivity of poly (acrylonitrile), viscose, cellulose acetate, and poly(viny1 It is also reported to be a stabilizer for nitric acid in oxidizer mixtures for rocket 2-Methylthietane 1,ldioxide is claimed to be superior to sulfolane (thiolane 1,l-dioxide) in the liquid extraction of aromatic hydrocarbons from mixtures with saturated hydrocarbon^.^^' A number of bis(3,3-alkoxy) thietane 1,l-dioxides have been proposed as intermediates in the preparation of cyanine dyes useful as photographic s e n s i t i ~ e r s . 4 ' ~ ~ ~ ' ~

489

Thietane 1,l-Dioxides (Thietane Sulfones)

2. A.

Properties

Structure and Conformation

X-ray analyses of single crystals have yielded bond angles, bond distances, and dihedral angles for the following substituted thietane 1 , l-dioxides: 3 - ~ h l o r o - ? ~ ~ ~ 3 - b r 0 m o - , ~ l 3~ -~h y d r o ~ y - ? ~3-acetoxy-,4'' ~ 2,2-dimeth~l-,4'~ 2,3-dichloro-4,4diphenyl-,422 2-chloro-3-morpholino-4,4-dimethyl-~23a trans-2-chloro-2,4,4trimethyl-3-m0rpholino-.~~~~ In the monosubstituted derivatives, the substituent is in an axial position in a slightly puckered ring (dihedral angles 170"). Introducing more substituents increases the puckering; dihedral angles of 157°,421 148.7" and 153.404" are obtained. Bond lengths (in A) for 3-chlorothietane 1,l-dioxide, which are fairly typical for the other compounds, are as follows: S-0, 1.419 (syn to Cl), 1.426 (anti); C-S, 1.791; C-C, 1.536; C,-H, 1.05 (syn), 1.03 (anti);Co-H, 0.85!18a Bond angles are C-S-C, 81.5"; S-C-C, 89.3"; C-C-C, 99.1"; 0-S-0, 117.9"; €I-C-H, 117"; H-C-Cl, 106"!18a

-

B.

NMR

The 13C nmr spectra of thietane 1,l-dioxides show unusual deshielding of the a-carbon atoms and unusual shielding of the 0-carbon atoms relative to other cyclic s ~ l f o n e s .1 ~7~0nmr ~ , ~shows ~ ~ unusual deshielding. These phenomena have been designated the four-membered-ring sulfone effect. Normally, carbon atoms a to a sulfone group are deshielded by 20-24ppm (downfield shifts relative to the sulfides); those 0 to a sulfone group are shielded by about 3-l0ppm (upfield shifts relative to the sulfides). The special a-deshielding effect is apparent in Table 3 which shows shifts of 34.8-39.9 ppm relative to the sulfides. The special 0-shielding effect is also demonstrated, the shifts being 13.7 to 22.4ppm upfield relative to the sulfides. The 1 7 0 chemical shift for thietane 1,l-dioxide is 182ppm downfield relative to HzO, which is more downfield than the shifts of the oxygen atoms of cyclic sulfones of higher or lower ring sizes.s5b The anomalous shifts for thietane sulfones are related to similar shifts in p-lactones and cyclobutanones and are attributed to the orbitals of these four-Inembered rings?23c The 'H nmr spectrum of thietane 1,l-dioxide in a nematic solvent indicates the ring is nearly planar with a very low barrier to planarity,39m a result that agrees with variable temperature investigations at 300 and ~ O O M H ZAn . ~ early ~ ~ nmr study compared the chemical shifts of thietane, thietane 1,l-dioxide,oxetane, and cyclobutane.62 The chemical shift (6) for the a-protons is 4.09 and for the /%protons, 2.14. The geminal coupling constant for the a-protons is - 14.0Hz and for the 0-protons, - 12.6 Hz. Other coupling constants are 'JCk = 10.3 Hz, 3Jm,, = + 6.3 Hz, 'JCk = 2.2 Hz, and 4Jmns = - 1.2 Hz.390b 3-Chloro-, 3-hydroxy, or 3-acetoxy 1,l-dioxides are believed to be slightly puckered in solution on the basis The magnitudes of of the relatively large coupling constant, 4J 4 Hz.4243425a-425b

+

+

Four-Membered Sulfur Heterocycles

490 TABLE 3.

I3C

NMR CHEMICAL SHIFTS FOR THIETANE 1.1-DIOXIDES Chemical Shift (ppm)'

Substituents

OrC

SC

Ref.

none 3-CH3 3-Ph 3-CH(COOEt) 2 3-NMe, 3-OH 3-OEt 3-OAc 3-OSiMe3 3-C1 3-BI 3-SEt 3-SPh 3-CH3, 3-Ph 2,4-(CH3),

65.6 71.1 71.9, 71.8 68.2 68.1 74.1' 65.3 71.7 73.9 75.4 76.9c 72.0 71Sb 75.6 70.3, 69.9

5.8 20.5 24.5, 24.4 19.3 46.4 52.7' 58.5 55.5 52.8 35.4 23.3c 22.7 24.2' 29.7 25.2. 24.7

55b 56c 56b, c 56b 56b 56b 56b 56b 56b 56b 56b 56b 56b 5 6c 56d

76.8

34.9, 21.4

56d

u I n CDCl, unless otherwise stated. 'In (cD,),co. 'In CD,CN.

the three-bond coupling constants favor axial orientations for these s u b s t i t u e n t ~ . ~ ~ ~ 'H nmr data on 3-hydroxy-3-methy15' and 3,3-dimethylthietanes'>2761,l-dioxides indicate nearly planar conformations. Analysis of the 'H nmr spectrum of 2,4diphenylthietane 1,l-dioxide indicates r i n g - p ~ c k e r i n g .53b ~ ~A' ~dihedral ~ ~ ~ angle of 145" has been computed for the c i s - i ~ o m e rThe . ~ ~ thietane-1,l-dioxide ring in both endo and exo adducts of thiete 1,l-dioxide with cyclopentadiene is nonplanar according to the proton-proton coupling constants.425bThe differences in proton chemical shifts for the two isomers are attributed to electrostatic and diamagnetic anisotropy effects of the sulfone group. Coupling constants for 130 have been analyzed, four-bond couplings being observed.426The nmr shift reagent E ~ ( f o d ) ~ , has been used to assign stereochemistry in an amino-substituted thietane 1,lThe cis and trans isomers of 131 were differentiated with this reagent.427 Nmr spectra of other compounds are frequently given routinely in reports on the syntheses of specific thietane sulfones.

C.

Acidity

The p K , of thietane 1,l-dioxide in dimethyl sulfoxide at 25" was estimated to be greater than 30.429Acyclic sulfones were more acidic.

Thietane 1,l-Dioxides (Thietane Sulfones)

130

49 1

131

D.

Mass Spectra

Loss of SO2 is prominent in the mass spectrum of thietane 1 , l - d i o ~ i d e . ' Ions ~,~~ also are observed from the loss of CH2=S02.98y'39 Other ions from thietane 1 , l dioxide are C2H4S0', CH2SOl, CH2S+,and C3H;.98

E.

Dipole Moments

The dipole moment of thietane 1,l-dioxide in benzene solution is 4.49 D.'03 The dipole moment of 3.33 D for 3-chlorothietane 1,l-dioxide is in better agreement with a planar than a nonplanar ring conformation.26a The dipole moments of 3-hydroxy-3-methyl-(p = 4.73 D, dioxane, axial OH)," 3,3-dimethyl ( p = 4.56 D, (cis, 2a, 3e, CC14)rs13-phenoxy-(p = 4.13 D, CC14),26f and 2,3-dichloro-4,4-diphenyl p = 4.51 D, C&; trans 2e, 3e, p = 3.32D, C6H6)24thietane 1,l-dioxides have been determined .

3. Synthesis (Table 8) A.

Oxidation of Thietanes

Treatment of thietanes with excess oxidizing agent usually gives the sulfones in good yields (see also Section 11.5.C). Reagents used are hydrogen peroxide (usually 3 0%),24 163,165 179b,180,249,277 hydrogen peroxide-acetic acid .26a,51,116,129-135,139,150, l61,168,169,179b,181,211,212,242,246,249,257,258,277,278hydrogen peroxide-formic acid 53a 146a3146b hydrogen peroxide-acetone,207b' 276,279 peracetic acid,15J' 52,125b, 141b,281b 9

9

perlauric acid,393 perbenzoic acid,1303398a m-chloroperbenzoic acid,'58b,170~202ai222ai 250 3381 sodium m e t a p e r i ~ d a t e , ' ~sodium '~ ~ e r m a n g a n a t e , 'potassium ~~ permanganafe,10a,113a,129 ,257,280~ and nitric acid.207b Care should be taken in concentrating mixtures from oxidation of 3-thietanol with hydrogen peroxide and acetic acid since explosions have been reported.430The use of sodium tungstate t o catalyze the oxidation is r e c ~ m m e n d e d . ' ~ ~

Four-Membered Sulfur Heterocycles

492

B.

Qcloadditions of Sulfenes

The discovery by Stork and BorowitzZM and Opitz and Adolph431 that the addition of sulfenes (RCH=S02) t o enamines gives good yields of 3-aminothietane1,l-dioxides (e.g., 132)431 has been extensively exploited in the synthesis of a variety of thietane sulfone derivatives. Truce, Breiter, Abraham, and Norell at about the same time showed that sulfene can add to ketene acetals to give 3,3-dialkoxy substituted thietane 1,l-dioxides (e.g., 133).432The sulfenes are generated by dehydrohalgenation of methanesulfonyl chlorides with triethylamine. [Attempts to add sulfines (e.g., PhCH=SO) to enamines to give thietane I-oxides were not successful.]433aSulfene additions have been reviewed.433b

n \

0'

N-CH=CHC2HS

W

+ PhCH2SOzCl

Et N A Et 2O RT

Ph

65%

133

Simple monocyclic thietane 1,l-dioxides have been obtained from mono- or dialkyl-substituted enamines,3a,8a,158a,158b,ZW,206,208,410,412,428,431,434-463 (e.g., 134,439 135442) aw]-substituted enamines,8a,141b,206 ,2O7b9209,381,388,407,449,453,454,464-468a, 468b,468c

(e.g., 1364,@' 137'09) and vinyl-substituted enamines445a'455~4694469b (e.g., enamines204,208,409,411,427,433b3 436,441,443,446,447, The use of 456,457,470-480 ( e g , 140204)or die near nine^^^^^^^^ (e.g., 141482) yields fused bicyclic systems, although the latter may also yield bis-thietane s u l f ~ n e s Enamines .~~~ derived from morpholine, piperidine, pyrrolidine, and dimethylamine are most commonly used, but derivatives of diethylamine,433a~464~468b~468c~469b di-n-propylamine,W piperazine,412,442,456,46%476 4-ben~ylpiperidine,4~~ methylpyrrolidine~,~~ h e x a h y d r o a ~ e p i n ,N-rnethyla~~iline:~' ~~~~~~ and have also been treated with sulfenes to give thietane sulfones. Asymmetric induction has been observed with the optically active enamine, 142.'58a Thietane 1,l-dioxides also are obtained by additions of sulfenes to ketene ace tals416,417,432,441,452,477,483-491 (e .g., 143490), vinyl (e.g.9 144493), vinyl sulfides4" (e.g., 145), /3-alkylthioenamines,4"a ketene &N aceta]s,417,486,494b,495a 4 0 - a ~ e t a l s , 4and ~~~ & S - a c e t a l ~ .(adducts ~~~ of these latter acetals lose an alkylamino, alkoxy, or alkylthio group to give 3-amino substituted thiete 1,I-dioxides.) 138,455

139469b).

Thietane 1,l-Dioxides (Thietane Sulfones) Et ,N

(CH,),NCH=C(CH3)2

493

( c H 3 ) 2 N ~ r H 3 ) Z

+ CH3S02CI E~,O

134

75-80%

fCH3S02Cl

-

+z

dioxane Et3N 76%

CHN

135

(CH3)2NCH=CHPh

+ CH3S02Cl

d138

(CzHS)zNCH=CHCH=CHz

Et,N

CH,CN 75%

136

\CH2

(3 H --

\p

+CH3S02Cl

Et,N 47%

N + CH3S02Cl Et6i% *

m s o z

139

Et N

+CH3S02C1 L dioxane

11%

140

H

494

&

Four-Membered Sulfur Heterocycles

+PhCH,SO,Cl

CH,CI, -1SO

141

13% CH3

I

CH3

I R(+) PhCH-N-CH=CHCH3 142

(CzHS0)2C=CHz

+ CHZ(SOCI)Z

143

OSi(CH3)3

Ph

I

I

(CH3)3SiOC=CH,

+ CH3S02Cl

(2) CH,OH

53%

144

CH,(CH,),SCH

(1) Et,N,-40°

=CH2

+ CH3SOzCl

p h p o , CH3S0;

Et,N CH,CN - 40'

145

*

7 5%

$0; CH3 SO2

In addition to the unsubstituted sulfene itself, the various substituted sulfenes used in the preparation of thietane 1,l-dioxides are listed in Table 4. Although the usual method for generating the sulfenes is by treatment of a methanesulfonyl chloride with triethylamine, sulfenes have been obtained by the reaction of phenylmethanesulfonyl fluoride with p h e n y l l i t h i ~ r n , @by ~~~ treatment ~~ of a-chloroethanesulfinic acid with refluxing triethylamine,459 by treatment of 4-nitroesters of arylmethanesulfonic acids with pheny1496bor 2-chlor0-4-nitropheny1,4~~~ potassium t-butoxide or 2,6-dimethylpyridine, respectively, by treatment of diazoand by thermolysis of a alkanes with sulfur d i o ~ i d e ~ ~(e.g., ~ , to ~ ~ give ? ~146)446 ' Diels-Alder adduct of ~ u l f e n e . ~ ' ~ 2-Methyl-3-piperidinothietane 1,l-dioxide has been resolved via its d-camphor10-sulfonate salt; the enantiomer obtained had a specific rotation of

Thietane 1,l-Dioxides (Thietane Sulfones) TABLE 4.

R’

SUBSTITUTED SULE‘ENES, R’R’C=SO,, THIETANE 1,l-DIOXIDES R2

495

USED IN THE SYNTHESIS 01;

Ref. 8a, 2 0 6 , 4 4 0 , 4 5 0 , 4 5 9 , 4 9 4 b 206,431,450,494b 440,494a, 494b, 495 494a, 494b 463 8a 411

H H CH, H c1 H CN H

H H H

477 483,485 436 452 440,458 206,440,483,494a, 494b 440 206,407,431,433a,440,445-441,450,463-465, 485-489,494a, 494b, 496b 440,441,483 407,440,465,483 407,483

H

445b. 446

CH,=CH Ph C1

H Ph H

Br I CI BI CN PhCO

H H

Br H H

449,475a, 475b, 483 446,496~ 4 0 9 , 4 1 0 , 4 2 7 , 4 4 0 , 4 4 3 , 4 5 3 , 466-468a, 483,485, 491,494b 421,440,453,467,468a 440,453,468a 468a 468a 440,460 440,448

CH30C 0

II

458

C,H,OC

H

445b

CII, H H

440,445b, 448 437,438,492-494a 490

p-CH,Ph P-CIPh p-N0,Ph

c1

0

!I

II

0

!I

C,H,OC CH,SO, CISO,

Four-Membered Sulfur Heterocycles

496

n N--CH=C(CH3)z+

u

0

+SOz

C H

99%

j3)2

146

+ 70.0"

Usually, a mixture of cis and trans isomeric thietane 1,l-dioxides is formed in the cycloadditions where isomerism is possible. The isomer composition may be determined by nmr, especially with the use of shift reagents such as E ~ ( f o d ) ~ .The ~ trans ~ ~ isomers ~ ~ ~ are ~ favored , ~ ~ ,products ~ ~ because they have fewer unfavorable nonbonded interactions than the cis isomers. One report . ~ ~a number of mentions the resistance of trans isomer 147 to i s o m e r i ~ a t i o n In a cisoid dipolar intercases where the cis isomer mediate (e.g., 148)@' has been suggested in which electrostatic interactions are f a v ~ r a b l e . Concerted ~ , ~ ~ ~ ni i~i or n," i ~ mechanisms i also have been considered for the cycloaddition reaction, but a stepwise mechanism seems most favored.440,4463447i4653495a More truns isomer is obtained in more polar solvents in which a cisoid dipolar intermediate would be of less importance.@6 15Sa, 158b

+

+

CN I Et,N (CH3)2NCH=C(CH3)2 + CH3CHSOZCl

Ets

147

r

148

Thietane 1,l-Dioxides (Thietane Sulfones)

491

C. From 7hiete I,I-Dioxides Although thiete 1,l-dioxides are usually made from thietane l,l-dioxides by elimination reactions, addition reactions to the double bond of the unsaturated sulfones can be useful in preparing thietane sulfones that may not be easily prepared by other methods. Addition of hydrogen to the double bond of thiete sulfones occurs readily either with hydrogen and a palladium catalyst3a~'41h~'58a~1s8b~ 16sJO7b,~sa,Wc,4n ,495b-d or sodium borohydride.141b,205,207b9468b The synthesis of R(+)-2-methylthietane 1,l-dioxide 149 was achieved by hydrogenation of the optically active thiete sulfone.1s8a,lsSb

,CH 3

[a]:: = + 21.0°

[a]$= - 20.4"

149

Addition of nucleophiles [OEt-, CN-, (CH3)2NH,C6HIINH2,CH3CH-N02, H2S] to the double bond of thiete 1,l-dioxides is generally 9495ci495d3497,498 (e.g., the formation of 150)20salthough ring-opening or isomerization of the double bond may occur with strong Addition of bromine (via N-bromosuccinimide) occurs in low yield.468a

150

Diels-Alder reactions of thiete 1,l-dioxides occur readilyz0s~473~499-s06 as exemplified by the syntheses of 15lSo2and 152.'" Adducts of thiete 1,l-dioxide with tetraphenylcyclopentadienoneso3 or a-pyrone'" are thermally unstable. Thiete 1,l-dioxides also undergo 1,3-dipolar additions with diazoalkanes,s07is08 (e.g., the formation of 153 from which the strained bicyclic thietane sulfone 154 is obtained)'07 nitrile oxides,s08b and cycloadditions with the N,N-dimethylenamine of isobutyraldehyde (e.g., the formation of 155).'01 Ph

89%

Ph

Ph 151

Four-Mem bered Sulfur Heterocycles

498

Br CH,=CH--CH

+

=CH,

(sealed tube)

62%

152

-so2 153

+

(CH3)2NCH=C(CH3)2

154

cH&02

66_ C H

L!O2

reflux 2 h

60%

(CH 3)2N H 155

D.

Miscellaneous Methods

Methods of preparing substituted thietane 1,l-dioxides involving substitution reactions on unsubstituted thietane sulfone precursors are discussed in Section 111.4. on reactions. Photolysis of 0 - or p-nitrophenylcyclopropanesin liquid sulfur dioxide gave 2-(0- or pnitropheny1)thietane 1,l-dioxide in unspecified yield.”’ The disulfide 156 was obtained by reduction of the thione or from the corresponding polysulfide by treatment with triphenylph~sphine.~~’ The rearrangement of 157 in liquid sulfur dioxide gave the unuusual tricyclic thietane sulfone 158.’11 The thione precursor of 156 may be converted into a spiroepisulfide by reaction of the diazoalkanes with the thiocarbonyl gro~p.’~’The iron derivative 160 was obtained by treatment of the alkene derivative 159 with liquid sulfur dioxide followed by the almost immediate removal of the sulfur 4.

A.

Reactions

Reduction to Thietanes

Lithium aluminum hydride in ether or tetrahydrofuran reduces thietane 1, I dioxides to t h i e t a n e ~ . ~ ~ ~ ~ ~ ” ~ ’93899441,456 This reduction was discussed in Section 11.4.E. Yields are generally at least 50% but in some cases it may be advantageous to add the hydride to a solution of the sulfone instead of the reverse in order to avoid ring-~pening.~” 3141b3203-209

Thietane 1,l-Dioxides (Thietane Sulfones)

49 9

156

CH

( 2 ) CH,ONa, C H , 6 H

75% 157 158

159

B.

160

Thermo-and Photochemical Extrusion of Sulfur Dioxide

The thermolysis of thietane 1,I-dioxides to cyclopropanes has been reviewed in the larger context of sulfone t h e r m o l y s i ~ . Dodson ~ ' ~ ~ and co-workers showed that ,I-dioxide gave a mixture of cis- and transeithei cis- or trans-2,4-diphenylthietane-l 1,2-diphenylcyclopropanes, the trans isomer 2P-Dimethylthietane 1,l-dioxide 161 gives 2-pentenes (about 12%) in addition to the cyclopropanes (about 50%)." A scheme involving diradicals was proposed and a preference for conrotatory ring-closure of 162 was ex~ressed.'~'Thietane sulfone itself gives c y c l o p r ~ p a n e ~ and ' ~ ~ propene - ~ ~ ~ ~has been detected as a product as we11.495~, S13c, S13e 3-Hydroxythietane 1,I-dioxide 163 gives a variety of oxygenated products.s13f Thermolysis (230") of truns-3-benzoyl-2-phenylthietane 1,l-dioxide gives trans-2-phenyl-1-benzoylcyclopropane(30%).'02 Thermolysis of ketals of 3-thietanone 1,l-dioxides has been s t ~ d i e d ! ~ ~Acyclic ~ ~ ~ ~products , ~ ' ~ are obtained, as exemplified by the thermolysis of 164.491Theimolysis of thietane sulfone 165 gives the cycloheptatriene 166 by loss of both sulfur dioxide and carbon monoxide.503A thietane sulfone intermediate 168 may be involved in the decomposition of sulfonyl azides 167.'"

Four-Membered Sulfur Heterocycles

5 00

CH3

cNH'CR

H

+ CH,CH=

350' ___)

pyrex beads

H

CH3

C6H6

H

contact time < 1 min.

H

H

39.2

161

CH3

CHCHzCH3 cis 11.5 trans 16.4

32.9

C H *3 H

CH3 162

+ CH3CHzCHO + (CH3)zCO + CHz=CHCHO

163

+ CHz=CHz

23O-Z5O0

-so,

0 11

CICH2CHZOCCHj

87%

164

0

II m-xylene

___)

z oPh *p

reflux 76%

Ph

166

165

PhCHzCHzSO2N3

400'

-[(poz] -[el 168

-[o] - Qo Thietane 1,l-Dioxides (Thietane Sulfones)

501

Photolysis of thietane sulfones (e.g., 169125")also yields c y c l o p r ~ p a n e s . ' ~ ~ ~ ~ ~ The need for a chromophore and a 2-substituent to stabilize an intermediate diradical has been e r n p h a s i ~ e d . 'The ~ ~ ~sulfone 170 undergoes an unusual transformation.250

tkPh2 5 4 nm

N2

CH,CI, or CH,OH

kPh R

83-9572

R = H, CH3, C2H5, PhCH2, CH*=CHCH2 169

170

C. Other Ring-Opening Reactions; Ring-Expansionsand Contractions The stabilizing effect of a sulfone group on an adjacent anionic center facilitates ring-opening of the strained thietane sulfones under conditions where such an anion

Four-Membered Sulfur Heterocycles

502

is created. The relative weakness of the carbon-sulfur bond and the relative stability of the sulfinate ion (RSO,) also play a role in ring-opening reactions. Attempts to polymerize thietane sulfones by cationic or anionic catalysts failed.398b Treatment of cis- or trans-2,4-diphenylthietane 1,l-dioxide with t-butoxymagnesium bromide or ethylmagnesium bromide gives sultines (cyclic sulfinate^)^^,^'^'^'' in which the stereochemistry is preserved (e.g., 171) and cyclopropanesulfinic a ~ i d s ' (e.g., ~ ~ 172). ~ ~Bases ~ ~such ~ as- hydroxide ~ ~ ~ ion or triethylamine cause ring-opening of 3-amino substituted thietane sulfones via an elimination reaction207b,454,455,462,464,465,475C, 521 as shown for 173.465 The enamines so formed may be hydrolyzed to carbonyl derivatives. Under acidic conditions,454,455,522~3 eliminations also may occur as in 174.s22a Addition o f sulfene to an enaminoketone gave an acyclic sulfone via decomposition of the intermediate thietane s u l f ~ n e The . ~ ~ decomposition ~~ of 175 may involve an elimination mechanism?90 Sulfur dioxide also may be eliminated during the course of the reaction with bases as shown for 176?98 Reversions of the cycloaddition reaction of enamines with sulfenes may be a two-step elimination?33a~454~455,46s The reaction is exemplified by the decomposition of 173 in ethanol to give enamine, l-dimethylamin0-2-phenylethylene, and ethyl phenylmethanesulfonate .465 ,468c749sc

dPh

rBuOMgBr

dPh

~

171

S02H

Ph 172

503

Thietane 1,l-Dioxides (Thietane Sulfones)

col N

-

-

H,O+

1 M HCI

5 8%

EtOH

&O2

L

174

CH (S O2C H C OOC H

)2

CN 1 N NaOH

THF-EtOH

Ph

176

rn

NCH A r C H n P h

Ar = p-N02C6H4, Ph

Nucleophilic sites present in certain substituted thietane sulfones may effect ring-opening,8a,170,408,433a,444,445a,481,514 as illustrated for 177.444A somewhat different type of ring-opening reaction apparently occurs with the intermediate thietane . ~ ~ sulfone 154 sulfone 178, obtained from a-pyrone and thiete 1 , l - d i o ~ i d eThe may be converted to 3,3-diphenylthiolane 1.1-dioxide (47% yield) by treatment with Raney nicke1.'07 The iron derivative 160 is converted to ring-expanded oligomer and polymeric material on standing in methylene c h l ~ r i d e .Thie ~ ~tane ~ , ~ ~ ~ ~ sulfones that are fused to a 1-pyrazoline ring decompose with loss of sulfur dioxide to m e t h y l p y r a z ~ l e s . ~ ~ ~

Four-Membered Sulfur Heterocycles

5 04

3

(CH3),N

&02 CH3CH I

CNH(CH

-

+

(CH3)2N\

--Hi

CH3CH

)2

177

(CH3)zNCH = CHSOZCH = CHCH3

I

-

178

&2s02H

-

PhCH2SOZSCH2Ph + PhCH2S03N

D.

Anionic Reactions 0.f Thietane 1,l-Dioxides

Some of the ring-opening elimination reactions discussed in Section C may proceed through anions of the sulfone.’46b1464,s16~s17 The p K , of thietane 1,ldioxide in dimethylsulfoxide has been estimated to be > 30.429It and the five- and six-membered cyclic sulfones are weaker acids than acyclic sulfones. The basecatalyzed hydrogen-deuterium exchange of 2-halo-3-morpholino-4,4-dimethylthietane 1,l - d i o ~ i d e ~and ’ ~ 2-methylthietane 1,l -dioxide has been i n v e ~ t i g a t e d . ’ ~ The exchange rate in the first compound is dependent on the halogen (I > Br > C1) and is greater for the trans than the cis compound. This difference between trans and cis isomers was related to the conformational preference of the exchangeable hydrogen with respect to the sulfone oxygen atoms. The rate of exchange and the rate of isomerization are essentially identical, the greater rate with the iodo compound being explained as due to relief of strain and the lesser repulsion of the base (OH-) by the more polarizable iodine.523 Optically active 2-methylthietane 1,1dioxide racemizes somewhat faster than the H-D exchange occurs; k,/k, = 0.600.67 (tBuO--tBuOD).sOO Exchange with inversion would give k,/k, = 0.5 and exchange with racemization would give k,/k, = 1.0. All four &-protons of 3-alkyl

Thietane 1,l-Dioxides (Thietane Sulfones)

505

or arylthietane 1,l-dioxides are exchanged on treatment with NaOD.'39i207b'389p524 The exchange of 2-acetyl-3-phenylthietane l,l-dioxide is very fast in dimethylsulfo ~ i d e - D ~ OThe . ~ ' ~2-proton of trans-2-phenyl-3-morpholinothietane 1,l-dioxide can be replaced by successive treatment with n-butyllithium and D20.449Isomerization does not occur. Isomerization of cis adducts of sulfenes with eneamines to trans adducts has been accomplished by treatment with n-butyllithium449y450 sodium methoxideM7or e t h ~ x i d e , ~potassium ~' t-butoxide,w and t r i e t h ~ l a m i n e . Trans-2,4-diphenyl~~'~~~ thietane 1,l-dioxide is converted to the cis isomer by treatment with sodium m e t h ~ x i d e ' 146b ~ ~ .and equilibration of 2-methyl-4-phenylthietane1,I -dioxide with bases gives mixtures containing 68-72% of the cis isomer.'46b The results may be interpreted on the basis of a puckered ring and a preference for substituents to adopt a pseudoequatorial conformation. Thietane 1,l-dioxides undergo hydrogen-metal exchange on treatment with n-butyllithium and the resulting lithium derivative may be alkylated'25b.451>525 or a ~ y l a t e d ? ~as' shown ~ ~ ~ ~for ~ sulfone 179.'25bTrimethylsilyl or trimethylstannyl groups may be introduced via their chloride^?^' The metalation may be stereo~pecific.4~~ tSz5

48%

179

E.

Halogenation

Metalation at the a-position of thietane 1,I-dioxides followed by treatment with sources of positive halogen gives fair to good yields of the a - h a l o ~ u l f o n e In .~~~,~~~ the example shown, the bromo derivative of Meldrum's acid was required to brominate 180; bromine, N-bromosuccinimide, and I-chlorobenzotriazole failed.526a Alternatively, 2-acetylthietane 1,I-dioxides undergo replacement of the acetyl group by bromine or iodine on treatment with the halogen and 5% sodium h y d r o ~ i d e ~ as ' ~exemplified ~ , ~ ~ ~ by 181!95b Under free-radical conditions thietane 1,I-dioxide may be halogenated at the 3-position.136dy505a-505c Either one or two halogen atoms may be introduced in this way as in the preparation of 182.505a-505c The use of bromine-chlorine gives some chlorination; chlorine gas may be used to obtain pure chloro derivatives.

F.

Reactions Involving Substituents on nietane 1,I-Dioxides

The availability of 3-amino substituted thietane 1,I-dioxides has prompted the application of the Hofmann3a,158a,158b,439,445a,445a,4R,473,495c or Cope (amine

506

Four-Membered Sulfur Heterocycles

85%

0 II

Br,, NaOH, KBr

dioxane

(CH3)2

(CH,), 181

Br(C1)

Br(C!) Br, -C1

Br,-CI,

___)

182

elimination reactions to prepare thiete 1,l-dioxides, as exemplified in the synthesis of 183,158b184,472 and 185.207b Dehydrohalogenation of 2- or 3-halothietane 1,l-dioxides also is a convenient and method of preparation of thiete l , l - d i ~ x i d e s , ’1683169,4403505a3 ~~~, elimination reactions of 3-phenylmethanesulfonate esters give good yields of thiete 94883489,514 or ketene suIfones.170~495cThe addition of ketene a~etals,@’~ N, ~-,417,494b,495aN,0-,495a or N,S-496aacetals to sulfenes frequently gives the thiete sulfone by elimination of one of the groups (OR, NR2, SR) from the intermediate 3-ketal derivatives of thietane 1,l-dioxide. Bromo- or iodotrimethylsilane effects elimination of methoxytrimethylsilane from 3,3-dimethoxy-2-trimethylsilylthietane l , l - C l i o ~ i d eEthanol . ~ ~ ~ ~has been eliminated from 3,3-diethoxythietane 1,l-dioxide by refluxing with 5% sodium hydroxide.514 The anti-elimination of hydrogen and 1,l -dioxides is favored so that chlorine from 3-N,N-dialkylamino-2-chlorothietane the isomer in which hydrogen and chlorine are syn is usually recovered in the elimination reaction^^^'^^^ , 5 2 7 as is shown in 186a and b.521When dehydrochlorina1,l -dioxide, treattion cannot occur as in 2-chloro-3-morpholino-3-phenylthietane ment with triethylamine leads to ring-opening or to ring-e~pansion.~’~ Elimination of water from the Diels-Alder adducts of benzoisofurans with thiete I,l-dioxides, for example, 15 yields naph th othiete 1,l - d i o ~ i d e s,499 . ~ ~ ~J~~ Loss of sulfur dioxide with formation of a dimer occurs in one case.499Desulfurization of the spiro derivative 187 gives the exo-methylene sulfone 188.510 3,3-Diethoxythietane 1,l-dioxide can by hydrolyzed to 3-ketothietane oXide)8a,207b,445c,464,468a,472,474,480,498,525

505b7521,527

507

Thietane 1,l-Dioxides (Thietane Sulfones)

[a]$= - 20.4'

68%

[ a ] E = + 70.0°

183

( 1 ) CH,I, 30% (2) &,O,

*

H,O

41%

C

E

(CH3)3C

O

2

184

(1) H,O,, HOAc, Ac,O (2) 6 5 ' . 2 h 80%

&r3 185

AH\,CH3

.c1

AH,, 0

N p +W

; H

(CH3)2

186a (cis)

186b (trans)

3

INNaOH C,H,OH

reflux

0

+ 186b 14%

(CH3)2

38%

Four-Membered Sulfur Heterocycles

508

1,l-dioxide with aqueous a ~ i d .3-hydroxythietane ~ ~ ~ ~ 1,l-dioxides ~ ~ ~can ,be ~ ~ converted readily to various derivatives of the hydroxy group: carboxylic peresters and peroxides,'79b ~ h l o r i d e , ' ~ ether,'69 ~ , ' ~ ~ and sulfonate e ~ t e r ~Cyano. ~ and ~ nitro ~ ~ groups ~ ~ in~thietane * ~ 1,l-dioxides ~ ~ ~ can be reduced (diborane and Hz-Ni, respectively) without harm to the sulfone g r ~ ~ pand, ~ ~ a 3-cyano group can be hydrolyzed in good yield to a carboxyl group that can be converted to an acetyl group by way of the acid chloride and d i m e t h y l ~ a d m i u m . ~ ~ ~ The 3-acetyl group can be converted t o a 3-(1-dimethylaminoethyl)group via the ~ x i m e . ~The ' ~ 3,3-bis-chlorosulfonylmethylsulfone 189 has been prepared and converted to the ar~ilide,'~' and the 3-(2-hydroxy-l-methylethyl)sulfone 191 is obtained from enamine 190.'01 Carboxylic acid derivatives of thietane 1,l -dioxide react normally with a m i n e ~ . ~ ~

189

190

VI.

191

THIETANE SULFOXIMINES AND SULFODIIMIDES

Thietane sulfoximines can be obtained either by addition of an iminosulfene (e.g., 192) to ketene d i e t h y l a ~ e t a or 1 ~by~ ~oxidation ~ ~ ~ ~ ~of sulfilimines as in the synthesis of 127.276Solvent shifts (CDC13, C6D6) in the proton nmr spectrum of 127 are greater for axial protons or methyl Sulfoximine 193 is stable to hydrochloric acid. An explosive sulfodiimide of thietane is obtained by treating the silylated sulfodiimide with S85C1.529b

VII.

THIETANIUM SALTS

Thietanium salts have been discussed previously (Sections II.S.A., B., D.-F., K., L.: Section III.4.D) and they have been reviewed.530Their stereochemistry has been

~

~

509

Thietanium Salts

0 II

CHJSCl

+ TsNCI2

-

N-N

W

II

CH3S-CI

TS zz P - C H ~ C ~ H ~ S O Z -

II

NTs

0

n

0

(cz H 5 0 ) 2

II

(C,H ,O),C=CH,

[CH, =S=NTsl

aNTs

33%

192

193

discussed.530b A m ass spectroscopic investigation has determined the heat of formation and appearance energy for S-protonated thietane.295b

1.

Synthesis

Methylation of the sulfur atom of thietanes 59a-c with trimethyloxonium tetraA stable methiodide salt of fluoroborate gives the unstable salts 60a-c.52’14731551255 a sterically hindered thietane has been r e p ~ r t e d . ~ ”S-Alkoxysulfonium salts of thietanes are likewise obtained from the corresponding sulfoxides.’397246,276~282 The S-amino salt 81 is obtained from thietane and O-mesitylenesulfonylhydroxylamine ,272-274 Thietanium salts have been put forth as intermediates in reactions involving a good leaving group or a cationic or carbenoid center appropriately situated with respect to a sulfide grOUp,123,247,259,263,269,271b-271d, 531-536 M any carbon electrophiles react with thietanes via thietanium ions (Section II.5.A.). 1-Phenyl-3-thietanone perchlorate, 193a is obtained from 1-diazo-3-(phenylthio)-2p r ~ p a n o n e .The ~ ~ ~carbonyl ~ absorption of 193a in the IR is at 1812cm-’. S-Benzyl and S-diphenylmethyl sulfonium analogs of 193a are unstable intermediates in the acid-catalyzed decomposition of the appropriate d i a z ~ k e t o n e . ~ ~ ~ ~ Compound 193a readily undergoes ring-opening with a variety of nucleophiles: triphenylphospine, thioanisole, thiobenzamide, ethyl dithiocarbonate ion, acetate ion, formate ion, and methoxide ion.536bIt was not possible to form ylides by treatment with n-butyllithium or triethylamine. Some reactions may involve the thiete salt 193b. Rearrangement of the tricyclic thiiranium ion 193c yields a thietanium ion 193d that rearranges further on treatment with t r i e t h y l a m i n ~ . ’ ~ ~ ~ II

Ph SCH 2 CCHN2

bS

0

0 HC‘04, CHCI, (83%)

+

\

Ph 193a

Nu

(Nu = Ph,P, PhSCH,, EtOCS;, O A C , H C O T

0 I/

NuCH2CCHzSPh

510

Four-Membered Sulfur Heterocycles

+

PhCSNH, dioxane

I

HO

0 OCH3 CH,C-CHSPh

\

ClO,

Ph

\

cio,

ClO,

Ph

(20%)

193h

-

- 60’

Et,N

CH

S-Ph SPh

193c

193d

The S-protonated thietane cationsla and the S-fluoro cation 194288have been detected by nmr techniques. A stable spirosulfonium dibromide 195 has been 258 rep~rted.’’~’

194

l-

195

A thietanium ion intermediate has been proposed in the photochemical ion.537 rearrangement of the 1,2,3,4,5-pentamethylthiophenium 2.

Reactions and Properties

The attack of n-butyllithium on the geometrical isomers of 1,2,4-trirnethylthietanium tetrafluoroborate occurs at the sulfur atom, effecting a low yield, but

Thietanium Salts

51 1

there is stereospecific desulfurization to the cyclopropane as s h ~ w n . ' ~ The ' ' ~ ~most likely pathway is given via the diradical 196 that undergoes conrotatory ringclosure. Proton nmr data are given for the isomeric starting material^.'^''^^

PH:

,-

3-rl-DU

H

I CH3

CH, 196

____)

CH3

CH3

Reaction of thietanium intermediates with other nucleophiles gives ring-opened products.l,2,78e,113a, l16,129,131,132a, 145, 149, 161,168,191,192,231a,256-258,259-268.530a,53lb531h,532,536,538

Some examples are given in Section II.5.A. Thietanium ylide intermediates, obtained by the action of carbenoid centers with a y-divalent sulfur atom, undergo the Stevens rearrangement as shown for 197.271c

s: CH,CH=CHR

197

-

7

(CH,),

yPh \CHCH=CHR

Hydrogen-deuterium exchange of the S-methyl protons of I ,3,3-trimethylthietanium tetrafluoroborate is faster (about 3 1,000 times) per hydrogen atom than the a-methylene protons.25s Decomposition occurs also. However, in l-ethylthietanium tetrafluoroborate, the four a-methylene protons are reported to exchange more rapidly than the cumethylene protons of the S-ethyl group.255The ring-proton exchange in four-membered sulfonium ions is approximately 100 times faster than exchange in sulfonium ions of larger ring-size. Displacement reactions (by OH-) at the sulfur atom of S-alkoxythietanium salts effect removal of the alkoxy g r o ~ p . ' The ~ ~displacement * ~ ~ ~ ~reaction ~ ~ ~occurs with inversion2463282 (e.g., 118),246possibly via direct displacement or through a

Four-Membered Sulfur Heterocycles

512

high energy sulfurane (tetravalent) intermediate.’” Pseudorotation in the I-ethoxy3-methylthietanium ion is less easy than in the phosphorus analog.539 Chemical shifts in the proton nmr spectrum of l-methoxy-3,3-dimethylthietaniumtetrafluoroborate are greater for the equatorial protons.276 Attempts to prepare the tosyl derivative of the sulfilimine 198 from the S-amino salt 81 resulted in cleavage of the S-N bond to give ammonia and thietane.’”

198

81

VIII.

SULFURANES AND PERSULFURANES OF THIETANES

Thietane sulfuranes and one persulfurane have been mentioned previously in Section II.5.D. The sulfurane 86 and persulfurane 87 are obtained from thietane and 3-methylthietane by treatment with trifluoromethyl h y p o f l ~ o r i t e . ’The ~~~~~~ sulfurane 86 (R = H) ionizes to the 1-fluorothietanium ion 194. Diiodosulfuranes have been r e p ~ r t e d , ” 13’ ~ ’ but the dibromo derivatives are unstable. These sulfuranes may be hydrolyzed to sulfoxides (Section III.3.B.).

IX.

THIETES; (THIACYCLOBUTENES)

Some aspects of thiete chemistry have been r e v i e ~ e d . ’Thiacyclobutene ~ is properly named 2H-thiete, but the designation of hydrogen as a substituent will be omitted in the following discussion. 1.

uses

Spiro[benzothiete] derivatives, for example, 199, are claimed to be useful in the preparation of dyes, plant protective agents, vulcanization accelerators, and hypertensive agent^.'^^-^^

H

199

513

Thietes; (Thiacyclobutenes) 2.

Properties

A.

Structure

X-ray analysis of the spirothiete 200a shows that the thiete ring is planar.545a Bond lengths are abnormally large (S-C4, 1.9268; S-Cz, 1.788 8;CZ-c3, 1.3608; C3-C4, 1.521 8) and bond angles are small (Cz-S-C4, 74.2"; C3-C4-S, 86.5"; Cz-C3-C4, 102.0"; S-C2-C3, 97.3"). The S-methyl sulfur atom is 0 . 2 4 8 out of plane. An x-ray analysis of 200b545bcorrected a structure proposed earlier.545cThe structures of 200c, d also involve long S-C4 bonds (1.937, 1.907 8,respectively.) The long bonds and acute angles in these thietes are evidence of considerable ringstrain.545d,545e

&- c \

/ 200b

200a

X

200c (X = H ) 200d (X = Cl)

B.

Theoretical

Zahradnik and Parkanyi calculated (HMO) n-electronic energies and electronictransition energies for the 6n-electron thiete anion 201 and its benzo analog 202 and for the thiete derivatives 203-205.5467547a The n-electron structure and a low resonance energy for 204 have been independently c a l c ~ l a t e d . ~Thc ~ ' thicte anions are expected to be less stable than the cyclopentadienyl anion, although variation of the Coulomb integral for sulfur has a large effect on the calculated delocalization energy.54s Electron repulsions, which are not properly accounted for by the simple Hiickel treatment, will undoubtedly make the anions even less stable. The pentalene analog 203 is predicted to be very unstable; the azulene analog 204, somewhat less

5 14

Four-Membered Sulfur Heterocycles

stable than azulene; the 1,8-naphthylene sulfide 205, only slightly less stable than a~enaphthylene.’~~

201

202

204

203

205

The valence tautomerism of thiete,s49S-protonated thietes49 b e n ~ o t h i e t e , ~ ’ ~ ~ ~ ’ ~ ~ azete, oxetc, and c y c l o b ~ t e n ehas ~ ~been ~ treated theoretically. Comparison with the valence tautornerism of cyclobutene-butadiene shows that replacement of a methylene group by a sulfur atom removes the energetic distinction between conand disrotatory modes of ring-opening and closing.s49 Ring-closure of propenethial to thiete is calculated to be slightly exothermic (2 kcal/mole); closure of the Sprotonated derivative is predicted to be endothermic (10 kcal/mole). However, the stability of the rings is overestimated by the single-determinant calculations (CNDO/B).s49 Extended Huckel MO calculations predict the ground state of benzothiete to be about 40 kcal/mole higher in energy than its ring-opened tautomer,ssOa a result in opposition to that obtained by MIND0 calculations which predicts . ~ ~ benzothiete ~ that have been benzothiete to be more stable by 9 k ~ a l / m o l e The made are stable.4733551-s59 Benzoxete is calculated t o be much less stable than benzotliiete relative to their respective tautomers.ssOa Calculations show that the unknown thiete-2-thione would be more stable than the carbene derived from the 1,2-dithioliumion by proton abstraction.ss0b

Molecular orbital calculations on the thiacylobutadiene 206 favor a planar conformation except for the proton on the pyramidal sulfur atom. An inversion barrier of 48 kcal/mole was estimated.560a There is considerable positive charge on sulfur and negative charge on the adjoining carbon atoms, which indicates that 206 possesses considerable ylide character. It is not predicted t o be aromatic, despite an earlier suggestion to that effect.560bElectron donating or withdrawing groups have the greatest stabilizing effect on 4~-electronsystems analogous t o 206.s60e

515

Thietes; (Thiacyclobutenes)

206

C.

Spectroscopic Properties

13C nmr spectra have been reported for a number of simple t h i e t e ~ and ~ ~ ~ ~ ’ ~ The carbon and proton chemical shifts (6) for thiete several benzothietes.ss3~s5s~5s7 (207),5403-phenylthiete (208),209and benzothiete (209)557are given as examples. (123.9)

Ph

3.80 H

(135.3)

H 6.76

(35.8)

(46.4)

H

(36.4)

H 207

H

208

209

Photoelectron spectra of benzothiete 209,”l the ketene derivative 210,5s1(not isolated), and the naphthothiete 205560chave been obtained and vertical ionization potentials reported. The unstable thiolactone 21 1 shows a carbonyi absorption at 1803 cm-’.560d The mass spectra of thietes usually show the molecular ion minus a hydrogen atom or other group as the most abundant species, thus suggesting the possible formation of a 4n-electron cation, for example, 212.208,209,s5s,557

210

21 1

212

Alkyl-substituted thietes have absorptions in the UV at 215-228 ( E 110-2270), 236-248 (E 2000-3050), and 285-294 ( E 50-567) nrn?’’ benzothiete has absorptions at 285 ( E 3000) and 241.5 (E 12,300) nm?” and the naphthiothiete 205 has absorptionsat 2 2 0 ( ~ 6 3 . 2x IO4),260(e 5 0 0 0 ) , 2 8 0 ( 2 8 0 0 ) , a n d 2 9 0 ~ h ( 1 7 0 0 ) n m . ~ ~ ~ is comparable to The UV absorption of 3-phenylthiete [301 (E 12,800)nm]209~5w that of methyl styryl sulfide [286 ( E 15,50O)nm] and styrene [248 ( E 15000)nml.

516

Four-Membered Sulfur Heterocycles

3.

Synthesis (Table 9)

Evidence for the first, although unstable, thiete was obtained in 1965;2°7asince then a number of more or less stable thietes have been prepared. The two principal methods for obtaining simple thietes (not fused to an aromatic system) are Ho fmann elimination from a 3-N,N-dialkylamino thietanez07a~208 ,561 or cycloThese methods addition of an acetylene to a thiocarbonyl group.545a-545d,562a-562c are exemplified in the preparations of 3-phenylthiete 213,'09 a stable, white solid, A number of other stable 3-arylthietes have been and the spirothiete 214.545b,545c ~ y n t h e s i z e d . ' ~Isomerization ~ of a 2-methylenethietane to a thiete has been reported.562d lZo9

4z Ph

KOtBu D M F , - 3 0 ° , N,

as%

+PhC=CPh

213

hv nrn) 7 (589

214

An attempted synthesis of thiete by thermolysis (300") of a Diels-Alder adduct with anthracene was unsuccessful, no doubt because of the thermal instability of thiete.205Thiete derivative 215563was obtained by other methods, and structure 217 was suggested as an intermediate in the desulfurization of 216.564aThe unusual dithiolactone 218b is formally derived from a cycloaddition of carbon disulfide with A 2-substituted-3,4-diphenyl-2H-thiete is obtained by treatment acetylene 218a.564b [e, h]-8-thiazulene, with diphenylcycloof the ylide, 8-methyl-l,3-diphenyldibenzo is one of several products p r o p e n e t h i ~ n e . ~2-Methoxy-3,4-diphenyl-2H-thiete ~~~'~ obtained on photolysis of diphenylcyclopropenethione in methanol.565c The first thiete fused to an aromatic system 219 (and an anthracene derivative) was reported in 1965 and was prepared by reduction of a naphthothiete ~ u l f o n e . ~ ~ ~ An attempt to prepare benzothiete by desulfurization of benzo-l,2-dithiolane was unsuccessful.201 Photolysis of benzo-l,2-dithiolane 1,I-dioxide in an attempt to ~ u naphtho~.~~~~ extrude sulfur dioxide to give benzothiete also was u ~ s u c c ~ s s The thiete 205, however, was prepared by extrusion of sulfur dioxide from 220552J53 and nitrogen from 221.559Thiete 205 also is obtained in 6-8% yield by treatment of 1,8-dehydronaphthalene with carbon d i s ~ l f i d eThe . ~ ~unstable ~~ thiolactone 21 1 was formed by a photochemical extrusion of benzaldehyde from 222560dand from 222a at 350°C.551The benzothietes 209,551,5569557 223,5549555 and 224558have been

Thietes; (Thiacyclobutenes)

517

CF3 fiC;CF3

CF, I N, R = Ph,

C 6 H l l r t-Bu,

N-R

H

217

216

Ph,

Ep3 \

rp\cp

\

Fe -C -CCH3

P/

L

P

I

Ph2

\

218b

Cp=n-CsH5 218a

obtained via contraction of five-membered rings. Several benzothietes are alleged t o be formed by treatment of o-mercaptobenzaldehydes with aryl arniness6& or o-chlorobenzaldehyde with sulfur and an ~ ~ , w - d i a m i n Benzothiete e.~~~ also is obtained by thermolysis (750°C) of o-mercaptobenzyl alcohol at low pressure.s66d Flash-vacuum thermolysis of sulfoxide 224a yields benzothiete 224b.566f

518

Four-Membered Sulfur Heterocycles

a

Et ?O LiAlH,

-

c

H

3

6 8%

219

220

205

22 1

hv, 77OK

Ph 222

m o

211

n r ; "700°

*

1 ooou

0.05 rnrn -CO, 0 2

45%

80%

222a

209

223

(1) NaOH, H,O,

(2) HCl

c1

67%

c1

COOH

heat

c1 c1 224

Thietes; (Thiacyclobutenes)

224a

519

224b

4.

Thietes as Intermediates

A thiete intermediate (225a) was proposed in the photochemical reaction of dimethyl acetylenedicarboxylate with 225,545cand similar intermediates were proposed in the addition of thiones or dithioesters to heteroatom-substituted acetylenes.567”’567b Th’iete 227 was suggested as an intermediate in the reaction of 226 with carbon d i s ~ l f i d e Reactions .~~~ of aryl vinyl sulfide derivatives (2,4,6trinitrobenzenesulfonate of a phenylthiovinyl alcohol,s69 a phenacyl derivatives7’)

COzCH3

CH 3 0 2 C C 225

Yis

-

dZH;

-ICH3-N 30zC

0

5 20

Four-Membered Sulfur Heterocycles

or /3-thiophenylpropiophenone~~~~~ with acids may yield transient thiete intermediates. Thermolysis of the adduct of 2,2,2-trifluorodiazoethane with 1,2,3,4tetra(trifluoromethy1)bicyclo [2.1.0]-5-thia-2-pentene may proceed through a thiete intermediate.571b Thiete structures have been suggested as fragmentation products in the mass spectra of a thietane fused to a P-lactam,’66 an ortho disulfide of a thiolbenzoate ester,572 n - p r ~ p a n e t h i o l , ’ thiirane ~~ carboxylic acid esters,574 i s o t h i a ~ o l e s , ~ ~ ~ , ~ ~ ~ 1,3-dithiolene-2-0nes,~~’ S-ethyl thiot h i a ~ o l e s , 1,3-dithiole ~ ~ ~ ~ ~ ~2-thione~,’~’ ~ benzoate,580 and thianaphthene ~ u l f o n e s . ~Tetramethylthiete ~’~ may have been formed on thermolysis of the p-toluenesulfonyl-hydrazone of 2,2,4,4-tetramethyl3-thietan0ne.’~’~ Thiete 2-thione may be an intermediate in the decomposition of 1,2-ditholium salts by the action of base^."^^ 2,2-Diphenyl-2H-thiete is suggested as an intermediate in the reaction of diphenyldiazomethane with 1,2,3-benzothiadiazole which yields 9-phenylthioxanthene and three other products.581c

5.

Reactions of Thietes

The thermal stability of thiete and alkyl-substituted thietes is low, but that of 3-arylthietes and thietes fused to aromatic rings is relatively high.

A.

Oxidation

Alkyl thietes may be oxidized in low yield to the sulfones with monoperphthalic acid.208 An IR absorption at 1067cm-’ suggested the presence of a sulfoxide in the oxidation of 228.’07 Oxidation of the dialkyl thietes 229a and 229b with hydrogen peroxide in acetic anhydride gave SO-SS% yields of (YJunsaturated aldehydes, possibly derived from an intermediate sulfoxide. 396 The naphthothiete 205 yields either the sulfoxide or sulfone with rn-chloroperbenzoic

)-s

-

228

229a R’ = CzH5, R2 = CH3 b R’ = n-C3H7, RZ = CzHs

L

52 1

Thietes; (Thiacyclobutenes) 0

205

205b

205a

acid, depending on the concentration of the sulfone with excess rn-chloroperbenzoic acid.”’ B.

Benzothiete is oxidized to

S-Alkylation

The sulfur atom of naphthothiete 205 may be methylated with trimethyloxonium tetrafluoroborate to give the stable salt.s53 3-Phenylthiete 213 may be alkylated with trimethyl- or triethyloxonium tetrafluoroborate or the trifluoromethanesulfonate e ~ t e The r salts ~ are ~ unstable. ~ ~ ~Alkylation ~ ~ of~ 218b ~ with ~ methyl iodide gives a ring-opened product, the reaction being facilitated by electron donation from the iron atom.564h

Ph CF,SO,OCH,COOC,H

I

CF3SO; CHZCOzCZHS

O o ,CH,CI,

213

218b

C.

Hydrolysis

Thietes are cyclic thioenol ethers and may be expected to undergo acidcatalyzed hydrolysis to 0-mercaptoaldehydes. Actually, only thiete 230 itself is reported to undergo h y d r o l y s i ~ , other ~ ~ ~ thietes , ~ ~ ~ being either stable to protons or undergoing electrocyclic ring-opening to a,P-unsaturated aldehydes.

Four-Membered Sulfur Heterocycles

522

El

[a+] [doH] -

H30+ *

H,O -H +

230

92%

D.

Reactions with Bases and Nucleophiles

The simple thietes are unstable with respect to treatment with strong bases or nucleophiles. Proton abstraction from thiete was observed via deuterium-proton exchange with CH30D-CH30-; it appeared to be faster than exchange with ally1 sulfide, but slower than that with phenyla~etylene.’~~ The thiete, however, could not be recovered from the reaction mixture. Treatment of thiete with potassium t-butoxide did not result in incorporation of deuterium when the reaction was quenched with DzO; treatment with potassium 1-methylcyclohexoxide resulted in the rapid disappearance of the nmr absorption of the protons of the thiete.548 Purple or wine-red colors are produced when thietes 228 or 230 are treated with . ~ ~color ~ was attributed to lithium piperidide, n-butyllithium, or t - b u t y l l i t h i ~ mThe a very unstable thiete anion or to an anion of a product of ring-opening. 2,4Dinitrophenylhydrazones of 2-mercaptocyclohexyl-1-carboxaldehyde and 2mercaptomethylcyclohexanone were obtained from the reaction mixture, and they may be formed via nucleophilic addition of piperidide ion to the double bond of isomeric thietes, 228 and 231, followed by elimination.548Addition-elimination also apparently occurs when thiete 230 is treated with triphenylmethyllithium; but treatment with triphenylmethylpotassium resulted in attack on the a-methylene group with displacement of the mercaptide to give the thioenolate ion of 4,4,4triphenylbutenethial. Attack on the a-methylene group by the anion of dimethylsulfoxide occurs with subsequent elimination of methanesulfenate to yield 3-butenethial or its isomer, 2-b~tenethial.’~’t-butyllithium and n-butyllithium attack the sulfur atoms of thietes 228 and 230, respectively, to give the corresponding Methyllithium attacked the sulfur atom of naphthothiete 205 to give 231 and Treatment oligomers 232 and 233 via 8-mercaptomethyl-l-lithionaphthalene.553 with lithium aluminum hydride followed by methylation gave 234.553Treatment of thiete 215 with triphenylphosphine leads to ring-expanded products possibly via nucleophilic attack by phosphorus on

E.

Ring-Opening to Enethials or Enethiones

The simple, nonaromatic fused thietes undergo facile ring-opening at room tem-

523

Thietes; (Thiacyclobutenes) LiNC,H -ZOO,

* 3(jJ1OQS

I.

CH,OCH,CH,OCH,

4

NCSHIO

+ Ph3CLi

THF

Ph3CCH=CHCH2SH

38%

2 30 (1) Ph,CK, CH,OCH,CH,OCH,,

/ (2) 2,4-(NO,),C,H,NHNH,

/

2 30

-20'

* Ph3CCH,CH 2CH=NNH Ar

96%

(1)

CH,SOCH,K, DMSO-THF, 15'

(2) 2,4-(N0,),C,H3NHNH,,

79%

* CH2= CHCH,CH

= NNHAr

+ CH3CH=CHCH=NNHAr CH2SBur

(1) r-BuLi, pentane, -10'

228

(1) n-BuLi, pentane, T H F , - 30°

( 2 ) H , O , 45%

205

* n-BuSCH2CI-I- CH2

+ H-BuSCHZCHCH~

23 1

5 24

Four-Membered Sulfur Heterocycles

232

233

(1) LIAIH,, T H F ( 2 ) CH,I, 72%

205

A,

NR

CF3

215

R=H

234

1

R

R

t

perature. The intermediate enethials may give polymers or oligomers, but can be trapped by reactions with 2,4-dinitrophenylhydrazine or semicarbazide as exemplified by thiete 228?08 The enethials also may be trapped by reaction with iron or 584b as shown for thiete cobalt carbonyls to give stable 230.583 An x-ray structural analysis of complex 235 was reported.5837585a An

Thietes; (Thiacyclobutenes)

525

investigation of the yellow thiete 236 by 13C nmr showed it to be in rapid A similar cleavage of equilibrium with the red a,P-unsaturated dithioester 237.562a thiete intermediates (e.g., 22%) formed via addition of acetylenes to thiones has The decomposition of thiete been suggested to account for the intermediate 227 very likely proceeds via an @-unsaturated thiocarbonyl derivative.s68 Ring opening by heat or light of benzothiete (209) to the a,O-unsaturated thioketone is supported by trapping experiments (e.g. with d i e n e o p h i l e ~ ) . ' ~ ~ ~

&-But

Bu'S

0 236

F.

0 237

Miscellaneous Ring-Opening or Expansion Reactions; Isomerizations

Diradical intermediates may be involved in the ring-expansion of benzothiete 209556,557 and the highly unsaturated derivative 217.565When naphothiete 205 is irradiated in the presence of carbon disulfide, a low yield of the thiocarbonate of 1,8-dimercaptonaphthaIeneis ~ b t a i n e d . " ~ The ring-expansion of thiete intermediate 238 is obviously ionic.569Cleavage of a carbon-sulfur bond in benzothietes, for example, 199, may occur on alkylation related to 214 is in assisted by a 0-amino g r o ~ p . ~ ~A~ 4- methylspirothiete ~@ equilibrium with the exo -methylene isomer.562c

1

- 6J-B

Four-Membered Sulfur Heterocycles

526

QE

1 ooo

209

-

Ph Ph+Ph

Ph Ph +Ph

flPhLDJ& Ph

Ph

21 7

'1

+

--Ht>D

'\

L.-/

D 238

Ph

H

6 2 H

s3

N

H+N CH,I

S-CH3

199

G.

Donor-Acceptor Complexes

Complexes of the donor-acceptor type have been obtained by treatment of thietes with 7,7,8,8-tetracyanoquinodimethane (TCNQ) and other electron acceptors.586The TCNQ complex with 3-phenylthiete is blue-black and a 1 : 1 complex.

X.

THIACYCLOBUTENE SULFONIUM IONS

Thiacyclobutenonium ions have been revieweds3' and are discussed briefly in Section IX.5.B. Stable salts are not common, probably because of the ease with which the strained ring is opened either unimolecularly or bimolecularly:

Thiacyclobutene Sulfonium Ions

rnS-R -nS-R

+

-/*

\

527

Nu:.

Nu

or

S-R

- F A

S+- R

ps+ R N u

3-Phenylthiete 213 reacts with trimethyl- or triethyloxonium tetrafluoroborate and the trifluoromethanesulfonate ester of ethyl hydroxyacetate at low temperaThey react with nucleophiles (CN-, ture to give S-alkylated thiete salts 239.582a,b S C N , CH30-, F-, R3N) t o give ring-opened or dealkylated products. A hygroscopic cobalt complex, tentatively assigned structure 240, has been prepared.582a,582h,587a CN

/-*RSCH=C-

ph)=q

Ls+-R 239

~

/

\\

Ph I

CSHS, Ph,

CHZCN

$"'

+

co

n-C,H,Co(CO),

hv, 7 5 %

240

Treatment of naphthothiete 205 with trimethyloxonium tetrafluoroborate gives the stable S-methyl ati ion."^ Reaction of the salt 241 with aqueous sodium hydroxide yields methyl I-naphthyl sulfoxide; reduction with lithium aluminum hydride yields naphthyl sulfides 242 and 243.553Treatment with pyridine resulted in demethylation to give 205. The stable perchlorate salt (193a) of I-phenyl-3thietanone may enolize to the thiete cation 193b which undergoes ring-opening with niethoxide ion t o give l-niethoxy-l-phenylthi0-2-propanone.~~~~ S-phenyl cations (e.g., 243a) were said to be obtained by treatment of P-phenylmercapto-n-propyl phenyl ketone, 0-phenylmercapto-fl-phenylethylphenyl ketone, or (3-phenylmercapto-fl-phenylethyl methyl ketone with phosphorus oxychloride and perchloric The 'H nmr spectra reported for 243a and 243b indicate the presence of only 14 protons instead of 15 as required by the formulas. The melting point given for 243b (2 12°C)588ais identical with the melting point of the thianaphthalenium salt 243c; the UV spectra reported for 243b and 243c are similar.588hCaution is advised in accepting 243a, b as stable entities.582hIt is claimed that these cations rearrange on heating with perchloric acid, and treatment with sodium hydride yields green material for which a thiacyclobutadiene structure (e.g., 244) was suggested. Addition of water to 243a is said to give two ketones, 245 and 246.587cThis work has not been able to be reproduced.582bAll evidence suggests that thianaphthaleniuni salts instead of thiacyclobutenium salts were obtained.582b

Four-Membered Sulfur Heterocycles

528

S

r-

YH3 BF,

NaOH, H,O

24 1 242 (54%)

243 (20%)

@,Eoi

*::;

CH 3

H

243a

-

i : :@ hp, H

Ph

YH3

243b

Ph

Ph 243c

+ ClO,

..

NaH. THF-Et,O

ClO,

HClO,

Ph

Ph

Ph

'Ph 244

ClO,

CHph3$, H

Ph

243a

H O

Ph I PhSCHCH2COCH3 (major) 245

CH3 I + PhSCHCHzCOPh 246

Thiete 1-Oxides (Thiete Sulfoxides)

529

S-Phenylthiete cations such as 243a, b were originally suggested as intermediates in reactions of 245, 246,571a’588aand 247570 with acids. The acid-catalyzed hydroCationic lysis of thiete 230 probably proceeds via a cyclic cation, C3H5S+.2087561 thiete structures have been suggested to account for fragments observed in the mass spectra of thietes208,2091555*557 (e.g., 212) and other sulfur-containing comp o u n d ~ . ~ ~ - ~ ~ ~ ~

Thiacyclobutadienes such as 244 were suggested to be 6-7r electron systems and, A b initio SCF molecular orbital calculations indicate the therefore, contrary; the thiacyclobutadienes are predicted to have considerable ylide character.56oa

XI.

THIETE 1-OXIDES (THIETE SULFOXIDES)

The oxidation of thietes is discussed in Section IX.5.A. A stable sulfoxide (205a) of naphthothiete 205 is obtained by oxidation with m-chloroperbenzoic acid; excess oxidant gives the The same sulfoxide was suggested as an intermediate in the oxidation of 221 to the naphthothiete sulfone 205b.559A stable benzothiete 1-oxide (247a) is obtained in 79% yield by oxidation of 224b with 2benzenesulfonyl-3-phenyloxaziridine,566f Thiete sulfoxides may be intermediates in the oxidation of thietes 228,’07 and 229a, b.396 The naphthothiete sulfoxide 205a is reduced by lithium aluminum hydride, possibly via a sulfenic acid and a thiolsulfonate intermediate.553 0

II

S (1) LiCIH,

NaOH

205a

g 75%

S02CH3 1

SCH 3 1

s-

+

247a

2

4%

6%

Four-Membered Sulfur Heterocycles

530

XII.

THIETE 1,l-DIOXIDES (THIETE SULFONES) 1.

uses

Certain 3-aminothiete 1,l-dioxides are said to have a n t i h_ y_ p e r t e n ~ i v eand ~ ~ ~antiinflammatory,4'0~590-s9z properties and may be useful in the preparation of cyanine dyes,417,593

2.

Properties

An x-ray structural analysis has been done on thiete l,l-dioxide (248),594 naphtho [ 1,8-bc]thiete 1,I -dioxide (205b),553and trans-2,5-dibromo-7-thiabicyclo[4.2.0]-1(6)-octene 7,7-dioxide (249).595A microwave spectrum of thiete sulfone has been obtained for which an 0-S-0 angle of 120.1' was preferred,596which differs from the value of 115.5" found in the x-ray analysis. Br

1.39

a

1240

1.77

1.52a

105'

1.325 '4

a

1 loo

i

1.438 0

Br

248

1.4328

0

0

\

S

/

205b

19z0

1.47'4 249

1.4378

85'

1.80 8

790s/0

0

Thiete 1,l-Dioxides (Thiete Sulfones)

53 1

The I3C nmr spectrum of thiete 1.1-dioxide (248) has been r e c ~ r d e d . 13C ~ ~ ~ ~ ' ~ ~ and 'H chemical shifts (6 in acetone-d6 with reference to tetramethylsilane) are shown below and the following C-H and H-H coupling constants (in Hz) have been x+ obtained:280c 'VC4,HA+ 150.5; 'Jc3,lfx+186.5; ' J c 2 , H M + 198.5; 2 J ~ , , ~ ~9.0; ' J C > , H ~ +6.5; ' J C , , H ~ - ~ .2~J, ~ 3 , ~1.8; ~ M 'Jc,,,yA+ + 6.5; ' J J C , , H ~ + 14.5; J A X + 1.60; J m - 0 . 5 2 ; JM,+ 4.10.

The proton nmr spectrum of thiete sulfone is anomalous because the 0-alkene the proton (H,) appears at lower field than the c d k e n e proton (HM);168,280c3s98a 13C chemical shifts are in the expected order 6Cz > 6 C3 > S C4. The mass spectra of several thiete sulfones have been interpreted on the basis of ring-opening t o the cyclic sulfinate (s~ltine).@'~~,~~~ Benzothiete sulfones lose sulfur dioxide t o give benzocyclopropenium ions.474,497The peri effect in 1,8-disubstituted naphthalene derivatives, for example, 205b, has been discussed.598b 3.

A.

Synthesis (Table 10)

Oxidation of Thietes or Thiete I-Oxides

As mentioned in Section IX.S.A., oxidation of thietes fused to an aromatic the method is not useful for system gives a good yield of the sulfone;473,552,553~557 the preparation of other thiete sulfones because the yields either are very lo^^^^^,^^^ or else ring-opening occurs.396Oxidation of the red azo derivative 221 with m chloroperbenzoic acid is believed to proceed via the sulfoxide 250;559a sulfoxide may be an intermediate detected in the oxidation of thiete 228.207a B.

Elimination Reactions of Thietane 1,l-Dioxides

Elimination reactions have been discussed in Section V.4.F. The availability of 3-N,N-dialkylaminothietane1, I -dioxides via cycloadditions of sulfenes to enamines (Section V.3.B.) has prompted the use of the Hofmann elimination via the methiodides%,158a,158b,439,445a,445~,472,473,495c and the Cope elimination via the amine oXides8a,s6b,207b,445c,464,468a,468b,472,474,480,498,525,599 in the synthesis of t h e t e

Four-Membered Sulfur Heterocycles

532

-

-

c

0

I1

m-CIC, H,CO, H

-

-

4

22 1

250

205a

71-93%

205b

1,l-dioxides. The Hofmann elimination has been effected by silver ~ ~ i d e by the synthesis of the optically active thietes, 251 and 251a,1s8a3158b lead oxide (in the synthesis of 252; no yield given),3a and a basic ion-exchange resin (Amberlite IRA 400).44sa>4nThe Cope elimination is usually done with 30% hydrogen peroxide in acetic acid-acetic anhydride, as in the preparaand perphthalic acidszs have also been tion of 185,2°7bbut peracetic acid472i480,498 used. In the Cope elimination, only the trans isomer of 253 yields the thiete of I-(NN-dimethylsulfone, as is expected for a syn e l i m i n a t i ~ n . ~Treatment '~ amino)-I ,3-cyclooctadiene (254) with methanesulfonyl chloride-triethylamine gives seven products among which is the thiete sulfone 255, possibly formed by a spon~ ~variety ' of taneous elimination of dimethylamine from an intermediate a d d ~ c t . A 3-arylthiete 1,I-dioxides has been prepared by the Hofmann elimination method.598d + W 3 ) 3 N.. 439~445c~472~495c as exemplified

psoz Ag,O, THF

ICH3

CH3E I O H

62%

I

H

z

251 [a: = + 1.32'&

optically active

-

Ap,O, THF 62%

(a:'

=

+ 21.6')

251a (a:.'

= -21.2')

,

~

Thiete 1,l-Dioxides (Thiete Sulfones)

254

53 3

255 (9-42%)

The first synthesis of thiete 1,l-dioxide 248 was achieved by elimination of hydrogen chloride from 3-chlorothietane 1 ,l-dioxide.'68The overall synthesis from epichlorohydrin (chloromethyloxiran) has been improved in several details.'69 3-Brornothietane 1, I-dioxide has been obtained by direct bromination of thietane has been obtained similarly.505b9c l , l - d i o ~ i d e ' and ~ ~ the ~ , ~3-chloro-derivative ~~~

Ho\

H\'

61%

E O , 248

3-Bromothiete 1,l-dioxide has been obtained by dehydrobromination of 3,3, ~ ~3-chlorothiete ~~ sulfone has been obtained in dibromothietane 1, l - d i ~ x i d e and the same way.505bThe cis (halogen. amine) isomers of 2-chloro, bromo-, or iodo-3-

5 34

Four-Membered Sulfur Heterocycles

morpholinothietane 1,l - d i ~ x i d e s and ~ ~ ~ 2-chloro-3-(N,N-dimethylamino)-2,4,4trimethylthietane 1,l-dioxideMo are dehydrohalogenated to thiete sulfones as shown for 256.521Elimination from the phenylmethanesulfonate esters of 3-hydroxythietane 1,l-dioxides give a good yield of thiete ~ ~ l f o n e s . ~ ~ ~ ~

NaOEt EtOH

___)

75%

256

Treatment of diethyl ketals of 3-thietanone 1,l-dioxide with bases (NaOH,485,514p h e n y l l i t h i ~ m ~ results ~ ~ ’ ~ ~in~ )the elimination of ethanol to give 3-ethoxythiete 1,l-dioxides, for example, 257.’14 3-Methoxy-2H-thiete l,l-dioxide is obtained by elimination of methoxytrimethylsilane from the ketal of 2-trimethylsilyl-3-thietanone 1,l-dioxide.526b The cycloaddition of ketene ~~~17,494b,495a,593,600 NOor flS-496a acetals to sulfenes derived from methanesulfonyl chloride derivatives yields 3-(N-dialkylamino)thiete 1,l -dioxides via elimination from the intermediate 3-ketals. Examples are the formation of 258495aand 259.496aThe solvent plays an important role in the determination of yields.495ay496a A side product that may become the major product in solvents such Hydrolysis of 260 may as acetonitrile is the ketene acetal derivative 260.495a9496a,600 >

¶ 495a3601

THF - 79% CsH6 -- 69% CH3CN - 0% DMF - 0%

258

535

Thiete 1,l-Dioxides (Thiete Sulfones)

259

X I RCHzSOZCH=CNR; X = NR;, SCH3 260

C.

Cjwloadditions of Suljenes to Ynamines

3-(N,N-Dialkylamino)thiete 1,l-dioxides also may be obtained by the cycloaddition of sulfenes to ynamines (~,N-dialkylaminoacetylenes)410~433a.46s~s9z~ 60z-606 as exemplified in the preparation of 261 .603 p-Nitrophenyl esters of arylmethanesulfonic acids 262 are useful sulfene The use of potassium-t-butoxide t o generate the sulfenes from 262 is said to avoid the doublebond isomerization that sometimes occurs in the presence of triethylamine hydrochloride,468b,591,602,603

60%

261

262 Ar = C 6 H s , p-CH3CsH4, p-CIC,H4

D. Miscellaneous Methods Treatment of 3-thietanone 1,l-dioxide with diazomethane, diazoethane, or ethyl diazoacetate gives 3-alkoxythiete 1 ,I-dioxides, for example, 263.607A similar reaction occurs with 2-phenyl-3-thietanone 1,l-dioxide and d i a z ~ r n e t l i a n e . ~ ~ ~ " Hydrogenation of the exocyclic double bond in 264 can be accomplished without

Four-Membered Sulfur Heterocycles

536

reduction of the endocyclic double bond that is reduced at higher p r e s ~ u r e s . 4A~ ~ ~ low yield of thiete sulfone 265 is obtained along with three other products by treat" ment of 2,3-diphenylthiirene 1,l-dioxide with a sulfonium ~ l i d e . ~ 4-Acetyl-3~ ~ been phenyl-2H-thiete 1,1-dioxide, previously proposed as an i n t e r n ~ e d i a t e ,has isolated in low yield from the reaction of 1-morpholino-1-phenylethenewith prop-2-yne-1-sulfonyl chloride in the presence of triethylamine .m9 Thermolysis of diphenacyl sulfone gives a small amount of a compound tentatively identified as 2-benzoyl-3-phenyl-2H-thiete, 1,l-dioxide.610 Spiro thiete 1,l-dioxides have been obtained by cycloaddition reactions of the exomethylene group of 2-methylene-4phenyl-2H-thiete 1,I-dioxide (264).495d

263 H , , Pd/C 1 atm, 50%

Ph

265

E.

n i e t e I,]-Dioxides with Exocyclic Double Bonds

Two exomethylene derivatives, 264 and 266,445cof thiete 1,l-dioxide and three 268a-c of a naphthothiete l,l-dioxide6'l have been reported. The simplest derivative, 2-methylene-2H-thiete 1,1-dioxide, has not been made.445c

3H7% 2 0 ,

jd:

CHZ

264

F.

Thiete I,]-Dioxides Fused to Aromatic Systems

2H-benzo[b]thiete 1,l-dioxide 269 has been obtained in a 19% overall yield Diels-Alder additions of from thietane 1,1-dioxide5O5and thiete sulfone 270.4803497

537

Thiete 1,l-Dioxides (Thiete Sulfones)

I-

PhCH'

I

ArOH - Ar, 0 85%

H 266

Ph ArCHO

NaOFt E tOH

Ph

Ph 26 7

benzo-isofurans to thiete 1,l-dioxides gives intermediates (e.g., 151) that can be ~ ~ ~ 267).473*502 ~~~~~~~~~'~ converted to 2H-naphtho [2,3-b It hiet e l , 1 - d i o ~ i d e s ~ (e.g., An optically active naphtho-2-methyl thiete 1,l-dioxide 271 has been obtained."' A different approach was used for the synthesis of the naphtho [ 1,2]thiete 1,l-dioxide 272.474The peri-naphthothiete sulfone 205b is prepared by photolysis of 271612,613 or oxidation of the sulfide 205.5523553

Br

270

er -

Four-Membered Sulfur Heterocycles

538

(1)

Ph

\

Ph

HG CH3

o 2

(2) HBr, HOAc, 93;

251a [R(-)]

Ph

271 (a" =

(1) H,O,,HOAC-AC,O,

+ 104.7O)

91%

(2) N-brornosuccinirnide, CCI,, 56%

272

00 205b

4.

Reactions of Thiete 1.1-Dioxides

A.

Reduction

Thiete 1,l-dioxides are rarely able to be reduced to the corresponding thietes. The a,a-disubstituted naphthothiete sulfone 273 and a similar anthracene derivative are reduced by lithium aluminum hydride to the both the sulfone and carbon-carbon double bond of 7-thiabicyclo[4.2.0]-1(8)-octane 1,I-dioxide are reduced by lithium aluminum h ~ d r i d e . ~In ' ~ most cases, the reduction involves opening of the strained, four-membered ring. Thiete 1,l-dioxide yields propanethiol upon reduction with lithium aluminum h ~ d r i d e , ~ "and a similar result was ~'~~ of 3-ethoxy-4-phenylobserved with 3-phenyl-2H-thiete 1, l - d i ~ x i d e . Reduction 2H-thiete 1,l-dioxide with lithium hydride gives the lithium salt of 2-ethoxy-lphenyl-1-propenesulfinic acid.514 The naphthothiete 1,l-dioxide 267 gives the mercaptomethyl derivative 274 on reduction with lithium aluminum hydride at 0" ,473,502 Work-up of the reaction done at -78" gave the naphthaldehyde 275

Thiete 1,l-Dioxides (Thiete Sulfones)

539

whose formation was rationalized by invoking an intermediate thiete anion and a thi~aldehyde.~” Reduction of benzothiete sulfone 269 at 0” gives o - t o l ~ e n e t h i o lwhich , ~ ~ ~ contrasts ~ with the behavior of the naphtho derivative 267. Ring-opening also occurs on reduction of 205b with lithium aluminum hydride; the thiete may be an i ~ ~ t e r m e d i a t e . ” ~

w H r3 z )

00

W

( 1 ) LIAIH,, E t , O _____)

(2) H 2 0 , 68%

(

C

H

00

Ph

3

Ph

273

eoz 1 (1) LiAIH,

(2) H,O, 4470

Ph

Ph

267

00 Ph

26 7

274

00

LIAIH,

Et,O, - 78’

l @

Ph

Ph Ph

Ph 275

)

z

Four-Membered Sulfur Heterocycles

540

269

LiAIH,, T H F , 20'

205b

The carbon-carbon double bond in thiete sulfones is readily reduced by catalytic bore-

~y~rogena~~on3a,l4lb,158a,l5~b,168,207b,~5a,~~c,472,49~b-49~d,6o9 or by sodium

hydride141a,2053207b3468b to give thietane sulfones. Lithium aluminum hydride reduces the exo-methylene double bond in the naphtho derivatives 268a-c without affecting the sulfone group.611

B.

Isornerization; H-D Exchange

The exocyclic double bond in thiete sulfone 276 may be isomerized to the endocyclic position by treatment with potassium Hydroxide ion also effects ring-opening of thiete sulfones (see Section D) so that it is not a general reagent for isomerizations of the double bond. Cycloadditions of sulfenes to ynamines frequently give two double-bond positional isomers,468b'603indicating that the triethylamine (or triethylamine hydrochloride product) used to generate the sulfene from the sulfonyl chloride is capable of causing the isomerization of the initially formed product to one in which the double bond of the thiete sulfone is more stable (e.g., by conjugation with a phenyl group as in the formation of 277a and b.)468b Sodium borohydride-aqueous sodium hydroxide can effect the isomerization, but reduction of the carbon-carbon double bond may occur.46xb Frequently, isomerization occurs on recrystallization of these sulfene-ynamine ad ducts.591 602 The naphthothiete sulfone 271 undergoes a-hydrogen-deuterium exchange in methanol-d catalyzed by sodium methoxide; the rate of exchange is essentially the rate of racemization unlike optically active 2-methylthietane 1,I-dioxide in which 1

276

270

541

Thiete 1,l-Dioxides (Thiete Sulfones)

277a

racemization is somewhat faster than exchange.5w Thiete 1,l-dioxide 248 undergoes exchange in pyridine-D20.280cAn anion of benzothiete sulfone 269 was considered an intermediate in its reaction with a lithio derivative of t-butyl mesityl sulfone.614a

248

D

C. Additions to the Carbon-Carbon Double Bond For addition reactions that lead to ringopening, see Section D. The use of addition reactions to synthesize thietane 1 , l-dioxides has been discussed previously (Section V.3.C.). Additions of the Michael type of nucleophiles to the carbon-carbon double bond of thiete 1,l-dioxides to give 3-substituted thietane 1,l-dioxides occur readily. The addition of hydrogen has been discussed in Section A. Nucleophiles include cyanide,8ai498the anion of nitr~ethane?'~the lithium salt of t-butyl o-tolyl sulfone ,614b dimethylamine ,'O5 i495d cyclohexylamine :95c e thoxide ,l 70i497, '1 and hydrogen sulfide.z05 The reaction is exemplified by the synthesis of 278.498 Additions to 3-chloro-2H-thiete 1,I-dioxide most likely proceed by an additionelimination mechanism; an example is shown for the addition of the anion of dimethylmalonate to give 279.s0scThe replacement of a 3-morphohnyl group by a 3-N-methyl-N-phenylamino group in thiete 1,l-dioxide is another example of additi~n-elirnination."'~An addition of ethoxide with elimination of p-nitrophenyl anion may occur with 268 (Ar = p-N02C6H4).611Addition of bromine via N-bromosuccinimide to the double bond of 4-phenyl-2H-thiete 1,l-dioxide occurs only in 1.5% yield.468a

Four-Membered Sulfur Heterocycles

542

NO2 I CH, CH

Ph

bso2

c1

C!;f(co2cH3),

NaH,

[

278

bo[

CH302C C02CH3

CH302C

C02CH3

%02 279

Diels-Alder cycloadditions involving thiete sulfones as dienophiles occur with 1,2,3,4-tetraphenyl~yclopentadiene,5~~ anthrab ~ t a d i e n e , cyclopentadiene,s06 ~~~’~~~ 1,3-diphenyl-2H-cyclopenta[l]-phencene.20s tetraphenylcycl~pentadienone,~~~ anthrene-2-0ne,’~~a-pyrone,sw 1-(N,N-dimethyl)- and 1-(N,N-diethy1)-1,31,3-diphenylisobenzof~ran~~~~~~~~~ butadiene,”l f u r a r ~ 2,5-dirnethylf~ran,”~ ,~~~ so2 i s o b e n z o f ~ r a n and ~ ~ ~ 1,3-diphenylnaphth0[2,3-c]furan.~~~ Generally, thiete 1,l-dioxide is used but the 3-brom0-?’~ 2-methyl-,sOo and 2,2-dimethyl-4733s01 2H-thiete 1,l-dioxides also react. Addition of 1,3-diphenylisobenzofuranoccurs preferentially at the exo-methylene double bond in 2-methylene-4-phenyl-2H-thiete 1,l-dioxide 264.495d Both exo- and endo-adducts are usually observed in Diels~ ~ endo-isomer ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ Alder additions to thiete l , 1 - d i o ~ i d e s .The predominates in the addition of cyclopentadiene to thiete 1,l-dioxide, the exolendo ratio depending on steric repulsions and stabilization of the transition states.s06Addition of tetraphenylcyclopentadieneone to thiete 1 , l-dioxide is said to give the ex0 isomer on the basis of nmr analysis.61s The exo isomer also is obtained . ~ ~reaction ~ of cyclopentadienones from isobenzofurans and thiete 1, l - d i o ~ i d e sThe (e.g., 280) with thiete 1,l-dioxide is complex, good yields of cycloheptatrienes being obtained, probably via an initial Diels-Alder adduct (165).’03 The initial adduct (178) of a-pyrone and thiete 1,l-dioxide also is unstable.sw A product (155) of a 2 2 cycloaddition of an enamine with thiete 1,l-dioxide and its dimethyl derivative has been reported.501

+

0

ow2

280

-so,,-co 65%

15%

Thiete 1,l-Dioxides (Thiete Sulfones)

543

1,3-Dipolar reagents, d i a z o a l k a n e ~nitrile ~ ~ ~ ~ ~ ~ ~ ~ and nitrilimines616 react with thiete 1,l-dioxide to give stable or unstable adducts. Diazornethane, diazoethane, phenyldiazomethane, p-methoxyphenyldiazomethane, dimethyldiazomethane, 1-phenyldiazoethane, and diphenyldiazomethane give 1-pyrazolines (e.g., 153, 281a, b),507>508a but ethyl diazoacetate gives the 2-pyrazoline 282.'07 The regioselectivity of the addition is said to be controlled by the coefficients of the highest occupied molecular orbital of the 1,3-dipolar reagent and the lowest unoccupied molecular orbital of the ~ u l f o n e and , ~ ~incorrectly ~ assigned structures in an early paperso7 have been corrected through the use of I 3 C nmr data.508" Nitrogen or sulfur dioxide may be lost from the adducts to give, respectively, thiabicyclopentanes (e.g., 154) and methylpyrazoles (e.g., 283).'07 The nitrilimine adducts are unstable and react with excess nitrilimine to give pyrazoles, for example, 284.616The regiochemistry is different for the addition of nitrile oxides to thiete 1,l-dioxide and t o an acyclic analog.508b

Po, R

RR'CN2

+

*

K

+

+

so2

281b

Ph

Et *o

oo, SS%

N zo$

R'

281a

PhCHNz

R'

pressure -SO,,

52%

H 283

CH3

Four-Membered Sulfur Heterocycles

544

Ph

CI

I

PhC = N N H P h (CzHs),N, 43%

*

IQL N

I Ph

D.

ph

CH,SO,C=NNHPh 284

Ring-Openingsand Expansions: Chemical, Thermal, Photochemical

The addition of hydroxide ion to thiete 1,l-dioxides yields acyclic sulfones~05~207b,4089445c~ 4643485,494b, '14 the ring-opening probably proceeds via initial addition of hydroxide to the carbon-carbon double bond followed by a reverse aldol condensation as exemplified for thiete sulfone itself.205 The reaction of the bicyclic thiete sulfone 276 with potassium t-butoxide gives the keto-sulfone 285 and i ~ o b u t y l e n e .The ~ ~ ~acid-catalyzed addition of water to 3-morpholinothiete 1,]-dioxide 258 also results in r i n g - ~ p e n i n g . ~ " ~ 0

Eo,

WOHL HlO

*

CH3, ,CH3 C-CH2-H

@

KOtBu

so,

___)

tBuOH, 66%

276

*

H1

0

-(CH,),C=CH,

so2

ao S02CH3

285

258

1

a&[

I

OH-HCO,

r Q o - H C C H 2 S 0 2 CI1 H 3

____)

+ (CH3)2S02 54%

di; so2

Thiete 1,l-Dioxides (Thiete Sulfones)

545

i-I, Refluxing 2,4-diphenyl-2H-thiete 1,l-dioxide in ethanol yields the acyclic sulfone 286.498 Treatment of naphthothiete sulfone 205b with methyllithiurn, sodium hydroxide, or lithium anilide gives products, for example, 287, resulting from nucleophilic attack o n the sulfur atom of the sulfone?53

( 1 ) C H , L i , ether, argon ( 2 ) H , O , 96%

205b

287

Electrolysis of benzothiete sulfone 269 yields the phenylmethanesulfinate anion (major) and the o-toluenesulfinate anion (minor).617 Thermolysis495c’49s’5’3e’513f~ 618,619 or p h o t o l y s i ~of ~ ~thiete ~ 1,l-dioxides proceeds via ring-opening to vinyl sulfines, for example, 288, which have been trapped by reaction with pheno1,495C,513e methanol,599or norbornenes.618These intermediates may recyclize to unsaturated sultines (cyclic sulfinate esters) (e.g., 289)495c,5’3e,513f,6131619 or lose sulfur monoxide to give mainly the trans isomers of a,O-unsaturated carbonyl compounds (e.g., 290)!98,513f Mass spectra also indicate the formation of unsaturated s u l t i n e ~ . @ ~ ~ ~ ~ ~ ~ PhOH

/

pso

heat

-[CH2=CHCH=S02] 288

2-CHCHZS020Ph

Four-Membered Sulfur Heterocycles

546

0 II

289

-[PhCH=CH-C Ph

-so

92%

o*

so2 II

G p ’ 6 6 ’

-Ph]+

:\/0

[PhCH=CHC-Ph]

0 II

PhCH= CH- CPh 290

Photolysis of naphthothiete sulfone 205b yields principally the disulfone 291 ; thermolysis yields a small amount of ~ e r y l e n e .Thermolysis ~ ~ ~ ’ ~ ~ of ~ the naphthothiete sulfone 267 yields the sultine 292 in the presence of dihydroanthracene; in its absence, thiophene derivatives 293 and 294 are formed.502’619

E.

Miscellaneous Reactions

An iron tetracarbonyl complex (295)620and a platinum bis(tripheny1phosphine) complex621a of thiete 1,l-dioxide have been prepared. Platinum complexes of 3-phenyl- and 3-@-bromophenyl)thiete 1,l-dioxide also have been prepared.621bNo complex was obtained with the 3-t-butyl derivative. The pale-yellow, crystalline iron complex decomposes in refluxing hexane in the presence of excess sulfone to Fe2S2(CO)9, indicating a drastic structural rearrangement.620 Other carboncontaining fragments were not observed. The bis(tripheny1arsine)platinum complex of 3-(p-bromophenyl) thiete sulfone is decomposed photochemically to the thiete sulfone.621b The same result is achieved on treatment of the complex with tetracyanoe thylene .621 Since 3-(N,N-dialkylamino)-2H-thiete1,I-dioxides are enamines, their hydrolysis (e.g., the to 3-ketothietane 1,l-dioxides occurs readily417~440~49sa~s21,527,600-602~606 hydrolysis of 296).601 3-methoxy- and 3-ethoxy-2H-thiete 1,l-dioxides also are hydrolyzed to the keto deri~atives.6’~ Thiete sulfone does not undergo polyrnerization with cationic or anionic catalysts.398b A 2 + 2 photochemical cyclization involving the exocyclic carbon-carbon double bond of 2-methylene-4-phenyl-2H-thiete 1,I-dioxide is reported to give a cyclobutane derivative in 12% yield.49sd An attempt to remove bromide ion from 2-bromo-4-phenyl-2H-thiete 1,l-dioxide with silver tetrafluoroborate was u ~ s u c c ~ s s ~ u ~ . ~ ~ ~ ~

541

30-33% 294

10-1 1%

293

295

n 0 wN 296

XIII.

H,Ot

B

O

Amberlite IR 120

*

74%

2-THIETANONES (0-THIOLACTONES)

Thiolactones (including P-thiolactones) have been reviewed.622 They are more easily formed and less easily ring-opened than their oxygen analogs, the P-lactones.

Four-Membered Sulfur Heterocycles

548

1.

uses

The 0-thiolactone analog of a prostaglandin 297 has less hypotensive activity than PGA2.623The 3-carbamoyl derivative 298 of a-amino-0-propiothiolactoneis Although said to be useful in the treatment of liver lesions and hypertension.6241625 penicillamine is effective in the treatment of rheumatoid arthritis, the thiolactone analog 299 is ineffective in decreasing the tensile strength of the skin of rats and, thus, may be ineffective against arthritis.626 p-Thiolactones are useful monomers in the preparation of rubbery, thermoplastic polymers, some of w h c h can be spun into filaments.627(See Section XII1.4.A.)

O

S

,

H

% s

+NH3 Br-

,

(CH,),

0

OH 297

298

2.

299

Properties

An x-ray analysis of thiolactone 300 indicates a puckered ring with a dihedral angle of 167°.628 There is an intermolecular NH-O=C hydrogen bond. The vibrational spectra of p-propiothiolactone (2-thietanone) has been analyzed.628cThe Raman spectrum indicates a planar ring (C, symmetry) and the carbonyl stretching ~ is .similar ~ ~t o the ~ stretching ~ frequencies reported for frequency is 1759 ~ m - This other derivative^.^^^^-^^^^ The 13C nmr spectra of 2,2,3,3-tetraphenyl- and 2,2-bis-pmethoxyphenyl-3,3-diphenylpropanothiolactone have been reported: 6 C=O = 194.0 and 194.7 ppm, respecti~ely.~~' The mass spectrum of the bis-p-methoxyphenyldiphenyl derivative indicated fragmentation to p-methoxythiobenzophenone and di~henylketene.~~'Others lose carbon o x y s ~ l f i d e . p-Propiothiolactone ~~~~ is reported to have no noticeable bitter taste.631

3.

A.

Synthesis (Table 11)

Intramolecular Cjdizations

Several schemes, exemplified by A-D, have been used to form the fourmembered thiolactone ring from an acyclic precursor. Scheme C is obviously related to A and B. In all these cases, thiolactones with substituents have been prepared most successfully. Unsubstituted p-propiothiolactone has been prepared by method C which is the most convenient one.

2-Thietanones (P-Thiolactones)

A

0

B

II

R = H , X = OSOZAr, OCOR, OH R = CHZPh, X = C1

C

549

D

The first P-thiolactone was prepared according to Scheme A by Knunyants and c o - w o r k e r ~ . ~A~ 'mixed anhydride of 0-mercaptocarboxylic acid and carbonic-acid ester is obtained by treatment of a salt of the mercapto acid with a chlorocarbonate ester.632-637 Cyclization to the 0-thiolactone occurs during the reaction; this synthetic method is exemplified by the preparation of 302 from 301.634A mixed carboxylic-sulfonic acid anhydride is involved in the formation of the thiolactone ring in 303 .623

302

HS

ACH(OCH3)z

n CHCI, w 52%

N-N,

303

The thiolactone 302 can be prepared in 62% yield directly from the acid 301 by use of the dehydrating agent, phosphorus pentoxide.6MCarbodiimides have been more extensively used to effect dehydration of the P-mercaptoacids to P - t h i o l a c t o n e ~ . ~The ~ ~ .method ~ ~ ~ - is ~ ~illustrated ~ by the synthesis of 304.641A

Four-Membered Sulfur Heterocycles

550

mercury(I1) salt of a 0-mercaptoacid gives a P-thiolactone on treatment with ethyl chloroformate .637

C2H5 opt. act.

I

HSCH2-CC02H

I

CH,CI,, 79%

CH3

+

56.9" 304

Treatment of acyl chlorides of P-S-benzylcarboxylic acids, for example, 305,629,643with two moles of aluminum chloride or bromide gives the /3-thiolactones in fair to good yields629a9m-6w (304 is obtained in 50% yield by this method).641

NHSO, I -CH,

a (1) 2-AIBr C H

PhCH,SCH,CHCOCI

( 2 ) H,O. 6 7 %

305

Fs

,CH,

0

Only one example of cyclization of a preformed 0-chlorothiol acid according to Scheme B hdS been r e p ~ r t e d but , ~ ~the 0-thiolactones prepared according to method C are very likely obtained via such intermediates. Treatment of 0-haloacyl halides with hydrogen or with sodium s d fide627,634,646a (as in C) give good to excellent yields of P-thiolactones as shown by the preparation of 306,635 307,646aand 302.634 The unsubstituted P-propiothiolactone has been prepared from 0-chloropropionyl chloride and hydrogen and from a-bromopropionyl chloride-anhydrous sodium sulfide (44% yield).647b

Br 0 I I1 CH3CHCH2CCI

dCH3

H,S, Et,N, CH,CI, ~

2 0 ° , 80%

0

306

CI-I,

c1 I

CICHZC -COCl I CH3

(1)

H , S , CH,CI,, - 20'

( 2 ) E t , N , Et,O, 5 6 %

*

cl*jz 0

307

55 1

2-Thietanones (P-Thiolactones)

302

Method D is not general; thiolactone 302 has been obtained in 31% yield by treatment of bromomethyl diphenylthiolacetate with triethylamine, but attempts with other compounds (e.g., PhCOCH2SCOCHzC1)gave six-membered rings.648

B.

ocloadditions of Thiocarbonyl Compounds to Ketenes and Carbon Oxysulfideto Alkenes

The thermal addition of 4,4’-di-N,N-dimethylaminobenzophenone, 4,4’dimethoxythiobenzophenone, and thiobenzophenone to diphenylketene was observed by Staudinger who considered a 0-thiolactone structure likely for the adduct with dimethylaminothiobenzophenone, but unlikely for the other two adducts because the former (not isolable) readily lost carbon oxysulfide and the latter did not.649 A 3-thietanone structure for the thiobenzophenone adduct was favored,6s0 but recently the P-thiolactone structure (308) was established by I3C nmr spectroscopy.630The reaction of thiobenzophenone with azibenzil and 4,4’dimethoxyazibenzil gives some 0-thiolactone, probably via rearrangement of the azibenzil to the k e t e r ~ e . ~ The ” addition of methyl and ally1 dithiobenzoates to diphenylketene gives the P-thioalkyl-P-thi~lactones.~~~~

308

Bis-(trifluoromethyl) thioketene 309 adds to ketene and methylketene to give 0-thiolactones, for example, 310, with an a-bis(trifluoromethy1)methylene suboxysulfide is said to add to alkenes, particularly highly s t i t ~ e n t . ~6s2b ’ ~ ~ Carbon ’ The phosphonium ylide halogenated ones to give 0-thiolactones (e.g., 31 la , b)653,6s4 312 reacts with carbon oxysulfide to give 313.6s5aTreatment of the triphenylphosphonium ylide of thioketene, Ph;PC=C=S, with isocyanates gives (p’-imino)-pof the triphenylphosphonium ylide of ketene, t h i ~ + l a c t o n e s ,and ~ ~ ~treatment ~ Ph$-C=C=O, with carbon disulfide may proceed via the ylide of 2-keto-3trip+henylphosphonia-4-thioketothietane, which loses carbon oxysulfide to yield Ph$-C=C=S ,655C

Four-Membered Sulfur Heterocycles

552

Oo,CH,CI,

(CF3),C=C = S

+CH2=C=0

44%

8F

0

309

310

Me,CO, hv

O = C = S +C12C=CFz

-7 2 O

311a (57%)

311b (2%)

t

+ Ph3P-C = C = N P h

pHNph

0

312

C.

cos 7 8%

313

Hydrolysis of 2,2-Dichlorothietanes

2,2-Dichlorothietanes are obtained by the photochemical cycloaddition of thiophosgene to alkenes (Section II.4.F.).239,2w Hydrolysis of the gemdichloromethylene group yields 0-thiolactones, for example, 314.239,240a

314

D.

Miscellaneous Methods

Treatment of 1,2-dithiolan-3-ones with triphenylphosphine or tris(dimethy1Yields amino)phosphine results in ring-contraction to ~-thiolactones.629e96s6a-656c vary from 24 to 98% and a chlorine substituent can be tolerated, for example, the

2-Thietanones (P-Thiolactones)

553

preparation of 315 .629e, 656a-656c However, thiete-2-ones cannot be obtained from ~~~~ for example, 316, the corresponding 1 , 2 - d i t h i o l e n - 2 - 0 n e s . Thietane-2,4-diones, can be prepared likewise.657 The keto-thione 317 yields the a-methylene-Pthiolactone 318, when it is treated with sodium hydride6" or triphenylphosphonium ~ n e t h y l i d e . ~Photolysis ~~" of 3 17659b and trispiro analogs659cgives 4-methylene2-thietanones. A nonhydroxylic solvent seems t o give best results.659cThe reaction of dithiolmalonic acids 319 with a-methylmethacrylate, acetone, acetaldehyde, acetophenone, benzophenone, diiodomethane, and dichlorodiphenylmethane gives thietane 2,4-diones, for example, 320.660 An acid (HzS04 or BF3-etherate) is required for all but the last two compounds. Dimethyldithiolmalonic acid also gives the 2,4-dione on treatment with trifluoroacetic anhydride, as does thermolysis of the dithiolmalonic

C1

p s

0

3 7 0

S

316

317

R

318

r

0 II

\

R '/

C

PSH

I'h,CCI,

\c 319

C,H,N, CHCI,

II

0

SH

*

80%, R = K' = CH,

..

0 L

3 20

Four-Membered Sulfur Heterocycles

5 54

Photolysis of thiocyclohexan-4-ones (e.g., 321) gives varying yields of P-thiolactones.661'662 The 0-thiolactones are not always the major products. Photolysis of 3,3,6,6-tetramethylthiacycloheptan-4,5-dione322 yields a,&dimethyl-~-propiothiolactone.1g6d~663~664 Diradica16M or ~ w i t t e r i o n i c ' ~inter~~,~~~ mediates were proposed.

S

322

L

4.

A.

Reactions

Addition of Nucleophiles;Polymerization

The 0-thiolactones behave as expected for thiolesters, addition of nucleophiles occurring readily at the carbonyl group to give ring-opened products. They undergo ring-opening somewhat less readily than their oxygen analogs, the P-lactones. For

2-Thietanones (P-Thiolactones)

555

instance, the carbobenzyloxy group of a-benzyloxycarbonylamino-P,P-dimethyl-/3propiothiolactone can be removed by hydrolysis with hydrobromic acid in acetic acid without rupture of the thiolactone ring.626,638 Nucleophiles that are reported to add to the carbonyl group are 647a,665-667 acids or ,,ters,629a,632,639,642,646a,667,668 primary amines,626,629% 632-635,638,646a,647a,668 secondary amines,665,666,669,670hydroxide ion 634964’3 water626 > (acid-catalyzed),6M@2 methoxide i 0 n , ~ ~ ~ ~ ~ ~(catalyzed ~ 9 ~by~lead ~ t e t r a a ~ e t a t e ) ethoxide ,~~~ ion,646an-butoxideion,646aethanol (acid-catalyzed),64zand triphenylphosphonium m e t h ~ l i d e . ~The ” ~ phthalimido derivative 323 is said to be inert to amine nucleophiles.w While most reactions involve the retention of the sulfur atom of the 0-thiolactone, several proceed via fragmentation with loss of a sulfur-containing moiety,646a3649 as shown for 308.671This 0-thiolactone is relatively inert toward n-butanethiol, sodium hydroxide, and sodium methoxide. The chloro derivative 307 undergoes a ringcontraction when treated with bases.666 With piperidine, 307 gives a compound of empirical formula, CgHI5NOS2,in yields up to 74%.666 The rapid solvolysis of 324 compared to its N-benzyl-oxycarbonyl derivative is believed to be caused by intramolecular acylation of the amino group.626 Reaction of 318 with hydrazine gives 325.658Several Wittig reagents (phosphonium ylides) convert the carbonyl group of 0-thiolactones to methylene groups without rupturing the ring.641b 0

323

7

n-BuNHLi

308

0

PhZC = CPh, 9 0%

0 11

PhzCpC(PhZ)S-C-NH-

CH, OCH,CH,OCH,

-

Tcr

II

+ [ n-BuNH-C-

S

-

-

BU

TZ-BUNH+ COS]

Four-Membered Sulfur Heterocycles

556

307

-

SH NH,

(CH,),C

I

1

-

CHCOOH

318

325

Polymerization of 0-thiolactones proceeds by nucleophilic attack by an initiator on the carbonyl carbon atom to give a free sulfhydryl group that propagates the process via attack on another carbonyl group to give polymeric thiol esters, which are acylating agents. Initiators of the polymerization, which may be in bulk or in ~~~’~~~~~~ solution, include aqueous sodium b i c a r b o r ~ a t e , ~aqueous water,643,672@’ tetrabutylammonium ~ e r s a t a t e , ~ ’ ~ ’d~i ~m’e~t h y l a r n i r ~ e , ~ ~ , ~ ~ ~ ” benzyl rnercaptan,6Ni643.673aand heat alone.6433640Optically active poly(thio1 304@Ia have been obtained; molecular esters) derived from L - ~ y s t e i n e ~ ~or* @ ~ weights (generally low) depend on the amount of initiator (e.g., dimethylamine) Polymerizaand kinetic studies of the polymerization have been tion of 324, however, gives a polyamide instead of a poly(thiolester)626 such as is obtained from 304.641aOptically active polymers from 0-thiolactones have been reviewed.673b

B.

Thermolysis;Photolysis

Thermal decomposition of 0-thiolactones may occur with loss of carbon a reversa16Y),646a,649,650,671 of the 2 2 cyclo-

oXysU~fide629d,6~,633,6s0,655c,657or

+

557

2-Thietanones (0-Thiolactones) 0 nBu,N (versatate 91 lk

l o o o . N , , 64%

II

1

CH3,,C2H5

-[ C -C

I,’

-

CH2-S

-I,

304

addition discussed in Section XIII.3.B. The former is exemplified by the decomposition of 326 and the latter by the reaction of 308 with n - b ~ t a n e t h i o lPhotolysis .~~~ of 318 in cyclohexane yields polymeric material; in methanol, ring-expanded products 326a, b are obtained.659b

ph2L<-piCH3

SCH,

i8oo,

-case Ph,C=CPh 1

(sealed tube) 80%

0 326

+ ph2Pph2 Ph2CS]

[Ph,C=C=O

0

308

( 1 ) n-BUSH, 65’

CH,OCH,OCH, ( 2 ) Si gel column

318

0 11

Ph,CHCS-nBu

+ Ph,CO

326a (30%)

C.

326b( 20%)

Anions of 0-Thiolactones

Treatment of 0-thiolactone 327 with sodium hydride followed by methyl iodide, ally1 iodide, or t-butyl bromoacetate gives the alkylated products, for example, 328

Four-Membered Sulfur Heterocycles

558

and 329.636,637 The ratio of epimers is dependent on the solvent; tetrahydrofuran gives a ratio of 1. Formaldehyde also reacts with the anion to give the aldol product that rearranges to 330.637Triethylamine catalyzes epimerization at the carbon atom adjacent to the carbonyl group of the thiolactone 327.636,637 CHzPh

I

( 1 ) NaH, O D , D M F

(CH,),

327

PhCH,CO

327

KOtBu

N

HCHO, 20%

330

D.

Desuljunzation

Several 0-thiolactones have been treated with Raney n i ~ k e 1 ~or~Raney ’ ~ ~ ~ ’ ~ ~ cobalt671 to give desulfurized products. Thiolactone 308 has been extensively studied; the principal product is tetraphenylethylene, but other products are formed depending on the activity of the reagent.671The reaction with Raney nickel W-2 is illustrative.671 Diradical intermediates were proposed to account for the products.

E.

Oxidation; Reduction

Oxidation of 0-thiolactone 308 with m-chloroperbenzoic acid gives a low yield of the mixed sulfinic-carboxylic acid anhydride 331 .671,674 Reduction of 308 with sodium borohydride gives 24% tetraphenylethylene; with lithium borohydride, 75% of 2,2-diphenylethanol and 16% of 2,2-diphenylethyl disulfide; with di-isobutylaluminum hydride, 39% 1,1,3,3-tetraphenyl-2-propanone and 30% of ben~ophenone.6~’ Lithium aluminum hydride gives four products that may be formed by way of cyclopropanone intermediate^.^^^

559

2-Thietanones (0-Thiolactones)

pp-: -Ph,C= :a,i C,

0

n,

CPh,

ren.

n

+

57%

308

22%

+ @0

+ (Ph,CH),CO 6%

Ph 12%

0

in-CIC,H,CO,H

p h 2 ~ p h CH,CI, z 0

II + Ph,CCPh + Ph2C0

*

308

17%

24%

331 (18%)

Ph, ( 1 ) LiAIH,, k t , O

*Ph,CHC(Ph),CH,OH

(2) ttOAc ( 3 ) HCI

+

40%

308

+ (Ph2CH)2C0 + Ph2CHC(Ph)2CH20Ac 15%

F.

3 0%

Ph2

12%

Miscellaiieous Reactions

The electrophilic reagents acetylsulfenyl methanesulfenyl ~hloride,6~’ sulfuryl or chlorine,635’676acleave the 0-thiolactone ring as shown for 332675and 307.676”Some disulfide may be formed along with the sulfenyl derivative. Various reactions involving substituents on the 0-thiolactone ring in which the ring remains intact are known. The trans-aldehyde 333, derived from 303, undergoes a Wittig reaction; reduction then gives a mixture of epimers of an interesting analog of prostaglandin PGAz 297 .623 a-Amino-0-propiothiolactone is acylated at nitrogen by nicotinyl chloride; the nicotinamide derivatives are said to be useful in treating hypertension and liver lesion^.^^^,^^^ In an investigation of 0-thiolactone derivatives of nocardicin (an antibiotic), the 0-lactam derivative 327 was converted to imide 334.677

560

1

rlh+,

Four-Membered Sulfur Heterocycles

:y38!:i*

CH3

0

y

C1-

332

S-CCH3

0 CH3 -CH3CSSCH2CHCOCI II i

CH3

I

* CISCHZC - COCl - 3 0 " , 77% CI,, CCI,

I

c1

307

CH,Ph COCHzPh 00 1 II II NH OCCCH3

4

h v , C,H,

CH COCO H

327

COCH2Ph

I

334

___)

(CH3)2

43%

2-Thietanethiones (0-Dithiolactones)

XIV.

56 1

2-THIETANETHIONES (0-DITHIOLACTONES)

Treatment of 2,2,4,4-tetramethylcyclobutane-l,3-dithione with trimethoxyphosphine gives a quantitative yield of the 2-thietanethione 335.678aThermolysis of the same dithione (940°C, torr) is said to give 335 which decomposes to thioketene and, with loss of carbon disulfide t o tetramethylallene.67sb A 75% yield is obtained by treatment of the dithione with sodium methoxide6’* or triphenylphosphonium m e t h ~ l i d e . ~ ” ”Unspecified yields are obtained from cyclobutaneand a small 1,3-diones and phosphorus pentasulfide in refluxing amount of dithiolactone is obtained by treatment of isobutyric acid with H2STiC14.679cCycloaddition of carbon disulfide to 312 gives the dithio analog of 313 in 78% ~ i e l d , 6 ”and ~ addition of carbon disulfide t o 226 gives a similar product 336568 that undergoes cleavage of the ring at 100”. The thiete derivative 218b is obtained by the formal cycloaddition of carbondisulfide to acetylene 218a.’64CIt undergoes ring-opening on treatment with methyl iodide (Section IX.5.B.). A triphenylphosphonium ylide of a $-keto-fi-dithiolactone was proposed as an intermediate in the reaction of the triphenylphosphonium ylide of ketene with carbon d i s ~ l f i d e . ~ ~ ~ ~ The intermediate decomposes t o the ylide of thioketene, Ph,$-C=C=S. A $-imino derivative has been suggested as being formed from the above thioketene ylide and is said i s o t h i o c y a n a t e ~ Electrochemical .~~~~ reduction of cyclobutane-l,3-dithiones to produce anion radicals of 2-thietanethiones, for example, of 335.680aThese anion radicals have been studied by electron-spin resonance.680b

335

+ Ph3P-C=C(OC2H5), 226

zf

+ Ph,P

”’

+

-

(OCZHS ) 2

S

336

1

ooo

+ Ph3P - T - CS2C,Hs

I

C0,C2H,

Four-Membered Sulfur Heterocycles

562

The ylide 336 is methylated at the thiocarbonyl sulfur atom to give thiete intermediate 227.568Triphenylphosphonium methylide attacks the thiocarbonyl group of 335 to give the ylide 337.6s9aHydrazine and 335 give the pyrazolinone 325 via an intermediate hydrazone.6s8 Photolysis of 335 proceeds most probably through an n-r* singlet state that behaves as a diradical to give 2,2,4,4-tetramethylcyclobutane1,3-dithione in aprotic solvents or the 1,2-dithiolane 338 in protic solvents.681,682

CH3

Ph+P-CH15%

S

S

+ II II Ph3P- CH-C-C(CH3)zCCH(CH3)2 337

335

335

XV.

2-IMINOTHIETANES 1.

Properties

An x-ray structural analysis has been performed on 339,683a339a,683b340,684and 341.68sIminothietane 339 is puckered with a dihedral angle (C-S-C, C-C-C) of

2-Iminothietanes

563

1 60°,683aLengthening of bond distances is believed to be due to steric factors.683aIn 340 and 341 the imine nitrogen atoms are nearly coplanar with the ring.6841685 13C nmr spectra have been obtained on several i m i r ~ o t h i e t a n e s , bis-imino~~~'~~~ t h i e t a n e ~ and , ~ ~ ~the tris-iminothietane, 341:685a- or la- RN=C, 145-190ppm; aArSO,N=C, 176- 184 ppm. The carbon-nitrogen stretching frequency is weak at 1680-1730cm-'; it is strong at 1590-1610cm-' for the iminosulfonyl for example, 339, show fragg r o ~ p . ~Mass ~ ~spectra > ~ ~of ~2-iminothietanes, , ~ ~ ~ ments corresponding to (CH3)2C=CPh2.687Mass spectra of his-iminothietanes, for example, 340, show fragments corresponding to Ph,C=C=NtBu, Ph2C=C=NC6H4C1, and ~ B u N = C = S .Other ~ ~ ~ spectroscopic data are included in papers detailing the synthesis and reactions of iminothietanes.

T sN 339a

'ac1 3 39

tBu

I

1.53 8

.74 4

1.77 8

1.528

340

34 1

2.

A.

Synthesis (Table 12)

Cycloadditions to Thiocarbonyl Groups

The cycloaddition reactions of ketenimines to thiocarbonyl groups to give both 1,2-(iminothietanes) and 1,l-adducts have been reviewed.686The frontier molecular orbitals of the reactants are important for the addition that is classed as a (,2,+ T2a) process.688 Steric factors play a role and the rate of 1,2-addition to give 2iminothietanes depends more on the substituents at the terminal carbon atom of the ketenimine than 1,4-addition to give a six-membered ring. The rate of 1,2-

Four-Membered Sulfur Heterocycles

564

addition is decreased by electron-donating groups on the nitrogen atom. The energy of activation for the reaction is relatively low and the entropy of activation is large and negative, for example, for the formation of 342, E, = 14.8kcal/mole and AS* (22") = - 34 cal/deg/mole.688 The polarity of the solvent has little effect on the rate.

(CH,), C=C=N

-@

CH3 + Ph,C

CHI

'CH3

342

A number of 2-iminothietanes have been prepared from ketenimines and thioor t h i ~ x a n t h o n e . ~Addition ~'~ of carbon oxysulfide or carbon disulfide to the phosphonium ylide of a ketenimine 312 gives an imino-0dithiolactone as previously noted.65sa,655b Arylsulfonylisothiocyanates undergo cycloaddition at 50°C to vinyl ethers to give 2-iminosulfonylthietanes in 50-76% A (n2, n2a) process involving zwitterions was suggested on the basis of the observed stereochemistry. Bis(imino) thietanes, 343, 344, are prepared by reaction of isonitriles with Reaction '~ of iminothiiranes or of ketenimines with p-tolylsulfonyl i ~ o t h i o c y a n a t e . ~ phosphonium ketimine ylides, for example, 312, and related compounds with isothiocyanates also gives bis(imino) thietanes, for example, 345 .6s5b,691b Treatment of arylsulfonyl isothiocyanates with trimethylacetoisonitrile yields tris(imin0)thietanes, for example, 341 .685

+

343

R,C=C=NR'

-0-0-

+ CH3

SO,N=C=S

.VNR R

Et,O Ft,O op200*

4S--54%

C

H

Q

SSOzN W

344

565

24minothietanes +

+ Ph3P -- C = C = N P h

Ar-S02N=C=S

+

2(CH3),CN=C

Et,O 61p65%

+

34 1

B.

Intramolecular Cyclization

Treatment of anions of fi-lactones 346 with phenyl isothiocyanate results in the formation of iminothietanes 347.692Zwitterions 348 are believed to be in equilibrium with the iminothietanes 349 on the basis of variations in spectroscopic data (IR, nmr) as the polarity of the solvent is changed.693 The dipolar structure is favored in liquid sulfur dioxide; the cyclic, in chloroform.

-

Ph

2 0%

H O

2 -CO,

PhN R = iPr (41%), t B u (52%)

CH,OSO,F

R = iPr 32%

** iPr

347

566

Four-Membered Sulfur Heterocycles

L

348

349

3. A.

Reactions

Thermal and Photochemical Ring-Opening;Fragmentation

Therrnolysis of 2-iminothietanes, for example, 347,692(R = iPr) results in ringopening, possibly via thiete i n t e r r n e d i a t e ~ ~(See ~ ~ ’Section ~ ~ ~ ’ ~IX.5.E.). ~~ Fragrnentation of the ring usually occurs by a cycloreversion process, as indicated in the (e.g., 350)687and 2,4-bis(imino)mass spectra of 2-iminothietanes655c,68’,689,691a,692 thietanes.6w The ring-opening of 349 was noted above.693A preliminary report of the photochemical fragmentation and rearrangement of 35 1 has appeared.691a

-

Ph S I /I iPrCH=C-C-NHPh

Ph 7

347 ( R = iPr)

Ph

(Ph),

-*

[Ph,C=CHPh]+

+ [PhCH=C=NMes]+

+ [MesN=C=S]+

2-Iminothietanes

567

NCH,

*

CH3NCS t

:CPh, t

B.

Ring-Opening und Ring-Expansion by Nucleophiles

The thietane ring of the carboxylate derivative 352 is apparently opened by loss of carbon dioxide,692possibly via a thiete intermediate. Isonitriles and ynamines effect ring-expansions of 2 , 4 - b i ~ ( i m i n o ) t h i e t a n e s , ~and ~ ~ similar reactions of enamines and ynamines with tris(imino)thietane, 353 have been r e p ~ r t e d . ~The ” methanol, ethanethiol, and diethylamine attack the a-carbon nucleophiles atom of 353, which bears the iminosulfonyl group, to give ring-opened products, for example, 353a.696The reactions with sodium azide or hydrazoic acid take a different course.696 ~

co;

P h - U :

~

--CO

Ph SR C H = CI - C1= NPh

PhN 352 I’Ii(’H=CHN(CH,),

tBu

353

66-76%

Four-Membered Sulfur Heterocycles

568

S

NtBu

I1

(Nu = OCH,, SC,H,, N E t , )

tBuNHC

I1

-

C - C = NS0,Ar

S0-91%

tBu-N

I

Nu

NHt-Bu

NaN

3 AI = Ph , 14%

1 t B u N = C -C =NSO,Ph 1 CN

353

\

HN3

E t , O , O", 5 9 - 8 1 %

t-Bu /"

,t-Bu

S-

SOzAr C.

Miscellaneous Reactions

The alkylation of an anion of 347, obtained by treatment with lithium diethylamide, with methyl iodide has been reported briefly.692p-Nitrobenzaldehyde undergoes the Wittig reaction with phosphonium ylide 345 to give the red-black derivative 354.655bThe acid-catalyzed ring-expansion of several 2-iminothietanes, for example, 355, has been described.691a

p

0

Ph

N

355

'CH3

3-Thietanones

XVI.

569

3-THIETANONES 1.

Occurrence

The only naturally occurring 3-thietanones are found in the South African Structure flowering plant, Berkheya barbata of the tribe Arct~tideae.~~~~~~'~~~''~ 356 is representative of the compounds obtained from these plants, which are identified by spectroscopy and independent synthesis. The thietanone structure supplants an earlier structure that featured a five- instead of a four-membered 0

CH3C=C 356

2.

Properties

An x-ray crystallographic analysis of the chromium pentacarbonyl complex

(357) of 3-thietanone shows a slightly folded (nonplanar) ring with bond distances

and angles as shown.699 Approximate octahedral symmetry is observed for the chromium atom with its attached ligands. The far IR spectrum of 3-thietanone itself in the gas phase indicates a planar structure.700A microwave spectrum showed that the ring-puckering vibration of 3-thietanone is lower in frequency than the corresponding vibration in 3-oxetanone because of the former's greater reduced mass and less angle strain and the lower bending force constant for C-S-C than C-O-C.701 The following bond lengths were estimated: C-S, 1.826 8; C-C, 1 . 5 2 8 8 , C-0, 1.2248.701 The C-C-C angle is 100.5". The dipole moment (p = 0.999D) of the ground state was estimated from the Stark effect.701 The effect of the carbonyl group on ring-puckering has been estimated by calculations using a one-dimensional potential function.23a The greater tendency of 3-thietanone to be planar as compared t o thietane is believed due to a reduction in torsional repulsions?3a Interaction of the sulfur atom with the carbonyl group is said to occur in the ground state because the IR spectrum shows two carbonyl absorptions; a band at 250 nm in the UV is reported.265Ab initio molecular orbital calculations of 3-thietanone are compared with the photoelectron spectrum; through-bond interactions are believed to be as significant as through-space interaction^.^^' 3. A.

Synthesis (Table 13)

Intramolecular Cyclization

Treatment of 1,3-dhaloketones with sodium h y d r o s ~ l f i d e , sodium ~ ~ ~ , ~sul~ fide ,510,703, m a or hydrogen sulfide-sodium methoxide706 gives, in some cases, a

570

Four-Membered Sulfur Heterocycles

I2.42A

1.158 -C

GC 1.158,

'

1.86 A 1.12'4

c+o

1 C C

-

0

1.14 A 0

357

3-thietanone, but the parent compound and its 2-methyl derivative cannot be made in this way.7" Only a 1% yield of the 2,2-dimethyl derivative was ~ b t a i n e d . ~The " reaction is exemplified by the synthesis of 358.706

358

3-Thietanones also have been obtained by treatment of aliphatic ketones with an usually in the presence of a a-methylene group with thionyl base707,708as shown for the synthesis of 359.707A 3-thietanone was suggested as a possible structure for the product obtained by the acid-catalyzed hydrolysis of the bis-thioglycolic thioacetal of substituted benzaldehydes, but an elemental analysis was the only evidence.710Treatment of l-diazo-3-phenylthio-2-propanone with acid gives the S-phenyl salt of 3-thietanone (Section VII.l .).s36b Similar S-alkyl salts may be intermediates, but they readily decompose either by loss of the S-alkyl group or ring-~pening.'~~~

B.

Oxidation of 3-Hydroxythietanes

This method is not very useful because of the ease of oxidation of the sulfur atom. Among the first preparations (18-2% yield) of 3-thietanone, itself, was the Oppenauer oxidation of 3-hydroxythietane with b e n ~ i 1 . IA~ ~72% ~ yield of

57 1

3-Thietanones

r

0 II

0 II

Cl

I

CH3CCH2CHzPh A CH3C - C - CHzPh SOCl

I

l’yridine

N , , 38%

“2

L

, -

s-CI

1

c1

2

I

,C-CH2Ph

- HCI

O w C H P h 359

3-thietanone is obtained by oxidation of 3-thietanol with dimethyl sulfoxidebenzoic anhydride.711 Oxidation by manganese dioxide gives a 3-thietanone when a 2-exomethylene group is present as in hydroxy analogs of 356.698b C.

Hydrolysis of Ketals of 3-Thietanone

3,3-Dimethoxythietane, obtained by treatment of 1,3-dibromo-2,2-dimethoxypropane with sodium sulfide, is hydrolyzed quantitatively by mineral acid to 3-thiet an one. lZ6 D.

Cycloadditions of Thiocarbonyl Compounds to Ketenes

Since it has been shown that this reaction generally gives 2-thietanones (0-thio-

lac tone^),^^^ reports of 3-thietanones being formed650,712y713 should be treated

skeptically (See Section XIII.3.B.). The chemical reactions and mass spectrum of the adduct of hexafluorothioacetone with diphenylketene have been interpreted on the basis of a 3 - t h i e t a n 0 n e . ~ ~ ~

E.

Miscellaneous Methods

Photolysis of 1,3-dithian-5-ones,for example, 360,714and 3-methyl-5-thiacyclogives 3-thietanones. A 3-thietanone intermediate was hex-2-ene-l-one, 361,7153716a of 8-thiabicyclosuggested in the photolysis of 3 - t h i a t e t r a 1 0 n e . ~ ~ Photolysis ~’~~’ [3.2.1.]-3-octene-2,6dione gives a 3-thietanone, 8-thiabicyclo[4.1.1]-4-octene3 , 7 - d i 0 n e . ~ lThermolysis ~~ of the a-diazoketone 362 gives the 2-exomethylene derivative 363.254d

Four-Membered Sulfur Heterocycles

512

b CxO

0 Freon hu 113

+

67%

89%

360

361

362

363

4.

A.

Reactions

Reactions with Nucleophiles

The carbonyl group of 3-thietanone reacts typically with nucleophiles such as to~ylhydrazine,~~~~ hydrazine (to give 364),2’& 2,4-dinitrophenylhydra~ine,’~~~~@’ ~ e m i c a r b a z i d e , ’and ~ ~ ~ phenylmagnesiuin bromide.12* It undergoes the Wittig reaction (e.g., the formation of 365); yields vary from 14 to 74%.717Sodium hydroxide cleaves the presumed 2,2-bis-trifluoromethyl-4,4-diphenyl-3-thietanone to diphenylacetic acid.712

0 NH,NH, 98%

*

365

3-Thietanones

573

Nucleophiles also react at the sulfur atom. The secondary amines, morpholine and piperidine, were believed to initially attack the sulfur atom of 3-thietanone to give sulfenamides, for example, 366, which underwent elimination of the amine to An intermolecular oxidation-reduction reation (see give l-thio-l,2-propanedione. the Cannizzaro reaction) gives the products, 367 and 368.718Thiopropanedione also could be formed via the enol of 3-thietanone 369, which is a thiete, the latter undergoing electrocyclic ring-opening (see Section IX.5.E.) to the enol of the thiodione. Phosphines react with the sulfur atom of sterically unhindered 3-thietanones to give ring-opened intermediates that can be trapped by reaction with methanol or furan, as illustrated for reaction of 2,4-dimethyl-3-thietanone370 with t riphenylphosphine .719a Treatment of 3 -thietanones with sodium hydrosulfide gives ring-expanded products, for example, 371-373 in low yield, or ring-opened products, for example, 374, depending on condition^.^^^*^^^ Mercaptoacetone 368 and other a-mercapto ketones are believed to be common intermediates derived, for example, from CH3COCH2SSH. The presumed 2,2-bis-trifluoromethyl4,4diphenyl-3-thietanone is desulfurized by lithium aluminum hydride to 4,4,4trifluoro-3-trifluoromethyl-1,l-diphenyl-2-butanone in 26% yield.712 S-substituted salts of 3-thietanone react with nucleophiles to give ring-opened products.536bi536c

CNH -

3- ’’ 3 0 It

-C,H,, N

[CH3C-CH2SN 366

It

II

[CH,C-CH]

0 It

CH3C-C-N

+[CH,CCH,SH]

367 (50%)

368

0 s II

OH CH, I

O w C H 3 CH3 370

CH,OH Ph3P

I

CH,CH=C -CH-

I

I

CH,

+ S -PPh3

CH ,OH - Ph,PO

0

* CH,CH,C

I1

-

SCH, I

CHCH,

tl

[ yi;]-. z

Four-Membered Sulfur Heterocycles

574

+s

37 1

NaOCH,, CH,OH

372

CH,COCH,SH

373

CH,

+ (CH3COCH2S-)2 +

368 (17%)

374 (1 8%)

0 II

(trace)

Reduction and Oxidation

B.

3-thietanones are reduced by sodium borohydride to 3-hydroxythietanes in good yields.'26,6y7,698a~ 704,706 The sulfur atom is oxidized to the sulfone stage510'719b or sulfoxide stage719cby peracetic acid. 6y8bi

C.

Aldol Condensations

Aldol condensations at one or both a-methylene groups of 3-thietanone have been accomplished with f ~ r r n a l d e h y d e , ~aromatic '~ aldehydes697'707, 720 (e.g., the and a ~ e t o n e . ~ " formation of 359), acetylenic

PhCHO

KOH, CH,OH 40%

D.

359

Thermal and Photochemical Reactions

The fragmentation of 2 2-bis-trifluoromethyl-4,4-diphenyl-3-thietanone in a mass spectrometer to diphenylketene and thiobenzophenone ions was used to con-

515

3-Iminothietanes

firm the 3-thietanone N o carbon oxysulfide was observed. Because similar fragmentation patterns have been observed with 2-thietanones ( P - t h i o l a c t ~ n e s ) ,such ~ ~ ~ evidence should be used cautiously. The conversion of 363 to 375 and 376 or to 377 occurs on irradiation in methanol or benzene, r e ~ p e c t i v e l y . ” ~A~ 3-thietanone intermediate 379 has been suggested in t h e photolysis of 378 t o 380.71s9716a

&L&A+m 377

\

378

379 CH2

(20%)

0

380

E.

Miscellaneous Reactions

Treatment of 2,2,4,4-tetramethyl-3-thietanone with diiron nonacarbonyl gives the binuclear iron complex 381.n1i72a 2,2-Dimethyl-3-thietanone undergoes oxidative dimerization t o 382 on treatment with potassium f e r r i ~ y a n i d e . ~ ” ~ Methylene-3-thietanones such as 359 add chlorine from thionyl chloride to the carbon-carbon double bond.709 2,2,4,4-tetramethyl-3-thietanone is converted t o the 3-thione in 14% yield by treatment with hydrogen sulfide-hydrogen Electrochemical reduction of the thione produces radical anions.

XVII.

3-IMINOTHIETANES 1.

Synthesis

The h y d r a z ~ n e ,2,4dinitrophenylhydra~one,’~~,~~ ~~~ s e r n i c a r b a ~ o n e , ’ and ~~~ 3 - p - t o l u e n e s u l f o n y l h y d r a ~ o n eof ~ ~ ~3-thietanone have been reported. The tosyl-

576

Four-Membered Sulfur Heterocycles

381

382

hydrazones of 2,2,4,4-tetramethyl-3-thietanoneand of 2-isopropylidene-4,4dimethyl-3-thietanone also have been mentioned.581b~716c An intramolecular cyclization yields the unique 2-rnethylene-3iminothietane 383.724The synthesis and properties of tris-iminothietanes are discussed in Sections XV. 1. and 2.A.685

H,SO,, C,H,OH

C2H502CCH2CH,

CH2CH2C02C2H,

C2H,O2CCH2CH2

CH2CH2C02C2H5 383

*

Methylene Thietanes

2.

511

Reactions

The hydrazone 364 of 3-thietanone reacts with hydrogen sulfide to give the dispiro derivative 384.254eThermolysis of the sodium salts of p-toluenesulfonyland hydrazones of 3-thietan0ne,~'~ 2,2,4,4-tetramethyl-3-thietan0ne~*~~ 2-isopr0pylidene-4,4-dimethyl-3-thietanone~~~~ yields allene or cumulene epiThe reactions of some tris-iminothietanes are sulfides, for example, 385 !'lb discussed in Section XV.3 .B.695'696

s>N

- N<S

H2S

p-CH3C,H,S0,H* CHCI,, -70'

384

XVIII.

METHY LENE THIETANES 1.

Occurrence

The presence of several 2-methylene-3-thietanonesand 2-methylene-3-hydroxythietanes in African plants of the tribe Arctotideae (e.g., 356) has been established .697,698a-698c

2.

Properties

An x-ray crystallographic analysis of thiamin anhydride derivative 386 shows that the thietane ring is planar when the formamide nitrogen and sulfur atoms are

0 CH3

386

CH3

Four-Membered Sulfur Heterocycles

578

&+

trans,725but twisted when cis.726The carbon-sulfur-carbon bond angles are 77.5" and 76.5", respectively, indicating considerable strain. All rings are nonplanar in 387 .727 (CH3)2 (CH3)2C

(CH3)Z

387

3. A.

Synthesis (Table 14)

Intramolecular Cyclization

2-Methylenethietanes may be obtained by cyclization of thioenolate ions derived from thiamin and related compounds (e.g., 388)728by treatment with base."4b, 725: 726,728-731d Sulfonate esters7" and phosphorus derivatives124h, 725, 726 may also be used in place of chlorides. The intramolecular cyclization of a porphyrin derivative to 383 has already been mentioned.724 r

L

388

Ph

-Ph

I

CCl The intramolecular cyclization of ketones by thionyl chloride to methylenethietanones has been discussed p r e v i o ~ s l y (Section ~ ~ ~ - ~XVI.3.A.). ~~

B.

Intermolecular Cyclization

The photochemical (n + n* long wavelength) cycloaddition of allenesz16~217~235~ (e.g., 390) t o a thio(eg., 389)240and

236,239,240a,562c,69lb,691c,732

Methylene Thietanes

579

carbonyl group gives generally good yields of 2-methylenethietanes (from allenes) and 3-allenic thietanes (from cumulenes). Cl,C= S

+ (CH,),C=C=C(CH,),

7 89%

389

(Cl),

hu

CHOCH,

( CH3 C H 3 ) Y CH3

hu

___)

90%

Bis-(trifluoromethy1)thioketene undergoes cycloaddition to alkenes to give 2-methylenethietanes.652”’652b, 734,735& 735b

C.

Aldol Condensations with 2-Thietanones

This method has been discussed in Section XVI.4.C. 2-methylene and 2,4dimethylenethietanes are obtained.6971698a>70777zo

D.

WittigReaction

3-Methylene derivatives of thietanes have been obtained by the Wittig reaction of 3-thietanones, as in the preparation of 365717and the phosphonium ylide 345 with p-nitrobenzaldehyde (to give 354).65sbA Wittig reaction also has been applied to a 2-thietan0ne.~~’~

E.

From 1,3-Cyclobutanediones and Thiones

Treatment of 1,3-~yclobutanedithiones with various nucleophiles or bases causes rearrangement to methylene derivatives of 2-thietanethiones (/3-dithiolactones)6s8~659a~678-680b,682 (see Section XIV). The rearrangement in one case is also said to proceed thermally.679a1,3-Cyclobutanedione and its monothione derivative also yield methylene derivatives with phosphorus pentasulfide and sodium hydride,

580

Four-Membered Sulfur Heterocycles

F.

Miscellaneous Methods

The unstable bis-3-methylenethietane 392 is obtained by desulfurization of the thiirane 391 that is derived from 384.254e The thermal rearrangement of a-diazoketone 362 gives the 2-methylene-3-thietanone 363 in quantitative yield.254d C,H,O,CN=NCO,C,H, THF, 71%

384

I'h,P

ligroin-toluene

C,H,, C,H,CH,

reflux 91%

39 1

392

4.

Reactions

A. With Nucleophiles The acid-catalyzed hydrolysis of the 2-methylene derivative 393 causes ringopening followed by a reverse aldol-type c ~ n d e n s a t i o n . ' Thiamin ~~ anhydride 394 is hydrolyzed to 2-acetylthietane, and the corresponding amine by 5% hydrochloric acid124b., it . reacts with para-substituted thiophenols to give 395-397, the yields .~~~ of 394 occurs on treatment with depending on the s ~ b s t i t u t e n t Ring-expansion 2,2-Dichloro-4-methylenethietanes are readily hydrolyzed to hydrogen 4-methylene-2-thietanones ?39,240a The reaction of 4-methylene-2-thietanones (e.g., 318) and 4-methylene-2-thietanethiones with hydrazine to give pyrazolinones 325 has been discussed previously (Section XIII.4.A.; XIV.).658

393

CH3 S - S - A r I

p-XC, H,SH

R -CHz-

N I CHO

I

/ CH-CH(CH,),SAr

CHO 394

395

+

581

Methylene Thietanes

396

397

cH3y3NH

R=

N /

394

CH3,

H2S DMF, 91%

* R - CH2-

B.

dCH<S I CHO

Oxidation

2-Methylenethietanes may be oxidized to the sulfones by hydrogen peroxide 216,2171652b Thiamin anhydride 394 is deformylated and converted to the sulfone by potassium p e r ~ n a n g a n a t e . 'Manganese ~~~ dioxide converts a 3-hydroxy-23-Methylenethietane 392 is rnethylenethietane t o the 2-methylene-3-thietan0ne.~~~ oxidized by peracetic acid to the ~ u l f o n e . ~ ~ ~

C.

Photochemical Reactions

Irradiation of 393 at 253.7 nm effects a reverse c y ~ l o a d d i t i o n . ~The ' ~ photochemical decomposition of the 2-methylene-3-thietanone 363 to 375-377 has been discussed previously25a (Section XV.4.D.). 4-Methylene-2-thietanthiones (e.g., 335) rearrange to either the 1,3-dithione or 338 in aprotic or protic solvents, respectively (Section XIV).6819682*733a

D.

Diels-Alder Reaction

3-Methylenethietane reacts with the tetrazine 398 with loss of nitrogen to give 399 .738

Four-Membered Sulfur Heterocycles

582

$‘HZ

+ CH302C<

N=N N-N

>

C02CH,

CO,CH, -HN

398

s&= CO,CH, 399

E.

Isornerization to Thietes

The products obtained by cycloaddition of xanthene or thioxanthenethiones to allenes or cumulenes isomerize to t h i e t e ~ . 733b ’~~~~

F.

Miscellaneous Reactions

Thermolysis of the lithium salt of the tosylhydrazone of 2-isopropylidene-4,4Treatment of dimethyl-3-thietanone gives 2,3-bi~(isopropylidene)thiirane.~~~~ 2-methylene-3-thietanoneswith thionyl chloride effects addition of chlorine across the carbon-carbon double bond.709Radical ions of 4-methylene-2-thietanethiones have been obtained by electrolysis and examined by electron-spin resonance680b

XIX.

THIETANONE 1-OXIDES (Table 15)

2,2,4,4-Tetramethyl-3-thietanone 1-oxide 400 is obtained in 69% yield by oxidation of the thietane with peracetic acid in benzene.719c Amides of 3-thietanone-2,4-dicarboxylic acid I-oxide are said to be obtained by treatment of amides of acetone dicarboxylic acid with thionyl chloride7,’ and 3-thietanone-1oxides may be intermediate in the reaction of ketones with thionyl chloride.709 may be an intermediate in the The S-oxide of 3,3,4,4-tetraphenyl-2-thietanone oxidation of the thietanone by rn-chloroperbenzoic acid, which is discussed in Section XIII.4.E.674 The S-oxide 400 undergoes ring-opening, presumably to the sulfenic acid 401, which cyclizes to five-membered products.719cThe intermediate may be trapped by reaction with trimethylsilyl chloride; it reacts with norbornene to give bisnorbornyl sulfoxide, probably via an elimination of 2,4-dimethyl-1,4-pentadien-3one from an initial a d d ~ c t . ~ ~ ’ ~

400

Thietanone and Thietanthione 1,l-Dioxides

583

0 II

25 % CH3

61%

XX. THIETANONE AND THIETANTHIONE 1 , l -DIOXIDES 1.

Uses

3-Thietanone 1,I-dioxides are intermediates in the synthesis of cyanine dyes used as photographic s e n s i t i ~ e r s . ~ ' ~ , ~ ~

2.

Synthesis (Table 15)

2-Thietanone 1,l-dioxides are unknown, although the tetraphenyl compound may be an intermediate in the oxidation of the 2-thietanone 308 with m-chloroperbenzoic acid to the sulfinic-carboxylic acid anhydride 331 .674 The methods discussed below apply to 3-thietanone 1,l-dioxides and derivatives.

A.

Hydrolysis of Ketals and 3-(N,N-Dialkylamino)-2H-Tkiete I ,1 -Dioxides

3-Thietanone 1,l-dioxide ketals and 3-aminothiete 1,l-dioxides are readily available by cycloaddition of sulfenes to ketene acetals and enamines, respectively ~ ~ ~ (Section V.3.B.). Hydrolysis of these k e t a 1 and~ the~ aminothiete sulfones (which are enamines)417~440~495a~521~527~600-602~606 gives 3-thetanone 1,1dioxides in fair to good yields, as exemplified by the hydrolysis of 133'14 and 402.602Aqueous mineral acids or acidic ion-exchange resins catalyze the reaction. Cis-2-chloro-2,4,4-trimethyl-3-morpholinothietane 1,l-dioxide reacts with 1N sodium hydroxide to give 38% 2,2,4-trimethyl-3-thietanone 1,l-dioxide, but the 3-Methoxy- and 3-ethoxythiete 1,ltrans isomer is recovered unchanged.5213527 dioxide (enol ethers) are also hydrolyzed to 3-thietanone 1, l - d i ~ x i d e . ~In' ~several cases, the hydrolysis products are written as enols of the 3-thietanone sulfone.602,606

B.

Oxidation of 3-Thietanones

2,2,4,4-Tetramethyl-3-thietanone is oxidized in 97% yield to the sulfone by peracetic acid.510i719b

~

~

5 84

Four-Membered Sulfur Heterocycles

Miscellaneous Methods

C.

The 3-thietanone 1,l-dioxide structure proposed741 for the product of the reaction of azibenzil with sulfur dioxide has been shown by 13C nmr spectroscopy to be incorrect.742 2,2,4,4-Tetramethyl-3-thietanethione 1,l-dioxide is obtained from the corresponding ketone (69% yield) by treatment with phosphorous pentasulfide.510

3.

A.

Reactions

WithNucleophiles

The reaction of 3-thietanone 1,l-dioxide with methanol to give the hemiketal has been observed by nmr spectroscopy; the equilibrium composition is 90% and the p-toluenehemiketal-10% ketone.743a The 2,4-dinitrophenylhydra~one~~ s u l f o n y l h y d r a ~ o n have e ~ ~ ~been ~ reported.

B.

Reduction

Catalytic hydrogenation of 3-thietanone 1,l-dioxide failed,514but the carbonyl group can be reduced to the alcohol in 56% yield by diborane in d i o ~ a n e . ~ ? ~ ' ~ Likewise, a thiocarbonyl group is reduced by sodium b ~ r o h y d r i d e . ~ ~ '

C.

?herma1 and Photochemical Reactions

Thermolysis of 3-thietanone 1,l-dioxide, 2,2-dimethyl-3-thietanone 1,I-dioxide, and 2-phenyl-3-thietanone 1,l-dioxide at 930-960°C results in extrusion of sulfur dioxide and carbon monoxide to give ethylene, isobutylene, and styrene, 13f Three-membered cyclic intermediates were p r o p 0 s e d . 4 ~ ~ ~ re spec tively .495c3

Thietanone and Thietanthione 1,l-Dioxides

585

Photolysis of 3-thietanone involves both singlet and triplet excited states; the initial products are sulfene and ketene, as determined by IR spectroscopy at liquid nitrogen temperatures in a pentane matrix.743aWhen the photolysis is done in methanol, isopropyl alcohol, or t-butyl alcohol, these intermediates are trapped as the acetate and methanesulfonate esters. In diphenylmethanol solvent, the bis-diphenylmethyl ether is formed by displacement of the alcohol on the sulfonate ester. Photolysis of tetramethyl-3-thietanone 1,l-dioxide gives d i m e t h ~ l k e t e n e . ’ ~ ~ ~

Thermolysis of the sodium salt of the tosylhydrazone of 2,2,4,4-tetramethyl3-thietanone 403 yields t e t r a m e t h ~ l a l l e n e . ~ ~ ’ ~ NaN- S 0 2 A r I

(CH3)2 403

D.

0-Alkylation

Treatment of 3-thietanone 1,I-dioxide607 and 2-phenyl-3-thietanone 1 ,l dioxide495c with diazoalkanes gives the enol ethers, 3-alkoxythiete 1,l-dioxides, (e.g., 404).

(39%) 404

E.

Miscellaneous Reactions

The a-methylene protons of 3-thietanone 1,I-dioxide are acidic (effervescence is observed in sodium bicarbonate solution).514 The base-catalyzed reaction of

Four-Membered Sulfur Heterocycles

586

3-thietanone 1,]-dioxide with benzoxazolium salts, benzthiazolium salts, and related cationic heterocyclic compounds leads to dyes, for example, 405, with extended conjugations that are useful as photographic ~ensitizers."~

2,2,4,4-Tetramethyl-3-thietanethione, obtained by treating the thietanone with phosphorus pentasulfide, reacts with diazoalkanes to give the episulfides 406 in yields of 61-97%~.'~'The disulfide 156 and related polysulfides are also obtained from the thione.'1° R2

sE2 (CH3)2

R1R2CN2&

(CH3)Z

(CH3)2

XXI.

R1%:H3)2

406

METHYLENETHIETANE 1 -OXIDES AND 1 , I -DIOXIDES 1.

A.

Synthesis

Oxidation of Methylene Thietanes

2-Methylenethietanes are oxidized to the sulfones by hydrogen peroxide'24b3'16, or perrnar~ganate;"~~ the 3-methylene derivative 392 is oxidized by peracetic 2173652b

B.

Miscellaneous Methods

The exo-allenic thietane dioxide 407 is obtained by cycloaddition of an allenic sulfene to an enamir~e.~"Desulfurization of thiirane 406 by triphenylphosphine

Methylenethietane 1-Oxides and 1,l-Dioxides

581

gives the 3-methylene derivatives in yields of 54-100%.5'0 The formation of 2-methylene derivatives of 3-thietanone 1 ,I-dioxide such as 405 has been described (Section XX.3.E).740 At attempted cyclization of an acetylenic sulfenic acid to a 2methylenethietane 1-oxide failed.743bThe 3-methylene derivative 279 (Section XII.4.C.) is obtained from 3-chlorothiete 1,l-dioxide and the anion of dimethyl mal~nate.~'~~

HC-CCH,SO,Cl

I

t. PhC=CH, 407

2.

Reactions

Hydrolysis of the allenic sulfone 407 gives the ring-opened product 408; the acetylthiete derivative 409 is formed with sulfuric acid.609 Flash-vacuum thermolysis of 3-methylenethietane 1,l-dioxides (e.g., 410) yields dienes510and, in the case of 411, also a methylenecyclopropane 412, probably via diradical interthe two methyl groups attached to the double bond of 411 are m e d i a t e ~ If .~~ deuterated, the two labeled methyl groups are found on both the double bond and on the ring of 412 (ratio 1:2).744An exo-methylenecyclopropane analog of 411 undergoes cleavage of the three-membered ring at 200°C.743d

I

Ph -C=CHSO,CH,COCH, 4 08

409

Four-Membered Sulfur Heterocycles

588

CO2C2H 5 % H :3 2'

770"

CH3 CH(CH3)z I I CHz=C- C = C H C 0 2 C 2 H 5

(CH3)2 410

XXII.

1 ,ZTHIAZETIDINES ( 1 -THIA-2-AZACYCLOBUTANES)

Examples of the parent compound are rare, the 1-oxides (Section XXIII) and especially the 1,l-dioxides (Section XXIV) being more common. 2,4,4-Triphenyl1,2-thiazetidin-3-0ne414 is obtained along with other products by thermolysis of 413 .745 Desulfurization of 414 by Raney nickel yields N-phenyldiphenylacetamide. Oxidation of 414 by rn-chloroperbenzoic acid gives the S-oxide in 27% yield. The mass spectrum of 414 shows ions corresponding to Ph2CS+ (a cycloreversion) and an ion produced by loss of a sulfur atom from the molecular ion.745 Sulfonium salts such as 415 are suggested as intermediates in the photochemical rearrangement of 1,2-thiazolesto 1 , 3 - t h i a ~ o l e s 747 .~~~'

Ph-N

,S-N-Ph

owph2 0

I l o o , 1 mm 24%

Ka Ni

/N - S

Ph Ph2 413

414

THI'

82%

II

PhNHCCHPh2

1,2-Thiazetidine 1-Oxides and 1-Imines (Sulfilimines)

XXIII.

589

1,2-THIAZETIDINE 1-OXIDES AND 1-IMINES (SULFILIMINES) 1.

uses

A yellow condensation product of p-N,N-dimethylaminobenzaldehydewith N-cyclohexyl-l,2-thiazetidin-3-one 1-oxide is said to be useful as a dye for polyester fibers.748

2.

Properties

Proton nmr spectroscopy distinguishes between axial and equatorial S-oxide isomers, for example, 416a and 416b, respectively.74gThe axial proton at C-3 is deshielded by axial S-0. In 1,2-thiazetidin-3-0ne I-oxides, the S-oxide absorbs at 1130-1 143 cm-' in the IR; linear sulfinylamides absorb at 1 0 2 5 - 1 0 5 0 ~ r n - * . ~ ~ ~ Absorption of the S-oxide occurs at 1080- 1090 cm-' in N-sulfonyl-l,2-thiazetidine l - o x i d e ~ . 13C ~ ~ 'nmr ~ spectra aided in establishing the structures of 2-substituted-3keto-4,4-dimethyl-1,2-thiazetidine 1

H (aromatic region) 66.06

H 63.40 416a

H 63.05 416b

An x-ray structural analysis of 3-keto-4,4-dimethyl-l-p-tolyl-l,2-thiazetidine I-oxide shows a planar ring with a C-S-N angle of 75.7", which indicates strain.751c Its carbonyl stretching frequency is 1770cm-1 and its mass spectrum indicates loss of sulfur monoxide or an isocyanate from the parent ion.751c

3.

Synthesis (Table 17)

The principal method of synthesis of the l-oxides is the cycloaddition of N-sulfinylsulfonamides, for example, 417, t o vinyl ether^.^^^^^^^,^^^^ N-phenyld i m e t h ~ l k e t i m i n e ~(correction '~~ of an earlier 752c proposed structure), and N-sulfinylamines, for example, 418,750to k e t e n e ~ ~or a~ l k,e n~e ~~. ~The "~~ ~ ~ ~ ~ adducts obtained from ketene itself are unstable above Treatment 78°.75017543755a

Four-Membered Sulfur Heterocycles

590

of amides 419 with thionyl chloride gives better yields than the reaction of the of sulfur ketene precursors, a-diazoketones, with N - ~ u l f i n y l a m i n e s .Addition ~~~ dioxide at - 78" t o ketenimines gives good yields of 3-keto-1,2-thiazetidine l - o x i d e ~ The . ~ ~addition ~~ of C-phenyl-N-phenylnitrone t o fluorenethione gives a 13%yield o f 2'3'-diphenylfluorene-9-spiro-4'-(l',2'-thiazetidine) l-o~ide.~~~~

+

CH3--@S02NS0

0Et,O 0"

91%

417

I

S "0

0-

NSO

+ Ph2C=C=0

418

Ph

I

Ph-X-CHCONHR

SOCI,

O&*-

C , H, N

C , H6 SS-757G

N-S

R'

Ph \ '

0

Oxidation of 414 by m-chloroperbenzoic acid is the only instance of this method for preparing thiazetidine 1-oxides. The yield was 27%.745 1,2-Thiazetidine 1-imines are obtained by treatment of vinyl ethers756 or ketene74S,757,758a,7S8bwith sulfur dimides, as exemplified by the synthesis of 420.745

tBuN=S=NtBu

-

O w P h 2

Ph,C=C=O o O ,Et,O 748

/N tBu

- S\\ 420

N- tBu

1,2-Thiazetidine 1-Oxides and 1-Imines (Sulfilimines) 4.

59 1

Reactions

An acidic solution of 2,4-dinitrophenylhydrazinereacts with N-p-chlorophenylsulfonyl-3-ethoxy-1,2-thiazetidine 1-oxide to give (80%) the bis-2,4-dinitrophenylhydrazone of g l y o ~ a l . ~The ’ ~ adduct ~ of N-sulfinyl-p-chlorophenylsulfonamide with ”~ of dihydropyran is inert to catalytic hydrogenation and b r ~ m i n a t i o n . ~Treatment two 1,2-thiazetidine-3-one 1-oxides (e.g., 421) with hydriodic acid results in ring. ~ ~ are ~ not oxidized to l,l-dioxides by peracetic cleavage and loss of s ~ l f u r They acid,750 but m-chloroperbenzoic acid accomplishes this oxidation.7s2bi755c The unstable adducts with ketene decompose to amides with loss of hydrogen sulfide and sulfur dioxide7” or may be trapped by reaction with aromatic amines as shown for thiazetidine l-oxide 422.754,755aAn aldol-type condensation has been reported for N-cyclohexyl-1,2 thiazetidine-3-one I-oxide and p-(N,N-dimethykamino)benzaldehyde.74RSulfur monoxide is lost in the flash-vacuum thermolysis of 422a.7s2b

O w P h 2 N-S / \\ Ph 0

H I , 60’

Ph2CHCONHPh

42 1

ArNH,

/

N-S

Ph

(CH,),CO.

\ ‘

0

- 78” S0-71%

0 /I

0 I1

PhNHSCH,CNHAr

422

Several of the S-imino derivatives (e.g., 423,7s6 424,7574257s8a)are unstable to heat and decompose with r i n g - ~ p e n i n g , ~ring-e~pansion,~’~ ’~ or fragmentation.758a Hydrolysis of 424 gives a 93% yield of N-diphenylacetyl-p-toluenesulfonamide757 and hydrolysis of 1-t-butylimino-2-t-butyl-4,4-dichloro-l,2-thiazetidine-3-one gives N-t-butyl-2,2-dichloro-2-(t-butyl)sulfinylacetamide.758b Aqueous ethanolic hydrobromic acid may cause ring cleavage with loss of sulfur as shown for 425.758a Desulfurization of 420 Methanolysis of 426 gives 427 with retention of with Raney nickel gives N-t-butyldiphenylacetamidein 92% yield.74s

Four-Membered Sulfur Heterocycles

592

-

O w P h z N- S 1 \\ Ts NTs

-

7 O'

100%

O w P h z / N , s A Ts Ts

424

PhNCO --/P h ,N-S\\ Ph

+ PhN=NPh + PhN=CPh, + Ph,CO 24%

40%

\ N-Ph

2%

10%

OOC,H5 HBr, C , H , O H

425

h

H2O

II I

+ PhNHCCPh, (60%)

-

CASO

,N-s\\ Ts

PhNH, * HBr

CH,OH 71%

NTs

Ts OC,H, I 1 TsNHS-N-CHCH20CH3 427

426

1 7

X

1.

1,2-THIAZETIDINE 1,l-DIOXIDES (P-SULTAMS) AND 3-KETO DERIVATIVES 1.

Uses

1,2-Thiazetidine 1, I -dioxides or 0-sultams can be polymerized to high-molecularweight p o l y s u l f ~ n a m i d e s . ~ ~1,2-Thiazetidin-3-one ~-~~~~ 1,l-dioxides react with aliphatic diamines to give polyamide-polysulfonamide polymers.7631764Fluorinated 3-keto and 3-imino derivatives were investigated as surface-active agents,766 and N-malonyl derivatives of 1,2-thiazetidin-3-one 1,l-dioxide are said to be yellow couplers for color photography.767

1,2-Thiazetidine 1,l-Dioxides (fi-Sultams) and 3-Keto Derivatives

593

Properties

2.

Cis and trans isomers of 428 have been distinguished by proton nmr spectroscopy, appearing at lower field in the cis isomers than 4H.768 The cis coupling constants for H3-H4 are greater by 1.3-2 Hz than the trans coupling constants. The asymmetric and symmetric IR stretching frequencies for the sulfone group of 428 are in the ranges 1298-1320cm-' and 1092-1 1 6 2 ~ m - ' , ~ ~ ~ r e s p e c t i vfor e l y3-keto ; derivatives, the frequencies are 1350-60 and 1135-1 150 cm-', respectively.769The stretching frequency for a 3-carbonyl group is 1785 (-NH) or 1775 (-N-R) cm-l .769 Spectroscopic data also are frequently given along with descriptions of the synthesis of the 0-sultams. Electron spin resonance data have been reported for nitrogen-centered radicals of 1,2-thiazetidine 1,l-dioxides and their n i t r ~ x i d e s . ~ ~ ' ~

/

CH, 3.

N - SO, 428

Synthesis (Table 17)

Intramolecular Cyclization

A.

Intramolecular cyclization of 2-aminoethanesulfonyl halides gives 1,2sultams),759i770-772 as exemplified in the synthesis of thiazetidine 1,l-dioxides (/I 429.770Treatment of 2-halosulfonylethanoyl halides with ammonia766,773-777 or primary amines762,7 6 4 , 7 7 7 , 7 7 8 yields 1,2-thiazetidin-3-0ne 1,l -dioxides, which are mixed sulfonic-carboxylic imides 430. A 3-imino derivative has also been obtained .773

CO2CZH5 I HC1. H2NCHCH2SOzCl

OK ' I/ I

xcc-S0,X I R2

NH,,

O o , CHCl, 70%

N - SO,

- 7' H'

429

R'NH,

/

N - SO,

K3

430

R2

5 94

Four-Membered Sulfur Heterocycles

B.

Cycloadditions

The cycloaddition of N-sulfonyl amines (N-sulfonyl imides) (e.g., 431781)to alkenes gives 1,2-thiazetidine 1, l - d i o ~ i d e s . ~ ~The ’ - ~ stereochemistry ~~ about the double bond of the alkene is preserved in the adduct, and a “tight” zwitterionic intermediate is favored.782 Considerable amounts of six-membered cyclic adducts also are formed in these additions. Yields vary from good to poor. Thermolysis of 432 yields sulfonyl amine 433; the higher reaction temperatures involving 433 enable less reactive alkenes such as cis-stilbene to be used successfully.783 The success of cycloadditions to enamines depends on the latter having no protons on the 0-alkene carbon or on an sp2 hybridized carbon attached to the a - p o ~ i t i o n . ~ ~ ~

78’

SO2

431

-

CH,CN 30-60’ \

CH3

OCH3

0

II [CH,OCN=SOZI

-” Ph

W

Ph

H

433

432

Ph

Ph

H, W . H N - SO2 / CH3OZC Cycloaddition of sulfenes to Schiff b a ~ e ~ ~(e.g., ~ 434)768 , ~ ~and~ c a r b ~ d i i m i d e syields ~ ~ , ~1,2-thiazetidine ~~~ 1,l-dioxides and 3-imino derivatives. A concerted mechanism was suggested.768An earlier report of the cycloaddition of a . ~ yields ~ ~ ~ sulfene to a Schiff base lacked proof for the structure of the a d d ~ c tBest are obtained with two equivalents of imine.768The cis isomers can be converted to trans by treatment with t r i e t h ~ l a r n i n e . ~ ~ ~

,

~

~

1,2-Thiazetidine 1,l-Dioxides (p-Sultams) and 3-Keto Derivatives

C.

5 95

Miscellaneous Methods

Photolysis of the diazoketone 435 is alleged to give the spiro 1,2-thiazetidin-3one I,l-dioxide 436, but only an elemental analysis for nitrogen and sulfur was offered as proof for the structure. This may be a typographical error, 437 possibly being the intended structure.788Oxidation of a 1,2-thiazetidin-3-0ne I-oxide with peracetic acid was not successful,750 but oxidation of two other derivatives with 755c N-substim-chloroperbenzoic acid gave the sulfones in 40% and 79% yield.752b3 tuted 1,2-thiazetidin-3-one 1,l-dioxides are obtained by alkylation with alkyl ’ e t h a n eA. ~sulfurane ~~ derivative halides,77497753789 dimethyl ~ u l f a t e , ~or~ d~i,a~~ ~o m 438 was proposed as an intermediate in the reaction of ketene dimer with N-arylsu~fiIimines. 790

PhCHzSOzCl

+ PhCH=NCH,

( C H ) N TH F (80%)

434

435

Phh/Ph /

N - SO,

CH;

49% cis 3 1% trans

436

4. A.

Reactions

Tautomerism; 0-Alkylation of 3-Keto Derivatives; Isomerism

The proton on nitrogen in 1,2-thiazetidin-3-one1,I-dioxides is slightly less acidic (pK, = 2.8-3.0)789 than saccharin; the potassium salt of the 4,4-dimethyl derivative

Four-Membered Sulfur Heterocycles

596

439 is obtained in 81% yield by the use of ethanolic potassium The tautomeric 3-hydroxythiazete sulfone structure of 439 is trapped by U-alkylation to give 440.789The 3-imino compound 441 tautomerizes to the thiazete sulfone 442.448Isomerization of cis- to trans-3-aryl-4-pheny1-1,2-thiazetidine 1,1-dioxides occurs on treatment with triethylamine for 15 h.768 (CH,),CHO i-PrI Ag 0

H

/

' l _

N - SO2

N

C,H,,45-5S0

439

- SO2

440

/

N- SO2

Call

C6H;1

44 1

442

B.

N-Alkylation

The nitrogen atom of 1,2-thiazetidin-3-one 1,]-dioxides is alkylated by alkyl dimethyl halides [with K2CO3 or (C2H5)3N],774i775~789 or diazomethane .774 C.

Reactions with Nucleophiles and Bases

Nucleophiles (water,759,760,772,774 hydroxide ion,774 methoxide ion,768 chloride ion772) attack the sulfur atom of 1,2-thiazetidine 1,ldioxides to give ring-opened products, as exemplified by the reaction of 443 (ethanesultam, anhydrotaurine) with water.772 Catalytic amounts of water give good yields of which also may be formed via a m i n o l y s i ~ . ~ ~ ~ ~ ~

n HN - SO2

" 2 0

H2NCH2CH2SO3H

443

The carbonyl group of 1,2-thiazetidin-3-one l,l-dioxides also is attacked by nucleophiles: water,774 amines,7649789 h y d r a ~ i n e , ~ ~and ~ , ~the ~ ' anion of 4,4dimet hyl-l,2 -thiazetidin-3 -one 1,l-dioxide (439) .761,762,765a Ring-opening is the result (e.g., the reaction of 439 with ammonia),789 and polymers may be

1,2-Thiazetidine I,l-Dioxides (0-Sultams) and 3-Keto Derivatives

597

formed,761,762,764,765aHowever, ammonia is said to form the 3-imino derivative of 4-fluoro-4-perfluoro-n-pentyl-1,2-thiazetidin-3-one 1, l - d i o ~ i d e .3-(N,N-Dialkyl~~~ amino)-2-alkyl-l,2-thiazetidine1,I-dioxides ( e g , 444)784 are hydrolyzed to ~-(N-alkylaminosulfonyl)acetaldehydes.781~ 784 Triethylamine effects a ring-opening elimination of 445 .781 CH3 0 NH,NH,

H

/

N

- SO2

EtOH

I

11

H2NSOzC - CNHNHZ

I

CH3 439

;c'i

k t

CH3

(CH 3)2

/

N - SO2

CH3

H2O (silica gel) 5 5%

I

CH3NHS02C- CHO

I

CH 3

444

Et,N

O

CZH.jOCH=CHSOzNHCOPh

445

D.

Reduction

Reduction of 4,4-dimethyl-l,2-thiazetidin-3-one 1,I -dioxide 439 by lithium aluminum hydride in ether gives 2-hydroxy-1,l-dimethylethanes~lfonamide.~~~

E.

Thermal Reactions

Thermolysis of 1,2-thiazetidine 1,l-dioxide at 400°C and 2 m m pressure is said to give e t h e n e s ~ l f o n a m i d e . ~Thermolysis ~' of either cis- or trans-2-methyl-3,4diphenyl-l,2-thiazetidine 1,I-dioxide at 220°C yields trans-stilbene and benzaldehyde in relatively low yields. The parent ion minus SOzH is the base peak in the mass spectrum of the above methyldiphenyl derivative, and there are also ions corresponding to PhC-N'CH, and the parent ion minus sulfur

Four-Membered Sulfur Heterocycles

598

XXV.

1,2-THIAZETE DERIVATIVES

The following isomers are represented: 2H, 4H; and 3H, 4H. A benzo-1,2thiazete 447 has been proposed as an intermediate in the reaction of phenyl nitrene (triplet) with the thiazo derivative 446;792a sulfurane structure 448 was suggested for one product of the reaction of perfluoropropyliminosulfur difluoride with perf l u ~ r o p r o p e n e .Stable ~ ~ ~ benzo- and naphthyl-l,2-thiazetyl radicals (e.g., 452) are Electronobtained by thermolysis of S-amino compounds 449,450, and 45 1?94-796a spin resonance studies established the structures. The magnitude of the spin density on nitrogen in derivatives of 452, which carry a substituent para to the nitrogen ~ ~ ~of~ sulfur from the atom, depends on the nature of the s u b ~ t i t u e n t .Loss naphthyl derivative 453 occurs at temperatures above 150°C.795

441

446

N--S--CF(CF,),

I

F 448

(PhNH), S 449

50-60' ' 6 H6

3 70-80"

diphenyl

45 1

45 3

1,2-Thiazete Derivatives

599

1,2-Thiazete 1-oxides, 455, 457, are obtained in low yields from N-sulfinylaryl 456 by amines and the pyrroline 1-oxide 454,797and S-methyl-S-phenylsulfoximide carboxylation of its lithium

ArN=SO

+

(Ar = Ph, 10%)

H

0-

455

454

0 I1

Ph-S-CH3 II NH

( I ) nBuLi, THI: (2)

co,

N=S -Ph

K

( 3 ) H,Of

456

457 (15%)

1,2-Thiazete 1,l-dioxides have been obtained by 0-alkylation of the 3-keto derivatives, for example, 439789(Section XXIV.4.A.). They are also obtained by tautomerism of 3-imino derivatives such as 441 obtained by cycloaddition of sul~ ~ ' ~ ~ ~ of benzothiatriazine dioxide 458 gives the fenes to c a r b o d i i r n i d e ~ . Photolysis benzothiazete 1,l-dioxide derivatives 459, the N-2,6-dimethylphenyl derivative,80°a or the Nmesityl derivative,smb being more stable than the N-phenyl compound. The latter reacts readily with water and aniline to give N-phenyl-o-aminobenzenesulfonic acid and 4N'-diphenyl-o-aminobenzenesulfonamide, respectively.8ma Ringopening also occurs on treatment of the N-mesityl compound with sodium hydroxide, methanol, and morpholine.800h The N-phenylthiazete 1,l-dioxide is photochemically rearranged to carbazole and thermally rearranged to the phenothiazine 5,s-dioxide. The more stable N-dimethylphenyl derivative gives an adduct 460 on photolysis in norbornene; thermolysis gives 461.800aIts mass spectrum shows ions due to the loss of SOz and S02N. The 3-isopropoxy 1,2-thiazete 1,l-dioxide 440 undergoes ring-opening with water, ammonia, hydrazine, and hydrogen peroxide.789 SMethyl 4-H-1,2-thiazete cations have been suggested as intermediates in the rearrangement of oxime tosylates of 2 - m e r ~ a p t o m e t h y l k e t o n e s . ~ ~ ~ ~ ~ ~ ~ hu, CH,C,H, ~

0 2

458

78"

60% (Ar = 2,6(CH3)2 C,H,) 459

Four-Membered Sulfur Heterocycles

600

459 (Ar = 2,6(CH3)2C6H3)

-

II

iPr- O M ( C H 3 ) ,

CI - 0-iPr N H , , EtOH

N-SOZ 440

43%

,(CH3)2CS02NH,

\

NNH, I1

NH C0,iPr I

(CH3)2CS02NH, (35%)

I\

CO-iPr I

+ (CH,)ZCS03H (37%)

60 1

-

CH3NOTs I II CH3S-C- C-Ph I CH3

0 II

% PhCN + PhCOC(CH3),S (53%)

CH3

(28%)

+ PhCOC(CH,),SCH, + CH3SH ( 13%)

XXVI.

1,3-THIAZETIDINES 1.

uses

Substances alleged to be N-aryl-l,3-thiazetidines have mycobacteriostatic and fungistatic properties."la 3-Arylsulfonyl-1,3-thiazetidines are claimed to be useful in the synthesis of dye developers in color photography.801c

2.

Properties

The p K , of N-cyclohexyl-1,3-thiazetidine in 95% ethanol at 25°C is reported as 2.6.802However, the structure of the compound investigated is probably an eightmembered cyclic dimer as indicated by later 3.

Synthesis (Table 18)

The older descriptions of the synthesis of 1,3-thiazetidine derivatives provide little in the way of structure proof beyond elemental analyses. In particular, lack of information about molecular weights leaves open the possibility that dimeric or oligomeric structures may have been obtained. For example, treatment of amines or imines with hydrogen sulfide and formaldehyde is reported to give N-substituted1 , 3 - t h i a z e t i d i n e ~ , ~ ~ ~but ~ * -a~ reinvestigation ~ of the synthesis of N-phenyl-1,3thiazetidinem showed that the product had twice the molecular weight expected.803 Nmr and mass spectral data of the product obtained from methylamine, formaldehyde, and hydrogen sulfide indicate it is an eight-membered ring.803b Caution also is advised with respect to the 1,3-thiazetidines supposedly formed by treatment of bis(chloromethy1) sulfide with benzylamine and by treatment of benzaldehyde with thiosemicarbazide derivatives.'" The structures of the exc-methylene 1,3-thiazetidines 462 have been established by molecular weight

Four-Membered Sulfur Heterocycles

602

A 1,3-thiazetidine intermediate has been sugand spectroscopic gested to account for the products of the addition of thioketenes t o amino-lazirines.'1° Ar I

CH3COCHyNyCHCOCH3

NaCN, D M F

s-s

55-7476

CH3COCH

462

Thioketenes, for example, 463, add t o i m i n e ~ ,carbodiimides,812a ~ ~ ~ ~ , ~and~ ~ ~ ~ azines8lZato give 1,3-thiazetidines with exocyclic double bonds, as exemplified by the synthesis of 464.73saA novel ring contraction of 464a gives 1,3-thiazetidine 464b.811c1,3-Thiazetidines are postulated as intermediates in the photochemical addition of thiobenzophenone to imines.81ZCThey fragment to the two possible thiocarbonyl components and imines.811b,'lZc

c6FS

463

464

hu dioxane 70%

____)

C0,Et

COzEt

464a

XXVII.

464b

1,3-THIAZETIDINE-2-0NESAND 2-THIONES 1.

Uses

A sulfa drug derivative of 1,3-thiazetidine-2-one is said to have a different mechanism of action from that of the known sulfa drugs.812d4-Iminosulfonyl-l,3thiazetidine-2-ones are said to be useful curing agents for elastomeric polythiocarboxylic acids.813

603

1,3-Thiazetidine-2-Ones and 2-Thiones

2.

Synthesis

Treatment of N,N'-disubstituted thioureas with phosgene yields 4-imino-l,3t h i a z e t i d i n e - 2 - 0 n e s ' ~ ~ - ~(e.g., ' ~ 4658143815 466816).Thermolysis of esters 467 yields the thiazetidinones 468,"* and a 1,3-thiazetidinone 470 has been suggested as an intermediate in the photolysis of 469.8191,3-Thiazetidine-2-0nes are obtained by cycloaddition of phenylsulfonyl isocyanate to the thiocarbonyl groups of a thioamide.820

465

466

R

=

c

,87%

hv EtOH, CH,CI,

469

470

Four-Membered Sulfur Heterocycles

604

Treatment of 3-amino-6-methoxypyridineor the corresponding thiourea 471 with thiophosgene gives the 1,3-thiazetidine-2-thione472.8211,3-Thiazetidine-2thiones are possible intermediates in the reaction of carbon disulfide or isothiocyanates with isothioureas,822a in the reaction of carbon disulfide with imines,822b-82% and in the reaction of salts of dithiocarbamic acids with a,Bunsaturated acid chlorides.822g4-Imino-l,3-thiazetidine-2-thione is suggested as an intermediate in reactions of isothiocyanic acid (HNCS).822h

S C H 3 0 e N H - C II - N € I e O C H 3 N-

47 1

CSCI, 33%

-N

h-s

S

472

3.

Reactions

Treatment of 4-iminophenyl-3-phenyl-1,3-thiazetidine-2-one (465) with ammonia or aniline gives N,N’-diphenylthiourea and urea or N,N’-diphenylurea, respectively.814 3-Alkyl analogs of 466 decompose to sulfonyl-l-chloroformamidines on treatment with hydrogen chloride.816 The 2-thione 472 reacts at the thiocarbonyl group with ethanol and n-butylamine.821 Thermolysis of 1,3t h i a z e t i d i n e - 2 - 0 n e s ~and ~ ~ ~2-thiones821i822a-822f ~~~>~~~ causes fragmentation of the ring, as exemplified by 466816and the mass spectrum of 472.821Compound 466 reacts with isonitriles, ynamines and phosphonium ylides to give ring-expanded or ring-opened products.822i

XXVIII. 2-IMINO- AND 2,4-BIS-IMINO-1,3-THIAZETIDINES The synthesis and reactions of imino-l,3-thiazetidine-2-ones, 2-thiones, and exomethylene derivatives have been discussed in Sections XXVI and

~~11.808,812-817,821

2-Imino- and 2,4-Bis-Imino-1,3-Thiazetidines

/ C , H ,r OH C* H 3 0

605

~ N H k l C 2 H 5

NCH30

472

n-BuNH, CH,CI,

466

1.

Uses

Several 3-substituted 2-iminoaryl-4-(bis-trifluoromethyl)methylene-l,3-thiazetid3-Substituted 2,4-bisines are water repellant and are used for treating imino- 1,3-thiazetidinesmay have pesticidal

2.

Properties

X-ray crystallographic analysis of 473,824474,825aand 475825breveal small C-S-C angles -- 74.3", 75.2" and 72.7", respectively - indicative of considerable strain in the planar rings. The structure of 476 was deduced from its dipole moment.826a An x-ray analysis of 476 (Ar = p-N02C6H4) indicates the ring is nonplanar with a fold about the S-N axis.826bThe Z,Z-conformation was established. The 13C nmr spectrum of 475 agrees with the structure.825b

3.

Synthesis (Table 18)

Treatment of N-substituted thioureas with diiodomethane yields 2-imino-l,3t h i a z e t i d i n e ~ , ~as ~ ~exemplified > ~ ~ ~ - ~ ~ by ~ the synthesis of 477.827Ethylene thiourea

606

Four-Membered Sulfur Heterocycles

473

474

476

reacts with aromatic aldehydes in the presence of boron trifluoride-etherate to give 2-imino-4-aryl-1,3-thiazetidines (yields 88-98%), in which the four-membered ring is fused to a five-membered ring derived from the thiourea.830aIsothiouronium salts derived from a-chlorodimethyl-sulfoxide give good yields of 2-imino-l,3thiazetidine salts on treatment with sulfuric acid followed by sodium tetraphenylborate.830b The dichloromethylene imine 478 reacts with thioureas to give 2,4-bisimino derivatives.

40-85%

477

The cycloaddition of isothiocyanates to imines gives 2-imino-l,3-thiazetidineS,822a,831a,832 some of which are unstable.822,831a-831d Cycloaddition of carbodiimines to bis(trifluoromethy1) ketene652a,812a and i ~ o t h i o c y a n a t e s ~ ~ ~ ~ ~ ~ gives 2,4-bis-imino-1,3-thiazetidines. The reaction of carbodiimides with 0,Odimethyldithiooxalate to give 1,3-dialkyl-5,5-dimethoxy-2,4-imidazolidinedithiones

2-Imino- and 2,4-Bis-Imino-1,3-Thiazetidines

607

C1

N= CCl,

+

bC1

61

C1

478

may proceed via a 2-imin0-1,3-thiazetidine.~~~~ Isonitriles react with 0,Odimethylin modest yield (40dithiooxalate to give 2-irnino-4-methylene-1,3-thiazetidines 44%).838e

RIN=C=NRZ

+ R3N=C=S

-

Early reports839-843of 2-irnino-l,3-thiazetidines (e.g., 479) being formed from thiosemicarbazide derivatives should be treated skeptically in view of the large obtained for the compound purported to have structure dipole moment (8.4 D)844a 479.840a Structure 480 was favored.844a Further examination of the older work suggests that some of the other structures obtained were 2-aniino-5-mercapto1,3 ,4-thiadiazolesW and not analogs of 479 which, incidentally, violates Bredt's rule.

I

479

P 11 480

4.

Reactions

The 2-imino- or 2,4-bis-imino-l,3-thiazetidine ring is thermally unstable. The ring fragments t o two relatively stable molecules,835bas exemplified by the decomposition of the intermediate 48lSza and the mass spectra of several comThe thermal reaction of 2-methylimino-3p o u n d ~ , for ~ ~example, ~ , ~ ~482.838a ~ phenyl- 1,3-thiazetidine with phenyl isothiocyanate, p-toluenesulfonyl isothiocyanate, and phenyl isocyanate gives cyclic six-membered heterocyclic compounds ~' and enamines react with derived from fragments of the t h i a ~ e t i d i n e . ~Nucleophiles the 2,4-bis-imino derivative 483 to give products derived from ring-opening and

Four-Membered Sulfur Heterocycles

608

In structure 484, the N-r-butyl and the N-tosyl groups may be fragmentation.825b7c reversed. Ring-opening to zwitterions can (e.g., 485835a).Hydriodic acid also effects ring-opening.830aOxidation of various 2-imino-1,3-thiazetidines 486 results in ring-expansions, probably via an S-oxide intermediate.846

* rBuN=C

? + (CH,),NCSCH,

=NTs

48 1

gH 1 1 \ N y N c 6

11

in n a s s spectrometer

J-s PhCO N

* [ PhCON=C =S]+’ + [C6H , N = C =NC6H, 1’’

482

/-

( I ) NaOCH,, CH,OH

NTs S CH3NHCOCH3 II + tBuNHCOCH, It

(2) H 3 0 t

CH,C-CN(C,

(73%)

(34%)

+

H, ) >

t-Bu-N 483

\

(32%)

(29%) 484

HN,

Et,O

N-N CH3NHI(

‘A

” I

t-Bu

(35%)

S CH3 I1 I [TsN--C--N=C=N-tBu]

485

475

N-N +

TsNH-(,

S’

‘h

(44%)

1,3-Thiazetes

609

L

486

0 L S = O (10-35%)

( 34- 7 2%)

XXIX.

1,3-THIAZETES

Four 4-aryl-2,2-bis(trifluoromethyl)-2H-l,3-thiazetes 488 are obtained by The thiazete is in thermal equilibthermolysis of the 1,3,5-oxathiazines 487.8479848 which react rium with the (perfluoroisopropylidene) thiocarboxamides 489,848-854e with phosphorus p e n t a s ~ l f i d e , ~ phosphorus ~’~~ p e n t a ~ e l e n i d e , 8 ’ ~ ,antimony ~’~~ t e l l ~ r i d e , ~ ~ n’ ,o~r’ b~ ~ r n e n e , a~vinyl ~ ~ , ether,848 ~~ an e~~amine,’~’ an ynamine,848 is on it rile^,^^,^^ d i m e t h o ~ y c a r b e n e , ~ ’ ~carbethoxycarbene,8” ketones,8” diphenylketene,8” dicyano- and t e t r a c y a n ~ e t h y l e n e . Inter~~~,~~~~~~ mediate 489 adds across cyano groups of the latter two reagents. A 1,3-thiazete-2one is suggested as an intermediate in the isomerization of N,N-dimethylcarbamoylN-cyandithiocarbimic isothiocyanate to N,N-dimethylthiocarbamoylisocyanate.8s5 2H-1,3-thiazetes may be interacid is believed to be 4-amin0-1,3-thiazet-2-thione.~~~~ in mediates in the reaction of thioketones with acetonitrile the reaction of carbon disulfide with g ~ a n i d i n e s , 8 ’and ~ ~ in the reaction of carbon oxysulfide with esters of carbamimidothioic

487

488

IR absorption for the 1,3-thiazetes is observed at 1602-1605 cm-’ and 15601585 cm-’.848 The mass spectra indicate fragmentation to ArCN’, CF3CS’, and ArCS’, in addition to an ion formed by loss of a sulfur atom.848

Four-Membered Sulfur Heterocycles

610

489

I

reflux 73-79%

xylene 140-160"

XXX. 1,2-OXATHIETANES; 1 ,ZOXATHIETANE 2-OXIDES (0-SULTJNES); 1 ,ZOXATHIETANE 2,2-DIOXIDES (p-SULTONES) The 1,2-oxathietane-4-ones described in the older literature are really acyclic, zwitterionic sulfonium carboxylates (e.g., 490).857-859Th ey were written incorrectly as cyclic sulfuranes (e.g., 491). 1,2-Oxathietanes are rare, having been suggested as intermediates in a few instances; but not one has yet been isolated. The S-dioxides or 0-sultines are more

611

1,2- Oxathietanes

0-S-

+

(CH,),SCH,CO;

I

CH

CH, 49 1

490

numerous, although hardly common. The S-dioxides or 0-sultones are the most abundant of the three classes, and the most common of these are fluorinated derivatives which have been reviewed.860 1.

Uses

1,2-Oxathietane 2,2-dioxides are claimed to be useful in the synthesis of pharmaceuticalsB61 and anti-inflammatory agents:62a in protection of plants from diseases,861 as insecticides and plant growth regulators,862c as a rusticide for beans,863 in the preparation of polymers and ion-exchange membranes,861'864a-864i as stabilizers of liquid sulfur t r i o ~ i d e , ~as~ ' surface-active agents,766 in the preparation of suppressants for chromic acid mist in the electroplating of chromium,866 as dye intermediate^,'^^ and as reagents for effecting the acylation of alcohols, phenols, and amines.868-872a0 t her uses of fluorinated p-sultones have been reviewed.860 A naturally occurring 1,2-0xathietane 2,2-dioxide in hiba oil is said to be an timicrobial .872c

2.

Properties

A theoretical treatment of 1,2-0xathietane indicates planarity with a S-0 bond length of 1.669 and a C-S-0 angle of 100.6" .873 The electronic spectrum was calculated. The character of the HOMO is largely that of the sulfur 3p orbital. A CNDO molecular orbital study of the retrocycloaddition of 1,2-0xathietane 2-oxide to sulfur dioxide and ethylene shows that strong heteroatom asymmetry lifts the stereoelectronic requirement that the thermal fragmentation occur by a suprafacialantarafacial path.874 The 1,2-oxathietane 2-oxide 492 has a puckered ring (dihedral angle 159.7"), as is shown by x-ray analysis.875 The sulfoxide oxygen atom is axial. The geometry of 3,3,4,4-tetrafluoro-l,2-oxathietane 2,2-dioxide has been discussed.876 The S-0 stretching frequency in the IR spectra of 1,2-oxathietane 2-oxides is observed at 1150-1 190cm-'.877-879 The carbonyl stretching frequency in 1,2oxathietane-4-one 2-oxide is observed at 1840 and 1856 cm-'.877 The sulfonate IR absorptions in 1,2-0xathietane 2,2-dioxides are 1370-1408 and 1 1761235 cm-',880,881 except for the fluorinated derivatives, the absorption of the tetrafluoro-0-sultone being reported at 1470 cm-'.882 Fluorine-19 (nmr) chemical shifts and coupling constants are useful in structural and conformational studies of

a

Four-Membered Sulfur Heterocycles

612

93.8'

86.4'

1.487 A

1.856 A

492

the fluorinated 0-sultones, although dihedral angles were not able to be ~ b t a i n e d . " ~ The mass spectra of several haloalkyl substituted /3-sultones show no molecular ion (M), but an ion, M-Hal-S02, is abundant.884

3.

Synthesis (Table 19)

1,2-Oxathietanes have not been synthesized, but they or their analogs have been suggested as intermediates in the addition of thiocarbonyl ylides (e.g., 493) to diphenylketene,885 in the decarboxylation of a-methylthiocarboxylic acids by N-chlorosuccinimide,886 in the reaction 0-acylsulfinamides with triethylamine :87a in the thermolysis of 1,2,3-0xadithiole-2-oxide,8~~~ and in the decomposition of sulfoxide-substituted n i t r o ~ o u r e a s . 8 ~ ~ ~

t-BuCH=$-CHtBu

+ Ph,C=C=O

-

493

tBu

Staudinger and Pfenninger long ago suggested that addition of sulfur dioxide to diphenylketenc gives an intermediate, 3,3-diphenyl-l,2-oxathietane-4-one 2-oxide, that decomposes to diphenylsulfene and carbon dioxide, the former yielding tetrap h e r ~ y l e t h y l e n e .Similar ~ ~ ~ ~ intermediates were proposed for the addition of sulfur ~ 1,l-difluorodioxide to pentamethyleneketene,888 k e t e n i m i n e ~ , ~ "ethylene,889 e t h y l e n e ~ , ~and ~ ' an aluminum trichloride derivative of the 1,2,3,4-tetramethylcyclobutene cation.891An intermediate adduct 494 actually has been isolated at

1,2-Oxathietanes

613

20°K from the photochemical addition of sulfur dioxide to k e t e r ~ e .It~ ~ ~ decomposes on prolonged irradiation at 20°K to carbon dioxide and, presumably, sulfine which could not be detected. Addition of sulfur dioxide to perfluoro-1,3butadiene gives the 0-sultine 495.879A stable 0-sultine is said t o be obtained from sulfur dioxide and q u a d r i c y ~ l a n e . ~ ~ ~ ~

hu

SOz + C H , = C = O

10-20°K Ar or N ,

494

* so,

CF,= CFCF=CF,

P,05 hu 1 S-ZO%

F

0-s

F

a F

\O 495

An intramolecular cyclization of 13-hydroxysulfoxides effected by N-chlorosuccinimide, N-bromosuccinimide, or sulfuryl chloride gives 1,2-oxathietane These cyclic 2-oxides, for example, 496,875 via a sulfoxonium sa1t.875,878~892 sulfoxonium intermediates have been suggested in the conversion of 8-hydroxy~ ~consulfoxides t o P - c h l o r ~ s u l f o n e s894 , ~ and ~ ~ ~to a,P-unsaturated s u l f o n e ~in, ~the version of P-ethoxycarbonylsulfoxides to alkenes and of 0-hydroxysulfides to 13-hydro~ysulfoxides,~~~~~ 896b and in the conversion of 0-hydroxy-8-vinylsulfoxides (e.g., 497) t o useful terpene building b l 0 c k s . 8 ~The ~ ~ yields of the products from 497 vary somewhat depending on the stereochemistry about the two chiral centers. The more highly substituted 1,2-0xathietane 2-oxides are the most stable, because of

0 OH PhSCH2&-CH=CH,

CH=CH,

1

CH3

-

cH3h

SO,Cl,

-

0-S+-Ph /I 0

CH3,

PhSO,CH,

/c=c /H

'CH,CI

Four-Membered Sulfur Heterocycles

614

increased steric interactions in the transition state for loss of sulfur 1,2oxathietane 2-oxides are suggested as intermediates in the addition of sulfur dioxide to k e t e n i r n i n e ~and , ~ ~in ~ ~the photolysis of thiolane l , l - d i o ~ i d e . ~ ~ ~ ~ 1,2-Oxathietane 2,2dioxides (e.g., 448)898aare isolated in good yields from the reaction of sulfur trioxide with fluorinated alkenes,766’898-905hfluorinated d i e n e ~ , ~ ~and ” ~ from the reaction of the sulfur+tri,oxide donor 499 with are suggested. fluorinated a l k e n e ~ . ~Zwitterionic ’~ intermediates ( )C-C-S020-) An explosion has been reported in the addition of sulfu: trioxide to tetrafluoroethylene.909 Tetrafluoroethane 0-sultone (498) also is obtained by treatment of fluorosulfonyldifluoroacetic anhydride with antimony t r i ~ h l o r i d e . ’ ~ ~ ~

F

F

so,, soo CF2=CF2

0-so*

I’arr hydrogenation) apparatus 93%

CF2=CI12

+ (CF,),C?(

498

O\,SO, 0

98%

F& 0-

so2

499

Unstable /3-sultones have been identified by nmr in the reaction of sulfur trioxide ~ ” addition ~~~ is said to be stereowith cis- and trans-2-butenes and 2 - ~ e n t e n e s . ~The specific. Addition of sulfur trioxide to other alkenes has been suggested to yield 500);912the /3-sultone from styrene is isolated at /3-sultone i n t e r m e d i a t e ~ ~ l ~(e.g., -~’~ 0°C by precipitation with ~ e n t a n eThe . ~ ~addition ~ of sulfur trioxide to ketenes is ~ ~ addition of sulfur claimed to yield 1,2-oxathietane-4-one 2 , 2 - d i o ~ i d e s . ’ ~The dioxide t o azibenzil originally was thought to yield a / 3 - ~ u l t o n ebut , ~ ~later ~ work showed that the products possessed six-membered rings.742 Sulfenes add to perhaloketones (low yield with p e n t a f l u o r o a ~ e t o n e ) ~and ~ ~ aldehydes to give p-sultones,458,861,863,880,881,919-921b for example, The yield of 0-sultone obtained from chloral increases with increasing “smallness” of the base used to generate the intermediate s ~ l f e n e . ~ ~ ~

5 00

1,2-Oxathietanes

CH3S02C1

Ft N -

[CH,

=

615

SO2]

I ]

[~HzSOzkEt31

15'

CCI,CHO

CC1,

) l +56-760/0 0-SO,

[CC13)7 + Q

50 1

SO,NEt,

Several b-sultones are claimed to be formed by treatment of alkenes with sulfuric acid862",912dor by heating alkenesulfonic acids.917 Treatment of 22-dimethyl-1,ldiphenyl-1-propano1 with concentrated sulfuric acid at room temperature is said to give 3-( 1,l-diphenylethyl)-3-methyl-l,2-oxathietane2,2-dioxide (96% yield).922 Treatment of sodium 3-bromo-2-hydroxybutanesulfonatewith phosphorus trichloride is reported to give a low yield of 4-(l-bromoethyl)-l,2-oxathietane2,2dioxide.923 1,2-0xathietane 2,2-dioxide is suggested as an intermediate in the reaction of /3-hydroxyethanesulfonyl chloride with trimethylamine to give the zwitterion 502.924The first four-membered monocyclic sulfurane oxides 502a have been reported.924b

L

J

502

R = M e , E t ; Ar = p-C1C6H4, p-Br -C,H,

4. A.

Reactions

Nu Cleop h ilic Ring-Open ing

Halogenated /3-sultines890 and halogenated ~-sultones766,876~898d-898h,899~904~905a, on heating or in the presence of nucleophiles t o fluorosulfinyl- and fluorosulfonylacetyl halides, for example, 503, respectively.

905g,907,908~916,92s~926a,926b isomerize

Four-Membered Sulfur Heterocycles

616

-

0 /I FS0,CXYCF 503

The reaction is believed to be a chain process initiated by attack of a nucleophile (e.g., fluoride ion) on the sulfur atom.926a The fluorosulfonylacetyl fluorides are likely intermediates in the reaction of fluorinated a-sultones with nucleophiles (water ,898b,898h,90Z,W6,908,925,927 hydroxide ion,773,898i,900,908,928 alcohols,893,898b,898d, alkoxide ions,926a carboxylic fluoride ion plus 2,2,3-trifluoro-3-trifluoromethyloxirane~30a a m i n e ~ , ~ ~ ~ 898h, 9 0 2 ~ 9 0 8 ~ 9 2urea,894 9 hydrogen sulfide,898dt h i ~ l s , ~931 ' ~ thiocyanate ~, ion,898a3 898d t r i a l k o ~ y p h o s p h i n e s , 8hydrogen ~~~ chloride926a).The fluorosulfonyl group of 503 is relatively inert, but it can react with strong n u c l e o p h i l e ~The . ~ ~ tetrafluoro-1,2~~ oxathietane 2,2-dioxide 498 is useful as a reagent for promoting the acylation of alcohols, phenols, and amines by carboxylic acids under mild condition^.^^^-^^^ A mixed anhydride 504 is a probable intermediate.8683869Nu cleophilic attack by phosphorus occurs at a fluoromethylene 898h79023903~908~92s,929

0-so, 498

RC0,H 0",- H F

0 0 [FSO,CF,C-0-CR]

9

% RCOR'

504

Other P-sultines878,892 and p-su~tones86~~,910,918"b'93Z,933a,933b react with nucleophiles, usually at the sulfur atom, to give derivatives of P-hydroxysulfinic or P-hydroxysulfonic acid, as exemplified by the reaction of 501 with m ~ r p h o l i n e . ~ ~ ' 2,2-dioxides to give Grignard reagents react with 4-trichloromethyl-l,2-oxathietane 2-hydroxy-3,3,3-trichloropropyl ~ u l f o n e s The . ~ ~trichloromethyl ~~ group of 501 is hydrolyzed to a carboxyl group in the hydroxide-ion-catalyzed r i n g - ~ p e n i n g . ~ ~ ' Nucleophilic attack also may occur via either SNl or SN2 mechanisms at the , ~ " >2,2~~~ 4-position (0-position) o f 1,2-0xathietane 2 - o ~ i d e s ~ ~ ~ and dioxides,910~912~913~g1s~918~9z~ as shown for the intermediate Soxide salt 505.894 1,2-Oxathietane-4-one2-oxides or 2,2-dioxides are attacked at the carbonyl group in preference to the sulfonyl sulfur atom.862c'888

617

1,2-Oxathietanes CCl,

n

0-

Ef,O, 100%

blso2

O w N H

-

OH CCl,CHCH,SO,N

A W0

501

L

B.

505

Retrocycloadditions

1,2-0xathietane 1-oxides thermally lose sulfur dioxide t o give alkenes,875~878~879, exemplified by 506.892The loss of sulfur dioxide is s t e r e o s p e ~ i f i c The .~~~ 0-sultones also may lose sulfur t r i o ~ i d e but , ~ ~the reaction is less clean; sulfur dioxide has been observed along with a variety of other products in the thermolysis of chlorotrifluoro f i - s u l t ~ n e s . ~ ~ ~ ~ Other retrocycloadditions may occur in the decomposition of 0-sultines, obtained by reaction of triplet sulfur dioxide with alkenes, to ketones and sulfines (or a carbene and sulfur monoxide)889and in the decomposition of 1,2-0xathietaneThe mass spectrum of 1,24-one 2-oxides to carbon dioxide and a oxathietane 2-oxide shows a fragment attributed to ~ u l f i n e . ~ ' ~ ~ 8929896a as

506

C.

Miscellaneous Reactions

1,2-Oxathietane decomposes t o mercaptoacetaldehyde which loses sulfur to give ~~~ of acetyladehyde or which loses hydrogen sulfide t o give k e t e r ~ e . 'Ring-opening S-substituted 1,2-oxathietane 1-oxide salts may occur via elimination reac507.895Elimination of fluoride ion with t i o n ~ . as~ is~shown ~ , ~for~ intermediate ~ ~ ring-opening occurs with fluorinated 1,2-oxathietane 2,2-dioxides on prolonged chlorosulfonic acid,926b* 936,937 standinga8' or on treatment with sulfuric

-

-

0

0" 0 Ph,CCH, SCH,

55%

507

J

Scheme b

Scheme a

A OH

c1 c1 c1

OR OR

B SO,H SO,H SO,R SO,OR S0,OR SO,OCH,

A OR

c1 c1

c1 C1

c1

Ph,C=CHS0,CH3

B

A

B

9

H NO H

c1 F CH=CH,

SOR S0,CI H NO POCI, PO(CHJC1

Boron trifluoride-triethylamine effects a ring-opening elimination of 4,4difluoro-3-trifluorornethyl-1,2-oxathietane2,2-dioxide to give fluorosulfonyltrifl~oromethylketene."~~Eliminations occur from intermediate 6-sultones, obtained by addition of sulfur trioxide to alkenes, to give alkenesulfonic aCids.913,914,918

1,2-Oxathiete Derivatives

619

4-Trichlorornethyl-l,2-oxath1etane 2,2-dioxide is a catalyst for the acylation of alcohols and amines under mild condition^.^^^,^^^^ It also catalyzes the polymerization of (NPC12)3.864iIt is suggested that six-membered cyclic sultones are derived from P-sultones transiently formed in the addition of sulfur trioxide to 1,2-oxathietane alkenes.914’921d Ring-expansion of 3,4,4-trifluor0-3-trifluorovinyl1-oxide occurs at 100°C t o give 4,4,5,6,7,7-hexafluoro-l,3-dioxa-2-thiacyclohept-5ene.879 Halogenation of 3,3,4,4-tetrafluoro-l,2-oxathietane2,2-dioxide in diethyleneglycol dimethyl ether gives haloethers of 3-hydroxytetrafluoroethane sulfonyl fluoride.942c 2,2-dioxide may give polyThermolysis of 3,3,4,4-tetrafluoro-l,2-oxathietanc mers of the composition (CF2CF2S02)x”3or (CF2),.w Polymer along with a cyclic sulfate and perfluorobutadiene is obtained by heating a 4-trifluorovinyltrifluoro-/3sultone at 100°C in a sealed tube.907 Heating 4-chloro-3,3,4-trifluoro-l,2oxathietane 2,2-dioxide and its 3-chloro isomer at 510°C gives sulfur dioxide and low boiling l i q ~ i d s ; 8 ”heating ~ at 45°C in the presence of sulfur trioxide is believed to give a cyclic dimer.898b Heating the tetrafluoro-P-sultone with 100% sulfuric . ~ ~ ~ ~ ~ ~ ~ also acid gives fluorosulfonic acid and carbon m o n o ~ i d eTetrafluoroethylene is formed, possibly via difluoroketene which decomposes to difluorocarbene and carbon monoxide.934 Thermolysis of 4-perfluoropropoxy-3,3,4-trifluoro-1,2oxathietane 2,2-dioxide at 200°C in a sealed tube is reported t o give perfluorocyclopropane and sulfur dioxide.903The explosion reported in the preparation of 3,3,4,4-tetrafluoro-1,2-oxathietane 2 2-dioxide (498) at 43°C and 15 psi is suggested to result from the exothermic reaction of sulfur trioxide with the 0-sultone to give sulfur dioxide and carbonyl fluoride.909 The intermediate 0-sultone 508, obtained by addition of sulfur trioxide to l-ethoxy-l-trifluoromethyl-2,2-difluoroethylene, decomposes to a 0-ketosulfonate ester.903 A similar reaction is observed with 4-( 1,2-dibromo-l,2,2-trifluoroethyl)3,3,4-trifluoro-I ,2-oxathietane 2,2-dioxide, except that a P-ketosulfonyl fluoride is 2,2~ b t a i n e d . ” ~Treatment of 3-perfluoro-n-amyl-3,4,4-trifluoro-l,2-oxathietane dioxide or the 3-trifluoromethyl analog with ammonia at 0°C gives the 4-imino derivatives.766 1

r

508

XXXI.

1,2-0XATHIETE DERIVATIVES

Blue monothiobenzil 511 is formed by photolysis of the oxathiol S-oxide 509 (incorrectly formulated in early reports as a thiirane S - o ~ i d e ) , ” ~ possibly ”~ via 3,4-diphenyl-l,2-oxathiete 510.”3-946 The appearance of an ion corresponding to

Four-Membered Sulfur Heterocycles

620

diphenylacetylene in the mass spectrum of monothiobenzil might be caused by the intermediate ~xathiete.”~” The green, glassy material formed from monothiobenzil when it is allowed to stand could be oxathiete 510, since it slowly reverts to monothiobenzil in solution in methylene ~ h l o r i d e . “Later ~ investigations showed no evidence for any photochemically induced isomerization of m o n o t h i ~ b e n z i l ~ ~ ~ or monothiopivaloylW8 or the N,N’-benzylamide of monothiooxalic acid.”g The S-oxide of 510 may be an intermediate in the decomposition of the sulfone analog 950 of 509 .”63

509

510

511

A benzooxathiete 512 obtained by photolysis of 5-methyl-l,3-benzoxathiol-2one was identified by its absorption at 290nm at .- 77°C in a methanol-ethanol matrix.”’ It was in equilibrium with monothioa-benzoquinone. An intense peak in the mass spectrum of 513 corresponding to C6H4S0 was suggested as belonging to the ion of b e n ~ o x a t h i e t e . ’Sulfuranes ~~ (e.g., 514)’” of benzoxathietes have been suggested as intermediates in the reaction of benzynes with dimethylsulfoxide.952i953

A naphthoxathiete 2,2-dioxide has been suggested as being derived by an intramolecular cyclization of 1-hydroxy-2,3,4,6-naphthalenetetrasulfonic

4 2 - and 1,3-Thiaphosphetane Derivatives

XXXII.

62 1

1,3-0XATHIETANE DERIVATIVES

Bicyclic 1,3-oxathietanes are said to be formed by treatment of hydrazomonothiodicarbonamide with concentrated hydrochloric acid.839a9839b,9ss The structures violate Bredt’s rule and reinvestigation of the early work indicates the compounds Another bicyclic 1,3are not 1,3-0xathietanes, but 1,3,4-thiadiazole~.~~~~~~~ oxathietane, whose structure also violates Bredt’s rule, has been reported as the product from 1,2-diaminonaphthalene and S-(ethoxycarbony1)-0-e thyldithiocarbonic acid.958 1,3-Oxathietanes are said to be obtained by treatment of 4,4’methylenebis( 1,2,3,4-tetrazol-5-thiones) with bromine water.9s9 They are not ‘desulfurized by treatment with mercuric oxide. The oxathietane supposedly formed with hydrogen sulfideby treatment of 1,2,4-tripheny1-2-butene-l,4-dione hydrogen chloride960may need revision of its structure in view of the correction961 of the 1,3-dithietane structure960allegedly obtained by treatment of benzoin with these reagents. 1,3-0xathietane intermediates are proposed for the reaction of bis-trifluoromethylt hio ketene with p-N,N-dimethylaminobe nzaldehyde ,652a and for the reaction of bis-trifluoromethylketene with cyclic, five-membered thioureas, for example, 515.962A l-methyl-l,3-oxathietane salt is a possible intermediate in the thermolysis of S-methoxymethyl thioacetate to S-methyl t h i ~ a c e t a t e . ~ ~ ~

S

R’-N A N - , ,

U

(CF,),C=C

CH,CI,

=o

*

515

(~)-(Cis-4-methyl-l,3-oxathietan-2-yl)phosphonic acid S,S-dioxide is an intermediate in the preparation of (*)&( 1,2-epoxypropyl)phosphonicacid. It is said to have antibiotic proper tie^.^^ Sulfur dioxide is lost from the intermediate either thermally or photochemically.

XXXIII.

1,2- AND 1,3-THIAPHOSPHETANE DERIVATIVES

The only known stable 1,2-thiaphosphetanes 516 are obtained in low yields by . ~ ~ ~rearrange treatment of alkylaminocrotonates with phosphorus p e n t a s ~ l f i d eThey

Four-Membered Sulfur Heterocycles

622

readily to the more stable oxaphosphetanes. A 1,2-thiaphosphetane intermediate has been suggested in the Wittig reaction of a thiocarbonyl group with a phosphon2,2,2-Triphenyl-1,2-thiaphosphetan-4-thiones have been detected by ium I3C nmr as intermediates in the reaction of carbon disulfide with ylides of triphenylphosphine.*'la Similar structures also have been postulated as interto thioketenes. m e d i a t e ~966c . ~ They ~ ~ ~decompose ~

NHR I

CH,C =CHCO,R'

-

R

1'4SIO

C , H,, 60°

P-s SQ \ SR'

-

CH3 <s I

b-0 SQ \

I

SR'

516

The 1,3-thiaphosphetane 517 sterilizes houseflies967 and amine salts of the corresponding acid and dithioacid are corrosion inhibitors for lubricants.968 0 CzH,O-Pl L S 517

An electron diffraction study of 3-oxo-3-chloro-l,3-thiaphosphetane indicates nonplanar structures in which that with a pseudoequatorial chlorine atom predominates.969IR970,97'and Ramang7' spectroscopic studies of similar derivatives in solution favor planarity for the ring. No conformational isomerism could be detected over a wide temperature range.971 The absorption of the phosphorusoxygen double bond is at 1250-1256 cm-', which is higher than that observed in acyclic derivatives (1 180-1220 ~ r n - ' ) . ~ ~Hydrogen ~ ~ ~ ' ' bonding of phenol with the phosphorus-oxygen or phosphorus-sulfur group is observed, but the shifts in the phenolic 0-H stretching frequency are less than with acyclic c o r n p ~ u n d s . ~ ~ ~ ~ ~ ~ Proton and 31P nmr studies in solution indicate that a time-averaged planar conformation is most likely for 3-0x0-3-chloro (or 3-alkoxy)-l,3-thiaphos~ h e t a n e . ' ~ ' - ' ~Dipole ~ moments and Kerr constants have been obtained for 3-0x0~ - ~ ' ~ angles from 130- 175" are calculated for and 3 - t h i o d e r i v a t i ~ e s . ~ ~Dihedral pseudoequatorial oxygen or sulfur. These 3-0x0- or 3-thio-l,3-thiaphosphetanesare prepared by cyclization of salts of bis(chloromethy1)phosphonic or thiophosphonic acids with sodium sulfide,974,977-979 as exemplified by the synthesis of 518.979Treatment of 518 with thionyl chloride gives the that reacts with alcohols, phenols, and amines to give esters and amides.974,979The ethyl ester of 518 may be obtained directly by treatment with t r i e t h o x y p h ~ s p h i n e .Treatment ~~~ of the chloride of 518 with phosphorus pentasulfide gives 3-chloro-3-thio-1,3-thiaphosphetane,which yields the anhydride 519 on addition of water.974The ethyl ester of 518 undergoes ring-opening on treatment with sodium ethoxide to give 520.979

623

Thiasilacyclobutanes and Thiagermacyclobutanes

86%

518

519

10% C , H , O N a

C , H , OH

0

* CH3SCH,P(OC,HS), 5 20

3,3,3-Triphenyl-l,3-thiaphosphetane 1,l-dioxides, for example, 521, are suggested as intermediates in the reaction of sulfenes (from dehydrohalogenation of me thanesulfonyl halides) with triphenylphosphine y l i d e ~ . ~ ~ '

RZ

521

XXXIV. THIASILACYCLOBUTANES AND THIAGERMACY CLOBUTANES 3,3-Dimethyl- and 3,3-diethyl-l,3-thiasilacyclobutanes are obtained by intramolecular cyclization of the bis(chloromethy1) silane with hydrosulfide ion,981,982 as exemplified by the synthesis of 522982 or by an intramolecular hydrosilation,982-984d as exemplified by the synthesis of 523.982 A chloropkatinic acid catalyst (Speiers catalyst) also has been used for the hydrosilation reaction, 983,984a-984c

Four-Membered Sulfur Heterocycles

624

H CH3 I I (C ,H s ) 2 SiCHSCH=CH2

(Ph,P), RhCl C6 H,

+

IOO", sealed tube 73%

523 (&:trans = 1 : l )

The mass spectra of these 1,3-thiasilacyclobutanesshow prominent ions corresponding to R2Si=CH2, R2Si=S, and R2Si.982,98sa,985b The 29Sinmr spectrum of 522 has been reported.981 Ring-opening occurs on treatment with mercury(I1) chloride or ethanolic potassium hydroxide,982as shown for 522.

522

OCZHS I (CH3),SiCH,SCH3

KOH

CH3 1 + (CH3SCH2Si),0 I

CH3 The rather unstable 2,2-diethyl-l-thia-2-germacyclobutane 524 is obtained by an intramolecular dehydrogenation or by treatment of 2,2-diethyl-2-germa-1,3dithiolane with t r i - ( n - b u t y l ) p h o ~ p h i n e .986b ~ ~ ~ ,It thermally decomposes to ethylene and diethylgermathione; the latter reacts with the thiagermacyclobutane to give a cyclic, six-membered 1,3-dithia-2,4-germacyclohexane. H

20%

524

(C H, ) Ge -S'

XXXV.

1 ,ZDITHIETANES AND 1,2-DITHIETES 1.

1 ,ZDithietanes

Four-membered and other cyclic disulfides have been reviewed.987Theoretical calculations (CNDO/B) have suggested optimized geometries for 1,2-dithietane (S-S, 2.146 A; S-C, 1.835 A; (S-C-S 99.1", C-S-S 80.9").873 Frontier orbital energies (--0.07, - 10.1 eV) and spectra (396, 242, 224, 201, 186nm) also were calculated. In the lowest unoccupied molecular orbital, the sulfur 3d orbital contribution was estimated as 45%.

1,2-Dithietanes and 1,2-Dithietes

625

The only well-characterized, stable 1,2-dithietane derivative is 3,4-diethyl-1,2dithietane 1,l-dioxide 525, obtained by dimerization of propanethial S - ~ x i d e . ~ ~ ’ The I3C and 170nmr chemical shifts have been determined: ring-carbon atoms 6 39.2, 97.9ppm; 170, 210 and 243ppm in acetone relative to water.55b A 1,2dithietane structure was proposed on the basis of an elemental analysis for the product obtained by treatment of a nitrovinylpyrrole derivative with hydrogen sulfide-sodium hydroxide.”’ 1,2-Dithietanes have been suggested as intermediates ’’~ in the reaction of sulfur and sulfur-rich compounds with f l ~ o r i n a t e d ~ ~ -and ~ n f l u o r i n a t e dalkenes. ~ ~ ~ An ion corresponding to 3,3,4,4-tetrafluoro-l,2-dithietane is observed in the mass spectrum of volatile material derived from a copolymer of The possibility of a 1,2-dithietane intersulfur and tetraflu~roethylene.~’~~’~~ or thermalg9& formation of tetrasubstituted mediate in the photochemica1994a-99~ ethylenes from thiocarbonyl compounds has been considered. A 1,2-dithietanyl radical is a plausible intermediate in the photolysis of 2,2-diphenyl-4H-pyran-4t h i ~ n e . ’ ~ ’1,2-Dithietanes ~ have been considered as possible intermediates in the radicals formed in the cathodic reduction of dimerization of 3,5-diaryl-l,2-dithiolyl 3,5-diaryl-1,2-dithioliumions:95b in the oxidative desulfurization of sym-trithianes and thioketals by iodine in dimethylsulfoxide,995C and in the Willgerodt r e a ~ t i o n . ~ ’ ’ 1,2-Dithietanes ~ also may be intermediates in the reaction of 2,2dimethyl-l,3-dithiolane with methanesulfenyl chloride or dimethyl(methylthi0)sulfonium te t r a f l u ~ r o b o r a t e . ’ ~ ~

2. A.

1,2-Dithietes

Properties

An x-ray analysis of 526 indicates an S-S bond length of 2.12 A, which is on the high end of normal S-S bond distance^.^'^ An electron diffraction study of 1,2bis(trifluoromethy1)dithiete reveals a structure of C2 symmetry: S-S, 2.05 A; C=C, 1.40 a; C-S, 1.73 8 ;(C-C-S, 100.8”.998aThe photoelectron and IR spectra (10°K) have been obtained for colorless b e n ~ o d i t h i e t e . ~ ~ ’ ~ Molecular orbital calculations have been performed on 1 , 2 - d i t h i e t e ~ . ~ ~ ’ - ’ ~ ~ Electron-releasing substituents favor the valence tautomers, the 1,2-dithiones,

626

Four-Membered Sulfur Heterocycles

526

whereas electron-withdrawing substituents favor the cyclic dithiete structure.999 The S-S bond order increases with increasing electronegativity of the substituent. Strain energy of unsubstituted 1,2-dithiete is calculated as 43 kcal/mole and the n-delocalization energy as 92 kcal/mole.lOO' The potential energy surface has been calculated for the equilibrium between 1,2-dithiete and ethane-I ,2-dithial, and for The the valence tautomerism of the hypothetical 1,2-dithietan-3,4-dithi0ne.'~~~ 1,2-dithiete dianion has been discussed t h e r ~ r e t i c a l l y . 'The ~ ~ electronic spectra of several unstable 1,2-dithietes, valence tautomers of 1,2-dithiones and dithials, have been obtained at 77°K in an organic matrix."@'

B.

Synthesis

The first stable 1,2-dithiete, 3,4-bis(trifluoromethyl)-l,2-dithiete527, was reported in 1960, as a result of the reaction of hexafluoro-2-butyne with boiling s ~ l f u r ;loo6 ' ~ other ~ ~ ~ fluorinated derivatives are prepared similarly.'007 The strained acetylene 528 reacts with sulfur to give dithietes.loo8Ring-contraction of 529 with loss of ethylene gives yellow needles of the benzo-l,2-dithiete 526.'Oo9 Benzodithiete (stable to 180°K) has been obtained by thermolysis of 529a-c998b or photolysis of 529a.948The benzodithiete structure proposed for the product of the is incorrect; the material is a oxidation of o-benzenedithiol by iodine"" 3,4-Di-t-butyl-l,2-dithiete is obtained by spontaneous cyclization of the dithione valence tautomer.lO"b

527 S , , HCON(CH,), reflux

x = s, 77% x = so,, 5 1 %

*

1,2-Dithietanes and 1,2-Dithietes

621

529

529a

\ 2 690°C

/

529b

i 720°C

529c

3,4-Dicyano-l,2-dithiete is an intermediate in the oxidation of the dianion of cis-

2,3-dicyano-2,3-dirnercaptoethylene 530 and related ~ o r n p o u n d s .1,2~ ~ ~ ~ ~ ~ ~

Dithietes are believed to be in equilibrium with 1,2-dithiocarbonyl compounds,"8, 1004,1013-1015 as exemplified by 531 .lol3 Several of these unstable 1,2dithietes are observed by their electronic spectra at 77"K.lW Theoretical considerations indicate that the photochemical conversion of an a-dithione into a 1,2dithiete is allowed; the thermal process is forbidden."16

WCN

CN

.

s-s

5 30

.

Four-Membered Sulfur Heterocycles

628

Ar hv

)+O Ar

50%

*

s/ I sII

Arc-CAr

s-s

531

Ar = P ~ C H ~ ) ~ N C ~ H ~

The mass spectra of several unsaturated sulfur heterocycles show the presence of 1,2-dithiete cation r a d i ~ a l s . ' ~ ' ~1~,2-Dithiete '~'~ cation radicals also are obtained by treatment of a-hydroxyketones or a-diketones with sodium sulfide, sodium thiosulfate or sodium dithionite, and sulfuric Bis(trifluoromethy1)-1,2-dithiete yields a cation radical directly when dissolved in sulfuric acid."" The electron-spin resonance spectrum of the benzo-l,2-dithiete cation radical (formed in chlorinations with sulfur-containing reagents) has been Thermolysis of a 1,4dithiin may go via a 1,2-dithiete.'0'9c C.

Reactions

1,2-Dithietes may be in equilibrium with 1,2-dithiones as noted in Section Thus, 1,2-dithietes react with a l k e n e ~ and~ acetylenes94s,1004-'006,1020 to give Diels-Alder adducts, for example, 532'Oo5 and 533,"" derived from the dithiocarbonyl intermediate. The adducts may not be thermally stable. Reaction also occurs with trivalent phosphorus derivatives'02'-'026 to give ring-opened products exemplified by 534.'OZ5 ~.948,1004,1013-1015

s-s 532

521

CH,O2CC=CCO1CH,

527

CH,OH, reflux

*

5 34

~

~

1,3-Dithietanes

629

Ring-opening of 1,2-thietes also occurs on treatment with various metal derivatives (e.g,, V,1027,1028 102&,1029 Mo,1018,1027-1032 W , 1 0 ~ 8 , 1 0 2 9 , 1 0 M ~ 1028b Cr > n, ~ ~ , l O 1 8 , 1 0 2 7 , 1 0 2 81033-1042 b,

~ ilOO4,1018,1028a, , 1032,1WZ,lO43

~ ~ , 1 0 3 6co,1028a, 1028b, 1039,1042,1043

m,l028b

1~,1028b

Pd,lW3 Pt ,Iw2 Au,lW3 In,'W4 UlM51.

( n = 4)

(n = 6 )

Occasionally, more complex structures for the products have been pro; some products are salts resulting from secondary reaction^.'^^^"^ posed'03331038a Among miscellaneous reactions of 1,2-dithietes are the dimerization of 527,'005,'006 the formation of 1,4-dithiins~99a"0M31012 and t h i ~ p h e n e s . ~ ~ ~ ~

1,3-DITHIETANES

XXXVI.

1.

Uses

(E)-2-(2-methyl-2-octen-6-ynyl)-l,3-dithietane appears in a patent involving the preparation of A-norsteroid derivatives.lMa Cepharnycin or cephalosporin derivatives that incorporate a 1,3-dithietane ring are highly bactericidal and inhibit hydrolysis by the cephalosporinases of various bacteria.'046b-'046y 1,3-Dithietane2,2,4,4-tetracarbonyl chloride is a monomer in the preparation of polyester coatings.lw6' Its corresponding ester and amide derivatives are useful as plasticizers for poly(viny1 chloride). Polyfluorinated 1,3-dithietane 1,l-dioxides are said to be nonflammable and are useful as fire-retardants and plasticizers for highly halogenated polymers.'046bb 2.

Properties

An x-ray analysis of 2,2,4,4-tetrachloro-1,3-dithietane indicates a planar ring with an unusually short S-S transannular distance S - - 4 , 2.683 A; C-S, 1.804 A; (SCS, 96.1'; CSC, 83.9°).'047a3bBond distances (C-S, about 1.82 and bond angles have been determined for the 1,3-dithietane obtained by dimerization of anhydride

a)

Four-Membered Sulfur Heterocycles

630

of dithioacetic acid.'047c Electron-diffraction studies on 2,2,4,4-tetrafluoro-1,3dithietane also indicate a planar structure (Dzh ~ y m m e t r y ) . ' Th ~ ~e 'two ~ ~groups ~ of investigators report somewhat different data about the size of the molecule; the data of Smith and Seip'04x may be preferred.'050 IR and Raman studies (18°K) on 1,3-dithietane suggest that the ring is puckered (C, symmetry), but is planar in an annealed crystal, the planarity being induced by crystal packing.'051 I ,3-dithietane was predicted theoretically to be planar.'052 A complete geometric optimization by the ab initio SCF method has been described.23b A semiempirical study of the potential surface of 2,4-dithiabicyclobutane indicates the 1,3-dithietane diradical IR and would be planar if d orbitals were significantly involved; bent, if and the tetrachloro Raman spectra of tetrafluoro-1,3-dithietane3xa~10s4i1055a~'055b d e r i v a t i ~ e ' ~have ~ ~ " been ~ ~ ~ recorded ~ and assignments made. Dzh symmetry is reported, but there may be some ring-puckering vibration^.^^^^'^^^^ 'H and 13C nmr spectra have been reported for 1,3-dithietane and its sulfoxide and sulfone derivatives.55b' I9F nmr spectra have been reported for tetrafluoro-1,3-dithietanein solution with nematic liquid crystals; Dzh symmetry is imputed.105x31059a Theoretical calculations of the transition energies and intensities of three different tetraalkyl-l,3dithietanes indicate a need for the inclusion of d orbital^.^' Theoretical calculations The U V spectrum of 2,2,4,4also have been made on a dimer of 1,3-dithieta11e.'~~~ tetrachloro-l,3-dithietanehas been interpreted with the aid of molecular orbital calculations, interaction between the two sulfur atoms is suggested.'059b The photoand 1,3electron spectra of tetrafluoro1060 and tetrachlor0-1,3-dithietane'~~~ dithietane itself have been reported. The negative-ion mass spectrum of tetrafluoro-1,3-dithietane has a base peak corresponding to fluoride ion; the base peak of tetra(trifluoromethyl)-l,3-dithietane corresponds to the anion of hexafluorothioacetone.1062 The oxidation potential of 1,3-dithietane does not show any unusual transannular interactions in the cation radical.'057b 3.

A.

Synthesis (Table 20)

Dimerization of Thiocarbonyl Compounds

Dimerization of thiocarbonyl compounds to 1,3-dithietanes occurs 1079-1093 in the presence of a thermally,1m7C, 1063-1078i photochemically,210~227~z29i714~ trace of a base 1075~10853 1094-1098 in the presence of methane sulfonic or in the presence of a complex of Mn(0).1099b The photochemical dimerization A d'ithietane structure was proposed as one proceeds via an n + n* triplet.227~229~1079 ~ ~ " ~thioketones ~ are resistant possibility in the reaction of t e t r a z o l t h i o n e ~ . ~Diary1 to dimerization and steric factors may inhibit dimerization of other thiocarbonyl compounds. Reactions leading to 1,3-dithietanes that may involve thiocarbonyl compounds as intermediates are: (a) reaction of elemental s ~ l f u r , ' and ~ ~ ~ ~ fluoroalkenes (this is not a general S4(SbZF11)2''04 or sodium h y d r o ~ u l f i d e " with

~

~

~

1.3-Dithietanes

631

reaction with sulfur because 1,3-dithiolenes often are produced)"03d; (b) reaction of carbon suboxide with sulfur dichloride;'046c,'lo6 (c) reaction of carbon disulfide with t h i o ~ r e a s ; " ~(d) ~ reaction of mercury(I1) sulfide with iodoperfluoroalkane^;"^^"^^^ (e) reaction of triphenylphosphine with di(perfluoroisopropy1) disulfide'06s or with a-chlorosulfenyl chlorides;"" (f) reaction of sulfur dichloride with derivatives of methyl acetoacetate;'"' (8) reaction of di- or trichlorothioacetic acid with aluminum chloride;H6b (h) reaction of dithioisobutyric acid with t-butyl isocyanide or the decomposition of bis(dithioisobutyry1) sulfide;'"2 (i) treatment of tetrafluorothiirane or thiotrifluoroacetyl fluoride with aluminum ~ h l o r i d e . ~ ~

B.

Miscellaneous Methods

1,3-Dithietane, itself, (mp 105-106°C) is obtained by reduction of 1,3dithietane-1-oxide by borane.10s7b31113aIJ-Dithietane tetracarboxylic esters are obtained by treatment of the a-chlorosulfenyl chloride of diethyl malonate with sodium dimethyl or diethylmalonate followed by treatment with potassium t-butoxide at - 78°C.1113bA 2-chlorocarbonyldisulfonyl derivative of the enolate of ethyl acetoacetate decomposes to give a low yield of 2,4-diacetyl-2,4-diethoxycarbonyl-l,3-dithietane.1''3c These latter two methods may involve thiocarbonyl intermediates. Treatment of FezSz(C0)6 with diazomethane gives an iron(0) complex of 1,3-dithietane along with other product^."'^^ 2-Dialkylamino-l,3-dithietane cations, for example, 535, are obtained by treatment of benzylidenebis(N,Ndialkyldithiocarbamates) with 70% perchloric acid, concentrated sulfuric acid, or dimethyl sulfate."'3e 2-Alkylthio-l,3-dithietane cations are obtained by alkylation of the thiocarbonyl group of the cyclic trithi~carbonate."'~Electrochemical reduction of these latter salts are said to yield dimers that were not ~haracterized."'~A l-methyl-l,3-dithietane cation was suggested as an intermediate in the thermolysis of the thiolacetate of l-thi~methylethanethiol,~~~ and the intermediate 536 was proposed to explain the exchange of fragments of sulfur-containing zwitterions.""

535

632

Four-Membered Sulfur Heterocycles

Several 1,3-dithietane structures reported to be obtained by treatment of chloroacetone ,111 6 , '11 benzoin,960'l 1 laa and acetophenone l 118b with hydrogen sulfide or by treatment of 1,3,5-trithianes with sulfur di~hloride"'~ are questionable; alternative structures have been proposed.9613 1120a,1120b Thiofluorenone dimer 1071,iimc-1120e apparently is not a 1,3-dithietane.w4e'1120f 4.

A.

Reactions

Ring-Opening

1,3-Dithietanes decompose to thiocarbonyl compounds thermally1057b~ 1065, or photochemically ;lo7031078e, 1090~1091~1093~1122

1078e-1078h,1087,1088,1094,1096,1121a-1121d

and fluoroalkyl-l,3-dithietanes decompose in the presence of nucleophiles or b a ~ e ~ . ~ 1078h:1123-1130 ~ ~ , ~ The ~ , thiocarbonyl ~ ~ ~ , compounds ~ ~ ~ ~ can , be trapped by ~ >sernicarbazide ,112331125 various nucleophiles ( a m i n e ~ , "112591127 ~ ~ ~ h y d r a z i n e ~ , " ~'lZ5 a~co~o~s,~075~l124,1126~1128 carbanions,l128~l129)~ienes,2~~ 1126 and alkenes,243,244,712, as exemplified by the reaction of 537,244 or they may dimerize with loss of sulfur to alkenes.1102bPolymerization also is observed.'057b Oxidation of 537 in DMF by potassium iodate or nitrogen dioxide in the presence of potassium fluoride gives hexafluoroacetone in good yield; oxidation with lead dioxide under the same conditions gives trifluoroacetyl fluoride.1078h Diphenyldiazomethane traps monothiobenzil formed in the thermolysis of its dimer.1078e A dihydrothiophene reportedly is formed in one case when heat is applied to a 1,3-dithieta11e."~~Reac1126,1130

1,3-Dithietanes

633

tion of oxygen atoms in their ground electronic state with 2,2,4,4-tetrafluoro-1,3dithietane results in ring-cleavage with formation of sulfur monoxide and thiophosgene.1131a Treatment of fluoroalkyl-l,3-dithietanes with mercury I1 sulfide is said to give p ~ l y s u l f i d e s Treatment . ~ ~ ~ ~ of 537 with sodium methoxide is reported Triphenylphosphine reacts t o give dimethyl 2-methoxy-2-methylthiomalonate.'07s with 537 to give the phosphonium ylide 537a, which can be trapped by aldehydes.l 1 31h

K 1' DMF'

537

+ Ph3P

Et >o

--780

anthracene

[(CF,),C=SI

* Ph3k(CF3),

ArCHO

ArCH=C(CF,),

537a

B.

Reactions at Sulfur

Oxidation of the sulfur atoms in 1,3-dithietanes gives sulfoxides and sulThe oxidation of fluorinated derivatives, which requires chromium trioxide and hot, fuming nitric acid, usually stops at the monois converted sulfone stage,'"6hhy lo9' although 2,2,4,4-tetrafluoro-1,3-dithietane directly to the disulfone by treatment with chromium trioxide and boiling, fuming nitric acid.1132 The conversion of 2,2,4,4-tetrachloro- or 2,2,4,4-tetrabromodithietane to the disulfone may be effected by oxidation to the monosulfone with potassium permanganate followed by treatment which chromium trioxide- nitric acid.1132Potassium permanganate oxidizes the dimer of thiocyclohexanone to the disulfone in 78% yield.'063 2,2,4,4-Tetrachloro-1,3-dithietane forms a bis adduct with mercury (I) nitrate,"33 whose structure was investigated by IR and Raman spectra. A cyclopentadienyl manganese(0) dicarbonyl complex of the dimer of 2,3-diphenylcyclo. propenethione has been reported.'099b Raney nickel desulfurizes the tetraester 5381106 and the desulfurization of the questionable dithietanes obtained by dimerization of thiofluorenone and thiobenzophenone give, respectively, bisfluorenylidene and tetraphenylethylene.'071 The electrochemical oxidation of 1,3dithietane has been investigated.'lm 2,2'-[Oxybis(methylene)]bis-l,3-dithietaneis inert to boron trifluoride etherate after 30 days at room temperature.'lMb

fOneS.40za, 1046e, 1057h, io95,1113a, 1132

Four-Membered Sulfur Heterocycles

634

s-tco /J-s

2c2H5,

(C2H,02C)2

KaNi C,H,OH

CH,(C02C2H,),

538

Hyper-4-valent and hyper-6-valent sulfur compounds are obtained by treating

2,2,4,4-tetrafluoro-1,3-dithietane 539 with electrophilic reagents, trifluoromethyl

~ ~ ~ ~and hypochlorite , l 135-1139 tris(trifluoromethyl)methyl h y p ~ c h l o r i t e , "1139h chlorine m o n o f l ~ o r i d e . " ~These ~ ~ ' ~ reactions ~~ have been reviewed.1136The ring of 2,2,4,4-tetrafluoro-l,1-(1,I -bis-trifluoromethyl-2,2,2-trifluoroethoxy)-1,3-dithietane is planar and e q ~ a t o r i a 1 . l ' The ~ ~ ~ring bond< to the 4-valent sulfur atom are long, 1.932 and 1.8878, compared with the lengths of the two other S-C bonds, 1.752 and 1.736 8.Bond angles are are follows: C-S(OR),-C, 77.4", which is especially small, C-S-C, 86.5"; S(OR),-C-S, 99.2 and 96.9".1'39b Chlorine was reported not 1,3-dithietane,l lo8 and the to react with 2,4-perfluoro-n-butyl-2,4-trifluorometh~lelectrochemical fluorination of 2,2,4,4-tetrachloro- and 2,2,4,4-tetrafluoro-1,3dithietane resulted in fragmentation of the ring.1142The hypervalent compound 540 derived from trifluoromethyl hypochlorite is thermally ~ n s t a b l e . ~ ' ~ ~However, '"~' 1,1,2,2,3,3,4,4-octafluoro-1,3-dithietane is stable at 300" and is stable to photolysis and 10% aqueous sodium hydroxide.1140 It is converted to the disulfoxide by silicon dioxide.1139h Treatment of hyper-6-valent compounds, (542) or 1,1,3,3-tetrachloro1,1,1, I ,2,2,3,3,3,3,4,4-dodecafluoro-l,3-dithietane 1, I ,2,2,3,3,4,4-octafluoro-1,3-dithietane (541), with the lithium salt of hexafluoroacetone imine1136,1141,1143 or methyl-bis(trimethylsily1) yields S-imino derivatives, for example, 543. The compounds are characterized by 19F nmr.

F2p'\(0CF3)2

1OOO

F25 39

540

539 \

F4

54 1

54 1

542

1,3-Dithietanes C.

635

Miscellaneous Reactions

Halogen exchange occurs on treatment of 2,2,4,4-tetrachloro-1,3-dithietane with antimony trifluoride.'046e,1075,1085,1088,1144a, Two or more chlorine atoms can be replaced by fluorine atoms. Hydrolysis of the gem-dihalo group in perchloro-l,3and tetrachloro-1,3dithietanes gives 1,3-dithietane-2-ones,"'06'~108'~1'45" dithietane gives a 2-imine on treatment with anilir~e."~' 1,3-Dithietane-2,2,4,4tetracarbonyl chloride reacts with ethanol and diethylamine to give the corresponding ester and amide.1046cA bicyclic 1,3-dithietane is believed to be formed via loss ,3-dithietane.lN7' of hydrogen sulfide from 2,4-dimethy1-2,4-bis(thioacetylthio)-l Treatment of 2,2,4,4-tetra(trifluoromethyl)-1,3-dithietanewith 2,3-diphenylpyrrole and triphenylphosphine gives a 14% yield of 2,3-diphenyl-4-(2,2,2trifluoro-1-trifluoromethyl) pyrr01e."~'~

5.

Sulfoxides and Sulfones (Table 21)

Molecular orbital calculations have been done on the dimerization of sulfine to

1,3-dithietane-1,3-dioxideand on the dimerization of sulfene to 1,3-dithietane-

1 , 1 , 3 , 3 - t e t r o ~ i d e . "Sulfenes ~~ were predicted to dimerize to disulfone more readily than sulfines to the disulfoxide. The dimerization of ethyl sulfine (propanethial S-oxide), previously reported to yield 2,4-diethyl-1,3-dithietane 1 , 3 - d i o ~ i d e , " ~ ~ , " ~ ~ the lachrymatory factor of the onion, has been shown to give 3,4-diethyl-1,2dithietane-l,1 dioxide.'" 1,3-Dithietane-l-oxide 544 is prepared by treatment of bis(chloromethy1) sulfoxide with sodium sulfide."'& The monosulfoxide is reduced by diborane to 1,3-dithietane which is reconverted to the sulfoxide by oxidation with iodobenzene dichloride. More extensive oxidation of 544 with iodobenzene dichloride or rn-chloroperbenzoic acid gives a mixture of isomeric 1,3-dithietane1,3-dioxides. The monosulfone 545 is obtained by oxidation of the monosulfoxide 544 with potassium permanganate; the sulfoxide-sulfone 545b is obtained by oxidation of 545 with peracetic acid at 0". The disulfone 546 is prepared by oxidation of the disulfoxide (545a), the monosulfone 545, or the sulfoxide-sulfone (545b) with peracetic acid at 100". An x-ray structure analysis of the disulfone 546 indicates a planar ring, nearly quar re.'^^^^,'"^ A short, nonbonded S-S distance of 2 . 5 9 0 8 was observed. A puckered structure of the monosulfoxide 544 was determined from the microwave spectrum of various isotopically substituted derivatives (dihedral angle = 140.8")'0s7b~"'~;the oxygen atom is equatorial. The S-S bond distance in 544 is also short, 2.600 8.2,2,4,4-tetrafluoro-1,3-dithietane-l,3-dioxide is planar with pyramidal sulfur atoms and a trans arrangement of the oxygen The S-0 bonds are shorter than those in dimethyl sulfoxide (1.481 vs 1.521 8).Ring-bond distances are 1.890 and 1 . 8 8 0 8 and bond angles are 79.4" (CSC) and 100.6" (SCS). The 13C nmr spectra of 1,3-dithietane (6 18.6), 544 (6 53.1), 545 (6 68.4) 545a (6 69.1, cis; 6 69.0, trans), 545b (6 87.4), and 546 (6 92.1) and the 1 7 0 nmr spectrum of 545 have been

Four-Membered Sulfur Heterocycles

636

ON

(ClCH,),S=O?

Na2S.9H,0 K,NHCI-

' 7 L,'j -1

0

36%

KMnO, (CH,),CO, MgSO,) --20°

544

545

545b

Therrnolysis of 1,3-dithietane-l-oxide544402a~'057b~'12'c~1149~1151 or 2,2,4,4-tetrarnethyl-1,3dithietane-l-o~ide~~~ gives the sulfines (thioformaldehyde S-oxide and thioacetone S-oxide, respectively) and thioformaldehyde or thioacetone. Thermolysis of 545a also yields sulfine but that of 545 results in extrusion of sulfur dioxide to give thiirane.'057b Ethylene and formaldehyde, but not sulfene, are observed in the thermolysis of 546.'057bThe thermolysis was followed by microwave spectroscopyma or photoelectron spectroscopy.'057b The photoelectron The p K , values in dimethylsulfspectra of 544-546 have been oxide of 545 (20.7), 545b (13.8), and 546 (12.5) have been determined.'057b

heat

\\

0

CH,=S=O

+ CHz=S

544

The disulfone 546, 1,3-dithietane-l,1,3,3-tetroxide, was believed to be nonplanar according to its dipole moment"52 but the x-ray analysis indicates a planar ~ t r ~ ~ tIts IR ~ spectrum r e . has~ been ~ ~ ~ ~ ~ and ~ a~phase ~ transition ~ ~ has been detected."54 X-ray analyses of 1,3-dithietane-2,2,4,4-tetrahalo(F, C1, Br)1,1,3,3-tetroxides and 1,3-dithietane-2,2,4,4-tetrachloro-l,l-dioxide indicate planar and nearly square s t r u ~ t u r e s . " ~ ~Th ~ "e ~planar ~ structure of the latter rnonosulfone contrasts with the puckered structure of the monosulfoxide 544. Dimerization of sulfene yields disulfone 546, whose protons are readily replaced Sulfone 546 reacts with by deuterium, bromine,"57a or trimethylsilyl 2,6-dimethyl-4-pyrone to give an exo-rnethylene and it may be tetramethylated.1057bOther disulfones are obtained by oxidation of 1,3-dithetancs with potassium ~ e r m a n g a n a t e " ~or~ chromium trioxide-fuming nitric acid for resistant d i t h i e t a n e ~ . " ~As~ mentioned above, peracetic acid oxidizes a disulfoxide, mono2,2,4,4sulfone, or a monosulfone-monosulfoxide to the disulfone 546.1057b>"13a Tetra(trifluoromethyl)-1,3-dithietane 537 is oxidized only to the monosulfone 547, the disulfone is only even with chromium trioxide-hot, fuming nitric

1,3-Dithietanes

631

a suggested intermediate in reactions of the ~ u l f e n e . " Oxidation ~~~ of 2,2,4,4tetrafluoro-l,3-dithietanewith the chromium trioxide-nitric acid reagent gives a 15% yield of the disulfone plus some m ~ n o s u l f o n e . " Reactions ~~ of this reagent with the tetrachloro and tetrabromo compounds were not successful, but tetrasulfones of these compounds could be obtained by a preliminary oxidation to the monosulfone with potassium permanganate followed by treatment with the chromium trioxide-nitric acid reagent Thermolysis of 547 yields an epis ~ l f i d e ' ~ ~ ~ and ~ ' 2,2,4,4-tetrachloro-1,3-dithietane 1,I -dioxide, tetrachloroare replaced ethylene."32 The chlorine atoms of 2,2,4,4-tetrachloro-1,3-dithietane by fluorine atoms on treatment with antimony trifluoride.'w6e Cyclic voltammetry suggests the of 2,2,4,4-tetrachloro- or tetrabromo-l,3-dithietane-l,1,3,3-tetraoxide loss of two halogen atoms with the possible formation of 1,3-dihalo-2,4-dithiabicyclo[ 1.1.O]butane-2,2,4,4-tetro~ide."~~ 2,4-Diaryl-2,4-dicyano-l,3-dithietane 1,1,3,3-tetroxide is suggested as an intermediate in the reaction of 2J-dibromo3,6-diaryl-1,4-dithiin 1,1,4,4-tetroxide with azide ion."s9 It is said t o decompose to a thiirane 1,l-dioxide that loses sulfur dioxide to give the alkene.

546

537

547

The first so-called ''en01 ether" (549) of any sulfone was obtained by treatment of a trimethylsilyl derivative 548 of disulfone 546 with trimethylsilyl perfluoro-nbutyl either and n - b ~ t y l l i t h i u m . " Addition ~~ of DzO t o 549 gives a quantitative yield of tetradeuterated 546. The trimethylsilyl derivative 548 is obtained as the trans isomer, which can be isomerized to a mixture of cis and trans isomers by treatment with triethylamine in petroleum ether.

Four-Membered Sulfur Heterocycles

638

XXXVII.

1,3 DITHIETANE-2-ONES AND 2-THIONES 1.

Uses

4-Phenyl-l,3-dithietane-2-thione is a component of a mixture said to confer scorch resistance in the vulcanization of rubber.1160 2.

Structure

A preliminary x-ray analysis of 4,4-dichloro-l,3-dithia-2-cyclobutanone revealed similarities with 2,2,4,4-tetrachlor0-2,3-dithietane.~~~~~~ 3.

Synthesis

Hydrolysis of 2,2-dichloro-(or 2,2-bis-trifluormethyIthio)-l,3-dithietanes yields the corresponding carbonyl derivative (Section XXXVI.4.C.)1w7a~b~1068ai1069~1 1145a Oxidation of 1,3-dithietane-2-thionewith nitric acid gives 1,3-dithietane-2-one (45%).1161 The reaction of phosgene with salts of 1,l -dimercaptoethylene derivatives, for example, 550,'162also yields 1,3-dithietane-2-0nes along with 2,4methylene-I,3-dithietane~."~~'~~~~ 1,3-Dithietane-2-thione is obtained in 30% yield by treating diiodomethane with KzCS3.1161

550

4.

Reactions

The 4-methylene-1,3-dithietane-2-ones lose carbon oxysulfide to give thioas exemplified by ketenes that dimerize to 2,4-dimethylene-l,3-dithietanes,1162-1'6s Reaction of several methylene 1,3the flash-vacuum thermolysis of 5 5 1 .ll@' dithietane-2-ones with secondary amines also appears to proceed via loss of carbon oxysulfide followed by addition of the amine to the thioketene.1162 An exception to the loss of carbon oxysulfide is the reaction of a guanidine derivative with 551 to give the ring-opened product 552.1166 Thermolysis of 1,3-dithietane-2-thione gives carbon disulfide and, presumably, thioformaldehyde."61 Treatment of the 2-thione with methyl fluorosulfonate gives The an oily fluorosulfonate salt of the S-alkylated thiocarbonyl electrochemistry of the 2-thione has been i n ~ e s t i g a t e d . " ~ ~

Imino-l,3-Dithietanes

63 9

- XHCN CN

cos

[(NC),C=C=S]

-I Ncx+

CN

CN

NC

551

hN 552

XXXVIII.

IMINO-1,3-DITHIETANES 1.

Uses

2-(Diethoxyphosphinylimino)-l,3-dithietane 553 (trade designations AC 64475, Nematak, Fosthietane) is a broad spectrum contact and systematic pesticide especially useful as a r ~ e m a t o c i d e " ~ ~and - ' ~ ~against ~ insects1172,1 1 8 5 , 1 1 ~1192-1198 , such as planthoppers. It is not toxic to earthworms,"86 but is said to be toxic to plants.1174The mutagenicity of the pesticide has been t e ~ t e d , " ~and ~ its ~ ' dermal ~~ toxicity to rabbits has been found to be less in poly(ethy1ene glycol).12o' The permissable residue in crops has been addressed"" and comparable toxicities in soil applications have been determined.lZo3Application of the pesticide has been related to an increase of downy mildew on soybeans.1204Other N-substituted imino-l,3dithietanes are herbicide^,'^^^-'^^^ b acte[icide s, 1205,1207,1208 insecticides,1209- 1215 tickicides1210,1211,1215,1223 (e.g., Nimidane, 554), fungicide^,'^^^,'^^^^ lZz4 a nematocide,lZo5a r n u l l u s c i ~ i d e , 'and ~ ~ ~a growth-promoter in animals.1225'

553

554

2.

Structure

Bicyclic imino 1,3-dithietane structures reported in the older literatureEmbare incorrect on the basis of large dipole moments.E44aThe earlier compounds are probably 1,3,4-thiadiazole derivatives.E44d

640

Four-Membered Sulfur Heterocycles

3.

Synthesis

The general synthesis of imino-l,3-dithietanes involves the reaction of a bis salt of a 1,l-dimercapto imine with a 1,l-dihalide or its equivalent.1168~11R-'178~1181y1183~ 1189,1204,1208,121 1,1213-1215,1223,1227-1231 A variation is the reaction of a 1,l-dichloroimine with a bis salt of a 1,l-dimercaptoethylene derivative.'20791232

H s

R_ii-CS-

-

7

-H+

RN=C

/'-

RN<S'CHz S'

CH,XY

'S-

?

R = (R'0)2P-, (R'O)*P-, aryl, heteroaryl, alkyl, R 2 S 0 2 X = Y = I, Br; X

= C1,

Y = SCN

Treatment of 2,2,4,4-tetrachloro-1,3-dithietane with aniline is said to give 2-(Nphenylimino)-4,4-dichloro-l ,3-dithietane.lo6' An N-methylimino-1,3-dithietane was suggested as an intermediate in the reaction of bis-trifluoromethylthioketene with methyl i s ~ t h i o c y a n a t e . ~2-N,N-Dialkylamino-l,3-dithietan-2-ylium ~~ salts are obtained by treatment of N,N-dialkyldithiocarbamateswith protons or dimethyl sulfate as exemplified by the synthesis of 555 and 556,respectively.830bi1113c

65%

555

88%

556

4.

Reactions

Thermal cleavage of 2,4-methanesulfonylimino-l,3-dithietane to methanesulfonylisothiocyanate has been reported.1232Reactions of the imino nitrogen atom of 557 have been observed with dimethyldithiophosphoryl chloride, methyl isocyanate, and acetic anhydride.1227The reactive methylene group of 558 reacts with N-phenyldiphenylimine to give an a ~ e t i d i n o n e . " ~The ~ iminodithietanyl group is not affected by alkylation reactions or epoxidations carried out on substituent groups.1212

Methylene-1,3-Dithietanes

s

+ (Me0)2Ps SC1

64 1

L S

557

Ph,C=NPh

P

26%

558

XXXIX.

METHY LENE-l,3-DITHIETANES 1.

Uses

Methylene 1,3-dithietanes such as 559 are antibiotics that are active against gram negative b a ~ t e r i a . ' ~ ~ ~ -Derivatives ''~' such as 560 are said to be ar~tibacterial,'~~' insecticide^,'^^^ and drugs that decrease blood plant v i r i ~ i d e s , ' ' fungicides,'240-'244 ~~ alcohol concentration, hyperglycemia, and are said to be useful in the prevention and treatment of liver disease.'246 A bis-methylene 1,3-dithietane derivative of a pyridopyrimidine was prepared as an intermediate in the synthesis of antiallergic compounds and prostaglandin antagonists,'247 and other his-methylene derivatives of cyanoacetic ester were claimed to be bactericides and f ~ n g i c i d e s . ' ~ ~ '

COOH

559

2.

I

Me

560

Properties

X-ray analyses of 561 1249,1250 and 56212" show short intramolecular distances S---0, 2.648; S---S, 2.71 and 2.67A. Extended Hiickel molecular orbital calculations indicate that any covalent bonding between the sulfur and oxygen atoms is either very weak or nonexistent.'252 The bond distances (a)and bond angles in the four-membered rings are as follows: 561, Sl-C2,1.718; S3-C2, 1.786;S1-C4,1.911, S3-C4, 1.8498;(C2-S1-C4,83.4'; (Cz-S3-C4,83.4";(S1-C2-S3,101.2';(S1-C4-S:, 92.1";562, SI-CZ, 1.766;S3-C2, 1.7648;(C2-SI-C4, 98.1";(C2-SI-C4, 82.0 . Charge densities and overlap populations for analogs of 561 have been calculated, both with and without incorporating d - o r b i t a l ~ . "Ab ~ ~ initio molecular orbital cal-

Four-Membered Sulfur Heterocycles

642

culations on 563 and cyano- and fluoro-substituted derivatives give energies relative to 1,2-dithietes and acyclic analogs.999bThe inclusion of d-orbitals is mandatory in energy comparisons between valent and hypervalent sulfur compounds; d-orbitals do not contribute as much to S-C bonds as to S-N bonds. Electron-attracting groups are said not to facilitate the participation of d-orbitals.

562

561

563

No correlation exists between the oxidation potentials and the energies of the lowest unoccupied orbitals of bis-(dicyanomethylene-1,3-dithietane).lZs3The 13C nmr spectrum of a bis-(dimethylene)-l,3-dithietaneshows, as expected, the ring carbons at lower field (136 ppm) than the other alkene carbons (1 13.5 ppm).811aThe photoelectron spectrum of dicyanomethylene-1,3-dithietanehas a first (lowest energy) band at 9.08eV that is associated with a transition from an orbital with considerable C-C double bond character.lZ5& The next band at 10.50 eVis higher in energy by 0.5-0.6eV than that for dicyanomethylene derivatives of five- and sixmembered cyclic analogs. The UV and IR spectra of bis(acylmethy1ene)-1,3dithietanes (called desaurins because of their derivation from desoxybenzoin and their yellow color, aurum) have been discussed.'254b The mass spectra of several of these desaurins show abundant molecular ions as well as ions originating from the acyl Thioketene ions are less abundant. The dipole moment of 5.84D of a bis(methylene)-l,3dithietane derived from camphor was interpreted to mean that the two carbonyl groups were on the same side of a plane bisecting the two carbon atoms of the four-membered ring.'256

3.

Synthesis

The two most common methods of synthesis of methylene-1,3-dithietanesare the reaction of 1,l-dihalides or their equivalents with salts of 1,I-dimercaptoalkenes,1235,l238,1241,1242,1246,1254b, 1257-1264 and the reactions of thioketenes which formally may undergo cycloadditions to give the desired dithietanes.652a'6583n5a>735b$ 811a,81lb,966b11017,1103a, 1105,1144b,l162-1164,1254b, 1262,1265-1309 Thioketene dimers are discussed in a review on thioketenes.1310 In the reactions of 1,I-dihalides, tin salts of 1,ldimercaptoalkenes give somewhat better yields (only an 18% yield of 564 is obtained with the disodium salt).'257 The reaction of active methylene compounds with carbon disulfide is a common method for obtaining 1,I-dimercaptoalkene derivatives, as exemplified in the synthesis of 565.'258 The reaction of dimercaptoalkene salts with phosgene yields 2-keto-4-rnethylene-l,3-dithietane~."~~~

643

5 64

FN 565

As mentioned above, a wide variety of reactions yielding methylenedithietanes appear t o involve cycloadditions of thioketenes. Caution must be used in assuming a general cycloaddition mechanism, especially under conditions (such as the presence of high concentrations of reactive nucleophilic reagents) that would lead to the destruction of the thioketenes more rapidly than their cyclization. Bis (trifluoromethyl) thioketene undergoes numerous cycloadditions, as exemplified by its reaction with isothiocyanates (e.g., to give 566)652"3735a and a novel "ene" type reaction with methyl-substituted aromatic compounds, such as mesitylene, to give compounds related to 567.735"Addition of thioketenes to other thiocarbonyl compounds give methylenedithietanes, as shown for isopropyl-t-butylthioketene and thiobenzophenone which gives 568.811 Dicyanothioketene produced in the flashvacuum thermolysis of 569 undergoes dimerization to the methylenedithietane 570.1164Analogs of 569 behave similarly.1162Not all thioketenes dimerize readily at the high temperatures used in thermolysis reactions.678bThe reaction of salts of 1,ldimercaptoalkenes with chloroformate esters to give 2,4-methylene-l,3-dithietanes may go via a t h i ~ k e t e n e . ' ~ ~ -Thermolysis '~~' of cy~lobutane-l,2-dithiones,~~~~~~~ 678b

methylene-l,3-thia~etidines,~~~~ 3,6-methylene-I,2,4,5-tetrathiane~~~~~* 1279

1,2,3-thiadia~oles,"~~ monothio- and dithiocarboxylic esters or amides and their enol derivatives966b,I262,1272,1273a, 1273b, 1274,1275,1289,1298,1303-1305 and photolysis of

2-methylene-1 , 3 - d i t h i o l a n e ~1278 ~ ~ ~yields ~ , methylene-1,3-dithietanes, possibly via thioketenes. Treatment of 2-methylene-1,3-dithiolanel,l-dioxides with base gives thioketenes which may d i m e r i ~ e . " ~ ~ ~

CF, 566 (37-79%)

Four-Membered Sulfur Heterocycles

644

CHj

'CH3

567

Bu' Pr 41%

568

~

cos

[(NC>,C=C=SI

CN

569

570

The formation of desaurins from ketones, carbon disulfide, and base1254b,12623 is believed to involve nucleophilic attack on a thioketene by as shown for the synthesis of 572. the dianion of a 1,1-dimercaptoalkene,1281 Related syntheses involve the use of thiophosgene652ai1275~1283~1284~1292~1308c instead ~ *p~h~o' ~ p h o n i u m 'and ~~~ of carbon disulfide and the use of d i a ~ o a l k a n e s % ~or sulfonium y l i d e ~ ' ~ ~ instead ~,'~'~ of a ketone and base. Treatment of perfluoroisobutylene with fluoride ion and elemental sulfur in a dipolar, aprotic 1301 or with sources of anionic sulfur (potassium sulfide,1017 sodium hydrosulfide,"05 potassium t h i ~ c y a n a t e , " ~sodium ~ t h i o ~ u l f a t e , " ~dithiocarbamate ~ salts,'301 dithiophosphate salts"05) give the dimer (573) of bis(trifluoromethy1)thioketene. Similarly, other 2,4-bis(metliylene)-1,4-dithietanesare obtained by treating 2,2-dichlorovinyl ketones57'a'5n'5n~574~575with anionic sulfur reintermediate was deemed possible, but unlikely, in the a g e n t ~ . ' ~ ~A ~ -thioketene '~~' base-catalyzed conversion of 574 to 5751299 Salts of 1,I-dimercaptoalkenes can be dimerized to 2,4-bis(methylene)-1,3dithietanes with the formal loss of hydrogen sulfide by treatment with electrophilic 1275,1281, 1282i1285-1290

645

7

PhCCH ,Ph

571

572

CF, 573

574

575

reagents such as oxalyl phthaloyl chloride,'294 benzoyl chloride,"62 acetyl chloride,'162 f ~ r n i a l d e h y d e , ' ~ ~iodine,"6231294 ' ammonium peroxydi~ulfate,'~"and dicyclohexylcarbodiimide.12gsLead and mercury salts thermally Thioketenes are possible interdecompose t o bi~(methy1ene)dithietanes.~~~~ mediates. Esters of monothio- and dithiomalonic acid apparently are sources of thioketenes that dimerize to the bis-methylenedithietanes.'zg6~'2g7Treatment of S-chloro-4-phenyl-3H-1,2-dithiol-3-ones with Grignard reagents is reported to give bis-methylenedithietane~;'~~~ the reaction of aromatic aldehydes with an a-ketodithiocarboxylic acid gives a monornethylene 1,3-dithietane that is a cyclic dithioacetal of the a 1 d e h ~ d e . lRing-contraction ~~~ of a 3,5-bis(methylene)-l,2,4trithiolane and a 3,6-bis-(methylene)-1,2,4,5-tetrathianeto a 2,4-bis(methylene)1,3-dithietane occurs on treatment with triethyl p h ~ s p h i t e ' ~ " or triphenylphosphine .1292

Four-Membered Sulfur Heterocycles

646

Novel base-catalyzed rearrangements of certain 3-hydroxy-5-alkylthio-1,2thiazoles, for example, 576, to methylene-l,3-dithietaneshave been reported.'2M. 1236,1237 An aldol condensation of 2,6-dimethyl-4-pyrone with 1,3-dithietane 1,1,3,31,1,3,3-tetroxide gives a low (2%) yield of a 2-methylene-1,3-dithietane tetro~ide."~~~

576

4.

A.

Reactions

Thermolysis

CF, I

573

B.

Desulfurization and Reduction

Tri(n-buty1)phosphine desulfurizes 564.1257Raney nickel effects desulfurization of desaurins,'280-'282 as illustrated by the reaction of 572.lz8l Two different pathways can occur depending on the condition of the reagent. Heating 572 with dry zinc dust or hydriodic acid is said to give ~ t i l b e n e , " ~although ~ a different result was reported for another desaurin.'280 Treatment of 572 with zinc and acetic acid gives 1,2-diphenyIpropanone, 1,2-diphenylpropene, and 1,2-diphenylpropyl acetate,1281,1282 A similar result, although without alkene and ester formation, is obtained with desaurin 577 .1312 Zinc and ethanolic sodium hydroxide also degrades desaurins to ketones.'281 A reduction potential of - 0.62 V is obtained for bis(dicyanornethylene)-1,3 dithietane and the anion radical is obtained on treatment with iodide ion in acetonitrile or propylene carbonate.12533

641

Methylene-l,3-Dithietanes

0

0

OAc I

fresh sponge Ni

Ph

35%

572

Ph 577

C.

Oxidation

Treatment of desaurin 572 with a mixture of nitric and sulfuric acids gives m-nitrobenzoic chromic acid in acetic acid yields benzoic acid.1281and potassium permanganate or ozone gives benzil and benzoic acid.'281,'282 A more soluble analog of 572 in which the benzoyl groups are replaced by acetyl groups undergoes oxidation of the latter to carboxyl groups with sodium hypochlorite.'28'

D.

Reactions with Nucleophiles

The most common reaction of 2,4-bis-(methylene)-1,3-dithietaneswith nucleophiles involves an apparent Michael addition to an electron-deficient double bond followed by ring-opening. Further reactions may ensue depending on the functional groups present. The reactions of 578 have been extensively investigated. Reactions have been reported with ethoxide ion'296 and thiolate ions,'316 ammonia and amines1269,1270,1287,1302,1316-1323c (e.g., the formation of 579),1318 hydraz i n e ~ , ' ~ h~ y~d- r' a~z ~i d e ~ ' ~ ~(e.g., ~ - ' ~the ~ formation of 580),'327azide ion133131332 l - ( ~ N - d i e t h y l a m i n ~ ) - p r o p y n e(in ' ~ the ~ ~ formation (e.g., the formation of 581),1331 (to give 583). The Michaelof 582), the anion of 2-cyan0-l-phenylethanone'~~~~~~~ type of addition also may occur with monomethylene-l,3-dithietane~~~~~ but nucleophilic attack on the unsubstituted carbon atom of the four-membered ring 584 has been reported.'2s8 The reaction of the spiro derivative 585 with 1-(4$ diethy1amino)propyne may proceed via a cyclopropenium cation.'2s7 The reactions of several methylene-1,3-dithietane-2-ones with amines"62 may involve a thioketene formed by loss of carbon oxysulfide.

Four-Membered Sulfur Heterocycles

648

Ar I NH EtOH refl.

Et02C

CN

CN CO2Et r :

%$___)

Et02C CN

0 579 (89%)

578 + PhCONHNH2

CHCl, EtOH,

6oo

*

NC

kTIH

Et02C

HN

I

COPh

580 (87%)

581

NHNHCOPh

-

64 9

582

S 578

PhCOCH,CN K,CO, D M F , 20°

EtO2C

CH(CN)COPh

Ph 5 8 3 (47%)

NC

585

E.

Miscellaneous Reactions

Treatment of desaurin 572 with P4S10 leads to extensive rearrangement with incorporation of additional sulfur atoms in the products.'335 The synthesis of the important dimer of bis(trifluoromethy1)thioketene 573 involves treating the tetraDepending on conditions, two, three or ester 586 with HF-SF4.652a,734~1144b~1292 four ethoxycarbonyl groups can be converted to trifluoromethyl The sulfur tetrafluoride must be very pure, otherwise, the preparation fails.652a Acetyl groups in desaurins may be oxidized to carboxylic acid groups by sodium hypochlorite without affecting the basic bis(methy1ene)dithietane structure .1281, 12" Treatment of 575 with bromine in chloroform effects replacement of the two methine hydrogen atoms by bromine atoms.'299 An unusual methylene- 1,3dithietane reacts with bis(trifluoromethy1)thioketene to give a complex structure embodying a new met hylene-l,3-dithie tane and a 2-methylenet hie tane. 735a Bis-

7:: -

650

Four-Membered Sulfur Heterocycles

&

p,s,o

phyli-~i-ph

s-s

ph'k,/&s+

Ph

Ph

Ph

Ph

(23%)

(48-52%)

572

2E ;t:Js

-@

s 4 k F 3

*

HF-SF, Hastelloy C b o m b 150-200° 69-15%

Et02C

C02Et

CF3

4s CF3

586

573

(2,4-dicyanomethylene)-1,3-dithietane570 forms a charge-transfer complex with tetrathiafulvalene (TTF);12@ it is an insulator unlike the complex of tetracyanoquinodimethane (TCNQ) with TTF, which is an electical conductor.

XXXX. FOUR-MEMBERED SULFUR HETEROCYCLES WITH ONE CARBON ATOM 1.

CSNO

The addition of thiobenzophenone to nitrosobenzene to give N-(diphenylmethy1ene)benzenamine is said to go via a cyclic intermediate that loses sulfur monoxide to give the product.994eA similar mechanism is invoked in the reaction of aldehydes with S,S-diphenylsulfilimine to give enamines or nitriles (e.g., Oxa-2,3-thiazete-2-oxides are suggested as intermediates in the dehydration of aryl amides to nitriles by thionyl ch10ride.l~~'The reaction of N-sulfilamines with aldehydes, which previously were suggested to give oxa-2,3-thiazetidine-2-oxides, has been shown to yield acyclic compounds.1338 (CH3)3CCHO

- Ph,SO

+ Ph,S=NH

DMSO

* (CH,),C-CH=NH

I

(cH3)3C7y HN- S- Ph2

Ph ,SO +

(CH3)3CCN 587 (66%)

Four-Membered Sulfur Heterocycles With One Carbon Atom

2.

65 1

CSNP

The first reported 1,3,2h5-thiazaphosphetidine ring system 588 was obtained by cycloaddition of isocyanates to 1 ,2h5-azaphospholes.'339 They are in equilibrium Two other 1,3,2-thiazaphosphetidines with 2,4,1Xs-diazaphosphetidine-3-thiones. (e.g., 589) have been obtained by treatment of N-nitrosoamines with 2,4-bis(pmetho~yphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide.~~~~~~~ The addition of carbon disulfide t o phosphinimes to give a phosphine sulfide and an isocyanate may involve a cyclic intermediate.'%lc

R'NCS

+

R2 I R2-P=N

CHCl,

C02Me

s

I1

C02Me 588

s

I1

K' = M e , I'h; R2 = Ph, Me#-, Ph+,

PhCO

589 (44%)

3.

A.

CSNz

Synthesis and Properties

1,6,2,4-Thiadiazetidin-3-ones are obtained by the reaction of isocyanates with tris(imid0)sulfur (VI) derivatives (e.g., 590).'342-1344 A n x-ray analysis of 591

indicated a nearly planar ring and the following bond distances and angles for the ring: SN, 1 . 6 5 0 8 ; NC, 1 . 4 1 5 8 ; N-S-N, 79.5'; S-N-C, 92.0'; N-C-N, 96.5'.lM2 ~~ The IR stretching frequency for the carbonyl group is high, 1 8 4 0 ~ m - ' . '3-Imino-

Four-Membered Sulfur Heterocycles

652

1,2,4-thiadiazetidin-I-oxidesare said to be formed in the cycloaddition of N-sulfinylsulfonamides with k e t i m i n e ~ 'or ~ ~carbodiirnide~;'~~' ~ but recent has disproved the structure proposed for the product of the reaction of N-sulfinylp-toluenesulfonamide with N-phenyldimethyl ketimine. 1,2,4-Thiadiazetidine intermediates have been suggested in cycloaddition reactions of i ~ o c y a n a t e s ' ~ and ~~~-'~~~~ i s o t h i o ~ y a n a t e s 'with ~ ~ N-sulfinylamines and sulfur imides. Prior to the formation was suggested as an of stable derivatives, a 3-imino-l,2,4-thiadiazetidin-l-oxide intermediate in the reaction of a carbodiimide and N-sulfinyl-p-toluenesulfonamide.835a l-Alkyl-1,2,4-thiadiazetidinezwitterions have been proposed in the rearrangement of N-sulfenylamidines.'348 A stable 1,2,4-thiazetidine-l,I-dioxide is proposed as the product of the reaction of sulfuric acid with 1,3,4,6-tetraphenyl2,5,7-triazabicycl0[2.2.1]hept-2-ene.'~~ A 1,2,4-thiadiazete was suggested as an intermediate in the reaction of thiocyanate ion with N-(N-chlorobenzimidoy1)S,S-dimethyl~ulfilimine.'~~~

+

BufN=Sl ,NBu' "But

FS02NC0

pentane

* But/

590

N-S"'

"NS02F

591

B.

Reactions

The 3-imino-3-methylene-or 3-keto-I,2,4-thiadiazetidin-l -oxides may thermally cleave, as is shown for 592,'345with an alternative mode of decomposition, as is illustrated for 593.752cThe mode exemplified by 592 is followed by many of the unstable thiadiazetidines. Treatment of 592 with acid, base, or Raney nickel gives 593a.lM5A thermal cleavage of 1X6,2,4-thiadiazetidin-3-ones analogous to that of 592 has been p o ~ t u l a t e d . ' ~ ~ , ' ~ ~

R1NwSo2R + heat

R'/

N-S

~

RS02N=C=NR'

"0

592

& y / s 0 2 0 C 1 3 3

Ph Ph'

N-S,,

"+

Heat

Ph NTs CH,CH=C-C-NHPh I I1 (81%)

0

593

592

-

R'N=S=O

* RSO,N=C(NHR')z 593a

Four-Membered Sulfur Heterocycles With One Carbon Atom 4.

653

CSOP

Thiaoxaphosphetanes are unknown. They have been proposed as internicdiates in the addition of sulfur dioxide to phosphonium ylides to give ~ u l f i n e s , in '~~ the ~ oxidation of a-phosphinosulfoxides by iodine,'352 and in the reaction of the anticancer alkaloid, acronine, with P4S

5.

csoz

1,2,3-thiadioxetanes have been considered as intermediates in the reaction of thiocarbonyl compounds and sulfines (e.g., 594)'3s4 with singlet oxygen'080,'354-'356 and ozone.1357Theoretical calculations support the intervention of thiadioxetanes in the reaction of singlet oxygen with thiocarbonyl compounds.'3s8

o,,

o=s-0 methylene blue SZOnm, CHCI,

594

0

95%

The cyclic sulfate, 1,2,4-thiadioxetane 1, I-dioxide (methylene sulfate), claimed to be prepared by treating paraformaldehyde with oleum (HZSO4.SO3)is in reality a cyclic, eight-membered dimer,'359i1360 and the bis(methy1ene sulfate) (the so-called glyoxal sulfate) obtained by treating 1,1,2,2-tetrachloroethanewith 65% oleum in the presence of mercury(I1) sulfate is likely to have a different structure.'359 A 1,2,4-thiadioxetane 1,l-dioxide was suggested as an intermediate in the reaction of sulfur dioxide with I-methoxy-2,3,3-trifluoro~yclopropene.'~~~ 3-(Bis-trifluoromethyImethylene)-1,2,4-thiadioxetane 1,I-dioxide (hexafluoroisobutenylidene sulfate) (499) is a stable, colorless liquid obtained by treatment of bis(trifluoromethy1) k e t e r ~ e , ' ~ ~ ' 3,3,3-trifluoro-2-trifluoromethylpropanoic or the anhydride of the latter with sulfur trioxide. It is said, on the basis of "F nmr data, to be in equilibrium with a cyclic, eight-membered dimer (Keq = 0.132 liter/mole at 34.5"C), analogous to the structure of the above-mentioned "methylene sulfate".'362 Hydrolysis of 499 gives 3,3,3-trifluoro-2-trifluoromethylpropanoic The cyclic sulfate is a powerful donor of sulfur trioxide, as exemplified by its reactions with fluoride, bromide, and iodide ions (but not chloride ions),'364 t r i e t h y l a m i r ~ e , 'd~ i~~ x a n e , 's~~ ~l f o l a n e , 'and ~ ~ alkenes (See

Four-Membered Sulfur Heterocycles

654

Section XXIX,3.).908’136531366It reacts thermally with sulfur trioxide to give the sixmembered cyclic derivative 595.1367In the reactions involving transfer of sulfur trioxide, bis(trifluoromethy1) ketene, which may undergo further transformations, is produced.

499 H,O

+ H2S04

+ (CF3)ZCHCOzH ( 100%)

F Et,N

CF3

* (cF-3)~P

o

f

Et&-so; (96%)

499 -

F F (94%) KI CH,Cl,

+

(CF,),C=C=O

+ [ISOJ

(84%)

SO,

150’

+

(CF,),C=C=O (73%)

(90%) 595

CHz=C(S03H)Z

+ (CF,),C=C=O

(85%)

(96%)

503me

o-20°

1 (CF3),CHC02Me + (CF,),CC02Me (5070)

(50%)

Four-Membered Sulfur Heterocycles With One Carbon Atom

655

CSzN

6.

An unstable N-methyl-l,2,3-dithiazetecation 596 was proposed as an interIt mediate in the reaction of sulfur dichioride with N-methylthi~benzarnide.'~~~ reacts with aniline t o give an amidine. An alternative structure is 597.

S II PhCNHMe

+ SC12

ypJ1;,-

PI1

CCI,

L

PhCONHMe

s-s

596

+ PhCSNHMe + S,

S Me

II I PhC NSCl

597

7.

cszo

It was suggested that the reaction of sulfur dioxide with sulfenes yields a cyclic that decomposes t o a ketone with intermediate, a 1,2,3-0xadithietane-2,3,3-trioxide the loss of disulfur t r i o ~ i d e . "1369 ~ ~ ~An alternative scheme involves the loss of sulfur monoxide from an oxathiirane 1-oxide derived from the sulfene. The reaction of sulfur dioxide with diphenylsulfene may proceed through a 1,2,43,3-Bis(trifluorome thy1)- 1,2,4-oxadithietane oxadithie tane-2.2.4-trioxide .496c 2,2,4,4-tetraoxide 598 is obtained by thermolysis of 595.'367It decomposes to 599 on further heating,'367 and it reacts in the presence of bis(trifluoromethy1) ketene to give a six-membered cyclic trisulfone and a thiirane ~ u l f o n e . " ~ ~ ~

656

Four-Membered Sulfur Heterocycles 8.

CSB

A 1,2,3-trithietane has been suggested as an intermediate in the exchange with sulfur-35 of the thiourea sulfur atom of the histamine receptor antagonist, a cationic 1,2,3-trithietane was suggested as the product of the ~netiamide;'~~' reaction of sulfur dichloride with dithiobenzoic acid, p-methoxydithiobenzoic acid, and a-dithionaphthoic acid.'371

XXXXI. FOUR-MEMBERED SULFUR HETEROCYCLES WITH ONE SULFUR ATOM AND THREE HETEROATOMS

The reaction of 1,3,2,4-dithiadiphosphetane-2,4-disulfides with phenyliso~~"~~~ a ~ i d e , or ' ~ bis(trimethylsily1)~~ cyanate (or i s o t h i ~ c y a n a t e ) , ' ~ trimethylsilyl for example, ~ n e t h y l a m i n e ' yields ~ ~ ~ 1-thia-3aza-2 4-diphosphetane-2,4-disulfides, 600.'375 The crystal structure of trans-600 was determined, and the following ring bond distances and angles were obtained: P-S, 2.116, 2.1258; P-N, 1.689A; P-S-P, 79.1"; S-P-N, 87.2, 87.5"; P-N-P, 106.1".'375 The ring is essentially planar. Other examples of this ring system are obtained by treatment of 601 with t r i m e t h o ~ y p h o s p h i n e 'or ~ ~by ~ treatment of dichlorophosphinothioyl compounds are suggested as interwith d i m e t h y l a ~ n i n e . ' ~l-Oxa-3-thia-2,4-diphosphetanes ~~ mediates in the reaction of cyclic oxophosphoranesulfenyl chlorides with A cyclic sulfinate ester involving trivalent nitrogen aiid phosphorus trich10ride.l~~~ pentavalent phosphorus may be an intermediate in the reaction of phosphinimines lM6' with sulfur dioxide or N - ~ u l f i n y l a n i l i n e . ' ~ '~~

S (I

S-P-Ar I I At--P-S

s 600

Ar = p-CH30C6H4

Four-Membered Sulfur Heterocycles With One Sulfur Atom

2.

657

SN20, SN2P, SN2Si, SNzB

3,4-Diaza-l-oxathietanes are formed in the reaction of l-amino-l,3-dihydro-2Hindole-2-one with dimethyl sulfoxide in the presence of lead t e t r a a ~ e t a t e ' ~and ~ ' as intermediates in the reaction of nitrobenzene and N - ~ u l f i n y l a n i l i n e . ' ~ ~ ~ Cyclic S-N compounds have been re~iewed.'~''Treatment of N,N'-(di-tertbuty1)sulfamide with phosphorus trichloride gives the diazothiaphosphetane, 602,1382,1383 The chlorine atom can be replaced with other groups: fluoro, dimethylamino, tetracarbonyliron. Reaction with sodium effects coupling of the two phosphorus atoms. Treatment of N,N'-(diethy1)sulfamide with phosphorus The eight-membered ring pentachloride gives a cyclic compound similar to 602.1384 603 may be converted to four-membered cyclic compounds.1384Other examples of the diazathiaphosphetane system have been reported'37631385-1390 (e.g., 604).13881 13" The cyclic boron- and nitrogen-containing sulfonamide 605 is obtained by treatment of bis(N,N-dimethy1amino)phenylborane with sulfonyl i s ~ c y a n a t e . ' ~ ' ~ N,N,N',N'-te trakis( trime thylsilyl) sulfamide or dilithium-N,N'-bis (trimethylsilyl) sulfamide reacts with tetrachlorosilane to give the spirosilazane 606.1392

602

Ph \

Et

P-N\

/

Et-N I SOf

so2 I

/"Et N-P-Ph

PCl, CCI, (93%)

/

Et

Et

Et

603

604

PhB(NMe2),

+ SOZ(NCO)Z

CH,CI,

RT

(97%)

Ph-B-N-CONMe, I I N-SO, /

CONMe, 605

Four-Membered Sulfur Heterocycles

658

(R = Me3Si)

Me+i

SiMe,

Me,Si

SiMe, 606

Molecular orbital calculations (CND0/2) on cyclic SN3 species, SN;, SN;, indicate the cation is more stable than the anion and that d-orbitals play an insignificant role.'393 Several tetrathiatetraphosphatricyclooctanescontain four-membered rings with three phosphorus atoms and one sulfur atom.13"-1396

XXXXII. FOUR-MEMBERED SULFUR HETEROCYCLES WITH TWO SULFUR ATOMS AND TWO HETEROATOMS 1.

SZNO

Examples of this ring system are known only as putative intermediates in the reaction of tris-iminosulfur compounds with N-sulfinylamines'344>1346c and the reaction of sulfoxides or sulfinamides with N-sulfinyl alkanaminium salts,'39731398 as shown for the reaction of 607.'398

B

r

c)

N+= SO SbCI,

CH,CN Me,SO

*

c N c s \\ O /

-25'

SbCl,

S I Me,

---+

C>N-S+Me, SbCl,

Cyclic S-N compounds including S2N2 have been reviewed.1381i1399An x-ray analysis of disulfur dinitride, S2N2, with alternating sulfur and nitrogen atoms indicates a nearly square planar array with S-N distances of 1.657 and 1.65 1 .A and angles NSN of 89.6" and SNS of 90.4°.'400~1401The structure of the bis(antimony pentachloride) complex is planar: S-N, 1.619 A; NSN, 84.9"; SNS, 95.1°.1402aAn S2N2 complex of copper (11) chloride also is planar: S-N, 1.633, 1.641 A; N-S-N,

Four-Membered Sulfur Heterocycles With Two Sulfur Atoms

659

85.2"; S-N-S, 94.7°.'402b The structures of 608, 609, and 610 have been determined.'w>'M6c While the ring of 608 is not planar, those of 609 and 610 are essentially so.

But

SiMc3

But

I

I

-Bur

I

SiMe3

Bur

610

609

The electronic structures of S2N2ring systems have been investigated theoretiThe participation of d-orbital functions for sulfur is especially important for S-N bonds, and their inclusion reverses the order of stabilities for 611 and 612 (611 becomes more stable).999bIn SzNz, of which the hypervalent resonance structure 61 1 is one representation, the bonding is believed to involve one S-S and two S-N-S 71 bonds for a total of 677 e 1 e ~ t r o n s . l ~ ~ ~

ally.^^^^, 1393

N=N I

s-s

61 1

of

Thermolysis of SJ,

s ~ N1401,1403 ~:

I

612

in the presence of elemental silver yields colorless crystals

660

Four-Membered Sulfur Heterocycles

Other SzNz compounds containing divalent sulfur have been obtained by photolysis ~~ of (CF3S)3N'4Mand by treatment of tertiary amines with sulfur d i ~ h l o r i d e , 'the products from the latter being of interest as fungicides and corrosion inhibitors. Platinum complexes of SzNz have been prepared by treatment of phosphineplatinum complexes with SqN4,1406 and a copper (11) complex has been obtained .l4OZb Derivatives of SzNz in which hexavalent sulfur is involved have been obtained by ' ~ ~ ~to ~ ~give ~ 613) and addition of sulfur trioxide to N - s u l f i n y l s u l f ~ n a m i d e s (e.g., by the reaction of sulfur triamides with perfluoroalkylisocyanates (e.g., to give 608)1346c or N-sulfinyl amines.'344~'346c

But

I

608

The thermal decomposition of SzNz results in a color change from colorless to blue-black (the acyclic SzNz diradical) and finally to a golden bronze which signifies Solutions the formation of the polymer, (SN),, which conducts of S2Nz in dichloromethane react with antimony pentachloride or boron trifluoride to form adducts coordinated through the nitrogen atoms.1m9Compound 613 and its trifluoromethanesulfonyl analog react with S y 4 and pyridines to give acyclic They react with nit rile^'^^^^'^'^ and arylisoproducts, for example, 614.'m8>1410 cyan ate^'^'^ to give six-membered heterocycles, for example, 615 and 616.

r* 0 F S O z N = Ii1= N z S 4

CH,CI,

614 (56%)

613 -I

Ph

c1

CH,Cl,

-

615 (60%)

SOzF

616 (23%)

Four-Membered Sulfur Heterocycles With Two Sulfur Atoms

3.

SZP,

A.

Uses

66 1

Derivatives of general formula 617 have been used as intermediates in the preparation of oil additive^,'^^^-'^^^ msecticides,~415-1419fungicides,1420,1421a-1421c bactericide^,'^^' and herbicides.1422 '

3

S-P-R I 1 S=P-s

I

R 617

B.

Properties

The cyclic structure 617 was proposed in 1952 for the so-called metadithiophosphonates or thionophosphine oxides. An x-ray analysis of 617 (R = Me) gives the ring P-S bond length as 2.14 and the bond angles of P-S-P and S-P-S are 84.2" and 95.8", r e ~ p e c t i v e 1 y . lThe ~ ~ ~relationship of the thiono sulfur atoms and the methyl groups about the two phosphorus atoms is trans. In 618, the exocyclic ligands are in a cis configuration and the mean P-S bond length is 2.144A.1425 Bond angles in 618 are P-S-P, 89.2", and S-P-S,90.4", in the nearly planar ring. The structure of 617 (R = NMe,) has been determined [P-S (ring) 2 . 1 2 8 ; angles P-S-P, 86.9", S-P-S, 93.1" 1426] as has the silver salt (R = SAg) [P-S (ring) 2.12 8; angles P-S-P, 86.2", S-P-S, 93.7°].1427

a

The mass spectra of a number of derivatives of 617 have been recorded; cation1429b The "F nmr spectra of a number of radicals RPS:' are most m- or p-fluorophenyl derivatives of 617 have been r e ~ 0 r t e d . l ~ ~ '

C.

Synthesis

Treatment of aromatic hydrocarbon^'^'^^ 143171432 or c y c l ~ h e x e n e '1423 ~ ~ ~with '

Palo (or sulfur and red phosphorus)1432at elevated temperatures usually gives good yields of 617 (R = Ar, 2-cyclohexenyl), as illustrated by the reaction of anisole to give 619.14,1 The compounds are sensitive to moisture and may polymerize in solution.

Four-Membered Sulfur Heterocycles

662

Reaction of alkyl-, aryloxy- or arylphosphonothionic dichlorides with hydrogen l4l8> 14"% 1421c,1429h31433-1436 as exemplified sulfide also yields derivatives of 617,14163 in the synthesis of 620.14% Related syntheses involve treatment of phosphorus dichlorides with hydrogen sulfide and pyridine, usually in the presence of added elemental

OCH, I

+p4s10

7 145-160' SI - 1! O O -C H 3

Q S=P-s

OCH,

619

c1

Cl

s-P-0 I I S=P-s I

620

Several syntheses of 1,3-dithia-2,4-diphosphetane derivatives may be considered as formally proceeding via dimerization through P=S bonds,1376analogous to the formation of 1,3-dithietanes by dimerization of thiocarbonyl compounds (Section XXXVI.3.A). These reactions include indirect methods involving the addition of elemental sulfur to aminoirninoph~sphines'~~~~~~~~ (e.g., the synthesis of 618) or phenylph~sphine'~~' and treatment of thiophenol with P4S10,1440as well as direct

(Me,Si)2N-P=NBu'

S

/,N-Buf

/ S\

(Me,Si),N'

P

\s/

P

"N(SiMe,),

618 (74%)

Four-Membered Sulfur Heterocycles With Two Sulfur Atoms

663

formation via dimerization of phosphine Miscellaneous syntheses of the S2P2 ring system have been reported involving addition of P4S3 to bis(dimethy1a m i n o ) ~ u l f a n e , ' ~and ~ the addition of elemental sulfur to phenylbis(trifluor0methyl)phosphine'441 or tetra-t-butylcyclotetraphosphane.'442

D. a.

Reactions

WITH NUCLEOPHILIC REAGENTS

Compounds of type 617 react with water,1423alcohols,1416~1417~'423,1436~ 1443-1448 eno1s,"5031451 o x i m e ~ , 't~h ~i o~ l ~ , 'thioacylhydra~ines,'~~~~ ~~ bis(dimethylamino)-~ulfane'~~~~ ammonia,1426 amines (primary, secondary and tertiary),1375,1426,1434,1435,1~8,1449,1453-1455 hydrazines,1456 hydr azone s, 1452a, 1456 a, 0-

~~ unsaturated a m i d e ~ , ' ~ ' ~c h l o r ~ n i t r i l i m i n e s , ' ~ a~ ~ t r i p h o s p h a ~ e n e , ' ~phosp h i n e ~ , ' 1426 ~ ~ ~and ' Grignard reagent^.'^^'-'^^^ The products are exemplified by the general structure 621. Further reaction of 621 occurs in some cases such as cyclization in the presence of a double or triple bond (e.g., to give 622)lM8or displacement of a sulfur atom as sulfide (or hydrogen sulfide) from 621 by reactive functional groups as in the formation of 6 2 3 y 6 or displacement of a neighbouring halogen by the sulfide ion of 621 (e.g., to give 624).lM5No reaction is observed with 0 - or p-nitroaniline and anomalous results are obtained with dibenzyl~~~ amine.14s3 An extensive rearrangement occurs with a c y c l o t r i p h o ~ p h a z e n e . 'If carbonyl groups are present in the reactants, they may be converted to thiocarbonyl groups (see next section).

I R

Nu 621

6 2 2 (46-79%)

?

S-P-Ar I I S=P-s

I

Ar

CE3

623

Four-Membered Sulfur Heterocycles

664

+

s

S-P -Me I

S=P-s Me I

7’1 ,Me

S,

HOl

JBr

I

Et,N dioxane

SO2

P

(80%)

SO2 624

b.

WITH CARBONYL COMPOUNDS AND PHOSPHINE OXIDES

Compound 619 and related compounds are useful reagents for converting a carbonyl group to a thiocarbonyl group. The following types of compounds have been investigated: ketones1077,1450~1464 (e,g., 625),1464 ketenes,1266 a-ketothioderivative^'^^^-'^^^ (e.g., 626),1469e ~ t e r a m i d e ~ , ~enaminoketone ~~’ (e.g., 627),’472t h i o l e s t e r ~ , 1468, ’ ~ ~1474p ~ 14” t e l l ~ r o p h t h a l i d e , ’a~m~ i~d e ~ , ’ ~ ~ ~ 14681 ? 1472,1475,1477-1485 peptides,1486 p-lactams1480 (e.g., 628), imides,838d,1421a,1480,1487 and h y d r a z i d e ~ . ’The ~ ~ ~thiocarbonyl ~ group may undergo further reaction with other functional groups present in the molecule as illustrated by 629.1482The cyclic disulfide derivatives 630 are obtained in high yields by treatment of 0-ketoesters with 619.14’0 Phosphine oxides are converted to phosphine sulfides by 619.’488,1489

d$J

625

+ (JI-CH~OC~H~PSO)~

I

qPh

Ph

626

619 C,H6, reflux (68%)

0

627

S

N S’ N ‘

(87%)

~

~

Four-Membered Sulfur Heterocycles With Two Sulfur Atoms

665

Ph

Ph 619 C,H,, reflux

____)

(87%)

628

7 NHCBu'

619 xylene, 140'

629

a

0 II COEt

0

N HC- BU

N=C-SH I

II

Bur

(93%)

630

c.

MISCELLANEOUS

The reaction of 619 with C-nitroso compounds gives azo- or azoxy compounds with N-nitroso compounds one obtains phosphorus heterocycles (e.g., 589) or elimination of HNO, and deoxygenated products are formed with nitrones or yields the unusual, purple 63 1. 1340 N - o ~ i d e s . ' p-Nitroso-RN-dimethylaniline ~~~~'~~~~ Sulfoxides are deoxygenated by 619, although some disulfide is formed.14" SQ

NO

NMe2

NMe, 631

S

Four-Membered Sulfur Heterocycles

666

Treatment of the phenyl analog of 619 (i.e., 617, R = Ph) with methyl bromide Chlorination of 619 gives p-CH30C6H8SCl2or effects ring-opening to give 632.1373 p-CH30C6H,+POC12,depending on conditions.1431Treatment of 617 with aluminum An chloride in refluxing benzene yields phenylphosphinodithioic oligomer, (CH&S ' 2)n, is obtained by reacting 617 (R = Me) with methylphosphonothionic d i ~ h l o r i d e . ' ~The ~ ' phenyl derivative of 617 is said to be desulfurized by the tri-butylphosphine to (PhP)5.1373Reaction of aryl-substituted derivatives of 617 with phenylisocyanate or phenylisothiocyanate gives heterocycles of the SNPz system (Section XXXXI.1).137231373 Treatment of 617 (R = Me, Et) with trimethylsilyl azide also leads to the SNPz ring system.'374 Ynamines react to give a sixmembered sulfur-phosphorus heterocycle.1420 The reaction with alkenes or polyalkenes gives uncharacterized products useful as intermediates in the formulation of sludge dispersant^.'^^^"^^^ Dienes react with 617 to give adducts, for example, 633, of the P-S double bond.1491a

S-P-Ph I

MeBr

I

S=P-s

80"(95%)*

I

f

PhP -SMe I

Br

Ph

632

SI1 S-P-R I I S=P-s

+

R'CH=C(R2)C(R3)=CHR4

+$R4

R'

s-P,

I

R

II R

S

617

(53-97%) 633

0-Lactones react with 619 to give six-membered heterocycles, for example, 634,I4'lb and two isomeric five-membered heterocycles are obtained from di-tbu tyldiaziridinone 635. 14"

toluene, 619 reflux

( R = H, CH3)

~

' C \ O O C H 3

8 634 ( 5 3 , 6 0 % )

Four-Membered Sulfur Heterocycles With Two Sulfur Atoms

667

SzSi2, SzGez,SzBz

4.

A.

Properties

Electron diffraction of 2,2,4,4-tetramethylcyclodisilathiane636 gives a Si-S bond distance of 2.18 A and bond angles Si-S-Si and S-Si-S of 75" and 105", resis planar: S-Ge, p e ~ t i v e l y . ' ~ ~ ~2,2,4,4-Tetra(t-butyl)-l,3-dithia-2,4-digermane ~'~"~ 2.246 A, angles Ge-S-Ge, 85.5" ; S-Ge-S, 94.5" .1494b 2,4-(N,N,N:N'-tetraethylamino)-l,3,2,4-dithiadiboretanealso is planar: B-S, 1.84 A; angles B-S-B, 76"; S-B-S, 105°.'49s The configuration about the nitrogen atom is trigonal planar. There is no dipole moment for 636;'496the Raman spectra of the solid and the ~ ~ Raman , ' ~ ~ ~spectrum of liquid are in agreement with planar, Dzh ~ y m m e t r y . ' ~The 2,2,4,4-tetrachlorocyclodisilathianealso has been r e ~ 0 r t e d . l ~The ' ~ dipole moment for (CH3)$i4S6 is in agreement both with structure 637 and another structure involving six-membered rings." Me

\

Me-Si-S I

I

S-Si-Me \ Me 637

636

B.

Synthesis

A number of syntheses of cyclodisilathianes may be classified formally as proceeding by dimerization of a silyl thione, R2Si=S, analogous to the dimerization of thiocarbonyl compounds to 1,3-dithietanes, a concept that has been explicity stated for the formation of the tetramethyl derivative 636 from thermolysis of 638.14" Tetraalkyl- and tetraarylcyclodisiladithianes have been obtained by (a) thermolysis of cyclotrisilathianes, with which the four-membered heterocycles are in equilibrium,1493,1S~-1s05a (e.g., 639),"04 or thermolysis of thioketals of silanones [e.g., RzSi(SEt)2] (b) by treatment of disubstituted dichlorosilanes, RR'SiC12, with hydrogen sulfide's06-1s10(cyclotrisilathianes also may be formed); (c) by treatment of dichlorosilanes with di-(trimethylsilyl)sulfide;'5'1"s12 (d) by treatment of tetra- or hexaalkyldisilanes or silacyclobutanes with elemental or sulfur h e ~ a f l u o r i d e . " Treatment ~~~ of boiling hexamethylcyclotrisilazane with hydrogen sulfide for 25 h gives a 70% yield of 636."14 Compound 637 (tentative structure) is or methyldichlorosilyl alkyl obtained by treatment of methyldi~hlorosilane'~~~ ethers's16 with hydrogen sulfide, and the phenyl analog of 637 is obtained by Tetratreatment of bis(trimethylsily1) sulfide with phenyltrichlorosilane.lsllJslz halocyclodisiladithianes are obtained by treatment of silicon tetrahalides at high temperatures with hydrogen sulfide,'498i''17 silicon d i ~ u l f i d e , ' '"" ~ ~ ~mercury(I1)

Four-Membered Sulfur Heterocycles

668

sulfide'519 or disulfur d i c h l ~ r i d e , ' ~by~ ~thermolysis of dihalodi(ethylthi0)s i l a n e ~ and ' ~ ~by ~ ~treatment of hexabromodisilane with sulfur t e t r a f l ~ o r i d e . " ' ~ ~ Polymers and oligomers have been obtained in some reaction^.'^'^ Tetra-t-butoxycyclodisiladithiane is obtained in low yield by treatment of silicon disulfide with 1522 a similar reaction with 2,2-dimethylphenol gives a 20% yield t-butyl of the tetraaryloxy~yclodisiladithiane.'~~~ Thermolysis of tetra(alky1thio)silanes 1524 yields te tra(alky1thio)~yclodisiladithianes.'~~~~~ 2,2,4,4-Tetra-t-butyl-l,3-dithia-2,4-digermacyclobutane 640 is prepared by treating di(t-buty1)dichlorogermane with hydrogen sulfide via a dimercapto intermediate or with potassium hydrosulfide in the presence of 18-crown-6 ether.'494b It is obtained in nearly quantitative yield by treatment of l11,2,2-tetra-t-butyldigermane with elemental Other examples of this ring system are obtained from bis(pentafluoropheny1)germane and elemental the disodium salt of diphenyldimercaptogermane and benzoyl chloride ,lSz6 and germanium disulfide and sodium sulfide. lSz7 1,3,2,4-Dithiadiboretanesare obtained by treatment of boron tribromide with hydrogen s ~ l f i d e (six-membered ' ~ ~ ~ ~ ~ ~ heterocycles ~ ~ also are by thermolysis of a six-membered borthiin, and by treatment of triethylamine borane with hydrogen sulfide.'531 2

638

636 Ph2 s/sl's

I

Ph2Si,

S

I

,SiPh2

300-31 5' 1mm (52%)

S-SiPh

I t * Ph2Si-S

639

640

C.

Reactions

Cyclodisilathianes may decompose thermally to silicon disulfide and silicon 1518i1524 or to trimers of R2Si=S.'5m' derivatives (R4Si) of the substituents'505c~ 1503,1532 Thermolysis of 636 with 2,2,3,3-tetramethyl-1,4-dithia-2,3-disilacyclohexane gives an equimolar mixture of 2,2-dimethyl-l,3-dithia-2-silacyclopentane and 2,2,4,4,5,5-hexamethyl-l ,3-dithia-2,4,5-tri~ilacyclopentane;'~~~ analogous reac-

Four-Membered Sulfur Heterocycles With Three Sulfur Atoms

669

tions have been reported for 2,2,5,5-tetramethyl-l-oxa-2,5-disilacyclopentane1s~ and 2,2,3,3,5,5,6,6-octamethyl1,4-dithia-2,3,5,6-tetrasilacyclohe~ane.'~~~ The S,Si2 ring system is susceptible to attack by nucleophiles, as is illustrated for 636. Examples of nucleophiles are alcohols (best with primary and secondary),1510' The 1s63-1538 phenol^,'^^^^'^^^ hydroxide ion,1s10water,'s40 and carboxylic boron compound 641 reacts with 636 to give the five-membered heterocycle 642.lS3'The electrophilic reagents, acetyl chloride and benzoyl chloride, react with tetraphenylcyclodisiladithianes to give the diacyl sulfide and dichlorophenylsilane.'341a

I I Me,Si-S S-SiMez

636

]I

OH I (Me,Si),O

(MeD"), 64 1 CH,CI,, pyridine -loo

Me2N-B-B-NMe

I

I

s\si/s I

Me2 642 (86%)

The dithiadiboretane (HSBS), gives a trimer on heating,'5z8 as do other derivat i v e ~ . ~ ~ ~ ~

XXXXIII. FOUR-MEMBERED SULFUR HETEROCYCLES WITH THREE SULFUR ATOMS AND ONE HETEROATOM OR FOUR SULFUR ATOMS Theoretical calculations show that ions of the hypothetical, four-membered heterocycle, S&, decrease in stability in the order S3N*3> S3N+ > S3N-.'393 The stability of S;' (known) is calculated to be greater than S4 ( u n k n ~ w n ) . ' ~ The ~~,'~~~ former is a 6n-electron system. Both S3N' and Siz are isoelectronic with SzNz( 2 2 electrons), but S&+ is a 4n-electron system. The cyclic cation S': is obtained by oxidation of elemental sulfur (s8) with excess S,06Fz, AsFs, or SbF5.lsM The cations Siz and S;," also are obtained. An x-ray analysis and a Raman spectrum of The Siz (FS03)2 has been obtained; a square-planar Siz ring is established.1s44~1s45a square-planar nature of S': also is supported by magnetic circular d i c h r o i ~ m . ' ~ ~ ~ ~ The S': cation is a strong Lewis acid. The colorless fluorosulfonate salt decomposes slowly in sulfur dioxide and rapidly in fluorosulfonic acid to Siz (blue). X-ray analysis indicates that the structure of the unusual black, air-sensitive 634 involves t w o weak S-S bonds in the four-membered ring."%

670

Four-Membered Sulfur Heterocycles

64 3

XXXXIV.

FOUR-MEMBERED H h TEROCYCLES CONTAINING SELENIUM OR TELLURIUM 1.

C3Se, C3Te

The microwave?*, 1547 IR,’548,1549 and Raman spectra 1549 of selenetane (trimethylene selenide) and its tetradeuterio derivative’549show it to be puckered with a dihedral angle of about 149”. The barrier height to a planar configuration is between 378.1 and 383.1 f and is greater than for t h i e t a r ~ e . ~The ’~ proton nmr spectrum of selenetane at 100 and 60MHz has been analyzed as an AA’BB’B‘IB”‘ system.’550 Chemical shifts and proton-proton coupling constants (Hz) are as follows: H a 3.12; Hp, 3.30ppm; 7.91; 2Jp&em)-12.10; 3Jcis8.70; 3J+rRns6.47; 4Jci,0.82; 4Jtrans - 0.41. Selenetane is a pungent liquid obtained in low yield by treating 1,3-dibromopropane with sodium ~elenide.’’~~ Substituted selenetanes have been obtained by treatment of 1,3-dihalopropanes (e.g., 644)’552with potassium s e l e r ~ i d e ’ ~or~ ~ ~ ’ ~ ~ ~ the cyclic monocarbonate of pentaerythritol with potassium ~ e 1 e n o c y a n a t e . l ~ ~ ~ 3-Hydroxyselenetane 645 [‘H nmr: 6 3.6 (J = 5.8) (Ha);3.85 (OH), 3.9-4.2 (m) (Hp) ppm] is obtained by electrolysis in a diaphragm cell of chloromethyloxirane (epichlorohydrin) in the presence of selenium It is also obtained by treatment of 1,3dibromo-2-propanol with NaSeH.’554C Tetravalent, fourmembered selenuranes are formed by treatment of 3,3-dimethylselentane with bromine at low t e m p e r a t ~ r e , ” and ~ ~ by treatment of the 1,I-dibromoselenetane 646 with the potassium salt of 2-phenyl-l , 1, I ,3,3,3-hexafluoro-2-propanol to give 647.’553Compound 647 shows a one-bond 13C-77Se coupling constant of 34Hz; the two alkoxy groups are equivalent in the I3C nmr spectrum, but the two methyl groups are not.1553A square pyramidal structure for 647 was considered. Earlier workers described d i i ~ d o s e l e n u r a n e s , ’ ~but ~ ~more ” ~ ~ ~recent investigations did not lead to stable products.’553A cyclic, four-membered dibromoselenetane or tellurane is obtained from norbornadiene and selenium or tellurium t e t r a l ~ r 0 m i d e . l ~ ~ ~

EtOH,N,

* 644 (68%)

Four-Membered Heterocycles Containing Selenium or Tellurium

0 &CI

+ Se + 2Na’ + H 2 0 + 2e-

- Dse HO

67 1

+ NaCl + NaOH

graphite

645 (50%)

Ph

646

647

Ring-opened products (e.g., 648, 649) are obtained by treatment of selenetanes with bromine above - 35°C,155211553 sulfuryl and methyl iodide.’55211553Oxidation of selenetanes by hydrogen peroxide or cyclization of salts of 3-haloseleninic acid are claimed to give selenetane l , l - d i o ~ i d e s , but ’ ~ ~later ~ investigations showed that some of the compounds obtained were lactones of seleninic acid 650.’553Thietanes are readily oxidized to thietane 1,l-dioxides, which do not readily rearrange to cyclic sulfinates (Sections 1I.S.C and V.4.C), and thiete 1 , l-dioxides require elevated temperatures for rearrangement (Section X11.4.D). These differences in behavior may be due to the greater stability of a carbon-sulfur bond over a carbon-selenium bond. Selenetanes form adducts with ~ ~are ~ ‘ polymerized ~~~ on treatment with light,’556 mercury (11) ~ h l o r i d e ’ ~and n - b ~ t y l l i t h i u m ’boron ~ ~ ~ trifluoride etherate-~ater,”~’or triethyloxonium tetraf l u o r o b ~ r a t e . ’ ~ The ~ ’ mercury (11) chloride adduct of selenetane decomposes on heating to mercury (11) selenide and 1 , 3 - d i ~ h l o r o p r o p a n e . ’ ~ ~ ~

I

Me1 EtOH

+

,

M eSeCH ,CMe ,CH I 649 (69%)

650 (20%)

672

Four-Membered Sulfur Heterocycles

2.

C2Se2, C2Te2.C2SeS, CSeN2

The structures of 2,2,4,4-tetrafl~oro-l,3-diselenetane'~~~ and trans-2,4benzylidene-I , 3 - d i t e l l ~ r e t a n e 'have ~ ~ ~ been determined: Se-C, 1.968 8; Te-C, 2.118A; Se-C-Se, 98.5", Te-C-Te, 100.3"; C-Te-C, 79.8". Both have short nonbonded chalcogen distances, which, in the case of selenium, is attributed to bonding between the two atoms. Bis-3,4-(trifluoromethyl)-1,2-diselenete651 is prepared by refluxing selenium ~ ~reacts with triphenylphosphine and triphenylwith h e x a f l u o r o - 2 - b ~ t y n e . ' ~ ~It arsine. Triphenylphosphine selenide was isolated, but no other compounds were ider~tified.'~~' Ring-opened complexes with nickel, copper, vanadium, molybdenum (652), tungsten, iron, and cobalt are analogous to complexes of the 1,2-dithiete (527) (Section XXXV.2.C.).

'"'

CF,CrCCF,

+ Se

:'*

n

Se-Se

651 (25%)

652 (59%)

The syntheses of 1,3-diselenetanes'558"562-1s69 and 1,3-ditelluretanes'ss9~'570~'573 can be classified as proceeding via dimerization of the selena or tellura carbonyl compounds analogous t o the formation of 1,3-dithietanes from thiacarbonyl compounds (Sections XXXVI.3 .A; XXXIX.3). These reactions are exemplified in the formation of 653,'563 654,'569 and 655.'572 The structure of compound 655 was previously misassigned as a 1,3-ditellur01e.'~~~ The 1,3-diselenetanes and ditelluretanes, while quite stable, are all presumed to be thermally capable of being decomposed into their as is shown for 656.'562 Treatment of tris(trifluoromethylse1eno)boron with 2,2,4,4-tetrafluoro-l,3-diselenetane 657 effects replacement of the fluorine atoms by the trifluoromethylseleno groups and decom~ ~ selenathietane sulfone 658 is position to the selenocarbonyl c ~ m p o u n d . 'The obtained by the reaction of divinylsulfone with selenium tet1-abr0rnide.l~~~ The compound is said to form a dibromoselenurane on treatment with bromine. The spiro selenurane 660 is formed from the urea derivative 659 and SeOC12.'s75 3.

Four-MemberedHeterocycles of Selenium and Tellurium Containing No Carbon Atoms

Dimerization of a phosphine selenide yields the heterocycle 661 1438 A similar dimerization may account for the formation of 2,2,4,4-tetramethyl-1,3-diselena-

Four-Membered Heterocycles Containing Selenium or Tellurium

6 5 3 (73%)

R

II

500-600" l o ~ , O O mTorr

+

[RCH=C=Sel R = H , Me, But

654

ArC=CNa

Te DMSO,

* [ ArCf C-Te-I

11CI

[ ArCrCTeH+ArCH=C=Te]

(Ar = C6115, pC€13-C6H4J

-

I

+-Te CHAr

t

655 (trurzs)

SeqC12 * C1,C=Se kse 300-3S0°

high vacuum

C1,

656

657

(CH,=CH)2S0,

+

SeBr,

-

BrCH, 658 (81%)

SiMe,

A-CO-N659

Me I

SiMe,

SeOCI, C H, C I ,, oo

* Ar-N,

,N-Me Se / \ Me-N N-Ar

U 0

660 (47%)

673

Four-Membered Sulfur Heterocycles

674

and the forma2,4-disilthiane from sodium selenide and dichlorodimethyl~ilane,~~~~ (or l ,3-ditellura-)-2,4-digermacyclobutane tion of 2,2,4,4-tetra-t-butyl-l,3-diselena from elemental selenium or tellurium and 1,1,2,2-tetra-r-b~tyldigermane.'~~~~ The selenium-nitrogen heterocycle 662 is obtained from SeOCl, and methylamine.1577It polymerizes on warming to - 25" and fragments completely at room temperature. A spiro silyl aminoselenurane is obtained from selenium tetrachloride and the dilithio salt of a b i s - a m i n o ~ i l a n e . ' ~ ~ ~

N(SiMe,), 661

SeOCI,

+ MeNH,

CH,CI, -350

*

o\ Se -N I

Me/

.Me

t

N-Se+

0

662

The species, Se;' and Te;', appear to be square-planar like S4+2,1545b whose similarity is supported by theoretical calculations that treat all of them as 6-n electron systems.'543 The yellow selenium cation is obtained by treating elemental selenium with fluorosulfuric acid, fuming sulfuric acid, sulfur trioxide, disulfuric acid, or antimony p e n t a f l u ~ r i d e . ' ~ The ~ ~ , 'red ~ ~ tellurium ~ cation is obtained similarly.lS8'

Acknowledgment. The authors wish to express appreciation to James R. Bodwell, Sharon M. Brosemer, and William F. Jarvis for assistance with the literature and to Claire Macri and Diane Piraino for typing the manuscript and especially to Diane Piraino for drawing the figures.

XXXXV.

TABLES

Selected examples of compounds are presented in the following tables in which the arrangement generally proceeds from least-substituted to most-substituted rings.

615

115 (760) 102-103 104-106 (760) 114-118 (760) 126-131 (760)

-

83.5 (23) 59.5 (2) 149-150 112-1 1 3 64-65.5

-

5

E

IA

z

0

a

5 %2

v

z7

127a, 168,169 178 2 179a,207b 180 0, CD wl 163 168 125a 207b 184a 3a, 119 5 3a 160a 160a 160a

205 208

30

(CH,),hi, H HO, H PhO, H CH,CO,, H CH,=CHCO,, H H,NCO,, H 3,5(NO ,C, H,CO,, H HO,C, H C1, H NCS-, H H, H H, H CH,, H Et, H n-Pr, H

56 40-65 48 82 74 42 20 33

180.5-1 82.5 209-210 dec. 51-52 (0.9)

(CH,),fjHCi, H

200 201 124a 207b 207b 132c

113a 33 i58a, 194 162

Ref.

100

11 10-20 16 50

Yield (%)

80 68 56 31 50

101-102 (760) 80-82 (1.5)

-

93.8-94.2 (752)

143 (0.1) 145-148 (760) Oil Oil 78-79 (2)

H, H D, D CH,, H Ph(CH,),, H

H D H H

mp "C or bp "C(mrn)

H, H H, H H, H t-Bu, H Ph, H HOCH,, H

H, D, H, H,

H, H H, H H, H H, H

0

4

Substituents

3

THIETANES

2

TABLE 5.

(CH,)

'"

uN-

l-7

0

,k

HO, H HO, Ph MeO, M e 0 2-naphthyl,

Ph,

O w N -

n

p-BrC,H,, CH, Ph, iPr 4CHZ)s-CH,-O--CH,PhCO, H HOCH,, HOCH, -CH20CH(Ph) OCH,Ph, (CH,),N

CH,CH, Ph, CH,

51

140 (760)

49

56.5-57.5 91-93 (0.1) 62-63 (12) 109-110 dec.

104-105

53

52

-

63 36 78-80

38

-

66 58 75 69 60

143

170 170 126 209

207b

206

139 139 139 136 202a 8b 8b 209

196d 139,141b

152

38 62 65

205

69

175-175.5

115-116 (760) 115-117 (12), 140-160 (15) 56-57 142-154 (10) 82-84 (7) 78 (12) 79-80 70-72 86-88 -

472

Oil

Four-Membered Sulfur Heterocycles W 0

hl W

m

N

N

N

m

*

3

3

m

4 0

.-(

3

W

hl 0

0

r-

0

0

v)

3

w

*

0

OI

m m

N

r3 0 N

. m c

s W

c I 0

2

N

3

I N 0

I

-4 r-

3

3

r

35

Dz

tj

m v) 3

I

rn m 3

c3.

N N N

d

m

o m

I

m e

3

w

3

d

N

W 0

d

m

I 1 CON N W

l

3:

3: 3: 0z- 3:- r;i

0 hl

3

2

N

O M

m w

3

I

z .

V P

.

0 N

d P

3

3

N

3

Zc) V

r

c

N

0

1 0 N W

w m

c a

679

N

t!

3

m

3

I

c

3:-

tN

h

2 "

Y

m

10

N

'?

h 3

W

r-

0 10

3

W I

m

P

I 0

I

m

I3

0

co

o\

H, H

-CH,OCOCH,-

I1

0

H, H

H, H CH, (cis and trans), H t-Bu (cis and trans), H Ph (cis), H Ph (trans), H pClC,H, (cis), H pClC,H, (trans), H p-BrC,H, (cis), H p-BrC,H, (trans), H HO,C, H CH,CO, (cis), H CH,CO, (trans), H PhO, H 2,4C1,C6H,, H HO, H C1 (cis), H C1 (trans), H H, H H, H Ph (cis), CH, Ph (trans), CH, HOCH,, HOCH, -(CHz) 5 -CH,OCH,-

CH,, H H, H H, H H, H H, H H, H H, H H, H H, H H, H H,H H, H H, H H, H H, H H, H H, H Ph, H Ph, H H, H H, H H, H H, H H, H H, H

H, H H, H H, H H, H H, H H, H H, H H, H H, H H, H H, H H, H H, H H, H H, H H, H Ph (cis), H Ph (trans), H H, H H, H H, H H, H H, H

H, H

H, H

4

H, H

Substituent

3

2

-

148-151 (760) 71

-

50-5 2.5 90-95 124-128 67-68 92-94 74-76 135.5-1 36.5 154-155 -

Oil

89-89.5 87-88.5 112-11 3 108- 109 95-100

-

-

-

-

-

-

56 89

-

-

42 -

-

39 38 -

-

-

-

91-91.5 Oil

-

-

-

-

88,60-63

Yield (%)

6 0 (1)

mp "C or bp "C (mm)

15j

280a, 280b, 286a 397a 207b 207b 207b 207b 207b 207b 141b 141b 125a 207b 207b 181 181 179b 207b 207b 53a 5 3a 141b 141b 15j 131 135

Ref.

M

m

.d

"'o

b

25 0

238-240

141b

141b

63

13

113-1 15

12-18

Four-Membered Sulfur Heterocycles TABLE 7.

Compound

THIETANE SULFILIMINES AND S-AMINO SALTS

m p “C

Yield (%)

Ref.

98

139

100

139

93

139

71

21 2

Br

92-93

682

CH,COz-, H HzNC02-, H pCH,C,H,SO,-, PhCH,SO,, H C1, H Br, H PhS, H

o,s>o-,

HO, H EtO, H PhO, H

0

HzN, H

H

NH-, H

H

H, H H, €1 H,H H, H H, H H,H H, H

H, H

H, H

H

O,S$,

Oil 37-39 101-102 154-155

H, H H, H H, H H, H

CH,, H (CH,),C, H Ph, H p-BrC,H,, H

H, H

-

D, D H, H

H, H H, H

D, D CH,, H (R and S isomers) H, H H, I1 H, H H, H

207b 163 168 495c 168 505a 205

62 117-117.5 229-230 129-131 189-190 136.5-137 153-155 7 2-7 3

89 86 94 92-95

-

169

181

63

13

169,514 205

80 68

165-165.5

99.5-1 02 50-52 147

495c

205

48

93-96 93-94

445a

207b 207b 207b 141b

113a, 505b, 495c 207b 158b

Ref.

80

88 65 50

-

88 2 1 W , 85"

89-94

Yield (%)

187-188

-

73-75

H, H

H, H

H, H

mp "C

4

3

Substituent

THIETANE 1,I-DIOXIDES

2

TABLE 8.

Four-Membered Sulfur Heterocycles

Lo

N

'0

0 N

3

* W

t-

m

W

d

0 Lo

I

I

m

0

Lo

0

0

3

tr-

'?

r-

rn

N N

W

N N

Z

T

zi

64

Z

N

N

A I

n

3g s -

v3,

G

0

z z" 684

L:

a

m

0 ‘ I )

W 0

‘I)

2

m

m

d

‘I) ‘I)

d

m

sm

‘I) 3

N

‘I) 3

I

‘?

h

t-

al

W N

W W r-4

*

685

r .

r-

‘I)

‘I)

0

N

3

m

r-

‘I)

0

0

‘I)

2 0

c-4 I

‘? r-

0 N

m

m

3

m 00 m

Ph, H (cis) Ph, H (cis) Ph, H (cis) CH,CO, H PhCO, H Ph, H (cis)

2

TABLE 8.

CONTINUED.

H, H €I, H H, H

HO, H EtO, H

NC, H CH,CH(NO,), H H,NCH,, H H, H H, H HO,C, H

HO, Ph Me.0, M e 0 Bu'O, Bu'O -O(CH,) 10Br, Br CH,, H

Ph, H

4

3

Substituent

236-237 181-182 110-113 54-55 127 223-224

78 74 50 75 95 89

498 498 498 495b 495b 498

278

139-141.5

170 487 487 491 505a 52

170 170 170

Ref.

141b

99

86 30 40 41 94 39

60

-

72

Yield (%)

135 dec

105 159.5-1 60.5 60-61.5 106-107 165-166 Oil

76.2-78 107-108 115-122 dec

mp "c

m 0 N

1

L d

dv,

W d

N

d d

d d

mr3 d m

. rr

iD

m

W

0 W

m

m m I or3 d m

0

m

r-

N

d

Ln

d 0 N

rr-

rn N

i N

m

r-

d

m r3

d

d

m r3 W

687

Me,N, H MeO, M e 0 EtO, EtO EtO, EtO. Bu'O, Bu'O EtO, EtO EtO, EtO

C1, H (trans) Ph, H CH,, H Ph, H Ph, €I p-NO,-C,H,, H CF,, H

Substituent

3

CONTINUED.

2

TABLE 8.

4

35 50 45 76 61 54 61

62

88-92

129 156-157 5 3.5-54.5 90-91 70.5-72 113-114 103-105

50 50

53 85

90

72-78

Oil

80-81

Yield (%) . .

mu "C

468a 487 487 487 487 483 483

505a

495b 495b

497

208

473

Ref.

?

E

vl

W

00

m

EtO,C, H

C1, H MeSO,, H Br, Ph

C1, H Br, H C1, H Me,Si, H (EtO),C=CHSO,, H Ph, H

0

m O z

SOZCH,

-O(CH,),OMe,SiO, Ph Br, H

EtO, EtO EtO, EtO -0-(CH,),-0EtO, EtO EtO, EtO EtO, EtO

H, H H, H H. H

93.5-94.5

259-260

166-167

43

93

70

68 53 24

445b

47 3

438

491 493 468a

490

45

117-1 18.5 184

483 487 491 45 2 490 487

31 10 68 95 68

72-74 69-70 117-118.5 97-99 135.5-136.5 55-68

477

13

46.5-48

Four-Membered Sulfur Heterocycles

rrd

m

i

W

m

N

0

10

v)

d d

rn W

N

I

N

0

m '0

W v)

0

d 03 3

m

m

rn W

3

i

i d

rn r(

I

I

I

03

d

0

3

v1

m

r-

m 4

i i

QI

10

m

n

8

% c

3:

O W Z

n

3:

s 6 90

a 5:

s"

a

3: U

n

8

zm

V

0

V

5:

3 3 v)

W

d

m

Iz

m

p'

00

Iz 3

I

3

I

m

p'

m

d

d

i 0

0

3: V

T

0

V

691

cn

p3

u2

I1 CF,C-, CF,

NPh

H,H CH,, H Et. H

H H H

50-55

76

Oil

Oil

93

36 67 85

78

79

20-30 85 72

Yield (%)

85 Oil Oil

64-65 dec.

€1

ferroceny 1 Et n -PI

-

50 (760) 88-90 dec. 123-125 dec.

H. H

H H H

H Ph S-nap hthyl

mp "C or bp "C (mm)

Oil

4

3

Substituents

H

THIETES

H, 13

2

TABLE 9.

563

208

208

505c 208 208

209

209

208,561 209 209

Ref.

tLo Lo

W"

D

Lo d

Lo

D

rd 4

In d Lo

W

Lo

0

OI

Lo Lo

+

m

Lo

In

Lo

W 0

Lo

tW

0

N d

I

m

3 3

693

3

Four-Membered Sulfur Heterocycles

Lo Lo Lo

d

rn

v)

Lo

td

0

m

m

W

Q

;

m

m

3 r-

r-

%

t?

n

$

694

H. H

H, H

H, H

H, H H, H H, H

€1, H

H, H

D,D

H,H

2

TABLE 10.

3 mp "C

120-123 76-77.5 101 5 1 0 3

142-143.5

H H H

H

Me,N Et,N PhN(CH,)

CN-

143-144

-

144-145 96

165-166

H H Ph CH,CH (OMe)

97-98

52-54 48-49 5 1.5-52.5 65-65.5 145- 147 141-142 214-216

H

H H H

€1

H D H

4

H

ferrocenyl H H

H H CH 3 But Ph C6F5 p-naphthyl

Substituent

THIETE 1,l-DIOXIDES Yield (%)

34

33 32 55

37

35 83 65

87

87

96 26 80 98 70 90

593

593

495a 496a 495a

445a

505c 495c 445a

598d

598d

168 280c 158b 207b 207b 598d 598d

Ref.

2

TABLE 10.

Ph

n-Pr

H H H Et

bo2

WCO),

H Ph Ph Me Et CH,

41-94

90

66

80-81

65-66

81 50 76 67 74

41-42 111-112 137-138 dec. 46-47

88-89; 89.5-90.5

48

97 51 24 88 100

92

Yield (%)

99-100

105 60 70-72 139-141 116-117

C1

-

Me0 EtO EtCH(Me)O Br

142-143

mp "C

BU~NHCONH

H

onrJ

W

4

Substituent

3

CONTINUED.

208

480

472,480

495c 495d 498 208 208 598d

620

505b, c

505a

589 607 607 487

593

Ref.

G

5a

7

crl 0

a, 0 N

m

m

m O M ?

'0

m

vl W

m

d

m

N

N

m m

d

d

& A O d

5

d,

C1

M

N

3

w m W V

m

N W W W

M m

d

vlw

d

I

a v, m

m m m o

,-I

W

0

N

N

O d 3 3 I

3

,

3

ssz

a a

,-I

m

*

d

d

a

F

8 n

z

sa

Four-Membered Sulfur Heterocycles

z

N

0 W

m m

3

m

d

m m d

Lo

3

m

W N

cu

‘0

0

oc

st 3

3

3

m

s

W

N

N

d

0

0

m

N

I UI

m

c--

d

I

m

3 0

N Lo

m

N

h

“ \ / C t!

E

; F

C

z; P c

c

698

d

m

r;’

m 3 00

00

m

3 ‘d

U

vl

d d

3 3

vl

W Q\

W

m

d a m

3

d

N

N

0

N

d

3

N

N

8 c

a

s

%6

2 a

699

Four-Membered Sulfur Heterocycles

Lo N W

O

c u m m m ~

W

~

rfNcnddbrW W d W W N W

~

O

WN

rn W

N

d

0 c c 0

u a

Locn

4

m d

cn N d

m

700

w w I d W

mr3 3

1 I Nr-N m r - o 3

3

3

I

Nr4NrC

m m m m W W W W

3 r 4 N *lOm

'

I

L

ii

L"

701

(CH,),C= Ph ,C=

CH3C=Cqc=C-CH=

CH3, CH, Ph, Ph Ph, Ph HOCH,, HOCH, PhCH= p-Me ,NC6 H,CH

CH,=C-, H HO,CCH,, I1 CH3, CH, CH3, H

0

0

H, H

CH,, CH, Ph, Ph CF,, CF, HOCH,, HOCH, H, H H, H

H, H H, H H, H CH,, H

H, H

H, H

y3

4

Substituent

3-THIETANONES

3

TABLE 13.

74

-

8-9

-

697 707 707

28 25 17 Oil 130-131

37.5

113.1-113.9

706 650 702 720 707 720 104

70 85 59

106-8 185-1 87 120-123 (1)

705b

704

252a -

-

-2

-

7 16a 705a 704 704

30 15 1 47

Oil 93.5-95

Ref. 127a

Yield (%)

25

63.5

mp "C or bp "C (mm)

2

E rt

vl

703

Four-Membered Sulfur Heterocycles m

W

9 N 10 W

m d

r-

N

I

I

I

d

I

'0

f

m 0

d

m

m

03 rd

r-

r-

W

N

W

r-

m

r'0

I

I

3:

3:

5

zi-

3 r-

W

d

3

03 v)

W

3

I

N

c a i a

3:

z"

n

I

z

Di

3:

d

3:

6

3:

II

z U 0

-d

u 1

Ill

V

Ill

u

704

0

LL

.

.

L?c u u

1

TABLE 15.

CH=

Substituents

a : k C H -

2

4

3-THIETANONE 1-OXIDES AND 1.1-DIOXIDES

44

232-233dec 230-231 dec

69 51 95 71 55 38

Yield (%)

106-109dec 98-99 (0.4) 218-223 108.5-1 10.5 172-174 108-109 104-105

92-93 dec

mp "C or bp "C (mm)

740

739 709 719c 709 495a 49% 495c 521 521 719b 741

Ref.

2 (CF 3) ,C= (CHJ ,C= H, H H, H H, H

TABLE 16.

3 H, H Ph, Ph CH,CH= (CH,),C= EtO,CCH=

Substituents

METHYLENETHIETANE 1.1-DIOXIDES

4 PCH,OC,H,, H H, H H, H H, H H, H

90

252

254e

652b 216 510 510 510

-

91 89 100 54

214.5-216 82-83 101-102.5 130-132

Ref.

Yield (%)

mp "C 91-97.5

R

5

l i

F

E

1/1

a

a

0 ct

5 3

0

crl

W

0

W

v)

r-

W

m

r-

om10 m l r - m - l 0

1010

N

I

m-l

M

I",

3

W 3

8 8 ci

CI

CI

I

3:

0

0

qg zI

c a

0 0 0 0 0

0

000dO 0

h n

a \ i a:

0 0 0 0

0600

Four-Membered Sulfur Heterocycles r-

0

m

m

00

v)

m

r-

t-

r-

0

W

m

W

rn

s

W

M

I

d

co

II 0

7 08

0

CI v)

0

N

TABLE 1 8 .

1,3-THIAZETIDINES Sub stit uent

2

3

H, H H, H H, H

C6H1,

Ph p-EtOC6H,

4

mp "C or bp "C (mm)

H, H H, H H, H

118-120 180 157-159

Cp

CH,+

Yield (%)

Ref.

-

804a 803a 801a

1s

811a

-

CH, CH,COCH= pCH,C,H,SO,N= CH ,SCON= p€H,C,H,SO,N=

Ph Ph Ph CH,

CH,COCH= H, H Ph, H BU~N=

181-182 15s 142 87-88

74 98 49 62

809 828 832 835a

Ph,PN= PhN=

P*i

PriN= C6H,,N=

Oil 75-76

-

c6H11

55

834 836

88 (12)

76

848

i

TABLE 19.

1.2-OXATHIETANE 2-OXIDES AND 2.2-DIOXIDES

Substituents

2

3

m p "C or bp "C (mm)

4 Ph, Ph CCl,, I1

97-99 (dec.) 98-100

H, H

Cl,FC, C1,FC F, F F, F m3 (C F, l2 0,

709

130-131 -

-

47-48 6 0 (180)

Yield (5%)

Ref.

4s 42

878 86 1

96

922 91 9

~

80 94 67

927 173 903

CICO, ClCO CF,S, CF, PriCS,, R i

co-

ClCO, ClCO CF,S, CF, PriCS ,, Ri

EtO,C, But EtO,C, Ph NC, Ph EtO,C, CH,CO CH,CO, CH,CO

EtO,C, But EtO,C, Ph NC, Ph EtO,C, CH,CO CH,CO, CH,CO

ao-

4

Substituents

1.3-DITHIETANES

2

TABLE 20.

1270

1106 1075 1112

55

30 100 13 79-82 55-56 (10) 145-146

-

360

1073 1066 1070 1111 1111

229

1057b, 1113 1075 1075 1075 1092 1075 1008 1080 1091 1075

Ref.

39 50 30

6

72

23

15 100 53

70 60

Yield (%)

76-100 89-91 128-128.3 125-1 26 165-1 66.5

305-306

-

105-106 47-48 (760) 89-90 (760) 130 (760) 77-77.5 110 (760) 63-64 247-248 128-1 29

mp "C or bp "C (mm)

o c-

0

a o 0

10

N

0

0

m

'm

E

71 1

I 10

d

m

j m r P

C

0

'

0

1

a11 w r oc

3.

1

m

o

L

c

lir

0.0

1

Substituents

TABLE 21.

2 0

-

3

4

1,3-DITHIETANE SULFOXIDES AND SULFONES

134 200 259-262

50.5 (8) 35 231-234

71-73.5 260 dec 141-143 104-105 (760) 89.5

mp "C or bp "C (mm)

1057b, 1113a 1057b, 1113a 1057b, 1113a 1046bb 1132 1132 1046bb 1046bb 1057b, 1113a 1057b, 1113a 1132 1132 1063

36

90 86 15 27 78

-

-

60 45

-

96

-

Ref.

Yield (%)

v)

CD

2

-

2

: g

E

C n

z

(D

a

8

5

$

H

3c

TABLE 22.

tls,

SELENIUM DERIVATIVES m p "C or bp "C (mm)

Yield (%)

Ref.

118-119 (779)

Low

1549,1551

38 (20)

40

1553,1557

58 (10)

50

1554

-

60

1565

154-156

96

1565

-

1565

59.2-60

73

1563

155-158

-

1568

112-1 1 3

81

1574

78-79 (84)

25

1561

93-95

-

1569

89

16

1563

HO

-

713

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Chemistry of Heterocyclic Compounds, Volume42 Edited by Alfred Hassner Copyright 0 1985 by John Wiley & Sons, Ltd.

Author Index Numbers in parenthesis are reference numbers and indicate that the author’s work is referred to although h i d h e r name is not mentioned in the text. Numbers in italics show the pages on which the complete references are listed Ahakumov, G . A , , 34(456), 167 Ahatjoglou, A. A , , 509(531a), 732 Ahbott, F. S . , 449(170), 459(170), 462(170), 491( 170), 492(464,465), 495(464,465), 496(465), 497( 170,498), 502(464,465,498), 503( 170), 504(464), 505(465), 506( 170,464,498), 508(170,498), 53 1(464,498), 532(498), 534(170), 541( 170,498), 544(464), 545(498), 720, 730, 731 Abdalla, S . O., 39(533), 169 Ahdel, N. A. R. O., 63(733), 175 Ahdel-Rahman, M. M. A,, 630(1064), 752 Ahdullahekov, I. M., 88(958), 181 Ahdullaev, F. Z., 123(1226), 189 Abdul-Malik, N. F., 327(189), 349 Abe, F., 611(872c), 744 Abe, M., 652( l345), 761 Ahe, T., 634(1140,1142), 754 Ahel, E. W., 465(298), 724 Ahenhaim. D., 78(885), 101(1052), 102(1052), 103( 1054,1055), 104( 1052,1054a, 1055,1059), 105(1052), 113(1102,1103), 179, 184, 185 Abou-Gharbia, M. A,, 342(163), 348 Abraham, D. J., 492(432,487), 495(487), 729, 73I Abraham, R. J., 440(63), 716 Ahrahamsson, S . , 476(382), 727 Ahramov, A. F., 92(980), 93(1001), 182 Abramovitch, R. A,, 499(515), 731 Abramsky, W., 333(205), 350 Accrombessi, G. C., 84(938), 86(938), 87(938), I80 Acheson, R. M., 512(540), 515(540), 733 Achini, R., 92(994), 182 Acker, R. D., 110(1084,1085), 184 Adam, W., 24(225), 37(496), 159. 168, 352(1,2), 354(1 lh,12), 355(30h,31,96,158), 356(9 1 ,I%), 357( 125,158), 358(158), 360(125,1J8), 361(126), 362(35,92,93), 363(92,93), 364(30), 366( 126), 369( 1 lh,12b,42,99), 371(21), 372(26),

373(21,30), 374(21,31), 375(12), 377(12b,35), 378(12h.31), 379(30), 380(30), 381(1 lb,lZa,h), 382(2a,b,30), 386(12a,57,57e,f), 388(91,124), 389( 1 lb,12h,74,93), 390(2b,57f, 126), 391(96,123), 392(30h,92), 395(57d), 396(68,69a,h), 397(70), 398(69), 403(83,84), 407(11b), 409(96), 413(57e), 414(57,116), 415(1 Ih,l I6,122a,h,123), 416(1 I), 4 17( 1 1,116), 4 18(37), 420( 142), 42 1( 144), 422, 423, 424, 425, 426, 427, 428, 429 Adams, D. L., 338( 143), 348 Adams, E. P., 446( 145), 449( 145), 457( 145), 468(145), 511(145), 719 Adams, J., 209(63), 238(63), 246(63), 272 Adaway, T., 458(262), 473(262), 51 1(262), 723 Addor, R. W., 639(1210,1211,1215,1223), 640( 121 1,1215,1223,1227a, 1229), 757, 758 Adinolfi, M., 44(570), 170 Adiwidjaja, G., 562(683b,c), 564(683h,c), 602(810), 738, 742, 765 Adkins, R. R., 658(1393), 659(1393), 763 Adler, A,, 38(527), 169 Adler, B., 520(579), 529(579), 628(1018h,c), 629(1018b,c), 734, 750 Adline, J., 232(173), 275 Adolph, H., 452(206), 468(206), 492(206,431), 495(206,431), 498(206), 721, 729 Aerov, A. F., 443( 1lo), 718 Agaev, F. Kh., SS(958), 181 Agafonov, S . A., 614(908), 615(908), 616(908), 654(908), 746 Agarwal, S. C . , 216(98), 230(153,154), 239(98), 273, 274 Agawa, T., 285(44,45), 289(44,45), 290(44,45), 303(70), 304(70), 326(91), 339(91), 341(45,70,161), 342(164), 344, 345, 346, 348, 588(745), 589(752c), 590(745,758a), 591(745,758a), 652(752c,1345-1347), 658(1346a), 740, 761 Agdeppa, D. A., 66(758), 175 Agosta, W. C., 138(1358,1359), 193

769

770

Author Index

Agrawal, K. C., 96(1016), 183 Aharon-Shalom, E., 672(1571), 768 Ahmad, F., 21(195), 158 Ahmad, I., 29(285-287,289), 161 Ahrnetovic, D., 550(643), 556(643), 736 Ahuja, H. S., 465(300), 724 Airoldi, G., 612(888), 616(888), 745 Aithie, G. C . M., 63(731), 175 Aizawa, T., 206(43), 207(43), 271 Akabori, S., 47(596), 171 Akaboshi, S . , 53(644), 172 Akagi, H., 256(270), 259(270), 262(270), 263(270), 264(332), 269(375), 278, 280, 282 Akamatsu, Y., 269(371), 281 Akasaki, Y., 453(237,238), 469(237,238), 722 Akazawa, T., 644(1312), 646(1312), 760 Akhmedov, I. M., 92(979), 182 Akhrem, A . A , , 27(262), 30(300), 34(442), 61(709), 77(709), 78(709), 160. 161. 166, 174 Akhtar, M. N., 202(23), 204(23), 205(36), 214(36), 219(36), 220(115), 221(23,115) 222(23), 233(36), 246( 1 IS), 262(115), 264(23), 266( 115), 271, 273, 326( 192), 349, 463(286b), 481(286b), 724 Akiba, K . , 41 1(45), 425, 606(834), 743 Akimova, T. I., 97(1024), 183 Akishin, P. A , , 440(66-69), 716, 717 Akiyama, F., 58(676), 173 Aktaev, N. P., 614(902), 616(902), 746 Akutagawa, S., 72(806,808,810,814), 177 Alagona, G., 118(1161), 187 Albanbauer, J., 609(847-849), 744 Albanov, A. I., 114(1113), 185, 623(981), 624(981), 748 Albeck, M., 672(1570,1571), 768 Albini, A , , 339(210), 350 Al’bitskaya, V. M., 121(1197), 151(1455), 188, 195 Albizati, K . , 637(1159), 755 Albone, E. S . , 438(4c), 714 Alder, A. P., 140(1368,1371), 193 Aldrich, P. E., 530(589), 735 Alekseev, A. A , , 653(1362,1364), 762 Alekseeva, T. A , , 125(1240), 189 Alexakis, A,, 100(1037), 107(1037), 183 Alexander, D. C., 24(242), 95(1014), 159, 183 Alferova, I. K., 31(355), 163 Ali, M. E., 96(1017), 183 Ali, S . M., 10(77), 155 All, J. N., 639(1188), 756 Allan, G. G., 29(277,278,280), 161 Allen, D. G., 54(652), 173 Allen, J. R., 259(307), 279

Allenrnark, S. , 443(125a), 462(279), 480(125a,279), 491(279), 719, 723 Allinger, N. L., 6(26), 153, 439(20), 715 Allison, K . , 30(314), I62 Almqvist, S . O., 672(1568), 768 Alois, H., 630(1089), 635(1089), 638(1089), 640(1089), 753 Alper, H., 74(844), 178 Alphen, J. V., 652(1349), 761 Alscher, A., 438( IOe), 714 Altenbach, H. J., 209(64), 224(131-133,136,139,141), 236(64), 239(132), 240(131,133), 248(133), 272, 274 Alterova, I. K., 39(531), 169 Althans, J. R., 232(174), 259(174), 275 Alzerreca, A , , 354(12b), 369(12b), 375(12b), 377(12b), 381(12b), 389(12b), 423 Amagasa, M., 83(932), 180 Ambartsurnyan, G. B., 92(977), 181 Ambler, A. P., 9, 9(49), 154 Ambrosius, K . , 672(1575), 768 Amin, J. H., 338(147), 348 Amirzadeh-asl, D., 657(1384), 762 Amman, A , , 512(542,544), 525(542,544), 733 Amos, R. A., 109(1080), 184 Anastassiou, A. G., 130(1306), 191, 249(233), 277 Anazawa, A,, 69(793), 176 Anclaux, A , , 54(658), 173 Andam, W., 414(11), 423 Anderegg, J . H., 356(106a), 362(106c), 364( 106b), 400(78,82), 408(82), 412(106), 426, 427 Andersen, K. K . , 439(55b,56c), 440(56c), 445(139), 446(139), 452(139), 461(139), 463(139), 465(303), 476(385), 477(55b,56c,139), 478(55b,56c), 479( 139), 480(139), 482(139), 484(139,385), 487(139), 489(55b), 490(55b,SSc), 491( 139), 498( 139), 505(139), 508(530), 509(139,530b), 5 1 1(139), 526(530b), 635(55b), 716, 719, 724, 727, 732 Anderson, A. W., 614(909), 619(909a), 746 Anderson, D. J., 459(265), 51 1(265), 569(265), 723 Anderson, E. L., 39(538), 169 Anderson, J. E., 395(64), 425 Anderson, M. W., 267(356), 281 Anderson, R. J., 107(1071), 184 Anderson, W. K., 16(155), 157 Ando, A,, 516(563), 522(563), 733 Ando, W., 372(26c), 424, 461(271a), 474(27 la), 576(7 16c), 577(7 16c), 582(7 16c), 723, 739

Author Index Andre, M. J., 199(16), 270 Andreeti, G. D., 492(467), 495(467), 730 Andreetti, G. D., 297(63), 317(63b), 320(63h), 345, 489(41 Xa,419,420,423a,b), 589(75 l ) , 612(751c), 614(751c), 729, 740 Andreev, N. A , , 662(1437), 663( 1443,1445,1446), 764 Andrejevic, V., 79(888), 179 Andrenos, L. J., 58(674), 173 Andrews, G. C., 114( 11 12a), 185 Andrews, M. A , , 34(460b), 36(460b), 167 Andronov, E. A , , 465(297,299a), 484(401), 724, 728 Andronova, L. G., 30(324), 162 Andruszkiewicz, Ch. A,, J r . , 137(1356), 192 Anello, L. G., 630(1078h,1103b), 632(1078h,1121d), 752, 753, 754 Anet, F. A. L., 12(109,113), 13(109,1lX,119), 156 Angerbauer, R., 227( 145), 274 Angier, R. B., 28(272), 160 Angyal, C. L., 13(131), 156 Annesini, M. C., 92(988), 182 Annis, G. D., 89(966), 131(966), 131(1313), 181, 191 Annuniiata, R., 28(271a), 50(616), 160, 172 Ansari, A. A , , 21(195), 158 Ansari, H. R., 42(553), 170 Anteunis, M., 443( 112a), 718 Antonova, N. D., 492(449), 495(449), 496(449), 505(449,450), 730 Antonova, T. N., 73(822), 177 Antoun, H., 333(124), 347 Ao, M . S ., 599(800a), 742 Aoki, M., 614(913), 616(913), 618(913), 746 Aoki, O., 590(758a), 591(758a), 740 Aoki, T., 83(932), 180 Aoyama, H., 630(1090,1093), 632(1090,1093), 753 Aoyama, T., 41 1(45), 425 Aparicio, F. J. L., 633(1134b), 754 Apella, E., 260(314,319), 279 Apparu, M., 63(732), 175 Appel, R., 88(954), 181, 657(1386,1387,1392), 762, 763 Appelman, E. H., 233(181), 275 Applequist, D. E., 498(509), 731 Apsimon, J. W., 69(794), 70(797), 71(797), 176 Arackal, T. J., 535(607), 546(607), 583(607), 585(607), 735 Arakawa, H., 30(299), 32(299,395), 161. 165 Arakawa, M . , 61 1(872c), 744 Arakawa, S . , 134(1337,1338), 192

77 1

Aramaki, M., 660(1408,1410), 763 Aranda, G., 10(78), 14(141), 155, 157 Arata, K . , 72(805-815), 177 Aratani, M., 16(153), 157 Arbuzov, B. A,, 9(54), 20(188), 79(896), 154, 158, 179, 439(26a,b,f,34), 440(34), 442(26a,f), 443(26f), 449( 172- l75,177,178,184a), 459( 177,268), 462(26a), 465(305), 466(268), 474( 177,178), 475(26a,177,268,375,377a,b), 479(26a,f), 480(26a), 491(26a,f), 51 1(268), 622(975), 715, 720, 723, 724, 727 Archer, W. L., 438(13e), 714 Arcoleo, J. P., 68(771), 118(1167), 122(1167), 176, 187 Ardecy, R., 327(191), 349 Ardissone, M., 610(857), 744 Ardon, R., 44(574), 170 Arduengo, A. J., 631(1115), 754 Arens, J. F., 99(1028), 183 Arhart, R. J., 42(556), 170 Arias, L. A,, 362(93), 363(93), 389(93), 427 Arihara, M., 46(591), 171 Aristova, N. E., 492(496), 506(496a), 534(496a), 731 Armarego, W. L. F., 3(6), 14(6), 15(6), 41(6), 47(6), 61(6), 77(6), 87(6), 115(6), 153 Armstrong, R. N., 204(34), 218(34), 256(34,264-266,268), 260(3 15,319), 26 1(268,27 1,3 15), 262(34,265,3 15), 263(264), 266(266,271,343), 271, 278, 280 Arnaud, P., X(41), 10(75), 12(111), 154, 155, 156 Arnold, A. P., 670(1554c), 767 Arnold, D. R., 142(1398), 194 Aron, A. J., 516(566a), 734 Arrington, C. A,, 636(1151), 755 Arrowsmith, J. E., 349(186), 324 Arshinova, R. P., 622(974-976), 748 Artmev, E. T., 398(76), 426 Arutyunyan, Kh. A ,, 125(1243), 189 Arya, V. P., 492(461), 730 Arzoumanian, H., 36(482,485), 168 Asahara, T., 16(158), 157 Asai, Y . , 458(2642), 472(264), 51 1(264d), 723 Ashby, E. C., 79(887,894), 179 Ashley, K. R . , 77(864), 178 Ashurov, D. A., 27(264,265), 160, 670(1554a), 76 7 Ashurst, S. W., 267(357), 281 Ashworth, R. W., 74(845), 178, 242(208), 254(208), 276 Askew, W. B., 630(1062), 752

772

Author Index

Aslam, M., 492(496), 494(496c), 495(496), 655(496c), 731 Asrnus, K. D., 464(294), 724 Asratyan, G. V., 120(1184), 188 Aston, J. L., 639(1190), 756 Asveld, E. W. H., 359(160), 361(160), 429 Atavin, A. S., 445(142), 719 Atkins, G. M., Jr., 594(779-781), 597(781), 741 Atkinson, A. M., 131(1313), 191 Audier, H. E., 14(141), 157 Aue, D. A , , 286(49a,b), 287(49a,b), 331(49), 345 Auge, W., 210(72), 272 Augustin, M., 643(1270), 647(1270), 759 Augusto, O., 421(146,153), 428, 429 Aulakh, G. S., 39(535), 169 Aumann, R., 254(249), 277 Auret, B. J., 258(296), 279 Aurich, H. G., 310(170), 348 Autrey, R. L., 599(800c), 742 Autrup, H., 258(288), 279 Avakyan, T. T., 32(383,397), 164, 165 Averbeck, H., 254(249), 277 Avetisov, A . K., 34(466,467), 36(466,467), 167 Avirah, T. K., 569(701), 738 Avnir, D., 216(93), 272 Avny, Y., 473(340), 726 Avrarnenko, V. I., 92(981), 182 Avril, J. L., 92(995), 182 Awad, S . B., 326(193), 327(189,193), 349, 517(566f), 529(566f), 734 Awerbouch, O., 24(212), 159 Axon, B. W., 589(755d), 740 Ayad, K. N., 446(145), 449(145), 457(145), 468(145), 511(145), 719 Ayame, A , , 34(466e,470), 36(466e,470), 167 Aycard, J. P., 17(169), 157 Aylett, B. J., 668(1519), 767 Ayral-Kaloustian, S., 138(1358,1359), 193 Azman, A., 17(168), 157, 307(22), 344 Baaij, J. P. B., 564(691a), 566(691a), 568(691a), 738 Baake, H., 22(208), 158 Baba, H., 634(1142), 754 Baba, S., 113(1104), 185 Babb, D. P., 634(1139a), 754 Babiarz, J. E., 545(618), 735 Babkina, E. I., 662(1437), 663(1443), 764 Baboulene, M., 125(1257), 190 Babst, H., 205(41), 211(41), 271 Baburina, V. A , , 669(1539,1541), 767

Baccouche, M., 34(459), 36(459,485), 167, 168 Bach, R. D., 17(167), 25(244), 66(759,760), 157. 159, 175 Bachhawat, J. M., 22(204), 158 Back, T. G., 620(949), 747 Backer, H. J., 444( 116,129- 13I), 445( 130), 457( 116,129-131,258), 462(116,129-13 1,258), 463( 129), 464( 129,13 1,258), 465( 1 16,129- 131), 480( 1 16,129- 13l), 481( 129), 482( 129,258), 483( 129,258), 484( 1 16,129,131,258), 491( 1 16,129,130), 508(130), 510(129), 511(116,129,131), 5 12( 129,13 l ) , 670( 1552), 67 I ( 1552), 718, 719, 723, 767 Backstrom, H., 550(646b), 631(646b), 736 Backvall, J. E., 92(990), 182 Backx, C., 34(466a,b), 36(466a,b), 167 Bacon. C. C., 508(529a), 732 Badcock, C. C., 612(889), 617(889), 745 Badea, F., 61(711), 174 Bader, J., 642(1280), 646(1280), 759 Baer, T., 469(319c), 725 Baganz, H., 593(770), 741 Bagirov, R. A., 123(1226), 189 Bahn, H., 647(1316), 760 Babnemann, D., 464(294), 724 Baiker, A,, 34(473), 36(473), 167 Bailey, C. W., 439(41b), 440(41b), 441(41b), 442(41b), 443(41b), 716 Bailey, P. S., Jr., 535(606), 546(606), 583(606), 735 Baird, W. M., 267(349), 281 Bak, B., 672(1569), 768 Bak, C., 630(1078e), 632(1078e), 752 Bakaleinik, G. A,, 20(188), 158 Baker, A. D., 14(147), 157 Baker, C., 14(146), 157 Baker, R., 103(1056), I84 Baker, R. L., 229(148), 274 Baker, T. N., 31(337), 32(367), 163, I64 Baker, W., 653(1359), 762 Bakhireva, S . I., 465(299a), 724 Bakhmutov, Yu. L., 43(567), 170 Bakker, B. H., 45(579), 170 Bakker, C. G., 91(974), I81 Balaban, A. T., 514(560b), 529(560b), 733 Balani, S. K., 221(118), 222(33), 264(33,118,328), 265(118), 271, 273, 280 Balanson, R. D., 601(803b), 742 Balasubramanian, K., 326(92), 346 Balbach, B., 636(1155), 755 Balch, A. L., 629(1036), 751 Balci, B., 24(225), 159

Author Index Balci, E., 209(64), 236(64), 272 Balci, M., 388(124), 428 Baldwin, J . E., 248(232), 277, 64l( 1249,1250,1252), 758 Ball, J. S., 439(41b), 440(41b), 441(41b), 442(41b), 443(41b), 469(311), 716, 725 Ball, M., 77(861), 79(892), 178, 179 Balog, I. M., 670(1555), 768 Balquist, J. M., 491(430), 497(503), 499(503), 536(61 I ) , 540(61 I), 541(61 l), 542(503), 729, 731, 735

Balsamo, A,, 117(1135-1137), 186 Bal'shakova, S. A , , 623(984d), 749 Baltagi, F., 439(28b), 715 Baltrop, J. A , , 135(1343), 192 Balzani, V., 415(120), 427 Ban, S., 621(956), 748 Ban, T., 247(227), 250(234), 264(227), 277 Banavali, 215(273), 273 Banerjee, D., 90(970), 181 Banister, A . J., 669(1546), 767 Banko, K., 49(607), 171 Banks, D. B., 62(725), 175 Bannard, R. A. B., 117(1148,1149), 118(1148), 186

Bannister, B., 457(259), 509(259), 51 1(259), 723

Bansal, R. K., 210(70), 272 Bao, L. Q., 131(1321), 192 Bapat, J. B., 337(137), 348 Baranne-Lafont, J., 229( 149), 274 Baranov, N. N., 24(236), 159 Barbarella, G., 456(255), 509(255), 51 1(255), 723

Barclay, G. A., 13(131), 156 Bardon, J . , 16(156), 157 Barili, B. L., 122(1212), 188 Barlow, J. H., 476(381), 477(381), 480(381), 492(381), 630(1047c), 635(1047c), 727, 751 Barltrop, J. A., 439(41c), 440(41c), 441(41c), 716

Barnett, G., 381(45b), 41 1(45b), 425 Barnikow, G., 642(1297), 645(1297), 750 Baronawski, A., 370(20), 424 Barr, J., 674(1579-1581), 768 Barrau, J., 96(1018), 183. 624(986b), 749 Barrau, J. B., 624(986a), 749 Barrett, J., 630(1059b), 752 Barrone, G., 44(570), 170 Bartha, B., 120(1188), 188 Bartholomew, J. T., 439(56b), 440(56b), 477(56b), 478(56b), 489(56b), 490(56b), 531(56b), 716

113

Bartkowiak, F., 46(588), 171 Bartleson, J. D., 661(1411), 763 Bartlett, P. A., 15(8b), 153 Bartlett, P. C., 16(161), 157 Bartlett, P. D., 37(502,511,512), 40(546). 168, 169, 170, 352(1), 360(134c), 361(39e,166), 362(166), 377(36), 379(39e), 382(39e), 413( 109), 41 8( 134a,b,c), 420( 139- l41), 423, 424, 427, 428, 429

Bartok, M., 3(8), 15(8), 73(824,828,829,831,833-835), 79(8), 83(929,930), 84(831), 87(834,835,948), 153, 177, 180, 181 Barton, D., 3(7), 153 Barton, D. H. R., 64(735), 175, 626(1009), 750 Barton, T. D., 623(983,984a), 748 Barton, T. J., 254(245), 277 Basch, H., 14(146), 157 Bashkatova, S . T., 473(355), 726 Basselier, J . , 356(161), 429 Basselier, J. J., 368(173a,b), 429 Bats, J. P., 89(964a), 181 Battaglia, A,, 563(686-688), 564(689,690), 566(687,689), 589(751c), 606(836), 612(751c), 614(751c), 738, 740, 743 Battiste, M. A,, 542(615), 735 Battistini, C., 13(134), 117(1136-1140,1141), 118(1171), 119(1139), 156, 186, 187 Batyrkanova, B., 662( 1434), 663(1434), 764 Bauch, H. G., 562(683b,c), 564(683b,c), 738 Bauder, A., 439(29b), 715 Baudy, M., 94(1009), 182 Bauer, D., 139(1361), 140(1367), 193 Bauer, S. H., 470(325), 725 Baughman, M., 118(1157), 187 Baukov, Y. I . , 492(452,493), 495(452,493), 506(526b), 534(526b), 730, 731, 732 Baulder, M., 663(1442), 764 Bauman, M. S . , 413(1 lo), 427 Baumann, E., 632(1118b), 754 Baumann, M., 46(585), 171 Baumgartel, H., 8(38), 154 Baumstark, A. L., 33(423a), 40(546), 166, 170, 3 5 3 127), 357( 127), 358(90b), 360(90a), 361(166), 362(166), 387(86), 389(127), 391(90,125), 392(127), 403(85), 412(86), 4 13(90,109), 418( 134a,b,d, 135), 420(139,141), 426, 427, 428, 429 Bavry, R. H., 535(606), 546(606), 583(606), 735

Baxter, S . L., 664(1471), 765 Bayanova, N. N., 30(324), 162 Bayomi, S. M., 53(641), 172

114

Author Index

Bazant, V., 34(475), 36(475), 168 Bazzi, A. A , , 439(55b,56d), 440(56d), 477(55b,56d), 478(55b,56d), 489(55b,423c), 490(55b,56d), 625(988a), 630(55b), 635(55b,988a), 716. 729, 749 Beames, D. J . , 108(1077), 184 Bean, R. A,, 639(1170), 755 Beatson, R . P., 492(459), 494(459), 495(459), 730 Beauchamp, J. L., 8(37), 154 Bechara, E. J. H., 358(90b), 359(90b), 360(90a), 391(90h), 398(77), 413(90b), 421(145), 426, 428 Becherer, J., 37(512), 169 Bechgaard, K., 625(995b), 749 Bech, H., 630(1061), 752 Beck, L., 34(474), 36(474), 39(474), 167 Becke, F., 512(541), 517(541), 733 Becke-Goehring, M., 657( 1388-1390), 659( 1403), 762, 763 Becker, H. D., 38(527), 169 Becker, M., 55(644), 173 Becker, R. S . , 141(1379), 142(1384), 193 Beckerbauer, R., 614(906), 616(906), 746 Beckett, A. H., 297(61), 298(61), 345 Bednarski, T. M., 40(541), 50(541), 169 Beecken, H., 589(750), 591(750), 595(750), 740 Beerman, D., 209(64), 236(64), 272 Beeson, E. L., 439(29a), 715 Beg, M. A , , 29(285-287,289), 61 Begland, R. W., 492(481), 503(481), 532(481), 730 Begot, B., 312(172), 333(172), 348 Behan, J. M., 60(693), 174 Beheshti, I., 364(87a,170), 365(87a), 367(87a), 407(87), 426, 429 Behn, N.S . , 12(110), 24(239), 156, 159 Behnke, J., 61 1(864i), 619(864i), 744 Behr, H., 604(822e), 606(822e), 630(1072), 742, 752 Behringer, H., 516(564a), 521(564b), 649(1335), 733, 761 Beisiegel, E., 599(800b), 742 Bekker, R. A , , 51(619), 80(900), 120(1184), I 72, I 79, I88 Beland, F. A , , 241(207), 276 Belaventzev, M. A , , 61 1(882), 614(899-901), 6 15(899,926a,b), 6 16(926a), 617(882,934-937), 618(937-941), 619(934,935), 653(1636), 745, 746, 747, 762 Belen’kii, G. G., 672(1566), 768 Bell, A . N., 630(1102b), 637(1102b), 753 Bell, R . , 587(743b), 587

Bellamy, F., 284(6), 331(6), 339(6), 343 Bellamy, L. S., 9(58), 154 Bellasio, E., 593(774,775,778), 595(774,775,789), 596(774,789), 599(789), 741 Bellucci, G., 117(1142,1143), 122(1212), 186, 188, 260(318), 280 Belnika, B. A,, Jr., 307(166), 348 Belogai, V. D., 43(567), 170 Belousov, V. M., 32(391), 164 Belskii, 1. F., 83(929), 180 Belyaev, V. A,, 30(317), 32(396,403), 162, 165, 398(73), 426 Belzecki, C., 286(47), 288(47), 291(57), 292(47,57), 293(47), 3 16(57,74), 3 17(47,68), 320(47), 333(205), 345, 350 Benati, L., 520(581c), 598(792), 734, 741 Bend, J. R., 245(221,224), 246(224), 266(221,224,341), 276, 280 Bender, S. L., 672(1559), 768 Benedek, I., 151(1462), 195 Benedetti, F., 492(455), 502(455), 730 Benedict, J. T., 122(1213), 188 Benitz, F. Z., 633(1134b), 754 Bennett, C. R., 630(1056), 752 Bennett, D., 127(1287), 191 Bennett, G . M., 457(256), 511(256), 723 Bennett, P., 53(643), 172 Bensel, N., 90(971), 91(973), 181 Benseler, E., 660( 1404), 763 Benson, R. C., 443(108a), 718 Benson, R. E., 146(1424), 194 Bentley, P., 260(310), 279 Benz, W., 604(821), 742 Ben-Zvi, Z., 245(224), 246(224), 266(224), 276 Beranek, J., 34(475), 36(475), I68 Berchtold, G. A , , 62(724), 74(845), 175, 178, 205(37,38), 206(37,38,44-47,52,56), 207(37,56,59,60), 208(52,56), 209(37,38,44), 21 1(37,38,44), 224(138), 231(38,44,56), 235(56,59,60,191), 236(37,38,44,47,191), 237(37,38,44-47,191), 242(40,90,208), 243(40,21 l), 244(40,21 I), 245(21 I), 247(37,40), 248( 138,230), 254(40,208), 271, 272, 274, 275, 276, 277, 544(661,662), 57 l(7 14-7 16a), 575(715,7 16a), 630(714,1091,1092), 737, 739, 753 Bercin, E., 604(822f,g), 606(822f), 742 Berenfeld, V. M., 398(76), 426 Berenjian, N., 625(995a), 749 Berezin, G . H., 530(589), 735 Berg, C., 6721569). 768 Berge, J. M., 10(77), I55

Author Index Bcrger, S., 199(8,13), 210(75), 212(75), 270 Bergman, H., 214(78), 272 Bergman, J., 578(728,729,731d), 672(1570), 739, 768 Bergmann, E., 632(1 IZOc), 754 Bergmann, E. D., 121(1199), 188, 465(307a), 724 Bergmann, W., 353(9), 423 Bergreen, H., 642(1283), 644(1283), 759 Bergson, G., 445(141), 472(141a), 541(141a), 625(1000,1001), 626(1001), 719, 749 Bergstrom, D. E., 469(323), 725 Berjersherger van Henegouwen, G. M. J., 309(208), 350 Berman, M., 450(196d), 456(196d), 471(196d), 554( l96d), 721 Bernardi, F., 514(560a), 529(560a), 563(688), 733, 738 Bernardi, G. C., 612(890a,h), 615(890a,b), 745 Bernardon, C., 113(1 102), 185 Bernath, G., 124(1230), 189 Berniaz, A . F., 629(1044), 751 Berry, M., 59(683), 173 Berse, C., 121(1193), 188 Berthelot, J., 362(168), 429 Bcrti, G., 3(4), 11(80), 17(4), 25(4), 41(4), 47(4), 51(4), 52(4), 56(4), 70(796), 71(796), 90(796), 117(1133,1137,1141,1142,1144,1145). 124(1231), 153, 176, 186. 189, 260(318), 280 Bertini, F., 55(662), 59(677), 173 Bertolasi, V., 562(683a), 563(683a), 564(683a), 738 Bertoniere, N. R., 127(1282), 131(1282), 132(1282), 191 Bcrtrand, M., 24(222), 82(908), 106(1066), 159, 179, 184 Bessikre, Y., 20(185), 158 Bessikre-Chrktien, Y., 27(266), 82(913,914), 160, 180 Best, L. R., 667(1504), 766 Bestmann, H . J., 22(198), 158, 519(568), 525(568), 551(655a,h), 561(568,655a,h), 562(568), 564(655a,b,691), 568(655h), 578(691b), 579(655h), 734, 737, 738 Betteridge, D., 14(147), 157, 642(1254a), 759 Beugelman, R., 129(1296), 191 Bevan, J. W., 477(386,387a,c), 727 Beyer, H., 629(1047a,b), 638(1047a,b), 751 Bezjak, A , , 548(628a), 736 Bhacca, N. S . , 143(1400), 144(1406a), 194, 215(94), 216(94), 239(94), 273 Bhadhhade, M. M., 516(565c), 734 Bhatia, A . B., 266(342), 280

775

Bhatt, T. S., 214(79), 272 Bhattacharjee, G., 331(199), 349 Bhattacharjya, A . K., 516(566a), 520(581b), 576(581b), 577(581h), 734 Bhattacharya, A. K . , 639(1192), 756 Bhattacharyya, A. A,, 658(1393), 659( 1393), 660(1406), 669(1393), 763 Bhaumik, M. L., 389(74), 426 Bianchi, R . , 57(673), 173 Bianchini, R., 1 l7( 1143), 186 Bienne, M. J., 123(1215), 189 Biezais, A., 445(141), 472(141a), 540(141a), 719 Biggs, J., 117(1122-1125), 186 Bigot, B., 7(35), 145(35,1409), 154, 194 Bikbulatova, G . Sh., 121(1203), 188 Bikeev, Sh. S., 19(180), 158 Billmers, R., 293(58c), 294(58c), 295(58c), 345 Billmers, R . L., 517(566f), 529(566f), 734 Biloski, A. J., 33(424c), 166 Binder, H., 656(1371,1372), 658(1394), 663(1452h), 666(1372,1373), 762, 763, 765 Birch, S . F., 447(150), 473(150), 474(150), 491(150), 719 Bird, C. W., 68(777), 176 Birkner, C., 438(10e), 714 Birum, G. H., 551(655c), 556(655c), 561(655c), 566(655c), 642(1265), 737, 759 Biscar, J. P., 438(5c), 469(5c), 714 Biscarini, P., 440(62), 480(392a), 489(62), 716, 728 Biskup, M., 223(130), 274 Bisnette, M. B., 629(1028b), 750 Bissig. P., 97(1020), 183 Bjerre, C., 672(1569), 768 Bjorgo, J., 287(51), 297(66), 298(66), 301(66), 315(51,66,73), 320(66), 321(51,73), 333(73), 345 Black, D. St. C., 285(41,46), 288(46), 296(46), 298(41), 299(41), 31 1(35), 327(41), 331(46), 337(137), 340(157-159), 344, 348 Black, S . D., 256(258), 277 Blackett, B. N., 66(747-751), 175 Blackman, N. A., 285(46), 288(46), 296(46), 311(35), 331(46), 340(158,159), 344, 348 Blackwell, C. S. , 569(700), 738 Blackwell, D. S . L., 609(856a), 630(1081), 744, 752 Blackwell, J. P., 488(414), 728 Bladon, P., 447(154), 719 Blagodatskikh, S. A,, 24(235), 159 Blair, A. S . , 442(102a), 718 Blair, E. A . , 473(337,337h), 474(337b,c), 726

776

Author Index

Blanc, A,, 36(482), 168 Blandina, L. A,, 83(934), 180 Blasche, J., 647(1330), 761 Blatter, H. M . , 488(410), 495(410), 530(410,590-592), 535(410,591), 540(591), 728, 735 Bledsoe, J. O., 72(813), 177 Bleisch, S . , 598(794-796), 741 Bleland, F. A., 245(222), 276 Blick, K. E., 630(1056), 752 Blidner, B. B., 524(584a), 734 Blitz, H., 353(4), 423 Bliznyuk, N. K . , 661(1416,1417), 662(1416), 663(1416,1417), 763 Blobstein, S. H., 267(350), 281 Block, E., 437(2c), 439(55b,56d), 440(56d), 443(2c), 477(55h), 478(55h), 484(402a), 489(55b,423c), 490(55b,56d), 51 1(2c), 575(723), 577(723), 625(988a,b), 630(55h, 105 1,1057h), 63 1( 1057b, 11 13a), 632(1057h), 633(402a,1057b,1113a), 635(556,988a,b, 1057b,1 113h), 636(402a,1057h,1149-1151), 714, 716, 728, 729, 739, 749, 751, 752, 753, 755 Block, F., 477(56d), 478(56d), 716 Blomstrorn, D. C., 625(999a), 626(999a,1003), 627(999a, 1012), 628(999a), 629(999a, 1012), 749, 750 Bloodworth, A. J., 421(143), 428 Blount, J. F., 327(187), 349, 604(821), 742 Bluhm, A. L., 339(168), 348 Blum, J . , 74(840-843), 87(853), 178, 181, 216(93,97), 244(97,214), 272, 273, 276 Blum, S., 214(77), 215(77), 216(77), 272 Blumfield, A. E., 473(334), 725 Bly, R. S ., 52(632), 172 Blymberg, E. A,, 15(151a), 34(151a), 157 Blyumberg, E. A,, 38(521,522), 169 Boar, R. B., 626(1009), 750 Boatright, A , , 639(1201), 757 Boberg, F., 642(1302), 645(1302), 646(1302), 760 Bobolev, A. V., 36(480), 168 Bobylev, B., 32(376,377,405), 164, 165 Bohyleva, L. I., 32(376,377), 164 Bocard, C., 34(452), 36(452), 167 Bocelli, G., 297(63), 317(63h), 320(63h), 345, 489(418a,419,420,423a), 492(467), 495(467), 730, 767 Bochkarev, M. N., 668(1525), 767 Bock, H., 514(560c), 515(560c), 628( 1019,1019d), 630( 1057b), 63 I ( 1057b), 632(1057h,l121c), 633(1057b), 635(1057b),

636(1057h,1121c,1149,1l50), 733, 752, 754, 755 Bodot, H., 17(169), 157 Bodrikov, I . V., 450(187), 721 Bodwell, J . R., 521(582h), 524(584h), 527(582h), 734 Boechrnan, R. R., Jr., 68(775), 176 Boeckman, R. K., Jr., 63(726), 175 Boehlert, C., 266(343), 280 Boekelheide, V., 517(566d), 734 Boelsrna, G. H., 68(778), 176 Boerger, M., 569(702), 738 Boerma, J. A., 509(535,536a), 51 1(536a), 732 Boeva, R., 31(358), 31(359), 125(1254,1255), 163, 190 Bogajian, C., 66(758), 175 Bogan, D. J., 37(510), 168, 372(24a,b), 382(24b), 412(24b), 424 Bogan, D. L., 386(57), 425 Bogatskii, A. V., 447(160), 720 Bogdanowicz, M. J . , 53(635,636), 172 Boggs, J. C . , 439(23h), 630(23b), 715 Boggs, J. E., 477(387c), 727 Bogucka-Ledochowska, M., 302(68), 3 17(68,176), 345, 349 Bohen, J. M., 589(754), 591(754), 740 Bohlmann, F., 569(697,698a-c), 571(698b), 574(697,698a,h), 577(697-698~), 579(697,698a), 581(697), 738 Bohme, B., 631(1113c), 632(1116,1117), 640(1113c), 642(1275), 643(1275), 644(1275), 753, 754, 759 Bohn, I., 647(1317,1329), 760, 761 Bohn, R. K., 439(16h), 715 Boie, I., 625(994c), 666(1491), 749, 766 Boigegrian, R., 41(550,551), 56(550,551), 170 Boireau, G., 101(1052), 102(1052), 103( 1054,1055), l04( lO52,1054a,1055), 105(1052), 113(1102,1103), 184, 185 Bokranz, H., 331(114), 332(114), 347 Boll, W. A,, 209(61), 223(130), 272, 274 Bollinger, F. G., 639(1206), 757 Bollyky, L. J., 370(15a,b,d), 372(25), 414(15a,b,d), 423, 424 Bolrnan, P. S. H., 469(322), 725 Bolster, J., 456(254d), 475(254d), 571(254d), 575(254d), 580(254d), 581(254d), 723 Bolster, J. M., 509(536d), 51 1(536d), 732 Bonaccorsi, R., 5(17), 153 Bonchev, D., 34(468), 36(468), 167 Bondarenko, A . V., 31(349), 32(349), 72(816), 73(816), 163, 177 Bone, S . A , , 628(1025), 750

Author Index Bonet, J., I3 I ( 13 19), 132( I3 19,1327,1328), 192 Bonifacie, M., 464(294), 724 Bonini, B. F., 590(755c), 591(755c), 595(755c), 740 Bonnett, R., 233(181), 275 Booth, H., 10(72), 155 Booth, J., 255(251), 264(325), 277, 280 Booth, M., 465(298), 724 Bopp, H., 492(468a), 495(468a), 496(468a), 497(468a), 506(468a), 53 1(468a), 541(468a), 546(468a), 730 Borch, R. F., 48(600), 171 Borders, D. B., 224(140), 230(140), 274 Bordier, E . , 34(436,437), 166 Bordwell, F. G., 447(148,157), 452(203), 465(148,303), 471( 157), 490(429), 498(203), 504(429), 614(914,915,918), 6 16(915,918), 618(914,918), 619(914), 719, 720, 721, 724, 729, 730, 746 Borgers, T. R., 439(35), 440(35), 715 Borisevich, A. N., 602(809), 742 Borissow, P. P., 353(6), 423 Boroujerdi, M., 267(356), 281 Borowiec. H., 603(820), 742 Borowitz, I. J., 452(204), 492(204,440), 498(203), 721, 729 Borowski, E., 317(176), 349 Borrmann, D., 611(861), 614(861,92la), 744, 746 Bortyan, T. A , , 39(531), 169 Bos, H. J. T., 516(545a,d,562a,d), 519(567a,b), 525(545~,562a,c,567a),564(691a), 566(691a), 568(691a), 578(691c,732,733a,b), 58 1(733a), 582(733b), 733, 734, 738, 739 Boscacci, A. B., 31 1(35), 344 Boschung, A . F., 37(503), 168 Boss, H. J., 34(466d), 36(466d), 167 Bost, P. E . , 30(318), 162 Bost, R. O . , 141(1379), 142(1384), 193 Bost, R. W., 443(114), 457(257), 462(257), 464(257), 465(257), 472(333), 473(257), 491(257), 511(257), 718, 723, 725 Boswell, G . A., J r . , 635(1145b), 754 Bottin-Strzalko, T., 13(124), 156 Bottomley, C. G., 625(992), 631(992), 749 Bouchaut, M., 96(1018), 183, 624(986a), 749 Bouget, H., 124(1235), 189 Bouma, W . J., 4(12), 153 Bourelle-Wargnier, F., 150(1448), 195 Bouwsma, 0. J., 230(150), 274 Boux, L. J., 215(108), 273 Bovenkamp, J. W., 117(1148,1149), 118(1148), I86

777

Bovey, F. A,, 11(79), 155 Bowen, R. D., 7(33), 153 Boyaiian, C. G., 125(1262), 190 Boyd, A . W., 8(42), 154 Boyd, C., 269(374), 281 Boyd, D. R., 202(21,23-25), 204(23-26,28-32), 205(36-38), 206(37,38,44), 207(37), 209(37,38,44), 21 1(37,38,44), 214(36,81), 2 18(30), 219(36,8 1, I 14), 220(21,115), 221(23,24,26,28-32,8 1,115,118,119), 222(23-26,28-33), 230(157), 23 1(38,44,163), 232(167), 233(36,81,163), 235(191), 236(37,38,44,191), 237(37,38,44,191), 241(191), 246(115), 247(37), 256(25,267,268), 258(167,296), 261(268,271), 262(115), 264(23-26,29,31-33,118,119,336), 265(28,30,118,119), 266(115,271), 269(157), 270, 271, 272, 273, 274, 275, 278, 279, 280, 285(40), 287(20,5 I), 288(20), 289(20,40), 290(20), 291(20), 293(20), 296(60), 297(40,64,66), 298(40,64,66,67), 299(20), 300(20), 301(66), 303(64,69), 307(20), 3 14(40,67), 315(51,60,66,67,73), 319(76), 320(66), 321(51,73), 322(64), 323(82,185), 326(192), 328(264), 333(73), 344, 345, 349, 463(286b), 481(286b), 724 Boyer, P. D., 354(14d), 420(14), 423 Boyland, E., 215(82), 216(99), 217(106), 231(159), 264(325), 269(369), 272, 273, 275, 280, 281 Boux, L. J., 217(108), 273 Bradamante, S . , 439(49), 440(49), 477(390a,b), 478(390a), 489(390b,424,425a), 490(425), 492(475), 502(475c), 504(523), 536(609), 540(609), 586(609), 587(609), 728, 729, 730, 732, 735 Bradshaw, J. S . , 620(952), 664(1471), 747, 765 Bradsher, C . K., 90(969), 181 Brady, B. A,, 26(257), 160 Braehler, G., 514(560c), 515(560c), 733 Braid, M., 631(1108,1109), 633(1109), 634(1 log), 753 Braillon, B., 440(59), 716 Braithwaite, E. R., 601(804b,805), 742 Brambilla, R., 120(1183), 188 Bramwell, F. B., 642(1253), 646(1253), 759 Brand, W. W . , 639(1212-1214), 640(1213), 757 Brandsma, L, 444( 115), 718 Brasen, W. R., 625(991,992), 631(992), 749 Bratholdt, J. S . , 476(383), 727 Brauer, H. D., 389(107), 413(108), 427 Braun, D., 94(1007,1008), 182 Braun, H., 53(637), 172

778

Author Index

Braun, M., 126(1276,1277), 190 Braun, R. A , , 147(1431), 195 Braunstein, A., 220(115), 221(115), 246(115), 262( 115), 266( 1 IS), 273 Brehm, L., 297(62), 345 Breitenstein, M., 625(998b), 626(998b), 749 Breiter, J. J., 492(432), 729 Bremholt, T., 38(527), 169 Breque, A , , 24(224), 159 Bresnick, E., 269(371), 281 Bretscher, H., 61 1(867), 620(867), 744 Breuninger, M., 209(65), 210(65), 251(65), 2 72 Brewster, K., 331(115), 332(115), 347 Bridges, A . J., 59(689), I74 Bridgewater, A . J., 70(798), 71(798), 176 Brightwell, N. E., 215(94), 216(94), 239(94,196), 241(196), 273, 276 Brill, W. F . , 30(313), 162 Brinck, C., 438(4a), 714 Brinkman, M., 631(1113c), 640(1113c), 753 Britten, A. Z., 124(1232), 189 Brizuela, C. L., 76(859), 178 Bro, M. I., 593(773), 597(773), 616(773), 741 Broadley, R. A , , 639(1173), 640(1173), 755 Brocker, U., 219(125), 273 Brode, G. L., 473(341), 474(341), 726 Brodersen, S . , 633(1133), 754 Brodski, L., 37(516), 169 Broer, W. J., 464(295b), 509(295b), 724 Brois, S . J., 661(1412,1413), 666(1413), 763 Brokatzky, J., 149(1443), 195 Brooker, L. G. S . , 583(740), 586(740), 587(740), 740 Brookes, P., 267(349,351), 281 Brooks, P. J., 418(135), 428 Brosowski, K . H., 622(966b), 625(994e), 632(994e,1120d,ll2Of), 642(966b), 643(966b), 644(966b), 650(994e), 748, 749, 754 Brouwer, A., 564(691a), 566(691a), 568(691a), 738 Brouwer, A. C., 66(756), 90(756), 175, 5 13(545a,d,e), 516(545a,d,562a), 519(567a), 525(545~,562a,567a),733, 734 Brown, C., 331(115), 332(115), 347 Brown, D., 36(489), 168 Brown, D. J., 10(62), 154 Brown, H. C., 77(866), 78(87 1-874,876,877,879-883), 80(877,879,880,901,902), 82(901,909), 83(923,924), 114(1107), 178. 179, 180, 185 Brown, I. D., 669(1545), 767

Brown, P., 14(140), 156 Brown, R. S. , 381(46), 425 Brown, S. B., 120(1190), 188 Brublevskii, A. I., 93(1000), I82 Bruice, P. Y . , 198(4), 207(4), 234(4,189), 235(4), 237(193), 238(4,193,194), 241(189,193,194,201), 245(223), 270, 275, 2 76 Bruice, T. C., 198(4), 207(4,59), 233( 186-188), 234(4,187-189), 235(4,59), 237(193), 238(4,193,194), 241 (188,189,193,194,20 1,205), 244(2 13), 245(223), 270, 272, 275, 276 Brule, M. R., 443(105b), 718 Bruza, K. J., 68(775), 176 Bryce-Smith, 34(464), 36(464), 167 Bryson, I., 69(781), 176 Bubel, 0. N., 92(980), 93(1000-1001a), 182 Bucciarelli, M., 297(63), 307(21), 315(21,63a), 317(21,63), 319(21,178), 344, 345 Buchachenko, A. L., 32(396), I65 Buchanan, J. G., 11(85), 61(708), 77(708), 115(708), 155, 174, 444(136), 719 Buchardt, O., 284(7), 307(7), 309(7), 339(210), 343, 350 Buchi, G., 130(1308), 151(1475), 191, 196, 355(33), 424 Buchman, O., 74(841,842), 178 Buchshriber, J. M., 492(459), 494(459), 495(459), 730 Buchta, E., 444(138), 719 Buckingham, D. A , , 6(26), 153 Budnik, R., 34(440), 35(440), 36(440), 166 Budzikiewicz, H., 14(138,139), 156 Buecher, D., 492(437,438), 495(437,438), 729 Buendia, J., 548(623), 549(623), 559(623), 736 Buening, M., 230(157), 259(306), 269(157), 274, 279 Buening, M. K., 256(268), 261(268), 269(375), 278, 282 Buincky, E. P., 31(341), 163 Bujnicki, B., 658(1397), 763 Bulavintseva, T. G., 21(190), 158 Bulgakova, A. P., 622(967), 748 Bullock, G., 656(1377), 762 Bullock, M. W., 450(190), 721 Bunikowskii, W., 38(523), 169 Bunina, N. A ., 630(1078d,f), 632(1078f), 752 Bunyatyan, Yu. A., 92(977), 181 Burchall, B., 260(311), 279 Burchardt, B., 148(1439,1440), 149(1442), 195 Burcsu, J. E., 446(146b), 491(146b), 502(146b), 504(146b), 505(146b), 719

Author Index Burfield, D. R., 124(1234), 189 Burford, A , , 364(87a), 365(87a), 367(87a). 407(87a), 426 Burger, K., 609(847-854~),744 Burgess, E. M . , 130( 1308), 191, 594(779-783). 597(781), 599(800a), 631(1115), 741, 742. 754 Burgess, R. H., 439(15h), 443(15h), 715 Burgoyne. W., 78(878a), 179 Burke, S. S . , 337(27b), 344 Burke, T. R., Jr., 232(171), 275 Burki, K . , 269(371), 281 Burkle, W., 46(593a,S93c), 171 Burlarnacchi, L., 441(91), 717 Burnett, M. G., 204(31), 221(31), 222(31), 264(31), 271 H., 400(78), 426 Burns, .I. Burns, P. A., 12(109), 13(109), 156, 248(231), 277, 358(39d), 360(39d), 362(39d,48), 363(32a), 364(30), 367(32h), 374(32a,h), 379(39d), 388(48b), 390(4Rb), 407(48b), 415(4Xh), 416(32b,48h), 424, 425 Burnside, C . H., 464(287), 471(287), 724 Burpitt, R . D., 630(1082), 752 Burros, B. C., 628(1024), 750 Burstall, F. H., 670(1551), 671(1551), 767 Burton, D. J . , 630(1103d), 631(1103d), 633(1131h), 753, 754 Busch, M., 601(808), 604(808), 607(840), 639(840b), 742, 743, 756 Busch, S., 29(292), 161 Bushhy, R. J., 498(510), 506(510), 569(510), 574(5 lo), 582(719c), 583(5 lo), 584(5 lo), 585(743c), 586(510), 587(510,744), 731, 739 740 Bushin, A . N., 30(317), 162 Bushnell, G. W., 667(1495), 766 Bussas, R . , 589(755b), 740 Bustfield, W. K., 630( 1057a), 752 Butler, A. R., 285(42), 330(42,103), 330, 344, 347. 604(822h), 606(822h), 742 Butler, J. J., 469(319c), 725 Butolo, Y., 8(40), 154 Butterham. T. J . , 10(68), 11(68), 154 Buttrill, S. E., 8(37), 154 Buyle, A . M., 473(348), 726 Buza, M.. 445(139), 446(139), 452(139), 461(139), 463(139), 477( 139), 479(139), 480( 139), 482(139), 484( 139), 487( 139), 491(139). 498(139), 505(139), 509(139), 511(139), 719 Byashimov, K.. 449(183), 720 Bystrov. V. F., 441(80), 717

119

Bystrova, V. M . . 552(656c), 553(656c), 555(670), 737 Cadilla, C., 415(122), 427 Cages, A , , 327(196), 349 Cahiez, C., 100(1037), 107(1037), 183 Caille, J . , 356(161), 429 Cainelli, G., 55(662,663), 173 Cairns, T. L., 625(999a), 626(999a, 1005), 627(999a), 628(999a,1005), 629(999a, IOOS), 749, 750 Calas, R., 114( 11 14), 185 Calderoni, C., 458(261b), 51 1(261b), 723 Calleja. P. G., 32(385). 164 Calo, V., 46(592), XX(95S), 128(1292), 171, 181, 191 Calvert, J . G., 385(54), 425, 612(889), 617(889), 745 Calvin, M., 307(80,118), 312(119), 322(80), 333(118,119), 336(135), 346, 347, 348, 439(41c), 440(41c), 441(41c), 716 Cal~afcrri,G., 625( 1002). 626(1002), 749 Camhie, R . C . , 69(792), 176 Campaigne, E., 632(1120e), 655(1371), 754, 762 Campbell, B. C., 418(134e), 428 Campbell, B. S. . 355(38), 379(38), 419(38), 424, 628( 1026) 750 Campbell, D. H., 38(519), 169 Campbell, G. A,, 332(116), 347 Campbell, R. M . , 232(167), 258(167), 275, 296(60), 297(66), 298(66), 301(66), 315(60,66,73), 321(73), 333(73), 345 Campbell, R. W., 320(66), 345 Campbell, T. W., 444(133,134), 462(133,134), 473( 134), 488( 134), 49 1(133,134), 60 1(803a), 719, 742 Campion, T. H., 118(1164), 187 Cancio, E. M., 397(69), 398(69), 426 Candelas, G., 269(371), 281 Canet, D., 12(100), 155 Cannie, J . , 93(998), 123(998), 182 Cano, J., 92(983), I82 Canonica, L., 67(762), 176 Canovas, A ,, 132(1327,1328), 192 Cant, N. W., 34(469), 36(469), 167 Cantacuzene, J., 12(104), 43(104), 100(1041,1042), 103(1058), 155, 183, 184 Cantrell, T. S . , 453(222), 462(222a), 491(222a), 721. 722 Canty, A . J., 670(1554c), 767 Capdevila, J., 267(354), 281 Capon, B., 17(170), 90(968), 157, 181

780

Author Index

Capozzi, G., 519(569), 525(569), 734 Capps, N. K., 602(811c), 742 a p u a n o , L., 589(753), 740 Caputo, R., 114(1113a), 185 Carboni, R. A,, 629(1046bb), 633(1046bb), 751 Carduff, J., 26(260), I60 Carlock, J. T., 42(552), 170 Carlsen, L., 484(402b), 61 1(873,874), 612(887b), 624(873), 653(1357,1358), 728, 744, 745, 749, 762 Carlson, R., 44(574), 170 Carlson, R. G., 12(110), 24(239), 83(926), 138(1357), 156, 159, 180, 193 Carlsson, S., 664(1477a), 765 Carlyle, D. W., 121(1198), 188 Caronna, T., 340(155), 348 Carpentier, M., 50(615), 172 Carr, M. D., 117(1128), 186 Carre, J. C., 149(1445,1446), 195 Carrel, H. L., 199(10,1l), 270 Carriera, L. A,, 439(43), 440(43), 716 Carroll, P., 672(1570), 768 Carter, S. D., 549(636,637), 550(637), 558(636), 736 Carty, A. J., 629(1038b), 751 Carty, D., 130(1307), 191, 205(42), 271 Casadei de Baptista, R., 421(145), 428 Casella, L., 34(461), 36(461), 167 Caserio, M. C., 625(996), 749 Casey, D. J., 548(627), 550(627), 556(627), 736 Cass, M. W., 354(13), 423 Cassady, J. P., 11(97), 155 Cassidy, E. S . , 219(114), 222(33), 264(33,328), 271, 273, 280 Castanedo, N. C., 647(1317), 760 Castel, A,, 89(967), 181, 327(196), 349 Castellucci, N. T., 209(68), 213(68), 272 Castle, L., 232(184), 233(184), 275 Castro, B., 41(550,551), 56(550,551), 170 Castro, E. R., 48(601), 171 Catalan, J., 118(1160), 187 Catalano, S., 70(795,796), 71(796), 90(796), I76 Catelani, G., 117(1144), 186 Caton, M. P. L., 123(1216), 189 Caupuano, L., 590(753), 740 Cauquk, G., 453(222b), 722 Caus, M. J., 132(1327), 192 Causa, A. G., 20(184), 158 Cava, M. P., 664(1464,1476), 672(1570,1571), 765, 768 Cavagna, F., 46(584), 171

Cavalca, L., 489(423b), 729 Cavazza, C., 548(624), 559(624), 736 Cave, A,, 332(117), 347 Cave, W. T., 8(44), 154 Cavitt, S., 34(454,455), 36(454,455), 39(455), 167 Cavitt, S. B., 36(478), 168 Cazaux, L., 477(390b), 728 Cazes, A,, 89(967), 181 Ceccarelli, G., 11(80), 155 Ceccon, A,, 54(645), 172 Ceder, O., 114(1112), 185 Cellura, R. P., 130(1306), 191 Cenini, S . , 34(435), 166 Cere, V., 458(261b), 511(261b), 723 Cerefice, S. A., 17(171), 80(171), 157 Cerniani, A , , 447(151), 462(151), 480(151), 719 Cerniglia, C. E., 232(174), 259(174,298-301), 275, 279 Cerny, J. V., 445(124), 449(124), 455(123), 472(123), 475(123), 509(123), 718 Cerveny, L., 16(156), 157 Cha, 3. S., 82(915), 180 Chabudzinski, Z . , 45(577), 170 Chait, E. M., 630(1062), 752 Chakladar, M. N., 626(1010), 750 Chakravarty, J., 285(43), 290(43), 298(43), 299(43), 344 Challis, B. C., 285(42), 330(42,103), 344, 347 Chamberlain, P., 18(175), 157 Chambers, J. Q., 631(1114), 638(1114,1167), 753 Chambers, R. J., 137(1354), 192 Champetier, G., 667(1509), 766 Chan, A. S. Y . , 69(794), 176 Chan, A. W. K., 642(1299), 644(1299), 649(1299), 760 Chan, T. H., 59(690), 88(690,959,960), 125(1256), 174, 181, 190, 216(100), 273 Chancellor, T., 243(212), 276 Chande, M. S . , 609(856d), 744 Chandross, E. A , , 370(16), 424 Chaney, M. O., 253(244), 277 Chang, C. C., 658(1396), 763 Chang, C. K., 233(185), 275 Chang, L. H., 62(717), 174 Chang, L. L., 628(1023), 750 Chang, P. L., 452(208), 492(209), 498(208), 515(208), 516(208), 520(208), 521(208), 522(548), 524(583), 524(548a), 525(208), 529(208), 53 1(208), 546(620), 721, 733, 734, 735 Chang, P. L. F., 513(548), 733

Author Index Chang, R. L., 204(27), 217(105), 218(27), 230( 157), 256(27,268), 259(306), 261(268), 268(360-364,366,367), 269( 157,374,376), 271, 273, 274, 278, 279, 281, 282 Chang, Y. C., 353(10), 423 Chano, K., 126(1267), 190 Chao, H. S . I., 206(45-46), 235(191), 236(45-47,191), 237(4S-47, I9 I), 241( 191), 271, 275 Chao, J., 443( 105b), 718 Chao, T. H., 661(1431), 666(1431), 764 Chapat, J. P., 11(98), 19(183) 44(183), 155, I58 Chapman, J. S . , 470(327), 725 Chapman, N. B., 117(1122-1125), 186 Chapman, 0. L., 239(39), 245(39), 271, 514(560d), 515(560d), 516(560), 733 Chapman, R. D., 614(915), 616(915), 746 Charles, H. C., 215(83), 216(83), 229(148), 272 Charrier, C., 664(1489), 766 Charumilind, P., 548(630), 551(630), 555(671), 556(630,67 l), 557(671), 558(671,674), 571(630), 575(630), 582(674), 583(674), 736, 737 Chasseaud, L. F., 246(225), 276 Chatterjee, A , , 90(970), 181, 509(531b), 511(531b), 732 Chatterjee, S . K., 509(531b), 511(531b), 732 Chatterji, S. M., 639( 1196), 756 Chattopadhyaya, J. B., 625(995c), 749 Chatzopoulas, M . , 82(913), 180 Chautemps, P., 10(75), 20(186,187), 26(186), 155, 158 Chauvet, F., 34(460c), 36(460c), 167 Chaykovsky, M., 52(624), 172 Cheer, C . J., 69(785,786), 176 Chen, C. H., 41(548), 170 Chen, F., 439(52), 442(52), 446(52), 456(52), 591(52), 499(52), 509(52), 51 1(52), 716 Chen, H. Y . , 20(184), 158 Chen, J. S ., 293(58c), 294(58c), 295(58c), 345 Chen, K. N., 131(1312), 191 Chen, L. S . , 498(512,513a), 503(512,513a), 731 Chen, M. J. Y., 34(460), 36(460), 167 Chen, S. C., 490(428), 493(428), 496(428), 729 Chen, S . M., 69(791), 140(1366), 176, 193 Chen, W. Y., 324(84), 331(111), 346, 347 Cheney, J., 550(644), 555(644), 736 Cheng, C. C., 355(96), 361(126), 366(126), 390( 126), 39 1(96), 403(83), 409(96), 426, 427, 428, 639( 1194.1 195), 756 Cheng, C. W. F., 34(460b), 36(460b), 167 Cherepanova, E. G., 19(181), 158

78 1

Cherkofsky, S. C., 635( 1145b), 754 Chernishkova, F. A., 83(928,934), 84(928), 180 Chernyshkova, F. A,, 73(823), 177 Chernyuk, K. Yu., 27(262), 160 Cherry, W., 452(210c), 630(210c), 721 Cherton, J. C., 356(161), 429 Chervinskii, K. A,, 31(347), 163 Cheung, H. T . A,, 70(798), 71(798), 176. 215(108), 217(108), 273 Chiang, J. F., 489(418b), 630(1049), 729, 751 Chiang, Y. L., 258(278), 278 Chiarello, R. H., 63(729), 175 Chiasson, B. A ., 206(52), 208(52), 271 Childs, R. F., 239(199), 241(199), 276 Chirniak, A,, 330(107), 347 Chittenden, R. A., 331(115), 332(115), 347 Chollet, A., 81(905), 279 Chong, A. O . , 32(399), 165 Chou, M . W., 263(339), 280 Chou, S. S., 642(1277,1278), 643(1277,1278), 759 Choudhari, K. G., 639(1180), 756 Chovin, P., 57(672), 173 Chow, F., 25(249), 160 Chow, M. F., 354(11b,c), 369(11b,59), 381(11b,c), 386(59), 387(59), 389(11b,59), 400(59), 407(11b,c), 414(11), 415(11b,c), 416(11), 417(11b), 423, 425 Chow, Y. L., 45(579), 170, 490(428), 493(428), 496(428), 729 Christensen, L. W., 46(583), 171, 492(496), 494(496b), 495(496b), 535(496b), 731 Christie, K . O., 381(44), 425 Christol, H., 13(122), 22(200,201), 44(568), 118(1150-1152), 156, 158, 170, 187 Christy, M. E., 449(168), 452(205), 457(168,205), 462(168), 465(205), 475(378), 491( l68,430), 497(168,205), 498(205), 506(186), 508(186), 509(205), 511(168), 516(205), 531(168), 533(168), 538(205), 540( 168,205), 541(205), 542(205), 544(205), 720, 721, 727, 729 Chu, S. Y., 269(374), 282 Chuche, J., 42(557-559), 147(1434,1435), 148(1437,1438), 150(1447,1448), 170, 195 Chuev, I. I., 34(456), 167 Chumaeveskii, E. V., 398(76), 426 Chung, V. V., 129(1299), 191 Chupp, J. P., 661(1418,1419,1422), 662(1418,1419,1422), 663(1447), 664(1422), 666(1418,1433), 763, 764 Churchill, M. R., 131(1312), 191 Churi, R. H., 12(108), 156

782

Author Index

Chvertkin, B. Ya., 661(1429b), 662(1429b), 764 Ciabattoni, J., 16(164), I57 Cicala, G., 25(253b), I60 Cieciuch, R. F., 601(801c), 742 Ciete, R., 639(1169), 755 Cilento, G., 352(1), 398(74), 42 1(144a,b, 145-147,149- 151,153,154), 422, 426, 428, 429 Cimarusti, C. M., 37(497), I68 Cimiraglia, R., 118(1162), 187 Cistaro, C., 477(390b), 489(390b,424,425a), 490(425), 728, 729 Claesen, M., 209(67), 212(67), 232(173), 272, 2 75 Claeson, G., 569(703,705a,706), 570(706), 574(706), 738, 739 Clapp, L. B . , 305(17), 344 Clardy, J . , 83(927), 118(1172), 180, I87 Clark, D. T., 5(16), 253 Clark, L. B., 441(73), 717 Clark, P. D., 472(330g), 725 Clark, P. W., 101(1048), 183 Clark, R., 42(553), 170 Clarke, R. A,, 370(15a,c), 414(15a,c), 423 Clausen, K., 663(1453), 664( I472,1474,1475,1477b,1480,1482,1486), 765, 766 Clauss, H., 667(1497), 766 Cleary, J. J . , 69(784), 176 Clemens, D. H., 658(1405), 763 Clezy, P. S . , 576(724), 578(724), 739 Clive, D. L. J., 59(691), 60(694,694a), 174 Closs, G., 34(458), 36(458), 167 Coates, J. E., 488(407), 492(407,465), 495(407,465), 496(465), 497(498), 502(465,498), 505(407,465), 506(498), 508(498), 531(498), 532(498), 541(498), 545(498), 728, 730, 731 Coates, R. M., 25(243), 54(654), 159, 173 Cobb, D., 261(271), 266(271,343), 278, 280 Cocher, W., 24(234), I59 Cockcroft, R. D., 147(1430), 195 Cocu, F. G., 51(618), 172 Cognion, J. M., 36(479), I68 Cohen, G. M., 267(357), 281 Cohen, L. A,, 593(771), 741 Cohen, M. J . , 658(1400), 660(1400), 763 Cohen, Y., 230(157), 269(157), 274 Coker, W. P., 39(528), 169 Colberg, H., 626( 1008), 750 Colchester, J. E., 447(161), 457(161), 462(161), 475(161), 491(161), 511(161), 720

Colclough, R. O., 151(1483), 196 Cole, J . O., 9(46), 154 Cole, K . C., 439(47), 440(47), 716 Collet, A., 123(1215), 189 Collins, C. J., 413(110), 427 Collins, D., 601(802,806), 742 Colln, R., 661(1421c), 662(1421c), 764 Colon, I., 442(98), 479(98), 491(98), 614(897b), 616(897b), 617(897b), 718, 745 Colonna, S., 50(617), I72 Colot, G., 199(16), 270 Combret, J. C., 48(602,603), 56(670,67 l), 100(1045), 171, 173, 183 Conia, J. M., 358(163), 429 Conn, M. W., 443(114), 457(257), 462(257), 464(257), 465(257), 472(333), 473(257), 491(257), 511(257), 718, 723, 725 Conney, A. H., 204(27), 217(105), 218(27), 221(120), 230( 156,157), 256(27,268,270,272,273), 257(276), 258(277), 259(270,302,306), 261(268,322), 262(270,277,322,331,338), 263(270,331), 264(277,330), 265(331), 268(360-367), 269(157), 271, 273, 274, 278, 279, 280, 281, 282, 379 Conover, W. W., 24(221), I59 Conrad, R. A,, 43(564), I70 Conreur, C., 332(117), 347 Contillo, L. G., Jr., 114(1112a), 185 Cook, G. L., 469(311), 725 Cook, R., 450(196c), 473(196c), 721 Cook, R. L., 569(701), 738 Cooke, B., 79(887,894), 179 Cookson, R. C., 103(1056), 184 Coombs, M. M., 214(79), 272 Coon, M. J., 256(258,262), 258(278,279), 277, 2 78 Cooper, C. S., 267(355), 281 Cooper, J. W., 470(327), 725 Coover, H. W., 475(380a), 727 Cope, A. C., 62(713-716,724), 174, I75 Corbel, B., 96(1019), I83 Corderman, R. R., 8(37), 154 Cordes, H. F., 370(19), 379(18b), 424 Corey, E. J., 52(624). 108(1077,1078), 112(1099), 172, 184, I85 Corey, E. R., 630(1057b), 631(1057b,1113a), 632(1057b), 633(1075b,1113a), 635(1057b,1113a), 636(1057b,1113a), 752, 753 Corkins, H. G., 49(612), I71 Cormier, M., 414(114,117). 415(117), 427 Cornelissen, P. J. G., 309(208), 350

Author Index Cornell, D., 499(513c,d), 731 Cornet, D.. 73(825-827), 84(825,826,936,939), 85, 85(825,936), 86(826,827), 177, 180 Cornforth, R . H.. 79(889), 179 Corter, C., 216(89,90), 217(89), 219(89), 272 Costa, N. E., 32(385), 164 Costa Novella, 32(371), 164 Costantini, M.. 30(318), 162 Coste, .J., 13(122), 44(568), l18(1150,115l), 156. 170, I87 Costerousse, G., 33(424). 166 Cottam, P. D., 587(743h), 740 Coulomhe, R., 121(1193), 188 Couret, C., 624(986b), 749 Coutlet, A , , 439(15f), 449(15f), 474(15f), 715 Coutrot, P., 48(602,603), 55(668), 68(769), 100(1045), 171. 173, 176, 183 Couturier, R., 630(3078i), 752 Cowan, D. O., 409(97), 427, 642(1253), 646(1253), 759 Cowles. C., 24(239), 159 Cowley, A . H., 657(1382,1383), 762 Cowley, B. R., 131(1317), 132(1317), 191 Cox, E. E . , 491(15j), 715 Cox, E. F., 439(15j), 462(35j), 474(15j), 475( 15j), 476( 15j), 488(15j), 715 Cox, J . D . , 441(88,89), 717 Cox, R . H., 245(221), 266(221), 276 Cox, W . W., 83(926), 180 Coxon, D . , 1 I(%), 155 Coxon, .J. M., 45(578), 66(746-752), 136(1351). 137(1352), 170. 175, 192, 339(169), 348, 542(615), 735 Corzens, R. F., 671(1556), 768 Craig, H. C . , 232(167), 258(167), 275, 583(740), 586(740), 587(740), 740 Craighead, P. W., 667(1517), 668(1517), 766 Cram, D. J., 599(798,799), 620(953), 741, 747 Crandall, J. K., 24(219,220,221), 61(706), 62(7 17,7 18,725), 67(76 I ) , 129( 1303), 145(1419-1421), 159, 174, 175, 176, 191, 194 Cravador, A , , 114(1 108a), 185 Crawford, P. A , , 412(106), 427 Crawford, R.. 362(106c), 400(78), 426, 427 Crawford, R. J., 146(1425), 147(1430,1436), 195 Crawford. T. C., 1 14(1112a), 185 Crawley, L. C . , 62(725), 175 Creighton, A . M., 447(153), 719 Criegee, R., 353(7), 423 Cripps, H. N., 625(992), 631(992), 749 Crist, D. R.. 330(104), 347 Crivello, J. V., 474(367), 727

783

Crochet, K. L., 604(822b), 606(822b), 742 Croisy-Delcey, M., 216(96), 262(338), 264(333), 268(364), 273, 280, 281 Cromartie, T. H., 43(560), 170 Cromwell, N., 512(540), 515(540), 733 Cromwell, N. H., 10(64), 154 Crosby, G. A . , 105(1062), 184 Crossland, N. M., 10(77), I55 Crotti, P., 13(127), 117(1134-1140,1141), 118(1171), 119(1139), 156, 186, 187 Crow, W. D., 642(1299), 649(1299), 760 Croy, R. G., 259(303), 279 Croiet, M. P., 456(254a), 723 Crump, D . B., 669( 1S45), 767 Crump, D. R., 438(3b,Sa), 451(196e), 452(5a), 714. 721 Crumrine, D., 136(1350), 192 Csizmadia, I. G., 4(9), 37(506,508), 118(1159), 153, 168, 187 Cucrto, O., 356(91), 357( 125), 360( 1 2 3 , 361(126), 366(126), 388(91,124), 390(126), 397(70). 403(83), 414(116), 415(122), 4 I7( 1 16), 426, 427, 428 Cumper, C. W. N., 442(103), 491(103), 718 Cunningham, G. L., Jr., 8(42), 154 Cunningham, M., 338(152), 348 Cura, R., 26(255), 160 Curci, R., 25(253a,b), 33(417), 39(537), 160, 165, 169, 441(81c), 465(81c), 483(399). 717, 728 Curi, S. M., 639(1191), 756 Curtis, P. J., 245(216), 276 Cushman. D. W., 555(669), 737 Cuvigny, T., 91(976), 181 Cvetanovic, R. J., 37(509), 126(1278), 127(1284,1285), 168. 190, 191 Cyeto, O., 415(116), 427 Cyskovskii, V. K., 34(429), 166 Czauderna, B., 571(711), 573(711), 575(721), 739 Dabrowska, U., 621(965), 748 Dabrowski, J . , 621(965), 748 Dadic, M., 549(639), 555(639), 556(639), 736 Dagli, D. J., 49(608), 171 Dahlmann, J . , 40(542), 169 Dahmen, F. J. M., 91(974), 181 Daigle, J . Y . , 75(849,850), 178 Daiker, K. C . , 118(1157), 187 Dalgaard, L., 642(1262), 643( 1262), 644( 1262), 759 Dalla Croce, P., 543(616), 735 Dalven, P., 106(1068), 184

784

Author Index

Daly, J., 260(308), 279 Daly, J. J., 662(1440), 764 Daley, J. W., 198(2,5,6), 202(21), 205(5,35), 206(50,5 l), 207(50,51,57), 208(50,51), 209(50,5l), 2 14(5,8l), 220(21), 221(2,21,50,51,8 l), 23 1(2,5,6,50,51,160- 163), 232(165,167), 233(81,163,177,182), 235(50,51), 236(50,51), 237(50,51,192), 238(2,192), 241(192), 246(2,5,35), 255(5), 258(167,296), 259(297), 260(309), 261(161), 262(161), 267(2), 269(6), 270, 271, 272, 275, 276, 279 Darniani, D., 117( 1140), 186 Darnodaran, N. P., 71(800,802), 177 Darnon, E. K., 612(889), 617(889), 745 Dan, S . , 516(566b), 734 Dang, H. P., 100(1039), 111(1039), 183 Dangyan, M. T., 92(977), 181 Daniels, K., 33(409a), 165 Danilova, T. A,, 472(330a,c,e), 725 Danks, L. J., 584(742), 614(742), 740 D’Annibale, A,, 439(49), 440(49), 716 Dansette, P., 216(88), 217(88), 218(88), 230(152), 259(302), 267(350), 272, 274, 279, 281 Dansette, P. M., 217(104,105), 219(104), 234( 189), 235( 190), 24l( 189,190), 245(224), 246(224), 260(317), 266(224), 268(366), 269(373,376), 273, 275, 276, 280, 281, 282 Dantor, Z., 317(176), 349 Darling, T. R., 360(79a), 400(79), 426 Darrnadi, A,, 674(1562), 672(1564), 768 Darnall, K. R., 25(247), 160 Darnbrough, G., 123(1216), 189 Darvich, M. R., 22(200,201), 158 Das, B. C., 453(231a), 457(231a), 51 1(231a), 722 Das, N., 323( 168), 275 Dasch, C., 470(325), 725 DaSilviera, S. G. P., 639(1191), 756 Datamanti, E., 439(15f), 449(15f), 474(150, 715 Daub, G. H., 241(204), 245(204), 276 Dauplaise, D., 514(560c), 515(560c), 733 Dauter, Z., 317(68), 345 David, F., 23(211a), 159 David, T. D., 24(229), 159 Davidenko, T. I., 447(160), 720 Davidova, H., 73(830,832), 87(830,832,950), 177, 181 Davidson, A. J., 29(290), 161 Davidson, D. W., 443( 112b), 718 Davidson, W. E., 668(1526), 767

Davies, A. G., 151(1458), 195 Davies, G. M., 602(811c), 742 Davies, J., 587(743b), 740 Davies, S . G., 12(112), 18(173), 59(683), 156, 157, 173, 238(195), 241(195), 252(238), 276, 277 Davis, D . D., 114( 11 1 l), 185 Davis, F. A,, 293(58c), 294(58b,c), 295(58c), 305( 167), 326(92,93,190,193), 327( 189- 191,193,194), 338(58a, 146), 345, 346, 348, 349, 452(207,208), 463(286a), 48 1(286a), 492(208,472), 497(472,497), 498(207a,208), 505(472), 506(472), 513(548), 515(208), 516(207a,208,561), 517(566f), 520(207,208), 521(561), 522(548), 525(208), 529(L07,208,561,5660), 531(207a,208,472,497), 532(472), 536(497), 538(472), 540(472,497), 544(497), 545(497), 553(658), 555(658), 721, 724, 730, 731, 733, 734, 737 Davis, H. E., 561(658), 562(658), 579(658), 580(658), 642(658), 643(658), 737 Davis, P. J., 231(164), 259(164), 275 Davis, R. A,, 502(516,517), 504(516,517), 732 Davis, R. E., 441(72), 717 Davison, A,, 629( 1029,1032,1042,1043), 672(1560,1561), 750, 751, 768 Davtyan, S. P., 125(1243), 189 Dawson, K. A,, 204(29), 221(29), 222(29), 264(29), 271 Dawson, T. P., 601(807), 742 Day, A. C., 135(1343), 192, 620(953), 747 DeAbajo, J., 458(264c), 472(264), 473(264c), 51 1(264c), 723 DeArnici, M., 497(508b), 543(508b), 732 Dean, F. M., 52(620), 172 Dean, R. A., 447(150), 473(150), 474(150), 491(150), 719 De’Ath, N. J., 418(134), 428, 628(1021,1024,1026), 750 DeBenedetti, P. G., 497(508a,b), 543(508a,b), 73I DeBoer, B. G., 131(1312), 191 Debono, M., 139(1361), 193 Declercq, J. P., 562(684,685), 563(684,685), 564(684,685), 566(684a), 567(696), 576(685), 577(696), 666(1492), 738, 766 DeCorpo, J. J., 370(20), 424 Defoin, A,, 229(149), 274 Deghaidy, F. S., 630(1059), 752 DeGraaf, C., 99(1034), 183 deGroot, A,, 509(535,536a), 51 1(536a), 732 Dehrnlow, E. V., 328(100), 346

A u t h o r Index DeJong, A. J., 31(336), 163 Dekerk, J. P., 562(684), 563(684), 564(684), 566(684), 567(694), 576(685), 589(752b), 595(752b), 604(822i), 606(822i), 652(752b), 738, 740 Deketele, M., 604(822i), 606(822i), 742 Dekkers, H. P. J. W., 365(171), 429 de La Mare, P. B. D., 22(205), 63(734), 158, I 75 de La Mare, H. E., 372(23), 424 Delavarenne, S . Y . , 29(279), 30(306,308,31I), 161. 162 Del Buttero, P., 492(453,467), 495(453,467,495), 497(495), 502(521), 504(523), 505(495,524), 506(521), 534(521), 536(609), 540(495,609), 543(616), 546(521), 583(521), 586(609), 587(609), 730, 731, 732, 735 Delepine, M., 635(1145a), 638(1145a), 754 del Fierro, J., 362(35,92), 363(92), 377(35), 392(92), 424, 426 Delker. D . A , , 9(61), 154 Del'tsova, D. P., 312(175), 349 DeLuca, M., 354(14a,d), 395(64a,b), 396(64b), 397(64b), 420(14a,d), 423, 425, 426 DeLucchi, O., 369(99), 427, 613(887d), 745 De Luze, H., 10(78), 14(141,142), 155, 157 Delventhal, .J., 663( 1463), 765 deMaijere, A , , 229(147), 274 DeMarainis, R. M., 207(59), 235(60), 242(40,60), 243(40,21 l), 244(40,21 I ) , 245(21 I ) , 247(40), 254(40), 271, 272, 276 DeMare, G . R., 5(15a.b), 37(508), 127(15b), 128(1288,1289), 153. 168, 191 DeMayo, P., 338(147,149), 348, 452(210a), 453(2 I8,2 19,228,229,240b). 4S6(218,2 19), 468(2 18,229) 469(218), 47 1(218), 495(495), 497(495c), 499(495c,5 13e,f), 502(495c), 505(495c), 506(495c), 53 1(495c), 532(495c), 534(495c), 540(495c), 541(495c), 545(495c,5 13e,f), 552(240b), 578(240), 583(495c), 584(495~,513f,743a),585(743a), 609(856a), 620(948), 625(994a,99Sa), 626(948,1004), 627(948), 628(948,1004), 629( l004), 630(2 10,227,229,1079,108 I ) , 721, 722, 731, 747. 749. 750, 752 DeMicheli, C.. 497(508a,b), 543(508a,b), 731 Deming, P. H., 24(237), 159 Demmin. T. R.. 51 l(53R). 732 Dcmpsey. M . E., 354( 13a). 420( l4), 423 Demuth, M. R., 22(202). 158 Denes. A . S.. 4(9), 153 Dcng. X. M.. 121(1206), 188

785

Deniau, J.. 102(1053), 114(1053), 184 Denis, J . N., 61(702), 174 Denisov, E. T., 34(427), 166 Denisov, V. R., 1 1 I( l090), 185 Dennison, D . J., 258(289), 279 Denney, D. B., 355(38), 379(38), 418(134e,D, 419(38), 424, 428, 464(288,289), 482(288), 5 l0(288), 628( 1021- 1024,1026), 724. 750 Denney, D. Z., 355(38), 378(38), 418(134e,f), 419(38), 424, 428, 464(288,289), 482(288), 510(288), 628(l022b-l024,l026), 724, 750 Denny, W., 37(495), 168 Denny, W. A,, 69(792), 176 Denyer, C. V., 59(691), 174 DePasquale, R. J., 92(989), 182 DePuy, C., 456(254a), 723 DeReinach-Hirtzbach, F., 68(770), 176 Derguini-Boumechal, F., 100(1040), 183 Derkachev, V. N., 654(1367), 655(1367), 762 Derouane, E. G., 13(121), 156 DeRuiter, E., 34(451), 36(451), 167 Dervan. P. B., 60(699), 174 Derzhinskii, A . R., 126(1274), 190 Desbene, P. L., 368(173), 429 DeSchryvcr, F. C . , 531(599), 584(743a), 585(743a), 735, 740 Desjardins, C. D., 630(1104), 753 DesMarteau, D. D., 302(39), 313(39), 329( 102), 344, 346 Desma7ieres, B.. 492(458), 495(458), 593(776,777), 614(458), 730, 741 DesRoches, D., 74(844), 178 Dessy, R. E., 629( 1027), 750 Dettwiler, H. R., 34(473), 36(473), 167 Detty, M., 76(853), 178 Detty, M. R., 76(855a), 178 Deutsch, J., 258(278,279), 278 Dev, S . , 34(433), 71(800-803), 166. 177 Devaquet, A., 7(35), 145(35,1409), 154, 194, 312(172), 333(172), 411(104), 414(104), 348, 427 Dcvdhar, R. S., 527(587c,588a), 529(588a), 734, 735 Deveux, R., 473(78e), 717 Devine, G. E., 264(328), 280 DeVos, A . M., 516(545d), 733 Devoto, G., 610(857), 744 deWaard, E. R., 613(897a), 616(897a), 617(897a), 745 Dewar, D. J . . 133(1332), 192 Dewar, M. J. S . . 37(491.492), 168, 199(14), 270. 41 I ( 103a.b), 427 DeWeck. G., 140(1374), 193

786

Author Index

Dey, A. K . , 140(1375), 193 Dhar, R . , 250(235), 277 Dhawan, K . L., 115(1119), 186 Diamond, J., 445(140), 446(140), 719 Diamond, S. E., 34(460a), 36(460a), 167 Dice, D . R . , 469(312-315,317-319a), 469, 470(315), 725 Dickore, K., 638(1163), 640(1232), 642(1163), 646(1163), 755, 758 Diderrich, G., 630(1089), 635(1089), 638( l089), 640( 1089), 753 Diemert, K . , 663(1460-1462), 765 Dietl, M., 656(13?4), 666(1374), 762 Dietrich, H., 142(1384,1388), 193 Dietrich, M. A., 614(89Ra), 616(898a), 745 Dietrich, W., 438(10e), 625(993a), 714, 749 DiFuria, F., 26(255), 33(417), 39(537), 160, 165, 169, 441(81c), 465(81c), 483(399), 717, 728 Dilcher, H., 335(129), 347 DiLonardo, G., 439(44), 716 Dimmock, J. R., 653(1353), 761 Dirnroth, K., 202(22), 222(127), 270, 273 Ding, J . Y., 355(22b,107), 356(22b,107), 357(107), 371(22b), 379(22b), 380(22b), 381(22b), 382(22b), 385(22b), 387(22b), 389(22b), 390(107), 392(107), 413(107), 418(22), 424, 427 DiNinno, F., 468(166), 720 Dinizo, S. E., 323(83), 331(83), 346 Dinur, D. , 216(93), 272 DiRaddo, P., 125(1256), 190, 216(100), 273 Dittel, W., 251(23?), 277 Dittrnann, W., 24(227), 159 Dittrnar, B. I . , 530(589), 735 Dittmer, D . C . , 439(55b,56b), 440(56b), 447( 149), 449( 168), 452(205,207a,208,209), 457( 149,168,205), 462(168), 465(205,306a), 469(306a), 477(55b,56b), 478(55b,56b), 489(55b,56b), 490(55b,56b), 491( 168,430), 492(208,209,472), 497( 186,205,472,497,502-505~,507), 498(205,207a,208,209), 499(503), 503(504,507), 505(472,505a,c), S06( l86,472,502,505a,b), 508( 186,530), 509(205), 51 I(149,168,530a), 512(540), 5 13(S48), 5 l5(208,209,S40), 5 16(205,207a,208,209,561),520(207,208), 521(208,561,582a), 522(548), 524(583,584a), 525(208,209), 526(530a,586), 529(207-209,561), 53 1(56b,168,207a,208,472,497,597),

532(472), 533( 168,505a-c), 536(497,505a-c,61 l), 537(502), 538(205,472,502), 539(502,505a), 540( 168,497,61l), 541(205,505~,61 l), 543(507), 544(205,497), 545(497,618,619), 546(502,619,620), 587(505~),619(943-945), 620(943,944,950), 630(55b), 635(55b), 642(1258), 647(1258), 716, 719, 720, 721. 724, 729, 730, 731, 732, 733, 734, 735, 747. 759 Dittus, G., 3(2), 99(2), 152 DiVincenzo, G., 492(482), 730 Divisia, B., 453(222b), 722 Dixneuf, P. H., 629(1038b), 751 Dixon, B . , 387(61), 425 Djerassi, C., 13(135), 14(138,139,140), 156, 442(101), 520(580), 529(580), 718, 734 Dmitriev, M. A ,, 614(898f,h,i), 615(898f,h), 616(898f,h,i,927-929,93 l ) , 745, 747 Dobashi, A,, 631(1113b), 753 Dobashi, S. , 100(1036), 183 Dobbs, A. J., 151(1457), 195 Dobinson, B., 151(1467), 196 Dobrynin, V. N., 61(709), 77(709), ?8(709), 174 Dodson, R. M., 439(53a), 446(53,146a), 462(53), 466(308), 477(53a), 480(53a,146a), 482(53a), 483(53a), 486(404,406a), 490(53a), 491(53a, 146a), 499(53a, 146a), 502(406a,5 16-5 19), 504(5 13,5 16), 505( 146a), 716, 719, 724, 729, 732 Doebler, C., 33(418), 165 Doenecki, J., 516(562), 733 Domagala, J. M., 17(167), 66(759), 157, 175 Dombi, S . , 30(319), 162 Dominguez, J. N., 630(1074), 752 Dominh, T., 142(1396), 194 Dominy, B., 131(1316), 132(1316), 191 Domschke, G., 598(794-796), 741 Donald, D . J., 111(1092), 185 Dondoni, A,, 563(686-688), 564(689,690), 566(686,687,689), 589(75 Ic), 605(826a), 606(826a,836), 612(751c), 614(751c), 738, 740, 743 Donelly, J. A., 118(1169), 187 Donnelly, J. A., 69(783), 150(1449), 176, 195 Donnely, J. A,, 53(642,643), 172 Donome, K . , 451(198-ZOO), 721 Donovan, T., 309(30), 31 1(29,30), 325(30), 344 Donskova, A. I., 9(54), 154 Doolittle, R. E., 111(1091), 185 Dopp, D., 336(134), 348

Author Index Dorer, F. H., 469(319b), 484(402c), 725, 728 Dorokhova, E. M., 650(1337), 761 Doschelli, D., 327(194), 349 Doshan, H., 370(18), 355(18b), 370(18), 379(18b), 398(18b), 424 Dotrenko, L. A , , 142(1390), 194 Dournaux, A,, 30(330), 162 Douslin, D. R., 441(85), 717 Dousse, G., 96(1018), 183, 624(986a,b), 749 Dowd, P., 59(680), 173 Downer, J. D., 447(161), 457(161), 462(161), 475(161), 491(161), 511(161), 720 Doyle, F. P., 446(145), 449(145), 457(145), 468(145), 511(145), 719 Doyle, L. C . , 127(1285), 190 Drabb, T. W., Jr., 639(1214), 757 Draber, W., 628(1019c), 750 Drabowicz, J., 658(1397), 763 Drake, A . F., 204(30), 218(30), 221(30), 222(30), 265(30), 271 Dransch, G., 593(770), 741 Dravid, R. N., 609(856d), 744 Dresdner, R . D., 598(793), 741 Dreyfuss, M. P., 151(1473), 196 Dreyfuss, P., 151(1473), 196, 458(262), 473(262,343,344), 51 1(262), 723, 726 Driessen, P. B. J., 612(891), 745 Drijvers, W., 473(346,348,350,352), 726 Drozd, J. P., 505(525), 732 Drozd, V. N., 492(449-451). 495(449,450), 496(449,450), 505(449-45 l), 506(525), 531(525), 532(525), 548(629d), 551(629d), 556(629d), 730, 732, 736 Druelinger, M., 336(136), 348 Drysdale, J. J., 626(1006), 628(1006), 629(1006), 750 Dryuk, V. C., 92(981), 182 Dryuk, V. G., 16(166), 157 Dubinskaya, E. I . , 114(11 13), 185 DuBois, G. C., 260(314,319), 279, 280 DuBois, G. E., 511(538), 629(1046a), 732, 751 Dubois, J. C . , 439(15f), 449(15f), 474(15f), 715 DuBose, C. M., 52(632), 172 Dubs, P., 438(9), 456(253), 714, 723 Duchet, J. C . , 73(825-827), 84(825,826), 85(825), 86(826,827), 177 Ducker, J. W., 95( 1015), 183 Duckett, J. A., 439(30,32,33), 440(30,32,33), 715 Dulcere, J. P., 33(424d), 166 Dumas, P., 151(1468), 196 Durnont, W., 54(656-660), 173

787

Duncan, D. P., 11 1(1092), 185, 667(1499), 766 Dungan, C. H., 667(1503), 668(1503), 766 Dunkin, I. R., 61 1(877), 613(877), 617(877), 745 Dunrnur, R. E., 642(1266), 664(1266), 759 Dunn, A . R., 509(531e), 511(531e), 732 Dunogues, J., 114( 11 14), 185 Dunston, J. M., 136(1344), 192 Dupin, J. F., 284(4), 343 DuPrez, E., 444(136), 473(136a), 719 Duran, W., 386(57), 387(57c), 421( 145-147,149-15 l), 425, 428 Durant, J. L., Jr., 382(24b), 412(24b), 424 Durbut, P., 31(335a), 32(335a), 163 Durham, D . L., 13(115), 156 Durig, J. R., 439(36,43), 440(36,43), 630(1054), 670(1548,1549), 715, 716, 751, 767 Durkin, J. A , , 31(341), 163 Durst, I., 68(770), 176 Durst, T., 54(646,653), 74(844), 115( 1 1 19), 172, 173, 178, 186, 443(125b), 491(126b), 501(125b), 505(125b), 61 1(875,878), 613(875,878,892-894), 614(875), 6 16(878,892-894), 6 17(875,878,892), 719, 745 Dutta, D. N., 621(958), 748 Dyatkin, B. L., 51(619), 80(900), 120(1184), 172, 179, 188, 437(2b), 443(2b), 511(2b), 630(1098,1102a,l103a,l105), 642( 1103a,l105), 644( 1105), 714, 753 Dyatlovitskaya, S. V., 458(264a), 466(264a), 472(264), 473(264a), 51 1(264a), 723 Dyckeroff, K . , 354(11), 378(11a), 381(11c), 407(11), 414(11), 415(11a), 416(11), 417(11), 423 Dynak, J. N., 235(191), 236(191), 237(191), 241(191), 275 Dzakpasu, A. A,, 355(41), 363(41), 372(27), 379(27), 424 Dzernilev, U. M . , 32(401), 33(401), 165 Dzhagatspanyan, R. V., 398(76), 426 Dzhernilev, U. M., 30(302), 161 Dzhundubaev, K . D., 662(1434), 663(1434,1454), 764, 765 Eade, R., 37(506), 168 Eaker, C. W., 41 1(45), 425 Eastharn, A. M., 15(1479-1482,1484), 196 Eastrnan, R. H., 10(63), 137(1353), 154, 192 Easton, N. R., Jr., 12(109,113), 13(109,118), I56

788

Author Index

Eberbach, W., 148(1439-1448), 195 Eberstein, K., 64(740), 175 Ebina, F., 233(185), 275 Ebisch, R . , 628(1018c), 629(1018c), 750 Echigo, Y., 126(1270), 190 Ecker, A , , 666(1491a), 766 Eckroth, D. R., 337(140), 348, 492(468b), 497(468b), 53 1(468b), 535(468b), 540(468b), 730 Edelman, F., 630(1099b), 633(1099b), 753 Edelman, M., 260(316), 280 Edelstein, N., 629(1029,1042,1045), 750, 751 Edmonds, C . G., 83(925), 180 Edmonds, J. T., 474(356,360,361,268), 726, 727 Edwards, J. O., 16(164), 25(253a), 33(417), 157, 160, 165, 305(16), 344 Eenkhorn, J. A , , 644(1311), 760 Effenberger, F., 589(752a), 591(752a), 603(818), 740, 742 Ege, G., 599(800b), 742 Eggersdorfer, M., 609(847), 744 Egorova, N. V., 475(377a), 727 Egsgaard, H., 484(402b), 612(887b), 728, 745 Ehlers, J., 642(1259), 759 Ehrchen, E., 34(474), 36(474), 39(474), 167 Ehrenberg, A., 267(353), 281 Eichenberger, H., 140(1369,1370~ 373), 193 Eickhoff, D. J., 33(309a), 165 Eikenberry, J. N., 11(92), 155 Eilingsfeld, H., 603(815), 604(815), 742 Eilmes, J., 476(379), 727 Eirich, 151(1486), I96 Eisch, J. J., 113(1101), 185 Eisenberg, R., 629(1035), 750 Eish, J., 59(679), I73 Eistert, B., 535(607), 546(607), 583(607), 585(607), 735 Elam, E. U., 553(658), 555(658), 561(658,679a), 562(658), 579(658,679), 580(658), 642(658), 643(658), 737, 738 El-Barbary, A . A,, 663(1449,1452a,1453,1456), 664( l449,1452a,1472,1477a), 764, 765 Eleev, A , , 618(942a), 747 Eleev, A . F., 614(905a), 615(905a), 654(1365,1366), 746, 762 Elferink, V. H. M., 519(567), 734 El Gaied, M. M., 20(185), 158 El-Gendy, M. A . F., 333(121), 347 El Hashash, M. A , , 101(1047), 183 Eliel, E. L., 6(26), 153, 444(137), 509(531a), 719, 732 El-Kady, M., 101(1047), 183

El-Kashef, H. S., 602(812d), 604(812d), 742 Elkik, E., 12(103), 155 Ellis, I. A , , 668(1519), 767 El-Sabbon, M. Z., 441(84), 717 El-Sayed, M. A , , 398(74), 426 El-Shafei, A . K., 602(812d), 604(812d), 742 El’tsov, A . V., 655(1368), 762 Emanuel, N. M., 34(426,427,443), 35(443), 36(480), 38(521,522), 166. 168. I69 Emmons, E., 325(3,8), 343 Emmons, W. D., 284(3,8), 305(8), 314(8), 322(3), 329(3), 330(3), 331(3), 332(3), 333(3), 340(3), 343 Empen, J. A., 41 1(78b,c), 473(78b,c,342,377), 474(342), 51 1(78c), 717, 726 Ender, E., 115(1118), 186 Enders, E., 438(10a), 462(10a), 480(10a), 488(10a), 491(10a), 714 Endo, T., 592(767), 741 Engberts, J. B. F. N., 593(765d), 741 Engel, E., 632(1120a), 754 Engel, J. F., 219(112), 221(112), 273 Engel, P. S., 391(71), 426 Engelhard, N., 519(570), 529(570), 734 Engelhardt, U., 268(362), 281 England, D. C., 614(905b,e,g), 615(898d,905g). 616(898a,d), 628( 1017), 630(1078g), 632( 1078g), 642( 1017,1300,130 la), 644(1017,1300,1301), 745, 746, 750, 752, 760 Engman, L., 664(1476), 672(1570,1571), 768 Engwall, R., 550(646b), 63 1(646), 736 Enikolopiyan, N. S., 125(1238), 151(1471), 189, 196 Ennis, M. D., 575(723), 577(723), 739 Entelis, S. G., 151(1461,1466), 195 Enzmann, F., 438(3a), 452(3a), 492(3a), 497(3a), 498(3a), 505(3a), 53 1(3a), 532(3a), 540(3a), 714 Epe, B., 199(12), 270 Epiotis, N. D., 514(560a), 529(560a), 733 Epstein, R . , 43(562,563), 170 Eranian, A . , 439(15f), 449(15f), 474(15f), 715 Erden, I., 37(496), 168, 229(147), 274, 361(126), 366(126), 390(126), 415(122), 427, 428 Ermakov, A. I . , 661(1429b), 662(1429b), 764 Ernst, J., 36(485), 168 Ernst, L., 622(966a), 748 Ershov, B. A., 61(710), 87(710), 174 Escher, S.,629(1046a), 751 Eskenazi, C., 319(77), 320(77), 345 Estabrook, R. W., 256(261), 278 Estep, R. E., 49(609), 171

Author Index Estes, J. E., 31(341), 163 Estes, V. M., 118(1156,1157), 187 Etienne, A , , 492(458), 495(458), 593(776,777), 614(458), 730, 741 Etienne, Y., 437(1), 443(1), 472(1), 511(1), 667(1508,1509), 714, 766 Etienne, Y. P. M., 474(357), 726 Etlis, V. S . , 448(164,165), 449(171,179b,180), 450(179b), 462(179b), 475(165,180), 480( 179b), 491(165,179b180), 719, 720, 721 Eudy, N . H., 509(531c), 511(531c), 732 Evans, F. E., 232(174), 259(174), 275 Evans, T. E., 490(428), 495(427), 496(427), 729 Evaratt, B., 13(123), 156 Evenhuis, K. J., 445(130), 719 Evenhuis, N., 444(130), 465(130), 491(130), 508(130), 719 Evleth, E. M., 411(102), 427 Evzerikhin, E. I., 32(372-374,392), 164 Exner, O., 605(826a), 606(826a), 743 Eyman, D. P., 465(302), 724 Fabian, J., 598(796c), 741 Faddei, F., 11(81), 155 Fadeev, Yu. N., 661(1416,1417), 662(1416), 663(1416,1417), 763 Fahmi, A . A , , 144(1406a), 194 Fahrenholtz, K. E., 604(821), 742 Faini, G. J., 395(64), 425 Falardeu, E. R., 302(39), 313(39), 344 Faler, G., 364(30), 373(30), 379(30), 380(30), 382(30), 392(30b), 424 Falijoni-Alario, A,, 421( 149), 428 Falko, V. S . , 520(581a), 529(581a), 734 Fan, J. Y., 466(308), 486(406a), 502(406a), 724, 728 Fancher, W. L., 661(1421a), 664(1421), 764 Fanghanel, E., 520(579), 529(579), 628(1018a-c), 629(1018a-c), 734, 750 Farberov, M., 32(405), 165 Farberov, M. I., 3 1(349), 32(349,365,376,377), 72(816,817-820), 73(816,822), 163, 164, 177 Farges, G., 76(856), 121(856), 178 Faria Oliveira, 0 . M. M., 421(145), 428 Farkas, L., 120( I188), 188 Farlow, M. W., 625(992), 631(992), 749 Farneth, W., 452(210c), 630(210c), 721 Farneth, W. E., 413(112), 427 Farona, M. F., 31(356), 163 Farquarson, J., 17(170), 157 Farral, M. J., 54(646), 172 Fasani, E., 339(210), 350 Fasco, M. J., 259(297), 279

789

Fava, A, , 456(255), 458(261b), 509(255), 511(255,26Ib), 723 Favorskaya, I. A,, 111(1090), 185 Fay, P., 661(1423), 663(1423), 764 Federsel, H. J., 578(728,729,731c,d), 739 Fedorov, V., 34(441), 35(441), 166 Fedorynski, M . , 48(604), 171 Feeya, D., 119(1173), 187 Feher, F., 667(1506), 766 Fehnel, E. A., 209(62), 236(62), 272 Feilen, M. H., 11(91), 155 Feit, P. W., 46(586), 171 Felcht, U. H., 46(584), 171 Feldman, D., 151(1462), 195 Feldman, R. J., 256(264), 263(264), 278 Feller, G., 411(102), 427 Femeck, G., 570(710), 739 Ferracutti, N., 48(601), 171 Ferrari, M., 67(762), 176 Ferrel, J. E., Jr., 241(206), 276 Ferretti, J. A., 266(344), 280, 440(58), 716 Ferretti, M., 117(1141,1142,1144), 118(1171), 186, 187, 260(318), 280 Ferri, R. A,, 492(454), 502(454), 730 Ferrin, L., 117(1132), 119(1132), 186 Ferris, J. P., 259(297), 279 Fetizon, M., 14(141), 44(569), 157, 170 Fctt, E. R., 443(109), 475(109), 718 Fetters, L. J., 474(362), 726 Fiandaca, P., 642(1293), 760 Fiandese, V., 46(592), 171 Fiato, R. A,, 21(192), 158 Field, F. B., 653(1359), 762 Field, G. F., 309(29), 344 Field, J. E., 9(46), 154 Field, L., 548(626), 555(626), 556(626), 626(101 la), 736, 750 Fields, D. L., 450(191-193), 457(191,192), 511(191,192), 721 Fields, E. K . , 17(171), 80(171), 157 Fields, R., 630(1102b), 637(1102b), 753 Filby, J. E., 355(22b), 356(22b), 357(22b), 371(22b), 379(22b), 380(22b), 381(22b), 382(22b), 385(22b), 387(22b), 389(22b), 390(95), 418(22a,b), 424 Filer, C. N., 207(60), 235(60), 242(60), 272 Filippov, A. P., 32(391), 164 Filippova, S . V., 121(1202), 188 Filippova, T. V., 15(151a), 34(151a), 157 Filyakova, T. I., 43(566), 80(899), 170, 179 Finan, J. M., 33(420e), 166 Finch, A. F., 117(1122), 186 Findeis, M. A,, 323(197), 349

790

Author Index

Findlay, J. D., 445(41), 452(141b), 462(141b), 477( 141b), 478( 14 Ib), 480( 14lb), 48 I (141b), 482(141b), 491(141b), 497(141b), 498(141b), 540(341b), 719 Finke, H. L., 441(93), 717 Finkenbine, J. R., 59(690), 88(690,959,960), 174, I 8 1 Finlay, J. D., 443(125b), 491(215b), 501(125b), 505(125b), 729 Finnegan, R. A , , 11(95), 18(95), 44(95), 155 Fiorentino, M., 25(253a,b), 160 Firestone, R. A , , 621(964), 748 Firl, J., 609(853,854b-e), 744 Firth, B. E., 66(758), 125(1262), 129(1300), 141(1378), 175, 190, 191, 193 Fischer, H., 128(1293), 191 Fischer, K . , 492(434), 494(434), 729 Fischer, M., 334(127), 347, 438(11), 714 Fish, I. S. 32(374), 164 Flad, G., 57(672), 173 Flanders, S. D., 553(659a), 555(659a), 561(659a), 562(659a), 579(659a), 737 Flath, R. A,, 667(1504), 766 Fleischer, J., 32(380), 164 Flemal, J., 666(1492), 766 Fleming, M. P., 59(682), 173 Fles, D., 548(628a,629a), 549(639-641a), 550(629a,642,643), 555(629,639,642), 556(629a,639-641a,643,673b), 558(642), 736, 737 Fletcher, A . N., 9(60), 154 Fletcher, R., 11(85), 155 Flid, M. R., 32(370), 164 Flood, P . F., 438(4c), 714 Flood, T. C . , 58(675), 173, 233(183), 275 Flowers, M. C . , 145(1411-1418), 194 Flowers, R. A., 639(1204), 757 Flowers, W. T., 509(536b), 51 1(536b), 527(536b), 570(536b), 573(536b), 732 Floyd, D. M., 37(497), 108(1076), 168, 184 Fluck, E., 642(1266), 656(1372,1373), 658(1394), 661(1426), 663(1425b, l426), 664(1266), 666(1372,1373), 759, 762, 764, 765 Flygare, H., 353(7), 423 Flygare, W. H., 443(108a), 718 Flynn, G., 413(112), 427 Foag, W., 609(849), 744 Fogarasi, G., 439(23b), 630(23b), 715 Fohlisch, B., 569(704), 570(704), 571(71 I), 572(704), 573(704,711,719a), 574(704), 575(704,721), 738, 739 Fokin, A. V., 114(1115), 185, 630(1097), 753

Foldi, V. S., 473(338), 474(338), 726 Follmann, H., 222(127), 273 Fombert, C., 469(321), 725 Fondy, J. P., 85(942), 180 Font, J., 92(983), 182 Foote, C. S., 12(109), 13(109), 34(462), 36(462), 156, 167, 248(231), 277, 355(41), 358(39d), 360(39d,79a), 362(39d), 363(41), 364(30), 372(27), 379(27,39d,c), 400(79), 424, 426 Forbes Cameron, A , , 245(216), 276 Ford, S. H., 105(1061), 184 Forgue, S. T., 259(307), 279 Formichev, A. A , , 439(54e), 716 Fornaroli, M., 612(888), 616(888), 745 Fornasier, R., 50(617), 172 Forni, A., 284(12), 297(63), 307(21), 315(21), 317(21,63), 319(11,21,178), 320(63b), 343, 344, 345 Fornoret, E. J., 136(1305), 191 Forrester, A. R., 336(206), 350 Forster, W. R., 516(562c), 578(562c), 582(562c), 733 Forstner, J. A , , 668(1531), 767 Forratti, P., 31(351,352,357), 32(389), 163, 164 Foster, B., 30(314), 162 Foster, C. H., 224(138), 242(40), 243(40), 244(40), 247(40), 248(138,230), 254(40), 271, 274, 277 Foster, M., 400(78), 426 Foucaud, A , , 28(273), 39(536), 146(1428,1429), 160, 169, 195 Foulger, N. J., 112(1095), 185 Foureman, G. L., 245(221), 266(221), 276 Fournier, Y . ,639(1169), 755 Fourrey, J. L., 453(231), 457(231a), 469(231c,d,321), 511(231a), 722, 725 Fourrier, N., 473(339), 726 Fox, B., 338(150), 348 Fox, F., 34(435), 166 Fox, M. F., 53(642,643), 172 Francotte, E., 251(236), 277 Franz, K., 29(292), 161 Fraser, R. R., 11(94), 155 Frazier, K., 76(855), 178 Freche, A . , 121(1195), 188 Frechet, J. M. J., 54(646), 172 Frederick, R. C., 332( 116), 347 Freedman, J. P., 506(500), 731 Freeman, J. P., 232(174), 259(174), 275, 337(141), 338(21 I), 348, 350, 447(158), 462(158b), 491(158b), 492(158a,b,445b), 495(445b), 496( 158a,b), 497( 158a,b,500).

A u t h o r Index 504(500), 505( 158a,b), 506( l58b), 531(158a,h), 532(158a,b), 537(500), 540( 158a,b), 541(500), 542(500), 720, 729, 731 Freer, A . A , , 245(216), 276 Freger, A. A., 472(254h,329), 723, 725 Frei, B., 140(1373,1374), I93 Freitis, A . M., 509(536h), 5 1 1(536b), 527(536b), 570(536h), 573(536h), 732 Frenette, R., 115(1117a), I86 Frenkel, K., 267(347,348), 281 Frenkel, M. M., 667(1511,1512), 766 Frenzel, C. A , , 630(1056), 752 Freon, P., 102(1053), 114(1053), I84 Freppel, C., 80(898), 83(898), I79 Frese, E . , 622(966b), 642(966b,1273), 643(966b,1273), 644(966h), 748 Freudenberg, K . , 317(75), 345 Freund, E., 653(1360), 762 Freymann, R., 636(1153), 755 Fridh, C., 4(1 I), I53 Fridland, D. V., 667(15 12,1514,I5 16), 669(1538), 766, 767 Fried, J . , 105(1061), 106(1068), 184 Friediger, A , , 607(844a), 639(844a), 743 Friedman, A . J., 326(191), 349 Friedrich, L. E., 21(192,193), 158 Fristad, W. E.. 37(500), 168 Frit7, H., 121(1192), 149(1443), 188, 195, 663( l452a), 664(1478,1483), 765 Frolkina, 1. T., 34(466,467), 36(466,467), I67 Frornm, E., 632(11 I&), 754 F r o n n , G., 439(49), 440(49), 462(280c), 4h3(280c), 477(390a,b), 478(390a), 489(390a,b,424,425a), 490(425), 491(280c), 531(280c), 541(280c), 7I6, 724, 728, 729 Frost, A . , 5(18), 153 Fruchier, A , , 69(794), I76 Fryer, R. I . , 328(187), 349 F u , P. P., 199(11), 241(207), 263(239), 270, 276, 280 Fuchigami, T., 652(1350), 761 Fuchita, T., 61(701), I74 Fuchs, P. L., 59(688), 109(1079), 114(1 lo), 174, 184, 185 Fueno, T., 37(507), 168, 411(45), 425 Fuess, H., 605(824), 743 Fugimoto, M., 86(945), I81 Fugitt, R. B., 119(1180), I87 Fuhr, K. H., 83(927), I80 Fuhrhop, J . H., 34(459), 36(459,485), 167, I68 Fujihara, H., 444(136b), 446( 136b). 447( 136h), 457(136h). 719

79 1

Fujimoto, H., 37(493), 118( 1 I%), 168, 187, 641(1234-1237), 642( 1235), 646(1234), 758 Fujino, Y., 93(1003), I82 Fujisawa, K., 451(198-200), 721 Fujita, S . , 312(33), 336(33), 344 Fujita, T., 92(978), 125(1237), 181, 189 Fujiwara, Y., 34(430), 35(430), 38(430), 58(676), 166, I73 Fukada, N., 642( 1295,1303,1304), 643(1303,1304), 645( 1295,13 l4), 760 Fukuda, M., 652(1345), 761 Fukui, K . , 37(493), 118(1158). 168. 187, 441(76), 669(1543), 674(1543), 717, 767 Fukurnoto, K . , 25(250), I60 Fukushima, T., 514(559), 516(559), 525(559), 529(559), 531(559), 733 Fukutome, H., 41 1(45), 425 Fukuyama, T., 16(153), 32(404), 157, 165, 245(219), 276, 439(19), 715 Fulcher, J. G., 59(685), 114(685), I73 Fullgrahe, H. J., 667( 1494h), 668(1494b), 674( l494b), 766 Furnasoni, S., 92(988), I82 Funahashi, K . , 122(1211), I88 Fung, A . P., 125(1255a), I90 Funk, K. F., 444(126), 571(126), 572(126), 573(118), 574(126), 719, 739 Furman, E. G . , 5(14,15), I53 Furst, H., 9(47), 154 Furstenberg, G. T., 663(1442), 764 Furukawa, J., 151(1460), 195 Furukawa, M . , 93(1003), 182 Furukawa, N., 444(136), 446(136h), 447(136h), 457(136b), 461(275), 463(275), 482(275), 487(275), 505(136d), 506(136d), 719. 723 Furuno, K., 97(1022), 183 Furuya, T., 629(1046), 751 Fusco, A,, 122(1213), I88 Fushimi, T., 445(120,121), 450(120), 472(120), 476(20), 718 Fusi, A , , 34(435,461), 36(461,484), 166, 167, I68 Fuson, R. C., 353(5), 423 Fusstetter, H., 669(1535), 767 Fuzesi, L . , 632(1130), 754 Gabdzhanov, Z. G., 38(517), 44(517), I69 Gabriel, S . K., 21(191), I58 Gacek, M. J., 438(7g), 475(7g), 714 Gadaginamath, G. S . , 204(28-30), 218(30), 221(28-30), 222(28-30), 230( 157), 256(267,268), 261(268), 264(29), 265(28-30), 269( 157). 271, 274, 278

792

Author Index

Gadelle, C., 34(452), 36(452), 167 Gadziev, T. A., 125(1242), 189 Gagarina, A . B., 34(443), 35(443), 166 Gaile, A . A,, 480(395), 488(415), 728 Gailyunas, I. P., 30(302,328), 32(328,402), 33(411), 161, 162, 165 Gainsford, G. J., 339(204), 350 Gairola, C., 232(168), 275 Gal, D., 30(327), 162 Gal, G., 29(290), 161 Galakhov, 1. V., 653(1362), 762 Galan, M. A , , 92(983), 182 Gallagher, R. N., 639( 1188), 756 Galle, J. A,, 113(1101), 185 Gallegos, E. J., 441(95,96), 442(96), 718 Galli, R., 340(155), 348 Gallo, C. J., 145(1410), 194 Gallo, G. G., 593(769), 741 Galloni, G., 439(44), 480(392a), 716, 728 Galloy, J., 326(193), 327(193), 349 Gamba, A., 462(280c), 463(280c), 491(280c), 531(280c), 541(28Oc), 724 Gambaryan, N. P., 312(175), 349, 437(2b), 443(2b), 51 1(26), 714 Gandolfi, R., 497(508a,b), 543(508a,b), 731 Gandour, R. W., 145(1410), 194 Ganem, B., 33(424b,c), 44(572), 166, 170, 206(53,54), 208(53), 21 1(53,54), 271 Gann, R. G., 372(24), 424 Gannon, J., 151(1475), 196 Ganschow, S . , 313(37), 344 Gapanovich, L. I., 550(645), 551(648), 736 Gara, W. B., 470(328a), 485(403), 725, 728 Garati, G., 297(63), 317(63b), 320(63b), 345 Garber, M., 639(1172,1181,1183,1189), 640(1172,1181,1183), 755, 756 Garbesi, A., 456(255), 509(255), 511(255), 723 Garbuzov, V. G., 443(110), 718 Gardner, P. D., 130(1309), 191 Garegg, P. J., 61(703), 174 Garibaldi, P., 497(508a,b), 543(508a,b), 731 Garito, A. F., 658(1400,1401), 659(1401), 660( 1400,l40l), 763 Garland, W. A,, 199(19), 200(19), 270 Garnish, F. W., 151(1474), 196 Garrett, P. E., 22(202), 158 Garson, D. H., 24(234), 159 Gasanov, F. G., 92(979), 182 Gasis, A . , 122(1213), 188 Gassman, P. G., 114(1116b). 185, 332(116), 347 Gattow, G., 609(856a), 638(1161), 744, 755 Gault, F. G., 84(939), I80

Gault, Y., 84(939), 180 Gavrilenko, V. A , , 32(372-374,392), 164 Gawdzik, A , , 34(463), 36(463), 167 Gawron, O., 85(942), 180 Gawronska, A , , 46(587), 171 Gaylord, G., 151(1485), 196 Gazzard, I. J., 12(99), 155 Gedra, A., 30(327), 32(386), 162, 164 Gee, G., 151(1483), 196 Geenen, P. V., 34(466b,d), 36(466b,d), 167 Geismann, C., 564(691b), 578(691b), 738 Geiss, K. H., 54(655), 173 Gelas-Mialhe, Y., 650(1336), 761 Gelboin, H. V., 258(278,279), 259(303,305), 261(323), 262(337), 278, 279, 280 Gel’bstein, A. I., 34(466), 36(466), 167 Geneste, P., 84(938), 86(938), 87(938a), 180 Gent, W. L. G., 13(133), 156 George, A. V. E., 516(562a), 525(562a), 733 George, D. A ,, 9(51), 14(51), 154 George, J . K., 630(1053), 751 Gerdeler, J., 606(832), 743 Gerell, R., 438(4a), 714 Gerkin, R. M., 68(776), 176 Germain, G . , 333(205), 350, 562(648a,685), 563(684a,685), 564(684a,685), 566(684a), 567(696), 576(685), 577(696), 666(1492), 738, 766 German, L. S., 80(899), 179, 672(1566), 768 Gersanova, E. L., 21(190), I58 Gershanov, F. B., 285(38), 286(38), 290(38), 313(38), 344 Gey, E., 598(796c), 741 Ghatah, K. L., 97( 1020), 183 Ghate, S. P., 492(461), 730 Gherepanov, E. G., 81(905a), 179 Ghersetti, S . , 480(392a), 728 Ghio, C., 330(105), 347 Ghirardelli, R . G., 125(1259), 190 Ghoudikian, M., 642(1302), 645(1302), 646( 1302), 760 Ghrayeb, J., 256(260), 277 Gianni, M. H., 10(73), 147(1432), 151(1454), 155. 195 Gibbs, H. H., 592(766), 593(773), 597(773), 61 1(766), 614(766), 615(766), 616(773), 619(766), 741 Gibson, D. J., 264(335), 280 Gibson, D. M., 142(1392), 194 Gibson, D. T., 259(298-301), 279 Gibson, J. S . , 670(1547), 767 Gibson, K. H., 438(7a), 714 Gibson, R. M., 31(339), 163

Author Index Giddey, A , , 51(618), 172 Giering, W. P., 60(696), 174 Giertz, H., 512(542,544), 733 Gilbert, B. C . , 151(1457), 195, 339(169), 348, 470(328a), 725 Gilbert, J. R., 442(99), 718 Giles, J. R. M., 471(328h), 725 Gill, N., 444( 117), 468( 117), 718 Gillespie, R. J., 669( 1544,1545), 674( 1579- 158 I ) , 767 Gillette, J. R., 266(344), 280 Gilli, G., 562(683a), 563(683a), 564(683a,689), 566(689), 738 Gillies, C. W., 8(43), I54 Gillis, H. A , , 464(294), 724 Gilman, S., 25(248), 160 Gilson, D. F. R., 439(46,47), 440(47), 716 Gilyazov, M . M., 622(979), 748 Gimharzevsky, B. P., 61 1(875,878), 613(875), 614(875), 616(878), 617(875,878), 745 Gimharzevsky, J. G., 613(878), 745 Ginot, Y. M., 267(355), 281 Ginshurg, D., 22(207), 158 Gioia, B . , 69(780), 176 Giordan, J., 628( 1019d), 750 Giorgianni, P., 563(686-688), 564(689,690), 566(687,689), 589(751c), 612(751c), 614(751c), 738, 740 Girard, J. P., 11(98), 19(183), 44(183), 155, 158 Girelli, A , , 441(91), 717 Girgenti, S. J., 249(233), 277 Girijavallahhan, M., 151(1456), 195 Giriya, C. K., 29(288). 161 Giuffre, L., 612(888), 616(888), 745 Gladiali, S., 47(596a), 171 Gladysr, J. A , , 59(685), 114(685), 173 Glaeske, G., 604(822g), 606(822g), 742 Glamkowski, E. J., 29(290), 161 Glase, W. H., 111(1092), 185 Glass, R. S . , 633(1134a), 754 Glassel, W., 656(1376), 662(1376), 663(1376), 762 Glassman, R., 497(507), 503(507), 543(507), 73I Glaumann. H., 260(313), 279 Glarkov, Yu. V., 98( l025), 183 Glazurina, I. I., 73(822), 177 Gleason, .I. G . , 452(201), 516(201), 721 Gleiter, R.. 589(752a), 625( 1002), 626( 1002), 740, 749 Glemser, O., 660( 1407). 763 Glidewell. C .. 604(822h). 606(822h), 742

793

Glotter, E., 118(1165), 120(1182), 187, 188 Glusker, J. P., l99( 10,l I ) , 270 Glusko, L. P., 1 l9( 1 I R I ) , 187 Gnedenkov, L. Yu., 19(181), 81(905a), 158, 179 Goddard, W. A., 111, 37(490), 168, 412(105), 427 Goddu, R. F., 9(61), 154 Goering, H. L., 11(92), 155 Goethals, E., 444(135), 445(135), 480(135), 491(135), 719 Goethals, E. J., 151(1472), 196, 441(78e), 444(136), 473(78e,136a,345-352), 671(1557), 717, 719. 726, 768 Goetzky, P., 151(1465), 196 Goff, D. L., 137(1355,1356), 138(1355), I92 Gogte, V. N., 512(540), 527(587c,588a), 529(58Rc), 733, 734, 735 Goh, S . H., 216(87,89), 217(87,X9), 219(89), 2 72 Gohta, N., 125(1261), 190 Golan, D. A,, 355( 127) 428 Golan, D. E., 357(127), 387(86), 389(127), 391(125), 392(127), 403(85), 412(86), 426, 428 Golding, B. T., 24(218), 159 Goldish, D. M., 589(755d), 740 Gol’dshtein, I. P., 464(293), 724 Goldstein, J. H . , 630(1058), 752 Golfier, M., 44(569), 170 Golik, U., 302(15), 305(15), 344 Gollinick, K., 37(494), 168 Golovkin, V. M . , 636(l l57d), 637(l l57d), 655( 1 157d), 755 Golovnya, R. V., 443( 1 lo), 718 Gomhos, J., 46(590), 171 Gomer, R., 127(1283), 191 Gomez, R. R., 355(107), 356(107), 357(107), 390(107), 392(107), 413(107), 427 Gompper, R., 642(1257,1260,1261,1294), 645( 1294), 646( 1257), 647( l257), 759, 760 Gonoboblev, L. N., 63(730), 175 Gonzale7, F. S., 632( 1134h), 754 Gonzalez, G., 661(1426), 663(1426,1452b), 764 Good, W. D., 441(90), 717 Goode, R . L., 268(366), 281 Goodman, A . L.. lO(63). 154 Goodman, I.., 450(188), 462(188), 468(188), 721 Goor. G.. 4 4 3 1 12a), 718 Gopichand. Y., 548(630), 55 1(630), 556(630), 571(630), 575(630). 621(962), 736, 748 Gopinathan, M. S., 490(426), 729

794

Author Index

Goralski, C. T., 490(427), 495(427), 496(427), 729 Gore, J., 37(514), 169 Gorelov, V. .F., 636(1157d), 637(1157d), 653(1363), 655(157d), 755, 762 Gorgues, A , , 629(1038b), 751 Gorski, R. A,, 66(755,757), 175 Gosavi, R. K., 4(9), 37(506,508), 153, I68 Gosciniak, D. J., 327(191), 349 Gosney, I., 642(1299), 649(1299), 760 Gossaver, A,, 622(966a), 748 Gosselck, J., 53(638), 172 Goth, H., 609(854a,b,e), 744 Goto, H., 339(202), 350 Goto, S . , 60(695), 174, 215(91), 216(91), 272, 452(202b), 499(202b), 721 Goto, T., 16(153), 33(420), 157, 166, 352(1,3), 354( 14b), 363(47a), 381(47a), 407(47a,47b), 415(47a,b), 420(3,14), 422, 423, 425 Gott, P. G., 534(601), 546(601), 583(601), 630( 1082,1084), 735, 752 Gotthardt , H., 453(2 16,Z17,221,224-226,232, 233,235,236,239,240), 462(216), 469(221,232,233,320), 472(320), 474(239,24Oa), 513(545b,c), 516(545b,c,562b), 519(545c), 552(239,24Oa), 578(216,217,235,236,239,240a), 581(216,217), 586(216,217), 722, 725, 733 Gottstein, W., 569(704), 570(704), 572(704), 573(704,719a), 574(704), 575(704), 738, 739 Goubeau, J., 667(1498), 674(1577), 766, 768 Could, E., 30(323), 31(323), 32(369), 34(432), 162, 164, 166 Gourcy, J. G., 637(1158), 755 Goutarel, R., 332(117), 347 Gowland, B. D., 115(1119), 186 Grabley, F. F., 602(810,81 la), 622(81 la), 638(1162), 642(811a,1162), 643(1162), 646( 1162), 647( 1162), 742, 755 Grabley, S . , 602(810), 604(822e), 606(822e,831a), 608(831a), 742, 743 Gradl, R., 629(1045), 751 Graf, C., 508(529b), 732 Graham, R., 298(67), 314(67), 315(67), 345 Granger, R., 11(98), 19(183), 44(183), 155, I58 Graslund, A., 267(353), 281 Grasselli, P., 55(662), 59(677), 173 Grauer, A., 216(93), 272 Gray, C. E . , 114(1111), 185 Gray, M. D. M., 61 1(875), 613(875), 614(875), 617(875), 745 Grayhill, G. R., 438(15), 714 Graymore, J . , 601(802,804b,805,806),742 Greatbanks, D., 245(216), 276 Gredy, B., 13(128,129), 156

Green, G. E., 68(779), 176 Green, M. J., 509(531f), 511(531f), 732 Green, M. L. H., 59(683), 173 Greenberg, K. A ,, 526(586), 734 Greene, R. M. E., 204(26,31,32), 22 l(26,3 1,32,118), 222(26,3 1-33), 264(26,31-33,118), 265(118), 272, 273 Greenfield, S. A., 639(1205), 640(1231), 757, 758 Greengrass, C. W., 23(209), I59 Greenhalgh, P. F., 24(230), 159 Greenwood, R. A,, 661(1431), 666(1431), 764 Greidanus, J. W., 630(1099a), 753 Greijdanus, B., 28(271), 160 Gremer, D., 224(i39), 274 Grieco, P. A,, 25(248), 160 Griesbaum, K., 150(1451), 195 Griffin, A. C . , 37(492), 168 Griffin, A. M., 658(1395), 763 Griffin, G. E., 144(1406), 194 Griffin, G. W., 127(1281,1282), 131(1281,1282), 132(1282), 141(1281,1379,1380), 142( 1382-1388,1391, 1392,1394,1395), 143(1399,1400,1404), 144(1406-1408), 145(1410), 190, 192, 193, 194, 2 15(83,94), 2 16(83,94), 226( 142), 229( 148), 230( 150,15 1 ,1 5 9 , 239(94,196), 241(196), 252(142), 254(248), 269(155), 272, 273, 274, 276, 277, 307(32), 344 Griffin, M. T., 121(1198), 188 Griffiths, V., 439(15h), 443(15h), 715 Grigg, R., 74(837,838), 75(837,838), 177 Grigo, U., 310(170), 348 Grill, H., 590(757), 591(757), 740 Grimaldi, J., 24(222), 82(908), 159, 179 Grimm, R. A , , 629(1046), 631(1106), 633(1106), 751, 753 Grimme, W., 252(239), 253(239), 277 Grinbevich, V. G., 305(184), 349 Grinev, M. P., 398(76), 426 Grinkevich, 0. A,, 93(1000,1001a), 182 Grishina, 0. N., 662(1437), 663( 1443,1445,1446), 764 Grishkevich-Trokhimovskii, E., 443( 113a), 457(113a), 462(113a), 465(113a), 466(113a), 472(113a), 491(113a), 511(113a), 718 Grisson, C., 82(913), 280 Critter, R. J., 3(3), 14(3), 127(1286), 141(1286), 152, 191 Grob, C . A., 376(34), 424, 599(800d), 742 Grobov, L. N., 449(180), 450(179b), 475(180), 491(180), 720 Groenweghe, L. C. D., 662(1433), 666(1433), 764

Author Index Gronowitz, S., 642( 1253), 646(1253), 759 Gross, M. E., 441(93), 717 Grosser, J., 100( 1044), 183 Groth, C., 643(1270), 647(1270), 759 Grover, P. L., 255(257), 267(257,346,355), 269(257,372), 277, 281 Grubb, S . D., 83(925), 180 Gruber, R., 452(202a), 462(202a), 469(202a), 491(202a), 499(202a), 501(202a), 721 Grubmiiller, P., 355(62), 356(62), 360(62), 362(62), 365(62), 389(62), 390(62), 391(62), 393(62), 413(62), 425 Grunberger, D., 258(28 l), 267(347,348), 278, 281 Grund, N., 438(3a), 452(3a), 489(421), 492(3a), 497(3a), 498(3a), 505(3a), 531(3a), 540(3a), 714, 729 Gruner, Ch., 663(1442), 764 Grunwell, J. R., 630(1091), 632(1091), 753 Guegan, R., 122(1207a), 188 Guenther, H., 664(1465), 765 Gucrra, M., 458(261b), 511(261b), 723 Guest, I . G., 70(799), 177 Guggenheim, T. L., 114(11 16b), 185 Guha, P. C . , 607(839a,b,841-843), 621(839a,b,955,958), 626(1010), 743, 748, 750 Guidon, Y., 115(1117a), 186 Guilhem, J., 439(18), 715 Guillaume, I., 443(108), 718 Guilmet, E., 39(536a-b), 169 Guiman, C., 439(21), 477(21), 715 Guixner, J., 28(271a), 160 Gundermann, K. D., 352(3), 420(3), 423 Giinther, H., 147( 1433), 195, 198(1), 199(7,8), 202(20), 205( l), 206(1), 209(1,20), 220(1), 221(1), 222(1), 239(1), 247(1), 254(1), 270, 271, 439(29b), 715 Gunthard, Hs. H . , 9(47), 154 Gupta, R. P., 612(887a), 617(887a), 745 Gupta, S . K., 631(1111), 753 Guroff, G., 231(162), 275 Gurria, G. M., 125(1248), 189 Gur’yanova, E. N., 464(293), 724 Gur’yanova, G. P., 484(401), 728 Guseinov, Sh. L., 34(466,467), 36(466,467), 167 Gusel’nikov, L. E., 624(985a,b), 749 Gusenkov, M. V . , 59(686), 173 Guseva, F. F., 449(174-177,184), 459( 177,184), 474( 177,184), 475( l77,184c), 720 Gusinskaya, S. L., 520(578), 529(578), 734

195

Gustafsson, K., 449( 169), 462(169), 491(169), 506(169), 508( 169), 533(168), 720 Gutman, A . D., 661(1415), 663(1415), 763 Gutman, D., 633(1131a), 754 Gutmann, V., 667(1518), 668(1518), 767 Gutowsky, H. S., 10(66), 154, 439(57b), 440(57b), 716 Guyon, R., 67(766), 68(766), 79(890,893), 176, 179 Guzikov, A. Ya., 98(1025), 183 Guzman, J., 458(264c), 472(264c), 473(264c), 5!1(264c), 723 Gwinn, W. D., 439(28a,37), 440(37), 715 G w i n n , W. M. D., 8(42), 154 Haaf, F., 656(1371), 762 Haake, M., 52(628), 53(628), 172 Haas, A , , 660(1404), 672( 1558,1562,1564,1565,1567), 763, 768 Haas, C. K . , 667(1499), 766 Haas, D. D., 253(242), 277 Haas, Y., 413(112), 427 Haddadin, M. J., 337(141), 338(211), 348, 350 Haddon, R. C., 625(999b), 626(999b), 630(999b), 642(999b,1253), 646(1253), 659(999c), 749, 759 Haddon, V. R., 51 1(538), 732 Hag, M. Z . , 353(5), 423 Hagen, H., 5!2(541-544), 517(541), 525(542-544), 733 Hagen, J. P., 457(260), 458(260,26la), 51 1(260,26la), 723 Haines, H., 13(123), 156 Haines, W. E., 439(41b), 440(41b), 441(41b), 442(41b), 443(41b), 469(311), 716, 725 Hajdu, I. P., 32(386), 164 Hakkinen, A . M., 439(54a,56a), 716 Hakushi, T., 37(499), 168 Hales, J. L., 630(1068a), 638(1068a), 752 Hales, R. H., 620(952), 747 Halevi, E. A , , 41 1(45), 425 Haley, N. F., 642(1264), 646(1264), 672(1559), 759, 768 Hall, C. R., 445(141b), 452(141b), 462(141b), 476(38 l ) , 477( 14 1b,38 l ) , 478( 14 Ib), 480(14!b,381), 481(141b), 482(141b), 491 (14 Ib), 492( 14 1b,38 I), 497( 141b), 498(141b), 540(141b), 546(621b), 719, 727, 735 Hall, D. M. C., 447(155,156), 475(156), 719 Hall, W. K., 34(469), 36(469), 167 Hallet, P., 133( l334,1334a, 1335,1335a), 192 Halmos, M., 9(57), 154

196

Author Index

Halovi, E., 12(100), 155 Halpern, A. M., 398(77a,b), 426 Halpert, J., 260(313), 279 Halstenberg, H., 88(954), 181 Halstenberg, M., 657(1386,1387), 762 Haltiwanger, R. C., 658(1396), 763 Hamada, M., 61 1(872c), 744 Hamada, Y., 25(251a), 160 Hamanaka, N., 438(7b-e), 443(7b-e), 446(7b-e), 447(7b-e), 714 Hamann, K., 24(227), 159 Hamberger, H., 143(1401,1402), 146(140 1,1402), 194 Hamblin, P., 622(968), 748 Hambrecht, J., 99(1031), 183 Hamel, P., 588(747), 740 Hamid, A. M., 492(433a), 495(433a), 502(433a), 503(433a), 535(433a), 729 Hamilton, G. A , , 39(532), 169, 215(84,85), 216(84,85), 217(85), 272 Hamilton, H . A , , 639(1171), 755 Hamilton, J. G., 202(23), 204(23,29), 220(115). 221(23,29,115), 222(23,29), 246(115), 262(115), 264(23,29), 266(115), 271, 273 Hamilton, L. A, , 465(307b), 724 Hamilton, R., 256(267), 278, 323(82), 346 Hammen, P. D., 486(404,406a), 502(406a,5 16-520), 504(5 16,517), 728, 732 Hammer, E. R., 546(621b), 735 Hammond, P. J., 628(1022b), 750 Hanafusa, H., 33(416), 165 Hand, C. W., 37(510), 168 Haneda, Y., 354(14c), 420(14), 423 Hanefeld, W., 604(822f,g), 606(822f,g), 616(921b,933a,b), 742, 746, 747 Haniu, Y., 576(7 16c), 577(7 16c), 582(7 16c), 739 Hanky, W. S., 548(626), 549(626), 555(626), 556(626), 736 Hann, R. A., 364(87a), 365(87a), 407(87), 426 Hannemann, K., 403(84), 426 Hanselaer, R., 44(575), 170 Hanson, J. R., 245(218), 276 Hansson, B., 114(1112), 185 Hanzlik, R. P., 16(165), 43(561), 157, 92(982), 120(1189), 157, 170, 182, 260(316), 280 Hara, S ., 631(1113b), 753 Harada, K., 124(1229), 189 Harada, M., 126(1265), 190 Harada, T., 639(1207), 640(1207), 757 Harakal, M. E., 327(189), 349 Hardgrove, G. L., 476(383), 727

Harding, B., 37(490), 168 Harding, D. R. K., 614(920), 746 Harding, L. B., 412(105), 427 Harding, M. J. C., 353(10), 423 Hardstone, D. J., 349(186), 324 Hardy, M., 210(74), 212(74), 272 Hargittai, I., 630(1050), 751 Hariharan, P. C., 14(145), 157 Harkanyi, J., 34(474), 36(474), 39(474), 167, 626(1006), 628( 1006), 629( 1006), 750 Harlow, R. L., 524(583,585), 734 Harpp, D. N., 452(201), 484(402b), 516(201), 620(949), 721, 728, 747 Harrington, H. W., 439(28), 715 Harris, C. C., 258(288), 279 Harris, C. M., 69(784), 176 Harris, C. R., 639( 1185), 756 Harris, D. O., 439(28a), 670(1547), 715, 767 Harris, L. E., 524(583), 734 Harris, M., 630(1082), 752 Harris, M. S . , 355(127), 357(127), 387(86), 389(127), 391(125), 392(127), 412(86), 426, 428 Harris, T. M., 69(784), 176 Harris, W . C., 630(1051,1055a), 636(1151), 751, 755 Harrison, C. R., 24(223), 159 Harrison, F. P., 639( 1170), 755 Harrison, J. M., 331(115), 332(115), 347 Hart, H., 21(194), 37(515), 69(791), 133(194), 139(1363-1365), 140(1366), 158, 169, 176, I93 Hart, M., 11(96), 155 Hart, R. W., 212(69), 272 Hartig, U., 36(482), 168 Hartke, K . , 93(1002), 182, 453(245c,d), 476(245c), 607(838c,d), 642(1273b), 643(1273b), 664(838d), 722, 743, 759 Hartless, R. L., 142(1396), 194 Hartman, B. C., 79(897), 107(1069), 179, 184 Hartman, R., 135(1342), 136(1350), 192 Hartmann, J., 114( 1109), 185 Hartshorn, M. P., 45(578), 66(746-751), 170, I75 Hartstock, F., 629(1038), 751 Harvey, A. B., 670(1548,1549), 671(1556), 767, 768 Harvey, R. G., 199(10,l l), 216(87,89,90), 217(87,89), 219(89), 241(207), 245(222), 267(349), 270, 272, 281 Harwood, H. J.,20(184), 158 Hasegawa, H., 34(457), 167, 191

Author Index Hasegawa, T., 630(1090), 753 Hasek, R. H., 492(495a), 495(495a), 496(495a). 506(495a), 534(495a,601), 535(495a), 541(495a), 546(495a,601), 583(495a,601), 731, 735 Hashimoto, S . , 438(7e), 443(7e), 446(7e), 447(7e), 714 Hashirnoto, Y . ,71(804), 73(804), 177 Hashmall, J. A,, 330(104), 347 Haslanger, M. F., 108(1078), 184 Hassan, K. M., 602(812d), 604(812d), 742 Hassau, M., 63(733), 175 Hassner, A,, 120(1204), 121(1204), 188, 307(166), 337(27b), 344, 348 Hastings, J. W., 395(66), 397(66), 426 Hasty. N. M., 358(39g), 379(39g), 424 Haszeldine, R. N., 630(1102b), 637( 1102b), 753 Hata, S . , 99(1029), 183 Hata, Y . ,286(165), 327(95), 329(195), 342(95), 346. 348, 349 Hatanaka, 110( 1085c), 184 Hatch, J. M., 52(625), 172 Hatsui, T., 37(498), 168 Hattori, H., 72(805), 177 Hattori, T., 121(1194), 188 Haun, M., 421(146), 428 Hauptschein, M., 631(1108,1109), 633(1109), 634( 1 108), 753 Hauser, E., 651(1341c), 656(1341c), 761, 762 Hauthal, G., 29(292), 161 Havel, J. J., 37(513), 169 Hawkins, D. W., 626(1009), 750 Hawkins, E. G . E., 340(156), 348 Haya, K., 438(8a), 449(170), 452(8a), 462(8a,170), 488(8a), 491(170), 492(8a,465), 495(8a,465), 496(465), 497(8a,170), 498(8a), 502(465), 503(8a,170), 505(465), 506(8a,170). 508(8a,l70), 53 1(8a), 534(8a,170), 541( 170), 714, 720, 730 Hayakawa, T., 31(353), 163 Hayami, S . , 303(70), 304(70), 341(70), 345 Hayashi, K., 119(1179), I87 Hayashi, M., 438(7b-e), 443(7c-e), 446(7b-e), 447(7b-e), 714 Hayashi, S . , 93(1003), 182 Hayashi, Y . ,644( 1312,1313), 646( 1312), 760 Hayasi, Y., 536(608), 735 Hayden, P., 36(481), 168 Hayers, R., 74(838), 75(838), 177 Hayes, D. M., 199(19), 200(19), 270 Hayes, E. F., 7(34), 153

797

Hayes, P. M., 439(41c), 440(41c), 441(41c), 716 Hays, H. R . , 444(132), 450(132c), 457(132), 464(194b), 468(132c), 719, 721 Healey, M. M., 26(257), 160 Heap, N . , 68(779), 176 Heap, P. F., 438(4c), 714 Heeger, A. J., 658(1400,1401), 659(1401), 660( 1400,140I), 763 Heeren, J. K., 62(716), 174 Heggs, R. P., 33(424b,c), 166 Hehne, A,, 400(81), 426 Hehre, W. J., 14(145), 157 Heibl, C., 638(1164), 642(1164), 643(1164), 646( 1 164), 755 Heicklen, J., 469(316), 725 Heidelberger, C., 241(202,203), 276 Heilmann, S. M., 627(1015), 750 Heilmayer, P., 667(1518), 668(1518), 767 Heim, P., 78(879), 82(879), 179 Heineman, U., 642(1257), 646(1257), 647(1257), 759 Heinrich, G. R., 68(775), 176 Heinz, G., 621(957), 748 Helder, R., 28(270), I60 Heller, C. A,, 370(19), 379(180), 424 Helling, D., 561(680b), 579(680b), 582(680b), 738 Helm, R. V., 439(41b), 440(41b), 441(41b), 442(41b), 443(41b), 716 Helquist, P., 107( 1075), 184 Hernandez, O., 245(221), 266(221), 2 76 Hempel, A., 317(68), 345 Henbest, H. B., 26(259), 160 Henderson, W. A ,, 136(1347), 192 Hendra, P. J., 474(372), 727 Hendrick, M. L., 142(1386), 193 Hendrickson, W. H., 379(40), 424 Henes, G., 210(75), 212(75), 272 Henion, R. S . , 491(430), 545(619), 546(619), 729, 735 Henjes, H., 656(1375), 762 Henke-Stark, Fr., 630( 1 IOO), 753 Henrickson, C . H., 465(302), 724 Henriksen, L., 642(1254a), 759 Henriquez, P. C., 443(104), 718 Henry, M. C., 668(1526), 767 Henry, Y . , 14(141), 157 Henry-Basch, E., 101(1052), 102(1052), 103( 1053), 104( 1052), 105( 1052), 113(1102,1103), 184, 185 Henscher, J. L., 625(998a), 749

798

Author Index

Henssen, G., 453(245c), 476(245c), 607(838e), 722, 743 Henton, D. E., 138(1357), 193 Hepel, A., 317(176), 349 Hercules, D. M., 414(114,117), 415(117), 427 Hermdon, W. C . , 514(560e), 733 Hernandez, O., 266(342), 269(376), 280, 282 Herr, R. W., 106(1067), 107(1070), 110(1067,1070), 184 Herscheid, J. P. M., 245(217), 276 Hertler, W. R., 447(149), 457(149), 511(149), 719 Hervey, J., 632( 1120c), 754 Herzschuh, R., 442(102h), 718 Hesp, B., 245(216), 276 Hess, H., 656(1375), 762 Hess, J., 380(63h), 425 Hesselho, T., 656(1370), 762 Hester, J. B., Jr., 311(198), 349 Hetschko, M., 53(638), 172 Hetther, M. R., 9(48), 154 Heuman, A,, 34(460c), 36(460c), 167 Heusser, H., 9(47), 154 Hevesi, L., 13(121), 46(581), 156, 171 Hewer, A., 255(251), 277 Hewett, W. A , , 447(148), 465(148), 719 Hey, R. G., 669(1546), 767 Heyne, H. U., 307(25), 309(25), 335(129), 344, 347 Hiatt, R., 30(323,329,334), 31(323), 32(334), I62, I63 Hihbert, H., 151(1477,1478), 196 Hickey, M. J., 439(20), 715 Hidaka, H., 94(1006), 182 Hiersemann, W. D., 667(1498), 766 Higa, T., 570(707), 574(707), 578(707), 579(707), 739 Higginson, W. C. E., 151(1483), 196 Highet, R. J . , 214(80), 258(80), 266(344), 272, 280 Hii, G. S. C., 136(1351), 137(1352), 192 Hildehrandt, A , , 642(1309), 644(1309), 647(1316), 760 Hildon, A . M., 24(229,230), I59 Hilgetag, K. P., 335(129), 347 Hill, D. R., 481(397a), 482(397a), 728 Hill, M. L., 130(1309), 191 Hillhouse, J. H., 615(924a), 616(924a), 746 Hino, M., 72(81 l), 177 Hinrichs, T. A , , 37(501), 168 Hinson, J. A , , 266(344), 280 Hinze, J., 411(45), 425

Hirahayashi, T., 630(1057b), 631(1057h), 632(1057b,l121c), 633(1057h), 635(1057h), 636(1057b,1121c), 752, 754 Hirai, K., 492(490), 495(490), 502(490), 580(736,737), 731, 738, 740 Hirano, A,, 641( 1238,124 1,1242), 642( 1238,1241,1242), 758 Hiraoka, T., 596(768), 741 Hirata, Y . , 60(695), 174 Hiratsuka, A,, 206(43), 207(43), 246(226), 271, 277 Hirobe, M., 216(86), 217(86), 219(86), 272 Hiroka, T., 593(768), 594(768), 597(768), 741 Hirose, C., 4(13), 6(13), 8(13), 9(13), 12(13), I53 Hirose, K., 121(1194), 188 Hirose, Y., 642(1295), 645(1295), 760 Hiroshi, K. H., 123(1222), 189 Hirota, E., 439(31), 440(31), 715 Hirota, H., 480(392c), 493(392c), 728 Hirota, R., 441(82), 717 Hirschmann, F., 353(9), 423 Hirukawa, H., 592(759,760), 596(759,760), 740 Hisashige, M., 84(937), 180 Hitchcock, P. B., 364(170), 429, 602(811c), 742 Hiyama, T., 54(649), 172, 312(33), 336(33), 344 Ho, M. S., 37(502), 168, 361(39e), 379(39e), 382(39e), 424 Hochstetler, A. R., 22(199), 39(199), 158 Hoch, H., 353(6), 423, 492(478), 730 Hock, A. L., 457(256), 511(256), 723 Hoda, M., 125(1237), 189 Hodge, P., 24(223), 159 Hodge, V. F., 355(157), 429 Hoechst, A. G., 24(228), 159 Hoeft, E . , 33(418), 165 Hoey, J. G., 53(642), 69(783), 150(1449), 172, 176, 195 Hoffman, D. M., 16(162), 157 Hoffmann, G., 574(720), 739 Hoffmann, H., 456(254e), 572(254e,717), 575(254e), 577(254e), 579(7 17a,720), 580(254e), 581(254e), 586(254e), 595(788), 723, 739, 741 Hoffmann, K. L., 210(76), 212(76), 272 Hoffmann, R., 142( 1393), 146(1393), 194, 199(15), 200(15), 270 Hoffmann, R. W., 537(612,613), 545(613), 546(612,613), 735 Hoffmann, W., 46(585), 171

Author Index Hofmann, H., 247(229), 277 Hofmann, P., 247(229), 277 Hoft, E., 306(19), 344 Hoft, V. E., 313(37), 344 Hogel, J . , 663( 1459), 765 Hogeveen, H., 254(250), 277, 498(51 I), 509(536d), 510(537), 51 1(536d), 612(891), 731. 732, 745 Hoggett, J . G., 492(460), 495(460), 730 Hohne, G., 385(55), 425 Holand, S . , 43(562), 170 Holbert, G. W., 206(53,54), 208(53), 21 1(53,54), 271 Holcomb, W. D., 499(515), 731 Holder, G., 259(302), 279 Holder, G. M., 215(108), 217(108), 273 Holl, P., 94(1011,1012), 182 Holland, D., 34(434), 166 Holland, D. O., 446( 145), 449( 145), 457( 145), 468(145), 511(145), 719 Holliday, J. M., 639(1174), 640( 1174), 755 Holm, A , , 672(1568), 768 Holm, R. H., 629(1029,1032,1042), 750, 751 Holmes, J. L., 8(36), 154, 442(102a), 718 Holovka, J. M., 130(1309), 191 Holt, G., 509(536b), 51 1(536b), 527(536), 570(536b), 573(536b), 732 Holtmann, H., 492(435), 729 Holubka, J. W., 25(244), 159 Hong, M., 266(344), 280 Honmaru, S . , 264(326), 280 Hopkins, T. A,, 354(13), 417(13), 423, 428 Hopkinson, A . C., 118(1159), 187 Hopfner, U., 626( 1008), 750 Hoppe, D., 4(8c), 15(8c), 32(8c), 153, 640(1233), 758 Horak, V., 441(81b), 465(296a), 717, 724 Hori, A , , 215(91), 216(91), 233(180), 272, 631(1112), 753 Hori, M., 516(565a,b), 525(565), 734 Horie, H., 7(30), 125(1239), 153, 189 Horn, K. A., 352(1), 355(51), 382(51), 386(51), 389(51), 405(51), 408(51), 422, 425 Horner, L . , 284(9), 327(9), 343, 664(1488), 766 Homing, M. G., 230(150,151), 274 Hortmann, A. G., 516(566a), 520(581b), 576(581b), 577(581b), 734 Hosegawa, T.. 632(1090), 753 Hoshimo, H., 97(1022), 183 Hoshino, M., 514(559), 516(559,566b), 525(559), 529(559), 733, 734

799

Hostlettler. F., 439(15j), 462(15j), 474(15j), 475(15j), 488(15j), 491(15j), 715 Hotta, H., 285(45), 289(45), 290(45), 341(45), 342(45), 344 Hotta, K., 653(1356), 762 Houk, K . N., 15(148), 145(1410), 157, 194, 441(94), 442(94), 718 House, H . O., 47(594), 66(745), 171, 175, 502(522a), 732 Houser, R. W., 492(445b,491), 495(445b,491), 497(501), 499(491), 508(501), 729, 731 Houston, P. L., 632( 1122), 754 Howard, E. G., 614(903), 616(903), 630(1065,1075,1085), 631(1065), 632(1065,1075), 635(1075,1085), 746, 752 Howe, B. R., 8(20), 153 Howe, D. V . , 629(1043), 751 Howe, G., 30(334), 32(334), 163 Howell, W. R., 151(1475), 196 Howes, P. D., 642(1291), 645(1291), 760 Ilowie, G. A , , 11(97), 155 Hrenoff, M. K., 10(65), 154 Hritzova, O., 606(838a), 607(838a), 743 Hromatka. O., 632(1 120a), 754 Hrudlik, A . M., 61(705), 174 Hsu, Y. F., 464(288,289), 482(288), 510(288), 628(1023), 724, 750 Huang, C., 628(1022b), 750 Huang, Z . T., 121(1206), 188 Hubbard, W. N., 441(92,93), 717 Huber, G., 53(637), 172 Huber, J . H. A , , 138(1357), I93 Huberman, E . , 262(337), 280 Hubert, A . J., 36(486), 168 Huckstep, L. L., 245(215), 276 Hudrlik, A . M., 61(700), 68(771), 174, 176 Hudrlik, P. F., 61(700,704,705), 64(741), 68(771,774), 110(704,1086), 118(1167), 122(1167), 150(1452), 151(1453), 174, 175, 176, 185, 187. 195 Hudson, R. F., 305(13), 307(13), 344 Huenig, S . , 492(478), 730 Huet, J., 118(1166), 123(1219), 124(1235), 187, 189 Huff, D., 611(864i), 619(864i), 744 Hug, P., 664(1478,1483), 765 Hughes, R . E., 516(553), 522(553), 527(553), 529(553), 530(553), 531(553), 537(553), 539(553), 545(553), 733 Hughes, S. A,, 601(801a), 742 Hiihnermann, W., 250(235), 277 Huisgen, R., 142(1397), 143(1401,1402),

800

Author Index

Huisgen, R. (Continued) 144(1405), 145(1408), 146(140 1,1408,1426,1427), 194, 195 Huisman, H . O., 613(897a), 616(897a), 617(897a), 745 Hulce, M., 125(1249a), 190 Hull, D. M. C., 466(155), 509(155), 719 Hull, P., 90(972), 181 Hummelen, I. C., 28(270), 160 Hummelen, J. C . , 40(540), 169 Hunt, C. J., 37(513), 169 Hunter, N. J., 447(150), 473(150), 474(150), 491(150), 719 Hunter, W. H., 446(145), 449(145), 457(145), 468(145), 51 1(145), 719 Hupkes, 3. G., 516(562d), 525(562c), 733 Huq, E., 67(765), 176 Hurley, L., 232(168), 275 Huss, 0. M., 513(545b), 516(545b), 733 Hussain, S. Z., 29(288), 161 Hutchins, R. O., 78(878,878a), 179 Huth, A., 94(1005), 182 Hutton, R., 13(115), 156 Hutzinger, O., 232(166), 275 Huybrechts, L., 567(695,696), 577(695,696), 738 Huynh, C., 100(1040), 183 Hvistendahl, G., 7(33), 153 Hylarides, M. D., 241(204), 245(204), 276 Hymann, M. G., 23(211), 159 Hyne, J. B., 483(400), 728 Iannotta, A. V., 370(15a), 414(15a), 423 Ibne-Rasa, K. M., 16(164), 157 Ichihara, R., 463(285), 481(285), 510(285), 724 Ichikawa, K., 118(1153,1154), 125(1263), 126(1265,1268), 187, 190 Ichimura, T., 629(1046r), 751 Ide, J., 599(800d), 742 Iden, R., 490(425b), 729 Iida, H., 49(604a,b), I71 Iijima, I., 125(1239), 189 Iijima, T., 7(30), 153 Iinuma, H., 331(108), 347 Iizuka, T., 132(1324), 139(1360,1361), 140(1367), 192, 193 Ikawa, T., 38(520), 169 Ikeda, M., 33(420a), 53(640,641), 165, 172, 461(272-274), 487(272), 509(272-274), 723 Ikeda, T., 25(251), 160 Ikegami, S . , 83(923,924), 180 Ikeuchi, T., 629(1046i), 751

Ikura, K., 497(503), 499(503), 542(503), 731 I l k , G. F., 93(1004), 182 Imagawa, T., 134(1336), 192 Imai, I., 461(271a), 474(271a), 723 Imai, Y., 592(759-765), 593(762), 593(764), 596(759-765), 740 lmaizumi, S., 84(935,937), 180 Imamura, 34(431), 166 Imaoka, K., 444(136), 446(136b), 447(136b), 457(136b), 505(136d), 506(336d), 719 Imes, R. H., 490(429), 504(429), 729 Imuta, M., 21(196), 158 Inagaki, M., 594(784), 597(784), 741 Inagaki, S., 37(493), 168 Inamoto, N., 41 1(45), 425, 606(833,834), 743 Inch, T. D., 331(115), 332(115), 347 Indictor, N., 30(313), 162 Ing, K. Y. W., 338(143), 348 Ingelmann-Sundberg, M., 260(313), 279 Ingrosso, G., 117( 1142,1143), 122(1212), 186, 188

Inokawa, S., 604(822d), 606(822d), 742 Inoue, I., 592(767), 741 Inoue, K., 34(460d), 35(460d), 167 Inoue, M., 118(1153,1154), 125(1263), 126( 1265,1267,1268), 187, 190, 629(1046i,k,m,o), 751 Inoue, S . , 16(153), 157 Inoue, Sh., 125(1244,1245), 189 Inoue, T., 76(852), 178 Inoue, Y . , 37(499), 168, 438(6), 630(1103d), 631(1103d), 633(1131b), 714, 753, 754 Ionescu, M., 619(921d), 746 Iraidova, 1. S., 475(377a), 727 Ireland, R. E., 509(531g), 511(531g), 732 Irngartinger, H., 364(1696), 429 Irwin, K., 30(323), 31(323), 162 Isaacs, N. S., 116(1121), 126(1269), 186, 190 Isaeva, Z. B., 79(896), 179 Isaeva, Z. G., 19(180), 20(188), 30(328), 32(328), 158, 162 lsaksson, R . , 664(1479), 765 Ishi, S . , 571(713), 739 Ishiba, T., 580(736,737), 739, 740 Ishibe, N., 653(1355), 762 Ishii, N., 31(350), 163 Ishi-i, S., 551(651), 737 Ishii, T., 642(1304), 643(1304), 760 Ishii, Y.,112(1094), 185, 458(264d), 472(264), 5 1 1 (264d), 723 Ishihama, T., 246(226), 277 Ishikawa, K., 142(1392), 143(1399,1400,1404), 194, 2 15( 83,94), 2 16(83,94), 226( 142),

Author Index 230( l50), 239(94), 252(142), 254(248), 272, 273, 274, 277 Ishikawa, N . , 453(243,244), 466(243), 472(243), 474(243), 571(712), 572(712), 573(712), 575(712), 632(243,244,712,1123-1129), 722, 739, 754 Ishikawa, R., 58(676), 173 Ishikawa, T., 31(353), 94(1106), 163, 182 Ishimori, M., 46(591), 171 Ishimoto, S ., 32(408), 165 Ishimmi, K., 206(54), 211(54), 271 Isihara, M., 112(1098), 185 Isobe, M., 33(420i), 166 Isogai, K., 83(933,938h), 180 Isogai, N., 16(154), 157 Ito, I., 388(79b), 426 Ito, M., 611(872c), 744 110, S . , 34(460d). 36(460d), 167, 239(200), 241(200), 276, 455(250), 462(250), 480(250), 485(250), 501(250), 722 Ito, Y., 354(1 Ih,c), 369(1 lb,79a,94), 381(1 lb,c), 388(94), 389(1 Ib), 400(79), 407( 1 Ib,c), 4l4( 1 l), 415( 1 Ih,c), 416( 1 l), 417(11), 418(94,136), 423, 426, 427, 428 Itoh, M., 72(805), 86(946), 114( 1107), 12Y(1299), 177, 181, 185, 239(197), 241(197), 276, 339(154,202), 348, 350 Itoh, O., 126(1267), 190 Itoh, T., 18( 174), 32(174,409), 34(430,453), 35(430), 36(453), 38(430), 165, 166, 167 Ittah, A . Y., 244(214), 276 Ittah, Y., 87(953), 181, 216(96), 262(338), 265(333), 268(364), 273, 280, 281 Itzel, H., 128(1293), 191 Ivanchenko, N . M., 652(1348), 761 Ivanov, S . , 31(358,359), 163 Ivasyuk, N. V., 622(977), 748 Ivie, G. W., 61(707), 174 Iwai, K., 45(579), 170 Iwamura, H., 13(125), 156 Iwanami, M., 4 4 3 122), 452(208), 476(122), 492(208), 498(208), 515(208), 516(208), 520(208), 521(208), 524(583,584a), 525(208), 531(208), 629(1046c), 631(1046c), 635( 1046c), 641(1234 1237), 642( 1239, 646(1234), 718, 721, 734, 751, 758 Iwanami, S . , 594(785,787a), 599(787), 741 Iwasa, A., 61(701), 174 Iwasaki, S . , 25(244a), 160, 232(172), 233( 179), 255(252), 275, 277 Iwasawa, H., 109(1082), 184 Iyengar, B. R. J., 610(858), 744

80 1

Iiumi, Y . , 119(1179), 187 Izydore, R. A,, 125(1259), 190 Jablonski, L., 132(1322), 192 Jackman, L. M., 10(67), 11(67), 154, 490(425b), 729 Jackson, B. L. J., 66(749), 175 Jackson, H. L., 353(5), 423 Jackson, J. B., 151(1483), 196 Jackson, W. R., 26(259), 160 Jacobsen, N., 626(1004), 627(1004), 628(1004), 629( 1004), 749 Jacobson, H. W., 630(1088), 632(1088), 635(1088), 753 Jacobson, S . E., 30(310), 162 Jacohsson, U., 619(946), 747 Jacquier, R., 13(130), 156 J a h , J. C., 110(1085b), 184 Jaeschke, W., 370(17), 424 Jaffe, I. A . , 548(626), 549(626), 555(626), 556(626), 736 Jaffrain, M., 636(1154), 755 Jaggers, A. J., 24(229), 159 Jahn, H., 151(1465), 196 Jahn, R., 625(994b), 749 Jahnisch, K., 328(99), 346 Jain, S . C . , 465(300), 724 Jakohiec, T., 438(8b), 445(8b), 714 Jakohy, W. B., 266(340), 280 Jambotka, D. K., 10(65), 154 Jaminon-Beekman, F., 34(476), 36(476), 168 Jancis, E. H., 439(53), 446(53), 462(53), 477(53a,b), 480(53a), 482(53a), 483(53a), 490(53a,h), 49 l(53a), 499(53a,h), 502(5 19), 716, 732 Jankovic, J., 79(888), 179 Jankowski, K., 75(849,850), 178 Janniah, S. L., 607(839a,h,843), 621(839a,h,955), 743, 748 Jarchow, O., 365(63a), 380(63a), 393(63), 425 Jatkar, S . K. K., 610(858), 744 Jeang, C. L., 639(1198,1200,1202), 756, 757 Jedlinski, Z . , 105(1063), 184 Jefferies, P. R., 10(69), 154 Jeffers, P., 470(325), 725 Jefford, C. W., 37(503), 168, 356(159), 357(159), 359(159), 429 Jeffrey, A. M., 223(128), 228(146), 230(146), 242(40,109), 243(40), 244(40), 245(210), 246(210), 247(40), 254(40), 258(281,288), 259(297), 266(210), 271, 273, 274, 276, 278, 2 79 Jeffrey, G. H., 443(105a), 718

802

Author Index

Jeger, O., 131(1315,1318,1319), 132( 1318,1319,1323,1324), 133( 13 15), 139( 1360-1362), 140( 1362,1367,1369-1374,1376), 191, 192, 193 Jehlicka, V., 605(826a), 606(826a), 743 Jerninet, G., 636(1152-1154), 637(1158), 755 Jenilev, U. M., 285(38), 286(38), 290(38), 313(38), 344 Jenkins, L. A,, 517(566f), 529(566f), 734 Jenkins, R., Jr., 293(58c), 294(58c), 295(58c), 326(93), 345, 346, 463(286a), 481(286a), 724 Jenkins, R. H., Jr., 326(190,193), 327(190,193,194), 349, 517(566f), 529(566f), 734 Jennings, B. W., 287(20), 288(20), 289(20), 290(20), 291(20), 293(20), 299(20), 300(20), 307(20), 344 Jennings, H. J., 11(86), 155 Jennings, W. B., 296(60), 297(66), 298(66), 301(66), 303(69), 315(60,66), 320(66), 345 Jensen, K . A,, 607(844a), 639(844a), 743 Jensen, K . G., 297(62), 345 Jensen, L., 642(1262), 643(1262), 644(1262), 759 Jentsch, R . , 97(1021), 183 Jerina, D., 217(104), 219(104), 273 Jerina, D. M., 198(2,5,6), 199(18), 202(21), 204(26-28,30,34), 205(5,35,36), 206(50,5 1,55,56), 207(50,5 1,56,57), 208(50,51,55,56), 209(50,51), 214(5,36,80,81), 216(88), 217(88,105), 218(27,30,34,88), 219(36,81,113,114), 220(21,115,117), 221(2,21,26,28,30,50,5 1, 81,115-120), 222(26,28,30), 223(128), 228(146), 230(146,152,156,157), 231(2,5,6,35,50,51,56,160-163), 232(165,167,169,175), 235(36,81,163,177,182, 187,188), 234( 187-189), 235(50,51,56,190,191), 236(50,5 1,117,191), 237(50,5 1,191,192,193), 238(2,192- 194), 239(39), 241( 188-194,20 1,205), 242(40,210), 243(40), 244(40), 245(39,210,223,224), 246(2,5,35,115,210,224), 247(40), 254(40), 255(5), 256(27,34,264-270, 272-274), 257(275,276), 258(80,167,277,296), 259(270,297,302,304,306), 260(308,309,3 12, 314,315,3 17,319,321), 261( 161,268,271,275, 315,321,322), 262(34,115,161,265,270,275,277, 3 15,322,331,338), 263(264,270,33 I ) , 264(26,118,119,277,329-335), 265(28,30), 266( 1 15,2 10,224,266,271,275,34 I), 267(2,350), 268(360-367), 269(6,157,373-379), 270, 271, 272, 273, 274, 275, 276, 278, 280, 281, 282.

297(64), 298(64), 303(64), 322(64), 326(193), 345, 349, 463(286b), 481(286b), 724 Jerman, B . , 549(641a), 550(643), 556(641a,643), 736 Jernstrom, B., 267(352,353,359), 281 Jerslev, B., 297(62), 345 Jessup, R . S., 7(29), 153 Jewell, L. M., 509(531a), 732 Ji, J., 531(598), 735 Jikali, G., 199(7), 270 Jikeli, G., 202(20), 209(20), 270 Joergensen, K. A., 651(1340,1341a), 665( l340,1341a,1490), 669( 1341a), 761, 766 Joers, J., 126(1264), 190 Jogun, K. H., 569(699), 575(721,722a), 738, 739 Johar, J . S . , 598(793), 741 Johnson, A . W., 52(621), 54(650), 172 Johnson, C. E., Jr., 11(79), 155 Johnson, C. K., 131(1316), 132(1316), 291 Johnson, C. R., 49(612), 52(622,628-630), 53(628-630,633), 54(647,648,654), 69(785,786), 106(1067), 107(1072), 110(1067,1072), 171, 172, 173, 176, 184. 452(207b), 461(276), 462(207b,276,281a), 463(207b,283), 465(207b), 476(276), 477(207b,281a,389), 479(207b,276,389), 480(207b,276,28 1a,389), 48 1(207b,283), 482(389), 484(207b,276), 487(276), 490(276), 491(207b,276), 492(207b), 497(207b), 498(389), 502(207b), 505(207b,389), 506(207b), 508(528,529a), 509(276), 512(276), 529(207), 53 1(207b), 532(207b), 538(207b), 540(207b), 544(207b), 721, 723, 724, 726, 727 Johnson, D. L., 511(191,192), 721 Johnson, D. M., 244(213), 276 Johnson, F. H., 354(14b,c,e), 420(14b,c,e), 423 Johnson, J. T., 258(294), 279 Johnson, M. R., 18(178), 109(1081), 158, 184 Johnson, P., 30(314), 162 Johnson, P. Y . , 450(196d), 456(196d), 471(196d), 554(196d,661-663), 721, 737 Johnstone, L. M., 340(158), 348 Johnstone, R. A . W., 60(693), 174 Jokisaari, J., 439(54b,56a,57a), 440(54b), 716 Jolley, K. W., 512(883), 745 Jolly, W. L., 660(1409), 763 Jonas, L. A , , 476(380c), 727 Jonczyk, A , , 47(595), 48(604), 49(607), 171 Jones, C. J., 629(1034,1037,1040), 750, 751 Jones, D. N., 476(397b), 477(397b), 48 l(397a-c), 482(397a), 483(397c), 486(406b), 488(397c), 502(406b), 509(53 If), 511(531f), 587(743b), 728, 732, 740

Author Index Jones, D. S., 37(504), 168 Jones, G., 129(1301), 191 Jones, J. I., 630(1068a), 638(1068a), 752 Jones, M., Jr., 142(1386), 193 Jones, M. J., 639(1174), 640(1174), 755 Jones, N. D., 253(244), 277 Jones, R. N., 9(59), 154 Jones, T. K., 78(884), 179 Jonsson, E. U., 508(528,529a), 732 Jordan, G. J., 330(104), 347 Jorden, G., 633(1133), 754 Jorritsma, H., 498(511), 731 Joshi, R. M., 441(83), 717 Joshi, V. S . , 71(800-802), 177 Jouin, P., 453(231b-d), 469(231c,d,321), 722 Joullie, M. M., 342(163), 348, 589(754,755~), 591(754,755c), 740 Juang, P. Y., 129(1300), 191 Judge, R. H., 470(324), 725 Julia, M., 122(1207a), 188 Julia, S., 28(271a), 122(1207a), 160, 188 Julien, J., 520(576), 529(576), 734 Jung, F., 613(892), 616(892), 617(892), 745 Jung, I. N., 668(1533), 767 Jung, J., 421(153), 429 Junici, A , , 199(17), 270 Jurgens, E., 284(9), 327(9), 343 Jurjev, J., 441(81b), 717 .Jurjev, V. P., 285(38), 286(38), 290(38), 313(38), 344 Just, G., 338(148,152), 348 .Jusudason, M. V., 585(743c), 740 Kaampchen, T., 250(235), 277 Kaba, M., 31(340), 163 Kabachnik, M. I., 661(1417), 663(1417), 763 Kabitzke, K. H., 625(994c,d), 749 Kabuss, S., 443(128), 572(128), 719 Kachar, B., 421(147), 428 Kagan, H. B., 33(415), 165 Kagan, J., 66(753,758), 125(1262), 129(1300), 140(1377), 141(1378), 175, 190, 191, 193 Kagan, M. Z., 438(4c), 714 Kagein, H. B., 319(77), 320(77), 345 Kageyama, K., 638(1160), 755 Kai, M., 588(746), 740 Kai, Y., 254(247), 277 Kaiser, C., 121(1192), 188 Kaiser, E. M., 83(925), 180 Kakiuchi, H., 7(30), 125(1239), 153, 189 Kakoi, H., 16(153), 157 Kalasinsky, V. F., 9(53), 13(53), 154, 630(1051), 636(1151), 751, 755

803

Kalikhman, I. D., 642(1306,1308a), 644( 1306,1308a), 760 Kalish, R., 574(719b), 583(719b), 584(719b), 585(719b), 739 Kaloustian, J., 32(393), 164 Kalsi, P. S . , 39(535), 169 Kaltschmitt, H., 642(1272,1274), 643(1272,1274), 759 Kaluszyner, A., 465(307a), 724 Kalyanaraman, V. S., 421(148), 428 Kalyavin, V. A ,, 447(160), 486(160b,405), 720, 728 Kaman, A. J., 29(282), 161 Kamataki, T., 255(253,254), 277 Kamatani, H., 123(1224), 189 Kamenski, D., 34(468), 36(468), 167 Kamernitskii, A. V., 27(262), 160 Kametani, T., 25(250), 160 Kaminiski, J. J., 653(1353), 761 Kaminsky, L. S . , 335(130), 347 Kamiya, Y . , 34(439,445), 35(439), 166 Kammereck, R. F., 465(304), 474(362), 724, 726 Kampchen, T., 581(738), 607(838e), 740, 743 Kamphuis, J., 516(562d), 525(562c), 578(691c), 733, 738 Kanaiwa, T., 439(54e), 716 Kanakarajan, K., 524(585b), 525(585b), 734 Kanamori, H., 37(498), 168 Kaneda, K., 18(174), 32(174,409), 34(430,453), 35(430), 36(453), 38(430), 157, 165, 166, 167 Kanehisa, N., 354(247), 277 Kanekeyo, E., 338( 145). 348 Kaneko, C., 331(112), 329(154,202), 347, 348, 350 Kanematsu, K., 247(227), 264(227), 250(234), 277 Kang, J., 81(903), 179 Kang, R., 59(680), 173 Kanghae, W., 49(611), 171 Kano, S., 45(580), 170 Kanoh, H., 34(466e,470), 36(466e,470), 167 Kantor, S . , 639( 1210,121 1,1215,1223), 640(1215,1229), 757, 738 Kao, J., 630( 1054, 751 Kapadia, D., 221(120), 262(331), 263(331), 264(331), 273, 280 Kapecki, J. A., 641(1249,1250,1252), 758 Kaplan, M. L., 373(28), 378(28), 424, 642(1253), 646(1253), 759 Kapoor, R., 672(1579-1581), 768 Karakhanov, R. A., 83(930), 180 Karakida, K., 439( 16a), 715

804

Author Index

Karaseva, A. N., 79(896), 179 Karavan, V. s., 87(952), 181 Kardouche, N. G., 96(1017), 183 Karges, G., 76(856), 121(856), 178 Kari, R. E., 4(9), 153 Karida, K., 439(16h), 715 Karimova, N. M., 559(675), 737 Karle, J. M., 230(157), 256(268), 261(268), 268(360,361,365), 269(157,378), 274, 278, 281, 282 Karlsson, O., 92(990), 182 Karinschky, I. A., 142(1398), 194 Karpenko, L. P., 32(383,397), 164, 165 Karus, G. A , , 56(669), 173 Kasahara, S., 578(731a), 739 Kasai, N., 254(247), 267(347,348), 277, 281, 588(745), 590(745), 591(745), 740 Kasai, T., 641(1246), 642(1246), 758 Kashiwahara, H., 339(202), 350 Kashman, Y., 24(212), 159 Kasperek, G. J . , 233(186-188), 234(187,188), 237(193), 238(193,194), 241(188,193,194,205), 275, 276 Kasyan, L. I., 19(181), 81(905a), 158, 179 Kataoka, T., 516(565h), 734 Katata, M., 1 18(1158), 187 Katekar, G. F., 52(630), 53(630), 172 Kato, H., 441(76,77), 453(234), 717, 722 Kato, K., 72(807), 177 Kato, N., 109(1083), 184 Kato, R., 255(252), 277 Kato, S., 37(507), 168, 631(1112), 753 Katritzky, A. R., 9(49), 154, 630(1063), 633(1063), 636(1063), 752 Katsuhara, J., 27(267), 160 Katsuki, T., 33(420,420a-d,g), 165, 166 Kattan, A . M., 338(21 I), 350 Kati, B., 11(97), 155 Katz, C., 441(92,93), 717 Katz, S., 439(46), 716 Katzenellenhogen, J. A , , 81(906), 109(1080), 179, 184 Kaubisch, N., 206(50,51), 207(50,51), 208(50,5 I), 209(50,5 l), 221(50,5 I), 23 1(50,5I ) , 233(188), 234(188), 235(50,51), 236(50,51), 237(50,5 l), 241(188,205), 271, 275, 276 Kauer, 3. C., 629(1046bb), 633(1046hh), 751 Kaufman, K. J . , 414(113), 427 Kaura, A . C . , 549(637), 550(637), 558(637), 559(677), 736, 738 Kausch, E., 602(810), 604(822a,e), 606(837), 607(822a), 638( 1166), 742, 743, 755 Kavrir, R., 16(157). 157

Kawabe, N., 24(226), 159 Kawada, K., 516(563), 522(563), 733 Kawada, Y . , 13(125), 156 Kawaguchi, T., 617(930a), 747 Kawahara, A., 588(746), 740 Kawakami, J. H., 83(923,924), 180 Kawakami, Y . , 92(984), 182 Kawaniski, M., 134(1336), 192 Kawano, Y., 629(1046t), 751 Kawasaki, T., 125(1261), 190 Kawase, T., 579(678a), 561(678a), 738 Kawashima, C., 34(457), 36(457), 167 Kaya, R., 31(350), 163 Kayano, M., 121(1194), 188 Kayser, M. M., 118(1155), 187 Kazakov, E., Kh., 121(1202), 188 Kazakova, E. Kh., 19(180), 158 Kaz’mina, N. B., 611(879), 613(879), 614(907), 615(907), 615(879,907), 619(879,907), 745, 746 Kazanskii, K. S., 151(1461), 195 Keana, J. F. W . , 331(109), 347 Kearns, D. R., 358(39g), 379(39g), 41 1(102), 424, 427 Keat, R., 656(1377), 762 Keary, R. E., 39(532), 169 Keck, G. E., 365(39f), 366(39f), 367(39f), 379(39i), 400(80), 407(80), 424, 426 Keck, H., 661(1428), 764 Kedzierski, B., 204(34), 218(34), 256(34,265,268), 261(268), 262(34,265), 271. 2 78 Keefer, L. K., 11(84), 155 Keegan, J. R., 118(1169), I87 Keek, H., 663(1463), 765 Kehoe, I., 36(483), 168 Keiko, V. V., 623(981-984c), 624(981,982,985b), 748, 749 Keinan, E., 125(1251), 190 Keith, L. H., 11(90),-155 Kelber, C., 642(1289), 643(1289), 644(1289), 760 Kellen, J. N., 474(371), 727 Keller, J. W., 241(202,203), 276 Keller, P., 131(1319), 132(1319), 192 Keller, R., 224(134), 274 Keller, W. D., 439(54a), 716 Keller-Schierlein, W., 291(56), 293(56), 331(56), 345 Kelley, P. L., 548(626), 549(626), 555(626), 556(626), 736 Kellogg, R. M., 359(160), 361(160), 429, 456(254), 475(254d), 509(536d), 510(537),

Author Index 5 1 1(536d), 554(664), 571(254d), 575(254d), 580(254d), 581(254d), 612(885), 723, 732, 737, 745 Kelm. H., 389(107), 413(108), 427 Kemp, D. R . , 625(994a), 749 Kemp, N. R . , 14(147), 157 Kcmmitt, R . W., 546(621b), 735 Kempe, T., 619(946), 747 Kende, I., 30(319), 162 Kennedy, J., 473(343), 726 Kennedy, J. A , , 26(257), 160 Kennedy, J. P., 458(262), 473(262,344), 511(262), 723 Keramat, A., 100(1041), 183 Keresztury, G., 30(319), 162 Kergomard, A., 76(856), 121(856), 178 Kermann, T., 565(692), 566(692), 567(692), 568(692), 738 Kcrvennal, J., 36(479), 168 Kesarev, S . A,, 32(377), 164 Ketcham, R., 437(2c), 714 Ketcham, R. G., 10(65), 154 Keul, H., 358(60), 386(60), 425 Keuning, K. J., 444(116,129), 457(116,129,258), 462( 116,129,258), 463( 129), 464( 129,131,258), 465( 116,129), 480(116,129), 481(129), 482(129,258), 483(258), 484(116,129,258), 491(116,129,258), 510(129), 511(116,129,258), 718, 719, 723 Keysell, G . R., 255(251), 277 Khaidukova, T. V., 97(1024), 183 Khair, G. T., 639(1179), 756 Khairullin, V. K., 661(1432), 764 Khalil, H., 49(610), 171 Khalil, M. H., 49(605), 171 Khan, S. A , , 480(393), 491(393), 728 Khcheyan, K. E., 32(394), 164 Khcheyan, Kh. E., 29(276), 31(355), 161, 163 Kher, A., 204(28), 221(28), 222(28), 265(28), 271 Khetrapal, C. L., 439(48), 440(48), 716 Khrnel’nitskii, R. A , , 520(578), 529(578), 734 Khodadad, P., 661(1427), 764 Khokhlov, P. S . , 661(1416,1417,1429b), 662(1416,1429b,1436), 663(1416,1417), 763, 764 Khorgami, M. H., 642(1302), 645(1302), 646( 1302), 760 Khripko, S . S ., 119(1177), 125(1240), 187 Khrostenko, V. I., 520(581a), 529(581a), 734 Khuddus, M. A., 117(1146), 186 Kibar, R . , 150(1451), 19.5

805

Kieczykowski, G. R., 112(1096), 185 Kiel, G., 638(1161), 755 Kielbasinski, P . , 630( 1047~).635( 1047c), 656(1378), 751, 762 Kienle, R . N., 450(189), 721 Kiers, C. T., 605(825a), 743 Kikkawa, S . , 19(182), 158 Kikuchi, O., 312(173), 349 Kikuchi, Y., 629(1046e), 633(1046e), 635(1046e), 636(1046e), 637(1046e), 751 Kikumchi, Y., 630(1046e), 751 Kildisheva, 0. V., 548(629e) 549(632,633), 552(629e), 553(629e), 555(629e,632,633), 556(633), 736 Kil’disheva, 0. V., 551(648), 552(656a,c), 553(656c), 555(666,668,670), 556(672), 559(675), 624(987), 737, 749 Kilshcirner, J. R., 449(182), 720 Kim, J. K., 625(996), 749 Kim, J. Y . , 74(846), 178 Kim, K. H., 604(822c), 606(822c,831c,d), 742, 743 Kim, L. F., 473(355), 726 Kim, S . C . , 78(874,877), 80(877), 178, 179 Kimling, H., 626( 1008), 750 Kimoto, K., 24(231), 159 Kimura, K., 553(659c), 737 Kimura, M., 30(303,304), 161, 293(58c), 294(58c), 295(58c), 345 Kindts, M., 267(355), 281 King, A. C . , 113(1104), I85 King, G. S. D., 605(825b,826b), 608(825b), 743 King, G. W., 470(324), 72.5 King, H. W. S., 267(351), 281 King, J. F., 492(459,478,496), 494(459,479), 495(459,495,496~),497(495c), 499(495c,513e), 502(495c), 505(495c), 506(495c), 508(495c), 53 1(495c), 532(495c), 533(495c), 534(495c), 540(495c), 541(495c), 545(495c,5 13c), 583(495c), 584(495c,742), 585(495c), 614(742,920), 6 15(924a), 616(924a), 655(496c), 730, 731, 740, 746 King, L. W., 494(496c), 731 King, R. B., 629( lO27,1028b,1030,1033,1038a,1041),750, 75I Kinoshita, M., 613(896a), 617(896a), 745 Kingsbury, C. A., 13(115), 156 Kingsbury, W. K., 463(283), 481(283), 724 Kingston, S. B., 482(398b), 502(398b), 546(398b), 728 Kinzig, C. M., 125(1248), 189

806

Author Index

Kipnis, I . S . , 418(134), 428 Kipnis, J., 628(1024,1026), 750 Kirby, A . J., 645(1315), 760 Kirby, R. E . , 14(147), 157 Kirchoff, R. A,, 52(630), 53(630), 172 Kirik, T. M., 31(349), 32(349), 163 Kirk, C. M., 470(328a), 725 Kirkpatrick, D., 126(1269), 190 Kirpichenko, S . V., 623(98 1-984d), 624(98 1,982,985a,b), 748, 749 Kirschner, S . , 41 1(103a,b), 427 Kirshnan, S . , 217(85), 272 Kisch, H., 92(987), I82 Kiselev, V. Ya., 475(376), 727 Kiser, R. W., 441(95,96), 442(96), 718 Kishi, Y., 16(153), 18(17), 32(404), 33(420e), 106(1065a), 109(1081), 157, 158, 165, 184, 245(219,220), 276, 352(3), 420(3), 423, 625(995d), 749 Kisin, A. V., 492(452), 495(452), 730 Kiso, Y., 125(1263), I90 Kiss, J. T., 73(831), 84(831), 177 Kissel, C. L., 62(723), 174 Kissel, T., 388(48b), 390(48b), 407(48b), 415(48b), 416(48b), 425, 476(245c), 453(245c,d), 722 Kistenbrugger, L., 561(680a), 579(680a), 738 Kita, Y., 125(1261), 190 Kitahara, Y., 215(109), 217(109), 218(109), 219(111), 273 Kitai, S . , 592(765b), 596(765b), 740 Kitamura, M., 33(420i), 134(1336), 166, 192 Kitazume, T., 453(243,244), 466(243), 472(243), 474(243), 632(243,244,1123-1129), 634(1135,1 137,1141,1143), 674(1577), 722, 754, 768 Kito, N., 602(812c), 604(812c), 742 Klaassen, J . , 29(292), I61 Klaboe, P., 630(1055b), 751 Klabunde, K. J . , 59(687), 174, 469(310), 725 Klaesen, K., 609(856a), 744 Klages, C. P., 561(680a), 575(722b), 579(680a,b), 582(680b), 738, 739 Klamerth, O., 625(989), 749 Klarner, F. G., 209(66), 237(192), 238(192), 239(66), 241(192), 272, 276 Klaska. K. H., 365(63a), 380(63a), 393(63), 425 Klaus, M., 130(1304), I91 Kleeman, M., 492(437), 495(437), 729 Klein, E., 13(135), I56 Klein, H., 252(239), 253(239), 277 Klein, H. A., 114(1 lox), 185

Klein, M. W., 25(244), 159 Kleinfelter, D. C . , 120(1190), I88 Kleinpeter, E., 88(956), 181 Klepel, M., 641(1248), 758 Kleppinger, J., 658( 1400), 660(1400), 763 Klever, H. W., 354(11), 378(11a), 381(11a), 407(1 l), 414(1 l), 415(1 la), 416(1 l), 417(1 l), 423 Klich, M., 548(623) 549(623), 559(623), 736 Kliegel, W., 124(1236), 189 Klimenko, P. L., 31(342), 163 Klimes, J., 630(1099b), 633(1099b), 753 Klimov, D. V., 661(1416,1417), 662(1416), 663(1416,1417), 763 Klimov, 0 . V., 662(1436), 764 Klinot, J., 45(576), 170 Klose, B., 40(542) 169 Klose, D., 34(474), 36(474), 39(474), 167 Klose, G., 439(53), 446(53,146a), 462(53), 477(53a), 480(53a, 146a), 482(53a), 483(53a), 490(53a), 491(53a,146a), 499(53a,146a), 502(518,519), 716, 719, 732 Kloth, B., 663(1442), 764 Kluck, D., 616(921b,933a,b), 746, 747 Klug, H., 630(1071), 632(1071), 633(1071), 752 Klug, H.-H., 227(143), 228(143), 274 Klug, J. T., 633(1134a), 754 Kluger, E. W., 293(58c), 294(58c), 295(58c), 338(58a), 345 Klyne, W., 13(135), I56 Krnel, M. P., 24(236), 159 Knapp, S . , 514(552,553), 516(552,553), 521(552,553), 522(553), 527(553), 529(552,553), 530(553), 531(552,553), 537(552,553), 539(553), 545(553), 733 Kneba, M., 128(1290), 191 Kneller, J. F., 451(197), 721 Knight, H. B., 9(48), 154 Knofel, W., 642(1273a), 643(1273a), 759 Knothe, L., 122(1208), I88 Knowles, R. G., 260(311), 279 Knunyants, I. I., 555(665), 737 Knunyants, I. L., 51(619), 80(900), 120(1184), I72, 179, 188. 437(2b), 443(2b), 5 11(2b), 547(622), 548(629c,e), 549(632-635), 550(645-647), 551(648), 552(656a,c), 553(656c), 555(629e,632-635,646a,647a,666-668,670), 556(646a,647a,672), 559(675,676), 61 1(860,865,868,870,876,879,882), 613(879), 614(898f,h,i,899-902,905a,907,908,9 16), 6 I5(876,898f,h,899,905a,907,908,9 16,925, 926a,b), 616(898f,h,i,900,902,908,925,926a,

Author Index 927-929,930~,93I ) , 617(879,882,926b,934-937), 618(937-942), 6 19(879,907,934,935), 630(1097,1098,1103a,I 105), 636(1157d), 637(1157d), 642(1103a,l105), 644(1105), 653( 1363,1364), 654(908,1365- 1367), 655(1157d,1367), 672(1566), 714, 736, 737, 744, 745, 746, 747, 753, 755, 762, 768 Kobal, V . M., 601(803b), 742 Kobayashi, J., 29(291), 161 Kobayashi, M., 32(408), 165, 232(170), 275 Kobayashi, T., 593(768), 594(768), 596(768), 597(768), 741 Kobayashi, Y., 335(128), 347, 516(563), 733, 522(563), 629(1046r), 733, 751 Kobrich, G., 100(1044), 183 Koch, B., 672(1558,1564,1567), 763 Koch, F. W., 661(1414), 666(1414), 763 Kochi, J., 34(440), 35(440), 36(440), 166 Kochi, J. K., 29(275), 30(275), 34(275,460), 36(460), 58(674), 161. 167, 173 Kocur, J., 569(698a), 574(698a), 577(698a), 579(698a), 738 Kodaira, K., 634(1142), 754 Kodarna, T., 439(17), 715 Kodess, M. I., 80(899), 179 Kodicek, E . , 27(263), 160 Koepke, B., 626( 101l b ) 750 Koerner, G. S . , I1(92), 155 Kogan, T. P., 476(397b), 477(397b), 481(397b,c), 483(397c), 486(406b), 488(397c), 502(406b), 728 Kogane, T., 441(82), 717 Koganty, R. R., 612(887c), 745 Kohashi, Y., 254(246,247), 277 Kohler, E. P., 353(4), 423 Kohmoto, Y . , 40(544a), 170 Kohn, G. K., 438(10c), 478(10c), 714 Kohn, H., 548(630), 551(630), 555(671), 556(630,67 I), 557(67 I), 558(67 1,674), 571(630), 575(630), 582(674), 583(674), 621(962), 736, 737, 748 Kohne, B., 520(572), 644(572), 734 Kohrman, R. E., 630(1092), 753 Koikov, L. N., 492(468c), 502(468c), 730 Koizurni, T., 453(237,238), 469(237,238), 602(812c), 604(812c), 722, 742 Kojirna, M., 588(746), 740 Kojirna, Y., l09( 1083), 184 Kolaczinki, G., 67(768), 176 Kolb, A , , 519(570), 529(570), 734 Kolb, R.. 606(831b), 743 Kole, J., 141(1379), 142(1384), 193

807

Kolenko, I. P., 43(566), 67(767), 80(899), 170, 176, 179 Koli, S. Z . , 639(1180), 756 Kollar, J., 30(315), 162 Kollman, P. A,, 199(19), 200(19), 270 Kollmar, H. W., 411(103b), 427 Kolomiet, A. F., 114( 11 15), 185 Kolomiets, A. F., 93( 1004), 182 Kolotilo, N. I., 31(347), 163 Kolosov, V. A,, 32(392), 164 Kolshorn, H., 514(550a), 733 Kornarov, V. G., 114(1113), 185 Komatsu, M., 285(45), 289(45), 290(45), 303(70), 304(70), 326(91), 339(91), 341(45,70,161), 342(45,164), 344, 345, 346, 348 Korneno, T., 10(70), 155 Komin, J. B., 24(221), 159 Korniya, M., 629(1046e,1046p), 630( 1046e), 633( 1046e), 635( 1046e), 636( 1046e), 637(1046e), 751 Komoto, K., 461(275), 463(275), 482(275), 487(275), 723 Komura, H., 267(348), 281 Konco, H., 369(94), 425 Konda, H., 388(94), 418(94), 427 Kondo, K., 100(1036), 114(1117), 183, 186, 461(271b,c,d), 509(271b,c,d), 723 Kondo, M., 667(1496), 766 Kondo, S . , 9(56), 154, 331(108), 347 Kondo, Y., 131(1314), 191 Kondrat’ev, L. T., 119(1174-1176), 187 Konetz, A , , 317(176), 349 Konieczny, M., 611(862a), 615(862a), 616(862a), 744 Konig, G., 149(1444), 195 Konitz, A,, 317(68), 345 Konizer, G. B., 52(632), 172 Konno, K., 85(943), 181 Konovalov, L. V., 465(299a), 724 Kontnik, L. T., 441(75), 630(75), 717 Konyushkin, L. D., 126(1274), 190 Koo, J. Y . ,352(1), 360(89), 387(61), 413(89), 414(113), 417(132), 422, 425, 426, 427, 428 Kooi, J., 554(664), 737 Koop, D. R., 256(258), 277 Kopaevich, Yu. L., 672(1566), 768 Kopecky, K. R., 353(8), 354(8), 355(107), 356(22,107), 357(22b, 128), 37 1(8,22), 379(22b), 380(22b), 381(8,22b), 382(22b), 385(22b), 387(22b), 389(128), 390(95,107), 392(107), 403(85), 413(107), 418(22), 423, 424, 426, 427, 428

808

Author Index

Koppenhoeffer, B., 46(593a,b), 171 Korbov, M. S . , 517(566c), 734 Koreeda, I . , 263(270), 278 Koreeda, M., 227(144), 256(270), 259(270), 262(270), 264(335), 265(332), 269(375), 274, 278, 280, 282 Korenowski, F. T., 629(1038a), 751 Kornblum, N., 372(23), 424 Korngold, G., 129(1301), 191 Kornobis, S., 639(1175), 640(1175), 756 Korol, E., 667(1511), 766 Korovina, G., 151(1466), 196 Korte, F., 589(750), 591(750), 595(750), 740 Korzeniowski, D., 256(263), 278 Kosakada, T., 641(1239), 758 Koshel’, G., 73(822), 177 Koshida, K., 34(457), 36(457), 167 Koshiya, D. J., 639(1192), 756 Kossanyi, J., 14(140), 156 Kostka, R., 595(788), 741 Kostyanovskii, R. G., 439(54c), 716 Kostyleva, T. A , . 439(26b), 715 Koteen, G. M., 267(358), 281 Kotin, S. M., 462(280b), 463(280b), 465(306a), 469(306a), 475(280b), 480(280b), 724 Kotone, A,, 125(1237), 189 Kotov, S., 125(1254), 190 Kotsuki, H., 15(8a), 153 Kouwenhaven, C . G., 546(621a), 735 Kovacs, E., 83(929), 180 Kowalczuk, M., 105(1063), 184 Koyarna, H., 578(725,726), 607(844d), 739, 743 Koyano, K., 312(182), 349 Kozhakhmetova, R. I., 663(1454), 765 Kozhin, S. A,, 24(233), 159 Koziar, J. C., 409(97), 427 Kozlov, N. S . , 124(1227), 189 Kozlowski, J., 110(1085a), 184 Koz’min, A . S., 672(1574), 768 Kozuka, S . , 461(270), 723 Kraas, E., 144(1406), 194 Krainov, I . S . , 36(480), 168 Krapcho, A. P., 553(659a), 555(659a), 561(659a), 562(659a), 579(659a), 737 Krasavtsev, I. I., 440(71), 717 Krassip, R., 8(38), 154 Kraus, G. A., 76(855), 178 Kraus, M., 73(830,832), 87(830,832,950), 177, 181

Kravets, V. P., 444(132), 457(132), 491(132), 511(132a), 719 Krebs, A., 365(63a), 380(63a), 391(123), 393(63), 425, 428(123), 626(1008), 750

Krebs, B., 629(1047a,b), 638(1047a,b), 651( 1342,1344), 652( 1342), 658( 1344), 659(1344), 660(1344,1346~),668(1527), 751, 761, 767 Krerner, E. D., 464(293), 724 Krentsel, B. A., 473(353-355), 474(354), 726 Krespan, C. G., 611(864a), 744, 6 14(903,905b-g), 6 15(905g), 6 16(903), 6 19(903), 625(990-992), 626( 1005- 1007), 628( 1005,1006,1017,1020), 629( 1005,1006,103 l), 63 1(992), 642( 1017), 644(1017), 653(1361), 744, 746, 749, 750, 762 Kresze, G., 53(637), 172, 251(237), 277, 589(755b), 590(756,757), 59 I (756,757), 658(1398), 740, 763 Kretchmer, 43(564), 170 Krief, A . , 13(121), 156, 46(581), 54(656-661), 61(702), 89(961), 114(1108a), 171, 173, 174, 181, 185. 199(16), 270 Kriegsmann, H., 667(1497), 766 Kriiger, C., 224(137), 274 Krilov, D., 556(673a), 737 Krimer, M. Z., 450(187), 721 Krimm, H., 284(10), 343 Krinsky, P., 118(1165), 187 Kriplo, P., 34(474), 36(474), 39(474), 167 Krishnamurthy, S., 77(866), 78(874,875,877,882), 80(877,901,902), 82(901), 178, 179 Krishnan, S., 215 (84,85), 216(84,85), 272 Kristen, H., 643(1270), 647(1270), 759 Kristensen, J., 664(1473), 765 Kristian, P., 606(838a), 608(838a), 743 Kristinsson, H., 141(1380), 142(1382,1385,1391), 193, 194 Krivosheeva, N. G., 24(236), 159 Krober, H., 642(1310), 760 Krohnke, F., 337(138), 348 Kroniger, A,, 444(138), 719 Kroon, J., 5 13(545a,d,e), 5 16(545a,d), 525(545c), 733 Kropf, H., 38(525) 77(861), 78(870), 79(82), 115(1120), 169, 178, 179, 186 Kropp, P., 141(1381), 193 Kroto, H. W., 630(1060), 752 Krow, G. R., 82(907), 179 Krubsack, A. J., 570(707,708), 574(707), 578(707,708), 579(707), 739 Kruger, C., 254(249), 277 Kruse, E., 40(541), 50(541), 169 Kruse, W., 40(539), 169 Krysin, E. P., 30(324), 162 Kryukov, S. I., 32(365), 72(817-820), 163, 177

Author Index Kubisa, K., 473(336c), 725 Kuchen, W., 661(1428), 663(1460-1463), 764, 765 Kucheruk, L. V., 464(293), 724 Kuchin, A. V., 78(886), I79 Kuchitsu, K., 439(16,19), 715 Kudrina, M. A,, 475(377a), 727 Kudryavtseva, M. I., 121(1201), 188 Kuebler, N. A , , 14(146), 157 Kuehne, M. E., 26(261), 160, 492(482), 535(603,604), 540(603), 730, 735 Kuentiel, H., 438(9), 456(253), 714, 723 Kiiffner, P., 535(607), 546(607), 583(607), 585(607), 735 Kugel, A. R., 121(1196), I88 Kuhle, E., 640(1232), 758 Kuhlmann, G. E., 619(943-945), 620(943,944,950), 747 Kuhn, D. G., 215(84,85), 216(84,85), 217(85), 2 72 Kuhn, N., 662(1438), 672(1438), 764 Kuidersma, K. A , , 509(537), 732 Kukushkin, Y. N . , 434(401), 728 Kukushkin, Yu. N., 465(296,299a), 724 Kulbach, N . T., 656(1376), 657(1385), 662(1376), 663(1376), 762 Kuleshova, N. D., 547(622), 548(629c), 550(629c,646,647), 555(665), 556(646,647), 736, 737 Kuliev, A. M., 123(1226), 189, 449(183), 720 Kulikov, N. S . , 492(468c), 502(468c), 730 Kulkarni, A. K., 61(705), 68(774), 174, 176 Kullmann, R., 667(1509), 766 Kulshreshtha, J. P., 639(1196), 756 Kumadaki, I., 516(563), 522(563), 733 Kumakura, S . , 439(17,24), 443(24), 479(24), 480(24), 489(422), 491(24), 715, 729 Kumar, A., 607(838d,e), 664(838d), 743 Kumar, S., 215(107), 217(105,107), 264(334), 268(362), 273, 280, 281 Kumar, S . A , , 421(148), 428 Kundu, N. G., 241(203), 276 Kung, H.-C., 267(356), 281 Kung, W. J . H., 140(1366), 193 Kunieda, N., 613(896a), 617(896a), 745 Kunina, E. A., 520(578), 529(578), 734 Kunwar, A. C . , 439(48), 440(48), 716 Kunre, U., 622(966c), 748 Kuo, C., 474(373), 727 Kuonanoja, J., 439(54a,56a), 716 Kupchan, S. M., 59(678), 120(1191), 173, 188 Kuran, W., 101(1050), I84 Kuranova, I. L., 122(1209,1210), 188 Kurata, T., 34(438), 166

809

Kurhanov, S. E., 92(979), 182 Kurilkin, V. I., 492(494a), 495(494a), 731 Kurita, Y., 667(1496), 766 Kurnsu, Y., 31(350), 163 Kurono, H., 639(1224), 64 1 (1238,124l,1242,1246), 642( 1238,1241,1242,1246), 757, 758 Kurono, M., 126( 1275), 190 Kurozumi, S . , 32(408), 71(804), 73(804), 165, I77 Kuryatninow, Yu. I., 398(76), 426 Kusters, W., 627(1013,1014), 750 Kutscher, W., 625(989), 749 Kutsuma, T., 53(644), 172 Kutter, E., 642(1260), 759 Kuwaba, K., 595(790), 741 Kuz’man, 0. V., 631(1113d), 753 Kuznetsov, 440(71), 717 Kuz’yants, G. M., 548(628b), 61 1(879), 61 3(879), 6 14(907), 6 15(907), 6 17(879,907), 619(879,907), 745, 746 Kvasha, Z . N., 661(1416), 662(1416), 663(1416), 763 Kwan, T., 74(846), 87(949), 178, 181 Kwant, P. W., 498(51 l), 731 Kwart, H., 16(162,163), 157 Kwast, A , , 47(595), 171 Kyba, E. P., 24(242), 95(1014), 159, 183 Kydd, R. A,, 439(32,42), 440(32,42), 7I5, 716 Kyi, H. J., 642(1279), 643(1279), 759 Kynaston, W., 630( 1068a), 638( 1068a), 752 Kyono, K., 369(79a), 388(79h), 400(79), 426 Kyotani, Y., 60(695), 174 Kyoung, R., 59(679), I73 Kyriakakou, G., 48(597), I71

Laane, R. W. P. H., 28(270), 160 Laasko, P. V., 642(1296), 645(1296), 647( 1296), 760 Labar, D., 46(581), 171 L’Ahbe, G., 342( 162), 348, 562(684,685), 563(684,685), 564(684,685), 566(684a,b), 567(694-696), 576(685), 577(695,696), 589(752b), 595(752h), 604(822i), 605(825b,826h), 606(822i), 608(825b,c), 652(752b), 666(1492), 738, 740, 742, 743, 766 Labro, L., 635( 1145a), 638( 1145a), 754 Ladd, M. F. C., 625(997), 749 Laganis, E. D., 520(571b), 734 Laishev, V. Z., 672(1572,1573), 768 Lakshmikanthan, M. V., 672(1570,1571), 768 La!, K., 509(532), 611(532), 732 Lalancette, J. M., 121(1195), 188

810

Author Index

Lam, B., 39(538), 169 Lam, J . H. W., 474(367), 727 Lam, Y.-S. P., 21(193), 158 Lamaty, G., 117(1130), 186 Lamazouere, A. M., 642(1256), 759 Lambert, J. B., 439(55b), 477(55b), 478(55b), 489(55b,423c), 490(55b), 630(55b), 635(55b), 716, 729 Lambert, J . L., 473(345), 726 Lambert, R. L., Jr., 55(666), 173 Lamchen, M., 333(122), 335(130), 347 Lamendola, J . , Jr., 293(58c), 294(58c), 295(58c), 345 Lami, G., 13(126), 156 Lamm, B., 449(169), 462(169), 491(169), 492(480), 506(169,480), 508(169), 531(480), 532(480), 533( 168), 536(480), 540(480), 545(617), 720, 730, 735 Lancaster, J. E., 224(140), 230(140), 274 Lancaster, M., 444(136), 505(136d), 506( 136d), 533(136d), 719 Landau, R., 30(326), 36(489), 162 Landen, G. L., 637(1159), 755 Landini, D., 504(523), 732 Landis, M. E., 40(546), 170, 352(1), 360(134c), 361(166), 362(166), 413(109), 418(134,135), 420(139,141), 423, 427, 428, 429 Landis, P. S ., 465(307b), 724 Lanford, C. A , , 10(76), 155 Lang, K. L., 3(8), 15(8), 79(8), 153 Lang, S. A , , Jr., 118(1172), 187 Lane, R. E., Jr., 39(528), 169 Lange, F., 635(1145a), 638(1145a), 754 Lange, G. B., 663(1451), 764 Langenbucher, F., 443(128), 572(128), 719 Langendries, R. F. J., 531(599), 545(599), 584(743a), 585(743a), 735, 740 Langin, M. T., 118(1166), 187 Langstaff, E. J., 117(1149), 186 Lankelma, H. P., 661(1423), 663(1423), 764 Lankin, D. C., 144(1406,1407), 194 Lansbury, P. T., 511(538), 732 Lanum, W. J., 443(106), 718 Larcheveque, M., 91(976), 181 Larin, G. M., 32(392), 164 Larricchiuta, O., 25(253b), 160 Larson, D. L., 373(29), 378(29), 424 Larson, H. O., 338(143,144), 348 Laszlo, P., 10(71), 11(71), 155 Lathan, W. A , , 14(145), 157 Latremouille, G. A,, 151(1481,1482), 196 Lattes, A,, 286(48), 333(123-125,205), 334( l23), 347, 350, 492(456,457,469a), 730

Lau, C., 668(1520), 767 L a w , H. A . H., 151(1457), 195 Lauer, R. F., 75(848), 178 Laughlin, C. W., 639(1186), 756 Laurence, K. A ,, 634( 1139a), 754 Laurent, E., 77(863), 79(891), 178, 179 Lautenschlaeger, F., 443( 15e), 455(246,247,249), 459(247), 462(246,249), 466(249), 468(246), 480(246,249), 482(246,249), 483(249), 484(246), 491(246,249), 51 1(246), 715, 722 Lautenschlaeger, F. K., 455(248), 462(278), 476(278), 488(278), 491(278), 509(246,247), 722, 723 Lauterbach, G., 120(1188a), 188 Lavayssiere, H., 96(1018), 183, 624(986a,b), 749 Lavie, D., 120(1182), 188 Lavielle, G., 50(615), 56(670,671), 172, 173 Lavrent’eva, L. A ,, 125(1241), 189 Lavrik, P. B., 37(515), 169 Lawesson, S. O., 630(1077), 642(1262), 643( 1262), 644( 1262), 651(1340,134la), 663( 1449,1450,1452a,1453,1456,1457), 664( 1077,1450,1466- 1469,1472- 1475, 1477a,b,1478,1480,1482- 1487), 665(1340,1341a,1490), 666(1341a,1491), 759, 761, 762, 764, 765, 766 Lawrence, A. H., 453(228,229), 468(229), 625(994a), 630(229,1079), 722, 749, 752 Lawson, A. J., 305(13), 307(13), 344 Lawson, H. F., 24(214), 159 Layton, R., 136(1350), 192 Lazurkin, E. A,, 32(403), 165 Lazzeretti, P., 11(81), 155 Leandri, G., 106(1066), 184 Lebedev, E. P., 667( 1507,151 1,15 12,1514- 15 16), 669( 1536-1539,1541), 766, 767 Lebedev, E. V., 31(342), 163 Lebedev, N. N., 29(283), 31(348,362), 32(348,368,383,387,397), 119(1174-1176), 161, 163, 164. 165, 187 Lebedev, V. N., 663(1444), 764 LeBerre, A ,, 593(772,776,777), 596(772), 741 Leblane, M., 12(103), 155 Leboeuf, M., 332(117), 347 LeBozec, H., 629(1038b), 751 Lebrasseur, G., 88(957), 181 Lebreton, P. R., 8(37), 154 LeBrumant, J., 439(40), 440(40), 441(79), 716, 717 Lecher, H. Z . , 661(1431), 666(1431), 764

Author Index Lechtken, P., 352(1), 355(62), 356(62), 358(60), 360(62), 362(62), 363(60), 365(62), 385(55), 386(58a,h,d), 387(58a,60a), 389(62), 390(62), 391(62), 393(62), 396(58,67,68), 399(65), 403(67), 410(58h), 41 1(45,58h,67), 413(58a,h,d,62), 414(115), 422, 425, 426, 427 Leclercq, D., 89(964a), I81 Lecoq, J . C., 29(284), 161 Lecoq, L. C . , 30(307), 162 LeCorre, M., 95(1013), 182 Leckonby, R. A , , 21(193), 158 Ledon, H., 59(684), 173 Ledon, H. J., 31(335a), 32(335a), 163 Lee, A . W., 33(420g), 166 Lee, D. C . S . , 414(114), 427 Lee, G. A., 133(1333), 143(1403), 192, 194 Lee, H. H., 62(715), 174 Lee, J., 395(65), 397(65), 414(114,117), 415(117), 474(371), 426, 427 Lee, K. H., 630(1081), 752 Lee, K. W., 366(129), 388(129), 415(129), 428 Lee, L. L., 443(105h), 718 Lee, S., 69(791), 176 Lee, Sh., 140(1366), 193 Lee, T. D., 331(109), 347 LeFevre, R. J., 13(13I), 156, 601(804a), 742 Lefferts, J. L., 55(666), 173 Leffler, S . , 258(281), 278 Legault, R., 74(844), 178 LeGeyt, M. R . , 661(1430), 764 Legg, K . D., 366(129), 388(129), 415(129), 428 LeGoff, N., 43(563), 170 Legon, A . C . , 477(386,387a), 727 Legraverend, C., 267(358), 281 Legris, CI., 68(769), 176 Lehmann, C., 131(1319), 132(1319,1323,1324), 192 Lehmann, H., 641(1248), 758 Lehmkuhl, H., 101(1049), 183 Lehn, J. M., 10(74), 155. 320(79), 346 Lehr, R., 215(107), 273 Lehr, R. E., 230(156), 259(306), 264(334), 268(36 1,362), 269(276-279), 274, 279, 280. 281 Lchr, W., 590(758b), 591(758b), 740 Leichter, L. M., 69(788), 70(788), 176 I x i n , M. M., 476(383), 727 Leinwetter, M., 92(982), I82 Lemal, D. M . , 520(571b), 734 Lempert, K., 603(819), 742 Ixmpert-Streter, M., 603(819), 742 Lena, L., 32(393), 164 Lendel, V. G . , 670(1555), 672(1574), 768

81I

Lenox, R. S., 81(906), 179 Lenz, W., 453(226), 722 Leonard, N. J., 469(323), 725 LePerchec, P., 358(163), 429 Leppard, D. G., 26(260), 160 LeQuesne, P. W., 212(69), 272 Lerdal, D., 248(231), 277 Leriverend, M. L., 69(787), 70(787), 176 Leriverend, P., 69(787), 70(787), 176 Lerman, C. L., 418(134), 428 LeRoux, J. P., 368(173a,h), 429 Leslie, T. M., 142(1396), 194 Lespieau, M. R., 13(128,129), 156 Leterte, G., 368(173h), 429 Leung, C.-C., 488(408), 503(408), 508(408), 544(408), 728 Leutr, J. C., 258(278,279), 278 Lev, I. J., 143(1399,1400,1404), 194 LeVan, W. I., 8(42), 154 Levand, O., 338(144), 348 Levchenko, E. S., 650(1337), 761 Levchuk, Yu. N., 440(71), 717 Lever Jun, 0. W., 248(232), 277 Levi, A , , 441(81c), 465(81c), 483(399), 717, 728 Levi, H. A , , 637(1159), 755 Levi, I . S . , 458(264a), 466(264a), 472(264,33 la), 473(264a), 5 11(264a), 723, 725 Levin, W., 204(27,34), 214(80), 217( 109, 218(27,34), 221( 120) 230( 156,157), 256(27,34,260,263-265,268,272-274), 257(275,276). 258(80,277), 259(270,306), 260(309,3 12,314,315,319,321), 261(268,27 1,275,315,321,322), 262(34,270,275,277,3 15,322,33I ,338), 263(264,270,33 I ) , 264(277,330), 266(266,271,275), 268(270,360-367), 269( 157,373-376,378,379), 271, 272, 273, 274, 277, 278, 279, 280, 281 Levina, M. I . , 24(235), 159 Levine, L., 77(865), 178 Levinson, M. I., 664(1464), 765 Levkovskaya, G. G., 642(1306-1308a), 644( 1306- 1308a), 760 Levy, G. C., 531(597), 619(943,944), 620(943,944,950), 735, 747 Levy, G. L., 13(117), 156 Lewars, E. G., 492(479), 494(479), 730 Lewis, A . J.. 45(578), 170 Lewis, D.. 266(343). 280 Lewis. D. W.. 11(93), 155 Lewis, M. D., 209(63), 238(63), 246(63). 272

812

Author Index

Lewis, N. A,, 465(299d), 724 Lewton, D. A,, 481(397a), 482(397a), 728 Ley, S. V., 89(966), 131(966,1313), 181, 191 Leyshon, W. M., 296(59), 309(31), 311(31), 328(98), 344, 345, 346 Lezina, V. P., 441(80), 492(494a), 495(494a), 717, 731 Lhoest, G., 209(67), 212(67), 272 Li, G. C . , 639(1199,1200,1202), 756, 757 Li, Y . S . , 439(43), 440(43), 716 Liao, C. C . , 37(500), 168, 453(228,229), 468(229), 625(994a), 630(227,229), 722, 749 Lidy, W., 114(1116), 185 Lien, M. H., 118(1159), 187 Liginova, V. A , , 31(354), 163 Lilienfeld, A,, 473(335), 725 Lilienfeld, L., 443(127b), 719 Liljefors, T., 664(1479), 765 Lim, C.-E., 66(752), 175 Lin, C. H., 105(1061), 106(1068), 184 Lin, J. W. P., 355(41), 363(41), 379(27), 424 Lin, L.-H., C . , 61(706), 62(718,725), 174, 175 Lin, W. P., 372(27), 424 Lindburg, J. G., 353(5), 423 Linde, H., 535(604), 735 Lindel, H., 664(1488), 766 Linden, G. L., 31(356), 163 Lindgrcn, B., 670(1553), 671(1553), 767 Lindgren, B. O., 44(573), 170 Lindsay-Smith, J. R., 215(92), 216(92), 232(92,184), 233(93,184), 272, 275 Lindsey, R. V., Jr., 614(898a), 616(898a), 745 Lindstaedt, J., 516(562c), 578(562c), 582(562), 733 Lin’kova, I. L., 555(632,634,635), 736 I h ’ k o v a , M. G., 547(622), 548(629c,c), 549(632,634,635), 550(629,656a), 551(648), 552(629e,656a), 553(629e,656a), 555(646a,647a,666,667,670), 556(646a,647a,672), 559(675,676), 624(987), 736, 737, 749 Linn, W. J., 146(1424), 194 Linstrumelle, G., 100(1039,1040), 111(1039), I83 Liotard, D., 439(20), 477(21), 715 Liotta, D. C . , 37(500), I68 Lipnicka, U., 45(577), 170 Lippert, E., 439(41a), 440(41a,60), 441(41a,7Ra), 716, 717 Lippert, E. L., Jr., 626(1011a), 750 Lippi, G., 11(80), 155 Lippman, E., 88(956), 181 Lipshutz, B. H., 110(1085a), 184

Listl, M., 453(235,236), 578(235,236), 722 Littke, W., 224(137), 274 Littler, J. S. , 39(534), 169 Litvintsev, I. Yu., 31(348), 32(348,375,379,383,387,388,397), 163, 164, I65 Liu, J . C., 354(12), 355(30b), 364(30), 369(12b), 372(26), 373(30), 375(12,12b), 377(12b), 378(12b), 379(30), 380(30), 381(12), 382(30), 386(12a), 389(12b), 423, 424 Liu, L. K., 611(880), 612(880,884), 745 Liu, T. S . , 639(1194,1195), 756 Livantsova, L. I., 506(526b), 534(526b), 732 Livinghouse, T., 107(1069), 184 Ljunggren, S . , 530(596), 735 Ljungstrom, E., 530(595), 735 Lobo, A. M., 330(103), 347 Locatelli, L., J r . , 601(801c), 742 Lockwood, P. A., 355(22b,107), 356(22b,107), 357(107), 371(22b), 379(22b), 380(22b), 38 1(22b), 382(22b), 385(22b), 387(22b), 389(22b), 390(107), 392(107), 413(107), 418(22a,b), 424, 427 Loew, G. H., 241(206), 276 Logemann, E., 664(1483), 765 Long, D. W., 639(1183,1189), 640(1183), 756 Long, R . C., Jr., 630(1058), 752 Longeray, R., 609(855), 744 Loong, W. A , , 570(708), 578(708), 739 Lopatin, V. E., 655(1368), 762 Lopez, J. A , , 357(128), 389(128), 428 Lopez, L., 46(592), SX(9S5), 128(1292), 171, 181. 191 Lora-Tamayo, M., 657(1379), 762 Lord, R. C . , 8(45), 154, 439(36,38,39), 440(36,38,39), 569(700), 630(38a, 1054), 715, 738, 751 Loreni, R., 335(129), 347, 653(1360), 762 Lorne, R., 100(1039), 11 1(1039), 183 Lossing, F. P., 8(36), 154 Lott, J., 79(894), 179 Loutfy, R. O., 625(994a), 749 Louw, R., 621(963), 631(963), 748 Love, G. M., 11(96), 155, 492(468b), 497(468b), 53 1(468b), 535(468b), 540(468), 730 Lovcll, F. M., 509(531c), 511(531c), 732 Lovell, J. B., 639(1210-1212,1215), 640( 12 15,1229), 757, 758 Lovett, M. B., 400(82), 408(82), 426 Lowenstein, M. Z . , 530(594), 735 Lown, J. W., 612(887c), 745

Author Index Lowrey, D., 7(32), 153 Loy, M., 370(15), 414(15a), 423 Lorac’h, R., 440(59), 716 Lu, A. Y . H., 256(259,270), 259(270,302,306), 260(309,332,3 14,319-321), 261(321,322), 262(270,322), 263(270), 269(378), 277, 278, 280, 282 Lu, K. C., 630(1049), 751 Lu, L., 614(909b), 619(909b), 746 Lubert, R. A,, 267(354), 281 Lucast, D . H., 66(760), 175 Lucchini, V., 441(81c), 465(81c), 613(877b), 717, 745 Luchkina, S. P., 30(324), 162 Ludwig, B. J., 445(140), 446(140), 719 Ludwig, E., 647(1323c), 761 Luhmann, U., 575(705b), 739 Lukaschina, N. N., 36(480), 168 Luke, W. K . H., 338(144), 348 Luknitskii, F. I., 61 1(871,872a,881), 614(881), 616(868-870,932), 619(871,872a), 744, 745, 747 Lumbroso, H., 437(1), 439(25), 443(1,25), 462(25), 472(1), 511(1), 636(1152), 714, 715, 755 Lumma, W. C., Jr., 571(715,716a), 575(715,7 16a), 739 Lunarzi, L., 439(49), 440(49), 716 Luntz, A., 439(28a,37), 440(37), 715 Iiipschen, R., 667(1506), 766 Lur’e, E. P., 43(566), 170, 312(175), 349, 614(907), 615(907), 617(907), 619(907), 746 Lusebrink, T. R . , 439(54a), 440(65), 716 Lusinchi, X . , 323(81b), 329(101), 330(81b), 331(110,113), 332(113,117), 346, 347 Luss, H. R., 672(1559), 768 Lutener, S. B., 147(1430), 195 Lutsenko, I. F., 492(493), 495(493), 506(526), 534(526b), 731, 732 Luttke, W., 575(705b), 739 Liittringhaus, A,, 443(128), 572(128), 719 Lutz, E. F., 444(132), 450(132c,194,195), 719 Lutz, F. F., 457(132), 468(132c), 719 Lux, D., 656(1375), 762 Lykov, Yu. V., 121(1196), 188 Lyle, G. G., 11(84), 155 Lyle, T. A , , 241(204), 245(204), 276 Lynch, T. R., 641(1251), 642(1254b,1281), 644( 3254b,3281), 645( 1254b), 646( 1281), 647(1281), 758, 759 Lyndmirova, V. L., 122(1209,1210), 188 Lyons, J. E., 30(331), 32(331,406), 34(444,446,450), 36(406,444,487-488),

813

75(847), 78(406), 86(406), 162, 165, 166, 167, 168. 178 Lysenko, S . N.. 11 1(1090), 185 Lytton, M. R., 462(281b), 488(281b), 491(281b), 724 Lyubovskii, I. S . , 92(991), 182 Lyuboptova, N. S., 441(74), 717 Ma, P., 33(420g,h), 166 McAllister, T., 480(393), 491(393), 728 McCabe, R. W . , 602(81 Ic), 742 Maccagnani, G., 589(751a), 590(755c), 591(755c), 595(755c), 740 McCall, E. B., 601(801a), 742 McCausland, D. J., 219(112), 221(112), 273 McCapra, F., 352(3), 353(10), 354(13), 364(170), 411(13b), 416(87b), 417(87b), 420(3), 423, 426, 429 McCaptra, F., 364(87a), 365(87a), 367(87a), 407(87b), 426 McCaskie, J. E., 497(504), 503(504), 524(583), 542(504), 545(618), 546(620), 731, 735 Macchia, B., 11(80), 13(126,127,134), I 17( 1 133- 1 137,1145), 124(1231), 155, 186, 189 Macchia, F., 13(126,127), 117(1133-1140,1141,1145), 118(1171), 119(1139), 124(1231), 156, 186, 187, 189 McCleverty, J. A , , 629(1034,1037,1040), 750, 75I McCloskey, C . J . , 418(135), 428 McCombe, K. M., 222(33), 264(33,328), 271, 280, 323(185), 349 McConnell, R. L., 476(380a), 727 McCourt, D. W . , 259(305), 279 McCready, R., 24(241), 25(252), 159, 160 McCullough, A. W., 210(70), 272 McCullough, J. D . , 464(291), 724 McCullough, J. P., 441(90,93), 717 McCurry, M., 19(179), I58 MacDiarmid, A. G., 658(1400,1401), 659(1401), 660(1400,1401), 763 MacDonald, C. J., 12(105), 155 MacDonald, H. H. J., 146(1425), 195 MacDonald, .I.G., 61 1(877), 613(877), 617(877), 745 MacDonald, R . N., 61(712), 150(712,1450), 174, 195 McDowell, M. V., 370(20), 424 McDuff, E. J . , 15(148), 157 McElroy, W. D., 417(130,131), 428 McElwee, J.,41(549), 170 McGhie, J . F., 626( 1009), 750

814

Author Index

McGower, J. C., 439(15h), 443(15h), 715 McGreadie, T., 255(257), 277 McGrew, F. C., 630(1078b), 752 McGuirk, P. R., 107(1075), 184 Machleder, W. H., 24(219,220,221), 67(761), 159, 176 Machon, J. P., 474(359), 726 Maciel, G. E., 439(55a), 716 McInnes, A. G., 210(70), 272 McIntosh, C. L., 239(39), 245(39), 271, 495(495), 497(495c), 499(495c,5 13c,f), 502(495c), 505(495c), 506(495c), 508(495c), 514(560d), 515(560d), 516(560), 531(495c), 532(495c), 534(495c), 540(495c), 54 1(495c), 545(495c,513e,f), 583(495c), 584(513f), 585(495c), 731, 733 McIntosh, J. M., 49(610), 171 McIntosh, R., 13(132), 156 McIntyre, D., 474(373), 727 McKellin, W. H., 452(203), 498(203), 721 McKennis, J. S . , 420(140), 428 McKenzie, L. F., 498(509), 731 McKillip, W. J., 438(14,15a), 474( 14,15a,369-37 l), 476( 14,15a,370), 714, 727 Mackle, H., 480(393), 491(393), 728 McKusick, B. C., 626(1005), 628(1005,1020), 629(1005,1031), 750 McLafferty, F. W., 14(135,136,144), 156, 157 464(295a), 724 McLauchlan, K. A,, 11(86), 155 McLean, J. A,, Jr., 660(1406), 763 McLeod, R. W., 639(1179), 756 McMills, M., 637(1159), 755 McMurry, J. E., 59(682), 173 McNeillie, D. J., 17(170), 157 McPhail, A. T., 120(1183), 188 McQuillin, F. J., 85(941), 180 McReady, R., 30(312), 33(312,422,423), 162, 166 Madan, V., 305(17), 344 Mader, H., 142(1397), 194 Madhavarao, M., 60(697), 174 Maeda, M., 331(108), 347, 588(746), 740 Maeda, T., 641(1234-1237), 642(1235), 646(1234), 758 Magee, T. R., 488(413), 728 Magnane, R., 61(702), 174 Mah, H. D., 204(27), 218(27), 230(157), 256(27,266), 264(332), 266(266), 268(360,367), 269(157), 271, 274, 278, 280, 281 Mah, T., 18(172), 157

Mahadevan, V., 264(335), 280 Mahdevan, S., 421(148), 428 Maheshwar, K. K., 571(714), 630(714), 739 Mahy, M., 567(694), 738 M a k r , G., 363(169a), 364(169b), 429 Maier, L., 662(1439,1440), 764 Maignan, C., 69(789), 70(789), 176 Mains, G. I., 32(367), 164 Maiorana, S. , 492(453,466,467,475), 495(453,466,467,475a,495), 497(495b), 502(475c,521), 504(523), 505(495b,524), 506(52 1,527), 534(52 I ) , 535(605), 536(605,609), 540(495b,609), 543(616), 546(521,527), 583(521,527), 586(609), 587(609), 730, 731, 732, 735 Maiorova, L. P., 668(1525), 767 Maizus, Z. K., 32(378), 34(427,447), 36(447), 164, 166 Majid, H . A., 474(372), 727 Majumdar, D. N., 607(841), 743 Makedonska, V. B., 260(317), 280 Maki, A. H., 629( 1029,1042), 750,751 Makitra, R. G., 16(160), 157 Makosza, M., 47(595), 48(604), 49(607), I71 Malacria, M., 37(514), 169 Malatesta, V., 340(155), 348 Malcherek, R., 642(1276), 759 Maleq, R., 117(1130), 186 Malhotra, K. C . , 672(1579), 768 Malinovskii, 24(236), 119(1181), 159, 187 Mallik, R., 90(970), 181 Malloy, R. M., 139(1361), 193 Malloy, T. B., 569(701), 738 Malone, J . F., 204(28,29), 221(28,29), 222(28,29), 264(28,29,328), 271, 280 Malpass, D. B., 105(1060), I84 Malrieu, J. P., 333(126), 347 Malsch, K. D., 364(169b), 429 Mamedov, G. Kh., 98(1026), 183 Mamedova, F. N., 449(183), 720 Mametova, N. A,, 663(1454), 765 Manaffey, W., 259(299), 279 Mancinelli, P. A , , 326(92), 346 Mandai, H., 614(910), 616(910), 746 Mangiaracina, P., 120(1183), 188 Mangoni, L., 44(570), 114(1113a), 170, 185 Manisse, N., 42(557), 150(1447), 170, 195 Mann, F. G., 632(1119), 754 Manni, P. E., 11(97), 155 Mannisse, N., 147(1435), 195 Manole, S . F., 9(55), 154 Manor, S . , 121(1198), 188

Author Index Manoury, P., 438(7f), 475(7f), 476(7f), 488(7f), 714 Mansch, B., 320(79), 346 Mansfield, W., 472(332), 725 Mantz, B., 456( l47), 719 Manti, I. B., 439(52), 442(52), 446(52,147), 456(52), 491(52), 499(52), 509(52,147), 51 1(52,147), 716, 719 Manuel, G., 22(197), 79(197), 158 Maranon, J., 439(29e), 715 Marazano, C., 453(231a), 457(231a), 511(231a), 722 Marchalin, M., 606(838b), 743 Marchese, L., 88(955), 181 Marchesini, A , , 69(780), 176 Marcil, M. J. V., 613(894), 616(894), 745 Marckle, H., 441(87), 717 Marco, B., 657(1379), 762 Marcou, A , , 636(1153,1154), 755 Marcus, E., 492(476), 502(522b), 730, 732 Marcus, R. A,, 415(119), 427 Mares, F., 30(310), 34(460a), 36(460a), 162, 167 Marfat, A , , 107(1075), I84 Margitfalvi, I., 31(348), 32(348,368), 163, 164 Mariage, 474(359), 726 Maricich, T. J., 620(951), 747 Marino, J. P., 108(1076), 110(1085b,c), 184, 482(398a), 505(526a), 728, 732 Marioni, F., 260(318), 280 Mark, C., 33(415), 165 Mark, H., 151(1485,1486), 196 Mark, J. E., 474(374h), 727 Mark, M. P., 42(552), 170 Market, J., 209(65), 210(65), 251(65), 272 Markcvich, V. S . , 31(354), 163 Markl, G., 52(627), 172 Markos, C. S . , 131(1320), 192 Markov, K., 125(1254), 190 Markova, L. I., 661(1416,1417,1429b), 662(1416,1429b), 663(1416,1417), 763, 764 Markovac-Prpic, A , , 548(629a), 549(639), 550(629a,642), 555(629a,639,642), 556(692a,639), 558(642), 736 Markovski, R., 143(1401), 146(1401), 194 Markowski, V., 144(1405), 146(1426,1427), I94 Marnett, L. J., 258(289,293-295), 279 Maroni, P., 477(390), 728 Maroni, S . , 67(762), 176 Maroni, Y., 22(197), 79(197), 158 Marples, B. A , , 70(799), 137(1354), 177, 192 Marsaioli, A . J., 421(150), 428

815

Marshall, H., 55(664), 173 Marsh, M. M . , l99( 18), 270 Marshall, H., 90(971), 91(973), 181 Marshall, J. H., 642(1253), 646(1253), 759 Marshall, P. A,, 82(910-912), 180 Marsili, A., 70(795,796), 71(796), 90(796), 176 Martens, C., 562(684b), 563(684b), 564(684b), 566(684b), 738 Martin, G., 441(79), 717 Martin, H. D., 490(425b), 497(506), 542(506), 729, 731 Martin, J. C., 42(556), 170, 488(416-417), 492(495a), 495(495a), 496(495a), 506(4 17,495a), 508(4 17), 530(4 17,593), 534(417,495a,593,601), 535(495a), 541(495a), 546(4 17,495a,60 l), 583(4 17,495a,601), 589(748), 591(748), 630(1082,1084), 728, 729, 731, 735, 740. 752 Martin, K. V., 630(1101), 753 Martin, V. S . , 33(420a,g,h), 165, 166 Martinelli, L. C., 119(1 IXO), 187 Martinez de La Cuesta, P. J., 32(371,385), 164 Martvon, A , , 606(838b), 743 Marty, R. A , , 584(743a), 585(743a), 740 Martynov, A . I . , 616(930c), 747 Martynov, B. I., 630(1098), 753 Marti, M. D., 254(245), 277 Maruyama, K., 134(1337,1339), 192 Maruyama, M., 59(678), 173 Maryanoff, C. A , , 97(1023), 183 Masai, H., 30(305), I61 Masamunc, S . , 33(420g,h), 130(1310), 166, 191, 209(68), 213(68), 272 Masamune, T., 89(963,964,965), 181, 329( 188), 349 Masana, J., 28(271a), 160 Mashaly, M. M., 602(812d), 604(812d), 742 Mashburn, J. H., 120(1190), 188 Mashiko, T., 33(412,419), 165 Mashimo, K., 629( 1046p), 751 Maskovich, Y., 34(441), 35(441), 166 Mason, S. F., 10(62), 154, 204(30), 218(30), 221(30), 222(30), 265(30), 271 Mastalerz, H., 653(1352), 761 Mastrorilli, E., 117( 1142,1143), 186 Mastumoto, M., 34(460d), 36(460d). 167 Masugi, T., 354(14c), 420(14), 423 Masuko, T., 33(413), 165 Masuyama, Y., 606(830b), 640(830b). 743 Matagne, R., 46(586), 171 Mataka, S . , 551(651), 571(713), 599(797), 737, 739, 741 Mateen, B., 233(181), 275

816

Author Index

Mateer, R. A,, 141(1380), 193 Mathey, F., 24(224), 60(692), 159, 174, 664(1489), 766 Mathias, P. L., 639(1174), 640(1174), 755 Mathur, N. K., 22(204), 158 Mathur, S. P., 639(1171), 755 M a t h , S . A., 360(175), 429 Matsubara, F., 34(438), 166 Matsuda, H., 92(985,986), 99(1029), 182, 183, 629(1046r), 751 Matsuda, I . , 99(1030), 100(1038), 112(1094), 183. 185 Matsuda, S . , 99(1029), 183 Matsuda, T., 452(202b), 499(202b), 721 Matsugo, S . , 360(165), 418(137), 428, 429 Matsumoto, H., 233(180), 275 Matsumoto, M., 100(1036), 183, 453(234), 722 Matsumoto, S., 312(183), 349 Matsumura, N., 24(232), 159 Matsunami, S . , 40(544), 170 Matsuo, S . , 592(767), 741 Matsushima, H., 53(640), 172, 461(272). 487(272), 509(272), 723 Matsuura, M., 629(1046k), 751 Matsuura, T., 352(1), 360(165), 369(79a,94), 388(79b,94), 400(79), 418(94,137), 422, 426, 427, 428, 429 Matthews, C. B., 630(1062), 752 Matthews, C. N., 551(655c), 556(655c), 561(655c), 566(655c), 642( 1265), 737, 759 Matthews, G. I . , 120(1204), 121(1204), 188 Matthews, R. S., 53(639), 172 Matucci, A. M., 29(296), I61 Matusch, R., 630(1083), 752 Matuyama, Y., 112(1098), 185 Matyjaszewski, K., 473(336c), 725 Madding, D. R . , 370(15c), 414(15), 423 Mauser, H., 331(114), 332(114), 347 Mauze, B., 55(665), 173 Mavlonov, M., 631(1113d), 753 Mawaka, J., 34(448), 36(448), 167 Maycock, C. D., 520(574), 529(574), 644(574), 734 Mayer, C., 444(119,126), 718 Mayer, R., 438(11), 548(631), 571(126), 572(126), 573(718), 574(126), 575(126), 598(794-796), 630( 1063,1070), 632(961,1070), 633(1063), 636(1063), 642(1370), 714, 719, 736, 739, 741, 748, 752, 760 Mayer, W. J. W., 22(207), 158 Mayers, D. A. , 66(758), 175

Mayfield, D. L., 667(1504), 766 Mayrargue, J., 92(995), 182 Mazanec, T. J., 465(306b), 724 Mazarguil, H., 492(469a), 730 Mazarguil, M., 492(456), 730 Mazenod, F. P., 403(84), 426 Mazitova, F. N., 661(1432), 764 Mazur, S . , 248(231), 379(39c), 277, 424 Mazur, Y . , 125(1251), 190 Mazzanti, G., 590(755c), 591(755c), 595(755c), 740 Meadow, J. R., 443(113c), 718 Medirnagh, M. S., 148(1438), 195 Meehan, G. V., 509(531d), 511(531d), 732 Meek, D. W., 465(306b), 724 Meen, R. H., 492(495a), 495(495a), 496(495a), 506(495a), 534(495a,601), 535(495a), 541(495a), 546(495a,601), 583(495a,601), 630(1082,1084), 731, 735, 752 Mehmet, Y., 483(400), 728 Mehren, R., 67(768), 176 Mehring, M., 630(1059a), 752 Mehrotra, S. K., 657(1382-1384,1391), 762, 763

ivlehta, D. R., 607(842), 743 Mehta, S. R., 492(462), 502(462), 730 Meiboom, S . , 12(101), 155 Meidar, D., 121(1200), 125(1255a), 188. 190 Meier, G. P., 653(1352), 761 Meier, H., 514(550a,554,555), 515(555), 5 16(554,555), 524(585b), 525(585b), 529(555), 733, 734 Meijer, E. W., 358(164), 359(164), 429 Meijer, J., 99(1034), 183 Meinetsberger, E., 516(564a), 521(564b), 649(1335), 733, 734, 761 Meinwald, J., 514(552,553,560~), 515(553,56Oc), 516(552,553), 521(552,553), 522(553), 527(553), 529(552,553), 530(553), 53 1(552,553), 537(552,553), 539(553), 545(553), 733 Meinzer, A. L., 439(23a), 569(23a), 715 Meissner, F., 642(1273b), 643( 1237b), 759 Mejer, S . , 132(1322), 192 Mekhteev, A. S., 123(1226), 189 Mekhtiev, E. G., 125(1242), 189 Meklati, B., 20(185), 27(266), 82(914), 158, 160, 180 Mel’der, U. Kh., 442(97), 718 Meleshevich, A. P., 5(14,157), 126(1280), 151(1280), 153, 190 Melikyan, G. G., 51(619), I72 Melillo, D. G., 502(522a), 732

Author Index Meller, A., 667(1494b), 668(1494b), 674( 1494b), 766 Melloni, G., 519(569), 525(569), 734 Mellor, I. P., 641(1251), 758 Mellor, M., 67(763,765), 176 Mel’nik, L . . 32(405), 165 Mel’nik, L. V., 32(376), 164 Melvin, L. S., J r . , 52(623), 108(1078), 172, 184 Menchen, S. M., 60(694,694a), 174 Meneghin, M., 26(255), 160 Menguy, P., 29(293-295), 161 Menyailo, A. T., 29(276), 161 Merchant, S. N., 129(1297,1298), 191 Merckel, R., 622(966c), 748 Merenyi, G., 578(731c), 739 Merenyi, R., 251(236), 277 Merkel, W., 605(827), 743 Merlino, S., 13(126), 156 Meron, J., 469(231c), 722 Merrall, G. T., 151(1481,1482), 196 Merritt, J., 598(793), 741 Merryman, P., 548(626), 549(626), 555(626), 556(626), 736 Mertens, H. J., 625(993a), 749 Merz, A , , 52(627), 172 Mesropyan, E. G., 92(977), 181 Metelitsa, D., 30(300), 161 Metelitsa, D. I., 15(151), 29(151), 30(151), 34(151), 157 Meteyer, T. E., 53(639), 172 Metrger, J., 32(393), 36(482), 164, 168 Metzncr, P., 630( l073), 7.52 Meunier, B., 39(536a,b), 169 Mews, R., 651(1342-1344), 652(1342,1343,1346~),656(1346c), 658( 1344), 659( I344,1346c), 660(1344,1346c,1407), 761, 762, 763 Meyer, E., 142(1388) 193, 307(32), 344 Meyer, H. J., 664(1487), 766 Meyer, V., 642(1284-1286), 644(1284-1286), 759 Meyers, A. I., 1 l3( 1 loo), 185 Mezey, P., 4(9), 153 Michaelson, R. C . , 32(407), 33(414), 165 Michaely, W. J., 260(316), 280 Michaillovic, M. L., 79(888), 179 Michalski, J., 656(1378), 762 Michaud, D. P., 256(264), 263(264), 278 Michejda, C. J . , 38(519), 169 Michelich, E. D., I13(1 loo), 185 Miconi, F., 54(645), 172 Middlemas, E. C., 24(214), 159 Middleton. M. J . , 453(242), 722

817

Middleton, W. J., 462(242), 491(242), 630( 1065,l075,l085- l087,1094-1096), 63 I ( 1065), 632( 1065,1075,1087,l094,1096), 633(1075,1095), 635(1075,1085), 636(1095), 637( 1095), 722, 752, 753 Miertus, S., 118(1162), 187 Migalina, Yu. V., 670(1555), 672(1574), 768 Migita, T., 372(26c), 424, 461(271a), 474(271a), 723 Mihelich, E. D., 18(176), 32(176), 33(176,409a), 43(564), 158, 165, 170 Mikesell, S. L., 474(363,364), 727 Mikhailov, I. E., 652(1348), 761 Mikheev, L. L., 614(901), 746 Mikhel’son, M. G., 655(1368), 762 Miki, H., 590(758a), 591(758a), 652(1346), 658(1346a), 740, 761 Miki, K., 254(247), 277 Miki, M., 86(946), 181 Miknis, E. P., 438(5c), 469(5c), 714 Mikolajczak, J., 656(1378), 762 Mikolajczyk, M., 630( 1047c), 635( 1047c), 656(1378), 658(1397), 751, 762, 763 Mikulla, W. D., 445(143,144), 446(143,144), 574(720), 579(720), 719, 739 Milulski, C . M., 658(1400,1401), 660(1400,1401), 763 Milinovic, I., 548(628a), 736 Milks, J. E., 136(1346), 192 Millard, B. J., 520(575), 529(575), 644(575), 734 Millard, M. M., 667(1500,1501), 668(1500). 766 Millauer, H., 40(545), 170 Millen, D. J., 477(386,387a), 727 Miller, E. C., 266(345), 269(368), 281 Miller, J., 629( l036), 751 Miller, J . A,, 63(731), 175, 266(345), 269(368), 281 Millie, Ph., 320(79), 346 Milliet, A , , 14(142), 157 Milliet, P., 323(81b), 329(101), 330(81b), 331(110), 346, 347 Mills, E., Jr., 127(1287), 191 Mills, I. M., 439(29d), 715 Milner, D., 34(434), 166 Milohnoja, M., 548(629a), 550(629a), 555(629a), 556(629a), 736 Milovanovic, J . , 79(888), 179 Milstein, D., 74(841,842), 178 Mimoun, H., 29(293-295,297,298), 32(298,398), 33(415), 34(452), 36(452), 161. 165. 167

818

Author Index

Min, T. B., 418(134), 428, 628(1026), 750 Minami, S., 629(1046m), 751 Minami, T., 285(44), 289(44), 290(44), 344, 588(745), 589(752b,c), 590(745,758a), 591(745,758a), 593(752b), 652(752b ,c, 1345- 1347), 658( 1346a), 740, 761 Minamikawa, J., 461(272-274), 487(272), 509(272-274), 723 Mine, S., 64 I ( 1238,1241,1242), 642( 1238,124 1,1242), 758 Mineshima, F., 645(1314), 760 Minisci, F., 340(155), 348 Mink, G., 34(466c), 36(466c), 167 Minkin, V. I . , 517(566c), 652(1348), 734, 761 Minshall, P. C.,658(1395), 763 Minton, N. A,, 639(1204), 640(1204), 757 Mio, S . , 33(420i), 166 Miocque, M., 92(995), 182 Mir, Q. C., 472(331c), 634(1139a,b), 635( 1139b), 754 Mirback, M. J., 400(81), 426 Mirek, J., 650(1338), 761 Mirskova, A. N., 445(142), 642(130&1308a), 644(1306-1308a), 719, 760 Mishima, T., 54(649), 61(701), 172, 174 Mislow, K., 462(282), 480(282), 484(282), 509(282), 51 1(282), 512(282,539), 514(560a), 529(560a), 724, 733 Misra, R. N., 61(700,705), 68(771), 118(1167), 122(1167), 174, 176, 187 Mistrik, E. J., 32(381,382), 164 Miszkowski, J., 46(587), 171 Mitchley, B. C.V., 269(372), 281 Mitchum, R. K., 232(174), 259(174), 275 Mitra, S. K., 621(960), 632(960,1118a), 748, 752 Mitrofanova, L. N., 37(505), 168 Mitsuhashi, S ., 629(1046i,k,m,o,v), 751 Mitsuhata, T., 34(477), 36(477), 168 Mitsui, S . , 84(935,937,940), 85(940,943,944), 86(945,947), 180, 181 Miura, I., 267(348), 281 Miura, R., 264(326), 280 Miwa, G. T., 260(320), 280 Miyadera, T., 629(1046t,x), 751 Miyamori, H., 30(305), 261 Miyano, T., 613(896b), 745 Miyashi, T., 456(252), 571(716b), 572(716b), 723, 739 Miyata, N., 219(111), 239(197), 241(197) 273, 276 Miyaura, N., 114(1107), 185 Miyazawa, K., 595(790), 741

Miyoshi, N., 114(1117), 186 Mizhiritskii, M. D., 669(1541), 767 Mizuguchi, T., 329(188), 349 Mizuno, A,, 25(251a), 160 Mizuno, M., 480(392c), 483(392c), 728 Mizuno, T., 632(1129), 754 Mizuta, M., 631(1112), 753 Mjoberg, J., 530(596), 735 Mkrtycheva, E. M., 125(1242), 189 Mochel, H. J., 520(573), 529(573), 644(573), 734 Mockel, H. J., 442(100), 718 Mockel, K., 621(957), 748 Modena, G., 33(417), 165, 447(151), 462(151), 480(151), 519(569), 525(569), 719, 734 Moedritzer, K., 661(1429a), 667(1502,1503), 668(1502,1503,1532), 764, 766, 767 Moegling, L., 34(474), 36(474), 39(474), 167 Moennighoff, H., 636(1157b), 646(1157b), 755 Moggi, G., 612(890a,b), 615(890a,b), 745 Mohamed, M. M., 101(1047), 183 Moharir, Y. E., 609(856c), 744 Mohl, H. R., 636(1157a), 755 Mohmand, S., 630(1057b), 632(1057b,l121c), 633( 1057b), 635( 1057b), 636(1057b,1121~,1149,1150),752, 754, 755 Mohn, G. R . , 309(208), 350 Mohrbacken, R. S., 10(64), 154 Moir, R. Y., 117(1148,1149), 118(1148), 186 Moisan, B., 146(1429), 195 Moiseenov, A,, 34(442), 166 Moiseenkov, A. M., 61(709), 77(709), 78(709), 174 Moiseev, I. I., 32(372-374,392), 164 Mokrosz, M., 476(379), 727 Mokrousova, I. Ya., 32(370), 164 Moldeus, P., 267(359), 281 Moldovan, L., 215(108), 217(108), 273 Molinari, H., 28(271a), 160 Molines, H., 11 I ( 1089), 185 Moller, J., 307(22), 344 Mollere, P. D., 441(94), 442(94), 718 Molloy, B. B., 245(215), 276 Momicchioli, F., 439(44), 716 Mondelli, R., 439(49), 440(49), 462(280c), 463(280c), 477(390a,b), 478(390a), 489(390b,424,425a), 490(425), 491(280c), 541(280c), 716, 724, 728, 729 Moniz, W. B., 670(1550), 767 Monks, T. J., 266(344), 280 Monma, H., 606(830a), 607(830a), 608(830a), 743 Monroe, B. M., 397(71), 426

Author Index Montanari, F., 24(215,216), 159, 287(50), 296(50,53), 314(50,71), 315(50), 320(50), 321(53), 322(53), 345 Montaufier, M. T., 44(569), 170 Montenarh, M., 657(1392), 763 Montevecchi, P. C . , 520(581c), 598(792), 734, 74I Montgomery, F. C., 353(5), 360(57a), 362(57a), 386(57), 412(57a), 413(109), 423. 425, 427 Montheard, J. B., 82(913), 180 Monti, H., 106(1066), 184 Monti, L., 13(126), 117(1144,1145), 124(1231), 156, 186, 189 Moody, F. B., 474(366), 727 Moody, L. S . , 667(1510), 669(1510), 766 Moolenaar, M. J., 613(897a), 616(897a), 617(897a), 745 Moolhuysen, J., 34(466b), 36(466b), 167 Mooney, E. F., 12(107), 156 Moore, D. R., 642(1254b,1281,1282), 644( 128 1,1282), 646( 1281,1282), 647( 128 1,1282), 649( 1281,1282), 759 Moore, H. W., 589(755d), 637(1159), 740, 755 Moores, C . J., 550(644), 555(644), 736 Mootz, D., 199(13), 270 Moran, D., 630(1102b), 637(1102b), 753 Moran, G. F., 13(116) 156 Morand, P., 118( 1155), 187 Morelli, I . , 70(795,796), 71(796), 90(796), 176 Moretti, F., 11(81), 155 Moretti, I . , 24(215,216), 159, 284(1 l), 287(50), 296(50,53), 297(63), 314(50,71), 315(50,63a), 317(63), 320(50,63b), 321(53), 322(53), 343, 345 Moretto, G., 70(795,796), 71(796), 90(796), 176 Morgan, E. P., 256(258), 277 Morgan, G. T., 670(1551), 671(1551), 767 Morgan, P. H., 297(61), 298(61), 345 Morgan, T. K., Jr., 137(1356), 192 Morgenstern, J., 630(1063), 633( 1063), 636( 1063), 752 Morgos, J., 120(1188), 188 Mori, A , , 614(910-913), 615(912), 616(910,912,9 l3), 618(913), 746 Mori, J., 455(250), 462(250), 480(250), 485(250), 501(250), 722 Mori, K., 109(1082), 184 Mori, T., 24(231), 159 Mori, Y . , 312(182), 349 Moriarty, R. M., 131(1312), 191, 230(152), 2 74

819

Morihashi, K., 312(173), 349 Morimoto, H., 441(77), 717 Morita, H., 449(185), 459(266,267), 509(531h), 511(266,267,531h), 721, 723, 732 Morita, M., 451(198-200), 721 Morokuma, K., 37(507), 168 Moron, J., 453(231b,c), 469(321), 722 Moro-oka, Y., 30(299), 32(299), 161 Morretti, I., 307(21), 315(21), 317(21), 319(11,21), 344 Morris, J. C., 443(106), 718 Morrison, G. A , , 118(1163,1164), 187 Morrissey, A. C . , 670(1548,1549), 767 Mortimer, F. S., 11(83), 155 Morton, M., 465(304), 474(362-364), 724, 726, 727 Mosinger, O., 605(824,827-829), 607(845), 608(845), 743 Moses, P. R., 631(1114), 638(1114,1167), 753, 755 Moshchenko, V. S. , 119(1178), 187 Moskalenko, V. A , , 492(450), 495(450), 496(450), 505(450), 730 Mostowicz, D., 286(47), 288(47), 291(57), 292(47,57), 293(47), 316(57,74), 317(47,68), 320(47), 333(205), 345, 350 Moss, S . J., 37(504), 168 Mossman, A . B., 24(240,241), 159 Mouk, R. W., 64(736), 175 Moulins, J., 89(964a), 181 Mousse, G. E. M., 39(533), 169 Mousseron, M., 13(130), 156 Moustafa, M. A . A., 232(173), 275 Movsumzade, M. M., 88(958), 98( 1026), 128(1291), 181, 183, 191 Moyne, J., 609(855), 744 Mrotzek, H., 642(1276), 759 Muccigrosso, D. A., 34(460a), 36(460a), 167 Muetterties, E. L., 668(1531), 767 Muir, C. N., 66(748,749), 175 Mukai, T., 312(34), 338(34,203), 344, 350. 456(251,252), 571(716b), 572(716b), 723, 739 Mukaiyama, T., 76(852), 126(1270), 178, 190 Mukhamedova, L. A., 121(1201), 188, 663(1445,1446), 764 Mukhametzyanova, E. Kh., 622(974,979), 748 Muller, B., 659(1402b), 660(1402b), 763 Muller, E., 99(1031), 183 Muller, G., 60(692), 174 Muller, H., 667(1505c), 668(1505c), 766 Muller, M., 353(9), 423 Mullis, J. C., 114(1116a), 185 Mulvey, D., 464(291), 724

820

Author Index

Mulzer, J., 565(692), 566(692), 567(692), 568(692), 738 Mumford, C., 352(1), 353(8), 354(8), 355(22b), 356(22b) 371(8,22b), 379(22b), 380(22b), 38 1(22b), 382(22b), 385(22b), 387(22b), 389(22b), 422, 424 Mumford, J. E., 357(22b), 424 Muneyuki, R., 13(125), 156 Murahashi, S. I., 81(904), 179 Murai, A , , 89(963,964,965), 181 Murai, N., 341(161), 348 Murai, S., 114(1117), 186 Murakami, K., 125(1250), 190 Muramatsu, M., 367(172), 429 Muraoka, M., 631( 1107), 642( 1295,1303,1304), 643( 1303,1304), 645( 1295,1314), 753, 760 Murase, K., 641(1235), 642(1235), 758 Murata, I., 239(200), 241(200), 254(246,248), 276, 277 Murata, K., 239(197), 241(197), 276, 641(1243), 642(1263), 758, 759 Murata, M., 438(6), 445(120), 450(120), 472(120), 476(120), 724, 728 Murata, S . , 76(854,854a,b), 112(1094), 178, I85 Murayama, E., 20(189), 158 Murray, A. S., 13(116), 127(1287), 136(1305), 156, 191 Murray, R. U., 39(530), 169 Murray, R. K . , Jr., 137(1355,1356), 138(1355), I92 Murray, R. W., 37(501), 168, 215(110), 273, 352(1), 373(28), 378(28), 423, 424 Murray-Rust, J., 476(397b), 477(397b), 481(397b), 728 Murray-Rust, P., 476(397b), 477(397b), 481(397b), 728 Musenko, D. V., 73(823), 83(928,934), 84(928), 177, 280 Musker, K. W . , 633(1134a), 754 Muthuramu, K . , 553(659b), 557(659b), 562(681,682), 566(681), 579(682), 581(681,682), 737, 738 Mutin, I. I., 125(1243), 189 Muto, S., 34(445), 266 Muzart, J., 132(1325,1326), l33(1330,1331,1334,1334a,1335,1335a), I92 Myers, R. J., 8(42), 154 Mysov, E. I . , 611(879), 613(879), 614(907), 615(907), 617(879,907), 619(879,907), 630(1098), 672(1566), 745, 753, 768

Nadeu, R., 229(147), 274 Nadir, U. K . , 293(58c), 294(58c), 295(58c), 326(92), 338(58a,146), 345, 346, 348 Nagahisa, Y., 85(944), 86(947), 181 Nagai, A. V., 655(1369), 762 Nagai, T., 492(446,447,477,488,489), 494(446,447,488,489), 495(446,447,477,488,489), 496(446,447), 505(447), 506(488,489), 534(488,489), 584(741), 594(784), 597(784), 614(741), 729, 730, 731, 740, 74I Nagano, K., 641(1237), 646(1237), 758 Nagano, N., 641(1234-1236), 642(1235), 646(1234), 758 Nagano, T., 216(86), 217(86), 219(86), 272 Nagano, Y . , 64 1(1 234- 1237), 642( 1235), 646(1234), 758 Nagao, M., 215(109), 217(109), 218(109), 273 Nagarajan, K., 490(426), 492(462), 502(462), 729, 730 Nagarajan, R., 245(215), 276 Nagarkatti, J. P., 77(864), 178 Nagasa, H., 60(695), 174 Nagasawa, C., 16(158), 157 Nagasawa, K . , 439(54e), 716 Nagase, S . , 634(1142), 754 Nagata, N., 219(111), 273 Nagata, S., 441(76), 717 Nagayama, I., 53(644), 172 Nagayama, M., 6 14(9 10-9 13), 6 15(9 12), 616(910,912,913), 618(913), 746 Nagy, F., 34(466c), 36(466c), 92(989a), 167, 182 Nagy, J. B . , 13(121), 156 Naik, K . G., 582(739), 740 Nair, V., 604(822c), 606(822c,831c,d), 742, 743 Nakagawa, T., 10(70), I55 Nakai, H., 126(1275), 190, 578(725,726), 739 Nakaido, S., 461(271a), 474(271a), 723 Nakajima, T., 126(1266), 190 Nakajima, Y., 124(1229), I89 Nakamoto, Y., 126(1266), 190 Nakamura, H., 69(782), 122(1207), 176, 188, 381(47a), 407(47), 415(47), 425, 536(608), 735 Nakamura, S., 438(13), 714 Nakanaga, T., 9(56), 154 Nakanishi, A,, 630(1076), 752 Nakanishi, K., 267(347,348), 281 Nakao, T., 93(1003), 182 Nakata, T., 109(1081), 184 Nakatsuka, S. I., 245(220), 276

Author Index Nakayama, J., 514(559), 516(566b,559), 525(559), 529(559), 531(559), 733, 734 Nakazaki, M., 264(326), 280 Nakazawa, H., 629(1046k), 75/ Nametkin, N. S., 624(985a,b), 631(1113d), 749, 753 Namikoshi, H., 492(477), 495(477), 655( 1369), 730, 762 Namy, J. L., 78(885), 101(1052), 102(1052), 103(1054,1055), 104(1052,1054a,1055,1059), 105(1052), 179, 184 Nanjo, K . , 38(526), 169 Narasimhan, P. T., 490(426), 729 Narayan, G. K . , 664(1481), 765 Naruchi, K., 338( 145), 348 Narula, A. S., 18(178a), 158 Naso, I., 46(592), 171 Nastase, M., 339(200), 349 Nasybullina, F. G., 121(1201), 188 Natsume, S ., 629(1046t), 752 Naulet, N., 91(976), 181 Naumov, V. A,, 622(969), 748 Nause, M., 114(1105), 185 Navarro, P., 657( 1379), 762 Nayler, J. H. C., 446(145), 449(145), 457(145), 468(145), 511(145), 719 Nazaretian, V. P., 614(904), 615(904), 746 Nease, A . B., 9(52), 13(52), 154 Nechaeva, M. A , , 663(1445,1446), 764 Nederlof, J. R., 613(897a), 616(897a), 617(897a), 745 Neese, A. S., 264(335), 280 Neff, J. R., 63(728), 175 Negishi, E., 113( 1104), 185 Negishi, S ., 616(930a), 747 Negoro, T., 553(659c), 737 Negri, D. P., 32(404), 165 Neidl, C., 413(14), 427 Neidlein, R., 590(758b), 591(758b), 740 Neifeld, P. G., 43(567), 270 Neill, D. C . , 287(20), 288(20), 289(20), 290(20), 291(20), 293(20), 299(20), 300(20), 307(20), 315(73), 319(76), 321(73), 333(73), 344, 345 Neill, J. D., 202(24), 204(26), 205(36), 214(36), 219(36), 221(24,26), 222(24,26), 233(36), 264(24,26), 272, 326( 192), 349, 463(286b), 481(286b), 724 Nekhaer, A . I . , 631(1113d), 753 Neklesova, 1. D., 475(377a), 727 Nelsen, T. R., 497(504,505a), 503(504), 505(505a), 506(505a), 533(505a), 536(505a),

82 1

539(505a), 542(504,505a), 546(626), 731, 735 Nelson, G. L., 13(117), 156 Nelson, J. A., 26(261), 160 Nelson, R. A , , 7(29), 253 Nelson, S. D., 199(19), 200(19), 270 Nelson, W. L., 232(171), 275 Nemes, I., 32(386), 164 Nemeth, A,, 30(327), 162 Nemota, H., 25(250), 160 Neogi, A. N., 29(277,278,280), 161 Neri, C., 57(673), 273 Neri, O., 114(1113a), 185 Nesmeyanov, N., 447( 160), 486(160b), 720 Nesmeyanov, N. A , , 486(405), 728 Nesnow, S., 214(78), 272 Neubauer, F., 94(1005), 182 Neubauer, G., 603(815), 604(815), 742 Neumann, G. S., 151(1467), 196 Neuss, N., 245(215), 276 Newallis, P. E., 661(1418,1419), 662(1418,1419,1433), 663(1419,1447), 666(1418,1433), 763, 764 Newcomb, M., 325(89), 326(89), 346 Newman, H., 28(272), 160 Newman, M. S. , 41(548), 170, 214(77), 215(77), 216(77), 272, 444(117), 468(117), 718 Newton, R. A,, 151(1476), 196 Newton, R. F., 476(397b), 481(397b,c), 483(397c), 486(406b), 488(397c), 502(406b), 728 Ng, L. S . , 338(148), 348 Nguyen, C. H., 54(653), 173 Nicco, A , , 474(359), 726 Nichols, P. C., 630(1080), 752 Nicholson, A . A,, 453(218), 456(218), 468(211), 471(218), 625(994a), 722, 749 Nicholson, C. R., 10(76), 155 Nicholson, D. C., 615(923), 746 Nickerson, J. D., 13(132), 156 Nickon, A,, 37(495), 168 Nicolaou, K. C . , 108(1077), 184 Nicolaus, B. J. R., 593(774,775), 595(774,775,789), 596(774), 599(789), 741 Nicoud, J. F., 319(77), 320(77), 345 Nieberl, S . , 453(224,225,232,233), 469(232,233,390), 472(320), 5 13(545c), 5 16(545c,562b), 5 19(545c), 722, 725, 733 Niedenzu, K . , 630( 1056), 752 Nief, F., 664(1489), 766 Nieh, M. T., 58(675), 173

822

Author Index

Nielsen, C. J., 439(27), 715 Niemeyer, J., 512(543), 525(543), 733 Niess, R., 603(818), 742 Nigro, M. M., 639(1213), 640(1213,1228), 757, 758 Niiyama, A,, 73(821), 177 Nikonova, L. Z., 439(26f), 442(26f), 443(26f), 479(26f), 715 Nikson, N. H., 630(1077), 661(1077), 664(1077), 752 Nilsen, B. P., 46(582), 171 Nimz, H., 78(870), 115(1120), 178, 186 Ninagawa, A,, 92(985,986), 182 Ning, R. Y . , 309(29,30), 31 1(29,30), 325(30), 331(11 I ) , 346(84), 324, 344, 347 Nirova, S. A,, 30(324), 162 Nishihara, A,, 438(13), 714 Nishimura, T., 34(470), 36(470), 167 Nishino, K., 254(246), 277 Nishio, T., 630(1093), 632(1093), 753 Nishiyama, K., 144(1407), 194 Nishizawa, M., 25(248), 160 Nishizawa, T., 29(291), 161 Nishizuka, T., 49(604a,b), 171 Nitzchke, M., 621(961), 632(961), 748 Nivard, R. J., 245(217), 276 Nivorozhkin, L. E., 517(566c), 734 No, V. B., 43(567), 170 Noda, S., 614(910,911), 616(910), 746 Noe, E. A,, 12(113), 156 Noels, A. F., 36(486), 168 Noguchi, H., 255(252), 377 Noguchi, M., 594(786), 741 Noi, R., 71(804), 73(804), 177 Nokami, J . , 613(896a), 617(896a), 745 Nolde, C., 664(1487), 766 N o h , R. L., 113(1100), 185 N o h , B., 8(45), 154 Noltemeyer, M., 667(1494b), 668(1494b), 766 Nornura, F., 97(1022), 183 Nornura, M., 19(182), 158 Nomura, R . , 92(985,986), 182 Nomura, T., 667(1493,1505a), 766 Nordenskjold, 267(359), 281 Nordlander, J. E., 63(728), 175 Nordqvist, M., 258(277), 262(277), 264(277), 269(379), 278. 282 Norell, J. R . , 492(432,439,483-485), 495(483,485), 499(485,514), 503(514), 505(439), 506(485,5 14), 508(484,485,5 14), 53 1(439), 532(439), 534(485,5 14), 544(485,514), 583(484,514), 584(484,514),

585(514), 611(863), 614(863,919), 729, 730, 731, 744, 746 Norell, R., 538(514), 731 Norin, T., 13(135), 156, 619(946), 747 Norman, A. D., 658(1396), 763 Norman, R. 0. C., 93(999), 151(1457), 182, 195, 339(169), 348, 470(328a), 725 Normant, H., 91(976), 181 Normant, J., 103(1058), 111(1089), 184, 185 Normant, J. F., 55(667), 100(1037), 173, 183 Normant, J.-M., 12(104), 43(104), 110(1087), 112(1093), 155, 185 Norton, T., 642(1290), 644(1290), 760 Noth, H., 669(1535), 767 Nothiesz, F., 73(829,831,833,834,835), 84(831), 87(834,835,948), 177, 181 Nouri-Bimorghi, R . , 100(1043), 110( IOXX), 183, 185 Novack, V. J . , 54(651a), 173 Novitskii, K. Yu., 440(68), 717 Noyes, W. A , , Jr., 127(1283), 191 Noyori, R., 13(125), 74(839), 76(854a,b), 156, I78 Nozaki, H., 18(177a), 24(231), 33(420f,421), 54(649), 64(742-744), 65(744), 68(772,773), 69(782), 114(1105,1106), 122(1207), 158, 159. 166, 172, 175, 176, 185, 188. 312(33), 336(33), 344, 536(608), 613(895), 617(895), 735, 745 Nuernberg, A,, 630(1055a), 751 Numan, H., 365(171), 380(63b), 425, 429 Nummy, L. J . , 206(48), 207(48), 208(48), 245(48), 271 Nunes, B. J., 23(211a), 159 Nunomoto, S., 99(1035), 183 Nuretdinova, 0. N., 439(26a,b,f,34), 440(34), 442(26a ,26f), 443(26f), 449( 172- 178,184a,c), 459(177,184~,268),462(26a), 465(305), 466(268), 474( 177,178,184~), 475(26a, 177,184~,268,375-377b),479(26a,f), 480(26a), 491(26a,f), 511(268), 715, 720, 723, 724, 727 Nutzel, K., 99(1027), 101(1027), 183 Nyburg, S. C . , 641(1251), 758

Oae, S., 289(55), 297(55), 298(55), 299(55), 345, 444(136), 446(136b), 447(136b), 449( 185), 457( 136b), 459(266,267), 461(275), 463(275), 479(391), 480(391,392~),482(275), 483(392c), 487(275), 505(136d), 506( 136d), 509(531h), 51 1(266,267,531h), 630(1076), 719, 721, 723, 724, 728, 732, 752

Author Index Ohata, N., 367(172), 429 Ohayashi, M . , 68(772,773), 176 Obendorf, S. K., 516(553), 522(553), 527(553), 529(553), 530(553), 537(553), 539(553), 545(553), 733 Oberhammer, H., 672(1558), 768 Obolentsev, R. D., 441(74), 717 O’Brien, P. J., 232(169), 275 O’Brien, S ., 150(1449), 195 Obsorne, A. D., 442(102a), 718 Ochard, P. F., 509(155), 719 Oda, R., 644(1312), 760 Oda, Y . ,74(839), 178 Odaira, Y . , 553(659c), 737 Odani, M., 653(1355), 762 Oddershede, J., 514(550b), 520(550b), 733 Odenthal, J., 626(1008), 750 Odo, K., 652(!350), 761 Oele, P. C., 621(963), 631(963), 748 Oesch, F., 260(310), 279 Ogasawara, M., 456(251), 723 Ogata, T., 604(822d), 606(822d), 742 Ogata, Y . , 25(251), 37(51 la,h), 76(857), 160, 169, 178, 305(14), 306(18), 344 Ogawa, A . , 92(984), 182 Ogawa, S . , 451(198-200), 721 Ogawa, Y . ,232(172), 233(179), 275 Ogiloy. M. M., 336(206). 350 Ogino, T., 83(933). I80 Ognevskaya, N . A , , 31(349), 32(349), 163 O’Grady, J., ISO(1449), 195 Ogura, K . , 232(170), 275 O’Hare, P. A . G., 441(87), 717 Ohgishi, H., 326(91), 339(91), 346 Ohloff, G., 13(135), 156 Ohme, R., 307(23-26), 308(28), 309(24,25,28), 327(97), 328(97), 329(94), 344, 346 Ohnishi. Y . .439(24), 443(24), 453(2 13-2 15,220,223) 462(2 13,2 14), 479(24), 480(24), 491(24), 715, 721, 722 Ohno, A , , 439(24), 443(24), 452(210b), 453(2 13-2 15,220,223,237,238), 462(213,2 14), 469(237.238). 479(24), 480(24), 491(24), 602(812c), 604(812c), 630(210b), 714, 715, 721, 722, 742 Ohno, M., 24(226), 159, 331(108), 347 Ohsawa. A,, 516(563), 522(563), 733 Ohshiro, Y . , 285(44,4S), 289(44,45), 290(44,4S), 303(70), 304(70), 326(9 I ) , 339(91). 341(45,70,16 I ) , 342(45,164), 344, 345, 346, 348 Ohta, H . , 615(924h), 746 Ohta, M., 607(844d), 743

823

Ohtorni, M., 47(596), 171 Ohtuki, S . , 631(1107), 753 Ohuchida, S . , 438(7h-e), 443(7c,d,e), 446(7h-e), 477(7h-e), 714 Ohya, S . , 629(1046x), 751 Oine, T., 312(34), 338(34,203), 344, 350 Oishi, T., 69(793), 176 Ojima, I., 461(271b,c,d), 509(271b,c,d), 606(833,834), 723, 743 Ojirna, N., 232(!70), 275 Oka, K., 631(1110,3113b), 753 Okabe, E., 645(1314), 760 Okabe, H., 93(1003), 182 Okada, A,, 151(1464), 196 Okada, K., 24(226), 159 Okamoto, T., 12(113), 156, 215(109), 217(109), 218(109), 219(111), 239(197), 241(197,198), 273, 276 Okanaa, M., 12S(1260), 190 Okawa, T., 16(154), 157 Okawara, M., 450(193c). 606(830b), 613(896b), 631(11!3e), 640(830), 743, 745. 753 Okazaki, M. E., 469(319b), 725 Okazaki, T., 53(644), 172 Okimoto, T., 77(860), 178 Okitsu, M., 516(565), 734 Okonogi, T., 52(626), 172 Okuda, H., 215(109), 217(109), 218(109), 273 Okuda, S . , 25(244a), 160, 232(172), 233(179), 2 75 Okuma, K., 615(924b), 746 Okumura, O., 61 4(9 10-91 2), 61 S(9 1 2), 616(910,912), 746 Okura, K., 125(1250), 190 Okuyama, K., 592(761-765), S93(762,764), 596(761-765). .597(761,762,764,765), 740 Olah, G. A , , 121(1200), 125(1255a), 188. 190, 441(81a), 464(8!a), 510(81a), 717 Oldham, G., 438(4a), 714 O’Leary, M. A,, 245(218), 276 Olehnovich, L. P., 652(1348), 761 Olesen, S. O . , 664( 1469,1480), 765 Olive, J. L., 84(938), 86(938), 87(938a), 180 Oliver, J. E., 126(1271), 126(1272), 190 Oliveros, E., 333(124126,205), 347, 350 Oliveros-Desherces, E., 333(123), 334(123), 347 Oliveros-Desherces, E. Q., 286(48), 345 Ollinger, J., 54(6S4), 173 Ollis, W. D., 3(7), 153 Olsen, R. J., 484(402a), 633(402a), 636(402a). 728

824

Author Index

Olson, H. G., 443(108b), 718 Olsson, K . , 550(646b), 631(646b), 672(1568), 736, 768 Omelanczuk, J., 656(1378), 762 Omote, S ., 638(1160), 755 Omote, Y., 453(211), 462(211), 468(211), 491(211), 630(1090), 632(1090), 721, 753 Onan, R. D., 120(1183), 188 Ondetti, M. A,, 555(669), 737 O’Neal, H. E., 360(57a), 362(57a), 364(106c), 385(53), 386(57), 410(53a,b), 412(53a,b,57a,106), 425, 427 Ono, H., 307(80), 312(119), 322(80), 333(119), 346, 347 Ono, K., 125(1250), 190 Ono, M., 40(544,544a), 89(963,964,965), 170, 181

Ookawa, A , , 78(874a), 179 Oostveen, E. A., 578(733b), 582(733b), 739 Opitz, G., 452(206), 468(206), 492(206,43 1,434438,469b-47 1,492,494b), 494(434), 495(206,43 1,436-438,492,494b), 498(206), 506(494b), 534(494b,600), 544(494b), 546(600), 583(600), 636(1157a), 721, 729, 730, 731, 735, 755 Oppenheim, A,, 642(1290), 644(1290), 760 Oppolzer, W., 92(994), 182 Orchard, D. G., 629(1034,1037), 750, 751 Orchard, P. F., 447(155,156), 466(155), 719 Ord, W. O., 85(941), 180 O’Reilly, E. J., 101(1048), 183 Orell, J., 396(68), 426 Oren, I., 22(207), I58 Oreshkina, G. A , , 473(353-355), 474(354), 726 Org, J., 353(5), 423 Orlando, C. M., 10(73), 155 Orlov, A. M., 548(629c), 550(629c), 555(665,666), 559(676), 736, 737 Orr, W. L., 464(290), 724 Orrell, K . G., 465(298), 724 Orrenius, S., 267(352,353), 281 Ortiz de Montellano, P. R., 107(1074), 184 Osborn, A. G., 441(85), 717 Osborne, C. E., 614(915), 616(915), 746 Oshima, K . , 18(177a), 33(420f,421), 64(742), 158, 166, 175 Oshima, T., 594(784), 597(784), 741 Oshin, L. A,, 32(370), 164 Oshiro, Y., 588(745), 590(745,758a), 591(745,758a), 740 Osman, S. M., 21(195), 158 Osterroht, C., 625(994c), 749 Osuka, A , , 135(1339), 192

O’Sullivan, W. I., 26(257), 160 Otaka, T., 453(243), 466(243), 472(243), 474(243), 632(243), 722 Otani, T., 34(431), 166 Oth, J. F. M., 11(89), 155 Otsuka, S . , 33(416), 165 Otsuki, T., 134(1337), I92 Ottenheijm, H. C . J., 245(217), 276 Ottlinger, R., 609(848,850-853,854b), 744 Ovar, F., 82(913), 180 Overheu, W . , 250(235), 277 Owen, L. N., 96(1017), 447(153-156), 466(155), 509(155), 630(1074), 719, 752 Owen, W. S., 124(1232), 189 Owens, I. S., 267(358), 281 Owens, T. A,, 575(723), 577(723), 739 Oyamada, H., 78(874a), 179 Oyanagi, K . , 439(19a), 715 Ozaki, A , , 30(299), 32(299,395), 161, 165 Ozaki, S . , 30(322), 162 Ozawa, N., 262(324), 280 Ozer, U., 663(1442), 764 Oztork, T., 145(1413), 194 Paddock, N. L., 661(1430), 764 Paddon-Row, M. N., 23(21 l), 159 Padwa, A ,, 37(516), 127(1281), 131(1281), 136(1349,1350), 141(1281), 169, 190, 192, 325(139), 337( 139), 338(139), 348, 452(202), 462(202a), 469(202a), 491(202a), 499(202a), 501(202a), 721 Pagani, G., 462(280c), 463(280c), 489(424), 490(425), 491 (280c), 492(466,475a), 495(466,47a), 502(475c), 506(527), 53 1(280c), 535(605), 536(605), 541(280c), 546(527), 583(527), 593(778), 724, 729, 730, 732, 735, 741 Pagani, G. A,, 477(390b), 489(390b,425), 728, 729 Pagnoni, U. M., 67(762), 69(780), I76 Paillous, N., 492(457), 730 Paladini, J. C . , 42(558,559), 147(1434), 148(1437), 170, 195 Palecek, M., 64(738), 175 Palermo, R. E., 33(414), 165 Palmer, G., 629(1039), 751 Palumbo, G., 114(1113a), 185 Panckhurst, D. J., 667(1517), 668(1517), 766 Pangam, J . P., 96(1019), 183 Panse, G. T., 527(588b), 735 Panthananickal, A., 258(293), 279 Panunta, T. W., 293(58c), 294(58c), 295(58c), 345

Author Index Papamidas, D., 61(703), 174 Pappas, S . P., 131(1321), 192 Paquer, D., 630(3078i), 752 Paquette, L. A,, 37(500), 83(927), 118(1l72), 168. 180, 187, 255(256), 277, 447( I%), 448( 163), 449( 163), 462( 158h), 475( 163), 491( 158h, 163), 492(158a,442-445~,473,474, 48 1,491), 495(443,445a-c,491,495), 496( 158a,h), 497( 158a,h,445a,c,473,493d, 499-501), 499(491), 503(444,445a,48 I), 504(500), 505( 158a-h,445a,473), 508(50l), 506( 158h,445~,473,474,499,500), 509(531d), 51 1(531d), 514(473), 516(473), 53 1( 158a,h,445a ,c,473,474), 532( 158a,h, 445a,c,473,481,495d), 536(445c,495d), 537(473,474,499,500), 538(473), 540(158a,h, 445a,c,495d), 541(495d,500), 542(473,495d, 499-50 I), 544(445~),545(445~),546(495d), 720, 729, 730, 731. 732 Parello, J., 286(48), 333(123), 334(123), 345, 347 Parilli, M., 44(570), 170 Park, B. K., 52(620), 172 Park, H. F., 597(791), 741 Parkanyi, C., 513(546), 514(546,560e), 733 Parker, D. .J., 85(942), 180 Parker, E. J . , 452(209), 492(209), 498(209), 515(209), 516(209), 521(582a), 524(584h), 525(209), 527(582a,587a), 529(209), 721, 734 Parker, M. B., 639(1204), 757 Parker, R., 443(105a), 718 Parker, R. E., 116(1121), 186 Parker, R. H., 59(681), 173 Parker, R. M., 145(1412,1414,1415), 194 Parker, T., 123(1216), 189 Parker, V. D., 625(995h), 749 Parlman, R. M., 438(12), 714 Parr, G. E., 256(258), 277 Parrelle, M., 63(732), 175 Parry, K., 11(85), 155 Parsons, W. H., 75(851), 178 Pasini, A., 34(435), 166 Pasqualucci, C. R., 593(769), 741 Pasquon, I., 31(351,352,357). 32(389), 163, 164 Passannante, A . J., 147(1432), 195 Passmore, J., 630( 1104), 669( 1544), 753, 767 Pasto, D. J., 632( 1 120h), 754 Paszyc, S..625(994a), 749 Patel, K. M.. 64(736), 175 Pater, R. H., 16(164), 25(253a), 157. 160 Pathan, H. R., 473(336a), 725 Patterson, C. S., 598(793), 741 Patton, B. D., 125(1253), 190

825

Patton, R. L., 658(1402a), 660(1409), 763 Patrina, N. D., 555(667), 737 Patriva, N. D., 549(634), 550(634), 555(634), 736 Patwardhan, B., 97(1020), 183 Patwardhan, B. H., 439(55h,56h), 440(56h), 452(209), 477(55h,56h), 478(55h,56h), 489(55h,56h), 490(55h,56h), 492(209), 498(209), 508(530), 51 1(530a), 515(209), 5 16(209), 521(582a), 526(530a,586), 527(582a), 529(209), 53 1(56h), 630(55h), 635(55h), 716, 721, 732, 734 Pau, J. K . , 625(996), 749 Paul, I. C . , 641(1249,1250), 758 Paulet, R., 474(357,358), 726 Paulsen, H., 64(740), 175 Paulson, D. R., 13(116), 34(458), 36(458), 127(1287), 129(1301,1302,1303,1305), 145(1419,1420), 156, 167, 191, 194 Paulus, E. T., 46(584), 171 Pavia, A . A , , 84(938), 86(938), 87(938a), 180 Paulik, F. J., 12(102), 155 Pavlov, V. M., 614(901,908), 615(908), 616(908), 619(935), 636(1157d), 637(1157d), 653(1362-1364), 654(908,1367), 655(1157d,1367), 746, 747, 755, 762 Pavluk, G. V., 31(347), 163 Payne, G. B., 24(237,238), 28(238), 43(739), 64(739), 159, 175 Payne, J. J., 642(1291), 645(1291), 760 Pardernik, L. J., 667( 1500,1501), 668( 1500), 766 Paidon, M. D., 445(139), 446(139), 452(139), 461(139), 465(139), 477(139), 479(139), 480(139), 482(139), 484(139), 487(139), 491(139), 498(139), 505(139), 509(139), 511(139), 719 Peake, S. L., 25(249), 160 Pearson, W. H., 509(531a), 732 Pechsiri, S., 9(53), 13(53), 154 Pecka, J., 441(81h), 465(296a), 717, 724 Pedersen, B. S . , 630(1077), 661(1077), 663( 1450), 664( 1079,1450,1474,1484,1485), 752, 764, 765 Pedersen, C. T., 514(550b), 520(550b), 625(995h), 733, 749 Pedrini, P., 590(755c), 591(755c), 595(755c), 740 Peet, J. H. J., 78(884), 179 Pele, B., 27(263), I60 Pelizzoni, F., 67(762), 176 Pelka, B. P., 13(116), 156 Pel'kis. N. P., 602(809), 650(1337), 742, 761

826

A u t h o r Index

Pell, A. S . , 7(28), 153 Penczek, S., 473(336c), 725 Peng, C.-T., 139(1364,1365), 193 Penn, R. E., 484(402a), 575(723), 577(723), 630(1057b), 631(1057b,Il13a), 632(1057b), 633(1057b,1113a), 635(1057b,1113a), 636(402a,1057b,1113a), 728, 739, 752, 753 Pennington, R. E., 441(93), 718 Penny, D. E., 145(1416-1418), 194 Pensack, J. M., 639(1225,1226), 757 Penzlin, G . , 34(459), 36(459), 167 Perekalin, V. V., 91(975), 181 Perez, M. A , , 658(1398), 763 Perez-Salazar, A , , 669( 1546), 767 Perkinson, N. A,, 509(531c), 51 1(531c), 732 Perotti, E., 29(296), 161 Perraud, R., 8(41), 154 Perrey, H., 621(959), 630(959), 748 Perrin, C. L., 385(52), 425 Perriot, P., 55(667), 173 Perrot, C., 14(142), 157 Perrotti, E., 57(673), 173 Perry, S ., 151(1477,1478), 196 Perveev, F. Ya., 63(730), 93(996), 175, 182, 555(633), 736 Pervova, E. Ya., 549(633), 555(633,668), 556(633,672), 736, 737 Pesaro, M., 438(9), 456(253), 714, 723 Pesce, G., 88(955), 181 Peseke, K., 64 1( 1248), 642( 1269- 127 l), 643( 1269- 127 111273a), 647( 1269,1270, 1317-1334), 758, 759, 760, 761 Pestunovich, A . E., 623(984d), 749 Pestunovich, V. A , , 623(981,983,984a), 624(98 1), 642(1306,13OXa), 644(1306,13OXa), 748, 760 Pete, J. P., 132(1325,1326), 133(1330,1331, l334,1334a, l335,1335a), 192 Peters, K . , 661(1426), 663(1426), 764 Petersen, E., 642(1274), 643(1274), 759 Petersen, D., 61(704,705), 101(704), 174 Petersen, U., 605(823), 606(823), 742 Peterson, M. L., 614(914,918), 616(918), 618(9 14,918), 6 19(914), 746 Peterson, M. R., 5(15a), 37(508), 153, 168 Peterson, P. E., 62(724), 175 Petit, J., 593(772), 596(772), 741 Petit, M. A , , 11(94), 155 Petit, M. G . , 670(1547), 767 Petka, L., 656(1370), 762 Petrasiunas, G. L. R., 630(1081), 752 Petree, H. E., 62(715), 174 Petrellis, P., 142(1384,1386-1388), 193

Petrenko-Kritschenko, P., 642(1288), 644(1288), 760 Petrov, A. A ,, 630(1078d,f), 632(1078f), 672(1572,1573), 752, 768 Petrov, M. L., 672(1572,1573), 768 Petrova, L. M., 472(254b,329), 630(1078d,f), 632(1078f), 723, 725, 752 Petterson, R. C., 142(1383), 193 Petukhov, A. A ,, 30(317), 32(396), 162, 165 Petukhova, N . P., 492(494a,496), 495(494a), 506(496a), 534(496a), 731 Pews, R. G . , 12(106), 155, 305(12), 343 Pez, G. P., 674(1581), 768 Pfeffer, B., 150(1451), 195 Heifer, H., 632( 11 17), 754 Pfeiffer, U., 50(617), 172 Pfenniger, F., 594(787c), 612(787c), 617(787c), 655(787c), 741 Pfister-Guillouzo, G., 439(20), 477(21), 715 Pflederer, J. L., 365(39f), 366(39f), 367(39f), 379(39f), 400(80), 407(80), 424, 426 Pfluger, C. E., 524(583,585), 734 Philbin, E. M., 26(257), 160 Philip, P. E., 23(210), 159 Phillips, T. R., 497(499), 506(499), 537(499), 542(499), 731 Pianka, M., 642(1291), 645(1291), 760 Picard, P., 89(964a), 181 Piccinni-Leopardi, C., 333(205), 350 Piccolo, D. E., 206(56), 207(56), 231(56), 235(56), 242(40), 243(40), 244(40), 247(40), 254(40), 271, 272 Picot, A., 329(101), 331(113), 332(113), 346, 347 Piekos, R., 668(1521), 767 Piepenbroek, A , , 605(825a), 743 Pierce, A. C . , 438(6), 551(653,654), 714, 737 Pierre, J. L., 8(41), 10(75), 12(111), 20(186,187), 26(186), 154, 155, 156, 158 Piers, K . , 495(495c), 497(495c), 499(495c,513e), 502(495c), 505(495c), 506(495c), 508(495c), 53 1(495c), 532(495c), 534(495c), 540(495c), 541(495c), 545(495c,5 13e), 583(495c), 584(495c), 585(495c), 731 Pierson, R. H., 9(60), 154 Pietrasanta, F., 22(200,201), 118(1150), 158, 187 Pietrzak, B., 388(124), 428 Pigenet, C., 636(1152), 755 Pignataro, F., 34(471), 36(471), 167 Pihlaja, K . , 439(22), 715 Pikver, R. I . , 442(97), 718 Pilcher, G., 7(28), 153, 441(89,90), 717

Author Index Pilcher, R. S ., 33(423a), I66 Pilz, H., 353(7), 423 Pinazzi, C., 473(339), 726 Pinkus, A . G., 353(5), 423 Pirig, Ya. N., 16( 160), 157 Pirikhin, L. V., 32(402), I65 Pirkle, W. H., 46(593), 171, 288(52), 289(54), 314(72), 315(52,54,72), 317(52,54), 318(52,54,177), 320(78), 345, 349, 574(719b), 583(719b), 584(719b), 585(719b), 739 Pitacco, G., 492(454,455), 502(454,455), 730 Pitt, B. M., 447(157), 465(303), 471(157), 720, 724 Pitts, J. N., 25(247), 160. 385(54), 425 Pizey, J. S., 570(709), 575(709), 578(709), 582(709), 612(887a), 617(887a), 739, 745 Pizzala, L., 17(169), 157 Plashkin, V. S., 67(767), 176 Platte, C., 657(1384), 762 Plechev, B. A , , 30(317), 162 Plenat, F., 13(122), 22(200,201), 44(568), 118(1150-1152), 156, 158, 170, 187 Plesch, P. H., 482(398b), 502(398b), 546(398b), 728 Plesnicar, B., 16(157), 17(168), 25(246), 157, 160. 307(22), 344 Pletnev, S. I . , 618(942), 747 Plinke, G., 11(89), I55 Plomp, R., 514(556,557), 515(557), 516(556,557), 525(556,557), 529(557), 531(557), 733 Plonka, J. H., 59(687), 174, 469(310), 725 Plum, C. N., 632(1122), 754 Pocar, D., 492(467), 495(467), 730 Pochelon, B., 51(618), I72 Pochetti, F., 92(988), I82 Pocker, Y., 41(547), 117(1129,1132), 119(1132), 170, 186 Podgornova, V., 32(405), I65 Pohl, G., 202(22), 222( l27), 270, 273 Pohl, L. P., 266(344), 280 Pohl, S., 661(1425), 662(1425), 668(1527), 764 Pohmakotr, M., 54(655), I73 Pointek, K., 224(137), 274 Poirier, M.-A., 22(197), 79(197), I58 Polacek, J., 459(123), 475(123), 509(123), 718 Polakova, J., 64(738), 175 Polchodenko, N. I . , 119(1181), I87 Poleschner, H., 628(1018a), 629(1018a), 750 Politzer, P., 118(1156,1157), 187 Pollard, M. D., 585(743c), 587(744), 740 Pollecoff, F., 630( 1 loo), 753 Polley, A . S . J., 137(1356), I92

827

Pollicino, S., 458(261b), 511(261b), 723 Polonski, T., 330( 107), 347 Polozov, G . I., 124(1228), 189 Pommelet, J. C., 42(557), 147(1435), 170, I95 Pommerening, H., 669(1535), 767 Pornmeret, J. J., 146(1423,1428), 194, I95 Ponaras, A. A,, 101(1046), 183 Pondaven-Raphalen, A,, 112( 1097), I85 Ponsfold, K . , 120(1185), 121(1205), 123(1185), I88 Poorker, C., 66(758), I75 Pope, W. J . , 632(1119), 754 Pople, J. A . , 14(145), I57 Popova, 0. A,, 548(629d), 551(629d), 556(629d), 736 Poppelstone, C. R., 118( 1170), I87 Poppenberg, O., 668(1529), 767 Porskamp, P. A. T. W . , 653(1351), 761 Porte, J., 520(576), 529(576), 734 Porter, S., 83(927), 180 Porter, S. K., 118(1172), I87 Posner, G. H., 106(1065), 125(12461249a), 189, 190, 242(209), 243(209), 276 Pospelov, M. V., 39(531), 169 Posselt, G., 120(1188a), I88 Posternak, T., 51(618), 172 Posynkiewicz, S., 101(1050), I84 Pott, G. T., 34(466d), 36(466d), 167 Potts, W. S . , 9(50), I54 Poupaert, J. H., 209(67), 212(67), 232(173), 2 72, 2 75 Pousa, J. L., 439(29e), 715 Povey, D. C . , 625(997), 749 Povodyreva, T. P., 79(896), 179 Powell, D. W., 653(1352), 761 Powell, L. S., 445(140), 446(140), 719 Powers, D., 443(108b), 718 Powers, D. E . , 630(1051), 636(115), 751, 755 Poyner, W. R., 473(336a), 725 Pozdnykova, T. M., 657(1380), 762 Pozhidaev, V. M., 125(1258), 190 Pradhan, S., 151(1456), 195 Praefcke, K., 520(572), 630( 1078e), 632( 1078e). 642( l273a, 1279), 643( 1273a,1279), 644(572), 734. 752, 759 Prager, R. H., 82(910-912), I80 Pragnell, M., 655(1371), 762 Prakaso Rao, A. S. C., 89(962), 181 Pralus, M., 29(284), 30(307,311), 161, 162 Preckel, M., 69(788), 70(788), 176 Preite, S . , 32(389), I64 Prescher, D., 614(917), 615(917), 746 Press, J. B., 509(531c), 511(531c), 732

828

Author Index

Pretzer, W., 223(130), 274 Price, C. C., 473(337), 474(337h), 726 Price, M. E., 356(106a), 362(106c), 364(106d), 400(78,82), 408(82), 412(106), 426, 427 Prigge, H., 439(41a), 440(41a,60), 441(41a,78a), 716, 717 Prileshaev, N., 16(152), 157 Prilezhaeva, E. N., 15(150), 126(1274), 157, 190, 492(494a,496), 495(494a), 506(496a), 534(496a), 731 Prikle, W. H., 24(217), 159 Pringle, W.. C., 439(23a), 569(23a), 715 Prinzhach, H., 22(203), 121(1192), 158, 122(1208), 130(1304), 158, 188, 191, 205(41), 209(65), 2 10(65,72), 2 1 1(41), 224( 134,135,137), 240(135), 251(65), 271, 272, 274, 443(127a), 570(127a), 572(127a,128), 575(127a), 719 Prishchepenko, V. B., 124(1227), 189 Pritchard, J. G., 14(143), 117(1126), 157, 186 Prochazka, M., 64(738), 175 Proksch, A , , 609(853), 744 Proll, T., 664(1470), 765 Proskuryakov, V. A,, 480(395), 488(415), 728 Protasova, L. D., 661(1416), 662(1416), 663(1416), 763 Prough, R. A., 267(354), 281 Pruitt, P., 285(43), 290(43), 298(43), 299(43), 344 Przhytek, J . T., 129(1300), 141(1378), 191. 193 Pudovik, A. N., 125(1258), 190 Pueschel, F., 614(917), 615(917), 746 Pulkrahek, P., 258(28l), 278 Pul’tsin, M. N., 488(415), 728 Purdy, R. H., 212(69), 272 Purick, R., 29(290), 161 Purkiss, S. C., 509(536h), 51 1(536h), 527(536h), 570(536h), 573(536h), 732 Purrello, G., 642(1293), 760 Qawiyy, 0. J., 639(1170), 755 Quante, J., 607(838e), 743 Quartieri, S., 497(508h), 543(508h), 731 Quast, H., 369(99), 427 Queen, A., 446(145), 449(145), 457(145), 468(145), 511(145), 719 Quigley, K . , 118( 1169), 187 Quinn, L. D., 24(213,214), 159 Quiroz, F., 362(35), 377(35), 424 Raasch, M. S., 514(558), 516(558), 551(652), 579(652a,h,734,735a,h), 58 1(652h), 586(652h), 602(735a,8 12a), 604(8 12a), 605(8 12a), 606(652a,812a), 621(652a), 640(735a),

642(652a,735a,h, 1267,1268,1292,1301a), 643(652a,735a), 644(65&,1292,1301), 645( 1292), 646( 1292), 649(652a,734,735a, 1292), 672(1563), 733, 737, 739, 759, 760, 768 Rahe, B. R., 612(889), 617(889), 745 Raher, H., 630(1059a), 752 Rach, J. F., 492(440), 495(440), 496(440), 505(440), 506(440), 534(440), 546(440), 583(440), 729 Rachwal, S., 650(1338), 761 Raciszewski, Z . , 29(281), 161 Radau, M., 93(1002), 182 Rado, M., 34(432), 166 Radorn, L., 4(12), 14(145), 153, 157 Radzahov, D. T.,. 92(979), 182 Radzicka, A , , 61 1(862a), 615(862a), 616(862a), 744 Raevskii, 0. A , , 439(26d), 442(26d), 715 Rafikov, S. F., 32(401), 33(401), 165, 285(38), 286(38), 290(38), 313(38), 344 Ragulin, L. I., 615(925), 616(925,93Oc), 617(934), 619(934), 653(1362), 746, 747, 762 Rahirntula, A. D., 232(169), 275 Rahrnan, L. K. A,, 472(330g), 725 Rahrnan, R., 743(340), 726 Rai, L., 639(1197), 756 Rajarnani, S., 639(1196), 756 Rajec, R., 453(230), 722 Raleigh, J. A , , 550(644), 555(644), 736 Ralowski, W., 530(596), 735 Ramage, R., 23(209), 159 Rarnachandran, V., 37(501), 168 Rarnamurthy, V., 452(210c), 453(228-230, 241), 468(229), 469(218), 516(565c), 553(659h), 557(659h), 562(68 1,682), 566(681), 579(682), 58 l(68 1,682), 630(210c,229), 721, 722, 734, 737, 738 Rarnhidi, N. G., 440(66-69), 716, 717 Rankers, R., 667(1513a), 766 Ranney, G., 353(5), 423 Ranz, J. A., 42(556), 170 Rao, A . V., 625(995c), 749 Rao, M. N. S . , 508(529), 732 Rapaport, E., 417(131), 428 Rasrnussen, J. B., 664(1466-1469), 665(1490), 666(1491h), 765, 766 Rasrnussen, P. W., 210(70), 272 Rastelli, A , , 497(508a,h), 543(508a,h), 731 Rastetter, W. H., 206(48), 207(48), 208(48), 209(63), 238(63), 243(212), 245(48), 246(63), 247(228), 253(240-244), 271, 272, 276, 277, 323(197), 349 Rastrup-Andersen, N., 46(586), 171

Author Index Rathke, B., 630(1068h), 635(1068h), 752 Ratton, S . , 609(855), 744 Ratzenhofer, M . , 92(987), 182 Raude, E., 640(1233), 758 Rauhut, M. M., 370(15a-c,e), 414(15a-c,e), 423 Rauk, A., 322(181), 349 Raulin, F., 443(11 I), 718 Ray, D. J. M., 38(518), I69 Raymond, K. N., 658(1402a), 763 Rayner, L. S . , 439(15h), 443(15h), 715 Raynolds, P. W., 630( 1084), 752 Razina, R. S . , 121(1197), 151(1455), 188, I95 Razuvaev, G. A., 448(164), 449(171), 668(1525), 720, 767 Re, F., 260(318), 280 Read, D. C., 639(1198,1203), 756, 757 Reames, D. C., 90(969), 181 Rehek, J., 24(240,241), 159 Rehek, J., Jr., 3(4a), 17(4a), 24(4a), 25(252), 30(312), 33(4a,312,422,423), 153, 160, 162, I66 Rebollo, H., 355(158), 356(158), 357(158), 358(158), 360(158), 429 Recktenwald, R., 369(99), 427 Record, K. A. F., 305(13), 307(13), 344 Reddy, S . , 664(1481), 765 Redmore, D., 50(614), 172 Reed, G. A., 258(289,294,295), 279 Reed, J . , 32(369), I64 Reeder, E., 328(187), 349 Reeder, R. H., 325(89), 326(89), 346 Reger, D. W., 639( 1172,118 1 , I 183,1189,1213). 640( 1 172,118 1,1183,12 13,1228), 755, 756, 757, 758 Regitz, M., 210(76), 212(76), 272 Rehnberg, G., 476(382), 727 Reibel, I. M., 9(55), I54 Reich, H. J., 25(249), 160, 207(58), 210(71), 212(71), 272 Reich, I. L., 207(58), 210(71), 212(71), 272 Reichmanis, E., 249(233), 277 Reid, A , , 469(309), 725 Reid, E. Emmett, 443(113c), 718 Reid, R. W . , 357(22b), 371(22), 418(22), 424 Reid, S . T., 339(207), 350 Reid, W. B., Jr., 632(1120e), 754 Reifegerste, D., 88(956), 181 Reik, L., 256(260), 277 Reikhsfel’d, V. O., 667(1507,1512,1514, 15 15,1516), 669( 153&1538), 766, 767 Reilly, J . , 82(907), I79 Reinhoudt, R. N., 546(621a), 735

829

Reinke, D., 8(38), I54 Reischer, R. J . , 52(630), 53(630), I72 Reise, J., 13(122), I56 Reissenweher, G., 355(62), 356(62), 360(62), 362(62), 365(62), 389(62), 390(62), 391(62), 393(62), 413(62), 425 Reit, H., 38(524), I69 Reith, B. A,, 623(980), 748 Rejtoe, M., 118(1165), 187 Remane, H., 442(102b), 718 Remizov, A . B., 439(34), 440(34), 715 Renard, G., 118(1150-1152), 187 Renken, T. L., 630(1057h), 631(1057b,l113), 632(1057b),633(1057h,I 113),635(1057h,1113), 636(1057b,1333), 752, 753 Renner, W., 607(840), 743 Rens, J., 44(569), I70 Repkin, A . I . , 114(1115), 185 Repta, A . J., 653(1353), 761 Rerick, M. N., 77(867), 178 Reshetova, 1. G., 27(262), I60 Reusch, W., 64(736), 131(1316,1320), 132(1316), 175, 191, 192 Reutov, 0. A , , 447(160), 486(160b), 720 Reutrakul, V., 49(611), 171 Revelle, L. K., 625(988a), 635(988a), 636(1150), 749, 755 Reverdy, G., 453(222b), 630(1081), 722, 752 Revinskii, I. F., 28(268,269), I60 Reynolds, D. D., 450(191-193), 457(191,192), 511(191), 721 Reynolds, W. F., 12(105), I55 Rheude, U., 636(1156), 637(1156), 755 Rhoades, H. L., 639( 1182,1184), 756 Riande, E., 458(264c), 472(264), 473(264c), 474(374b), 5 11(264c), 723, 727 Ricard, D., 100(1042), I83 Richard, T. J., 209(63), 238(63), 243(212), 246(63), 247(228), 253(243,244), 272, 276, 277 Richards, H. J., 438(14), 474(14,371), 714 Richards, K. E., 66(747,760,751), 175 Richardson, D. G., 353(10), 423 Richardson, J. D., 207(59), 235(59,60), 272 Richardson, W. H., 353(5), 355(157), 356(106a), 360(57a), 362(57a,106c), 364( 106h), 385(53), 386(57), 400(78,82), 408(82), 410(53a,b), 412(53a,h,57,106), 413(109), 423, 425, 426, 427, 429 Richarz, W., 34(473), 36(473), 167 Richelme, S., 341( 160), 348 Richer, J., 80(898), 83(898), 179 Richer, J. C . , 79(197), 22(197), 158

830

Author Index

Richey, W. F., 34(465), 36(465), 167 Richman, J. E., 492(439), 505(439), 531(439), 532(439), 729 Richmond, J. R., 668(1519), 767 Richter, H. P., 370(19), 379(18b), 424 Rickborn, B., 62(719-723), 68(776), 79(897), 107(1069,1073), 110(1073), 174, 176, 179, 184 Rieche, A,, 306(19), 344 Riecker, A,, 199(8), 210(75), 212(75), 270, 272 Ried, W., 492(468a), 495(468a), 496(468a), 497(468a), 506(468a), 531(468a), 541(268a), 546(468a), 605(824,827-829), 607(845), 608(846), 630(1071), 632(1071), 633(1071), 730, 743, 752 Riegler, N., 364(169b), 429 Riehl, J. J . , 10(74), 155 Rieker, A , , 199(13), 270 Rieth, K., 492(436,437), 495(436,437,492), 729, 73I Rigaudy, J., 229(149), 274 Riko, E. A., 31(362), 32(387,388), 163, 164 Rimbault, C . B., 356(159), 357(159), 359(159), 429 Rinaldi, P. L . , 24(217), 46(593), 159, 171, 288(52), 289(54), 314(72), 31 5(52,54,72), 317(52,54), 318(52,54,177), 320(78), 345, 349 Rio, G., 206(49), 211(49), 271, 362(168), 368(164), 429 Rioult, P., 551(650), 556(650), 558(650), 571(650), 737 Ripmeester, J. A., 443( 112b), 718 Ritchie, E., 536(610), 735 Rittmeyer, P., 628(1019b), 750 Rivest, R., 465(300), 724 Rivett, G. A , , 667(1495), 766 Riviere, M., 286(48), 333(123-126,205), 334(123), 492(457), 345, 347, 350 Riviere, P., 89(967), 327(196), 341(160), 348, 349 Riviere-Baudet, M., 341(160), 348 Rigaudy, J., 353(5), 423 Rizvi, S. Q. A., 327(191), 349 Roach, B. L., 458(261a), 511(261a), 723 Robb, M. A,, 37(506), 168 Robbins, C. M., 118( 1168), 122( 1168), 187 Robert, A , , 11(82), 28(273), 39(536), 94( 1009), 146(1423,1428,1429), 155, 160, 169, 182, 194, 19s Roberts, B. G., 370(15a-d), 414(15a-d), 423 Roberts, B. P., 470(327,328a), 471(328b), 485(403), 725, 728 Roberts, D. R., 411(102), 427

Roberts, J. S., 59(687), 69(781), 174, 176, 469(310), 725 Roberts, M. L., 18(175), 157 Roberts, M. R., 75(851), 112(1096), 178, 185 Roberts, N. K . , 54(652), 172 Roberts, S. M., 10(77), 155 Robin, M. B., 14(146), 157 Robinson, P. M., 258(296), 279 Robotti, K., 463(284), 480(284), 724 Rocas, J., 28(271a), I60 Rock, S. L., 443(108a), 718 Rodier, N., 661(1427), 764 Rodriguez, J., 33(424d), 166 Rodriguez, O., 354(11b), 369(11b), 381(11b), 389( 1Ib), 397(69), 398(69), 407( 1Ib), 414(1 I), 415(1 lb,122), 416(1 I), 417(1 I), 423, 426, 427 Rodwell, W. R., 4(12), I53 Roe, F. J. C., 269(372), 281 Roemming, C., 663(1457), 765 Roesky, H., 657(1391), 763 Roesky, H. W., 508(5296), 656(1374), 657( 1381- 1383), 658( I38 1,1399), 660(1408,1410), 666(1374), 672(1575), 732, 762, 763, 768 Roesner, R., 199(12), 270 Roessler, F., 622(966), 748 Roeterdink, F., 339(201), 349 Roettig, G., 667(1513b), 668(1513b), 766 Rogers, D., 131(1313), 191 Rogers, D. Z., 125(124&1249), 189, 190, 242(209), 243(209), 276 Rogers, P. E., 53(633), 172 Roggero, J., 520(576), 529(576), 734 Rokach, J., 588(747), 740 Rokaszewski, E., 123(1225), 189 Roller, P. P., 259(305), 261(323), 279, 280 Romanko, I. L., 92(980), 182 Romanov, G. V., 125(1258), 190 Romanova, T. Yu., 78(886), 179 Romanovskii, B. V., 59(686), I73 Romaskina, L. L., 119(1174-1176), 187 Romero, A,, 125(1249), 190 Rona, R. J., 61(700,704), 68(771), 118(1167), 122(1167), 174, 176, 187 Ronald, B. P., 41(547), 117(1129,1132), 119(1132), 170, 186 Ronchi, A. U., 55(662,663), 173 Rondan, N. G . , 145(1410), 194 Rondestvedt, C. S., Jr., 614(918), 616(918), 746 Rondestvedt, G. S., 618(918), 746 Ronzini, L., 46(592), I71

Author Index Roobeek, C. F., 254(250), 277 Ropalo, P. P., 615(925), 616(925), 746 Rorg, D., 614(909b), 619(909b), 746 Rose, C. B . , 99(1032,1033), 103(1057), 183, I84 Rosen, M., 492(444,445a,c,474), 495(445a ,c,495), 497(445a ,c ,495d ,50 I), 503(444,445a), 505(445a), 506(445c,474), 508(50 I), 53 1(445a,c,474), 532(445a,c), 536(445c), 537(474), 540(445a,c,495d), 541(495d), 542(495d,501), 544(445c), 545(445c), 546(495d), 729, 730, 731 Rosen, M. H., 488(410), 495(410), 530(410,590-592), 535(410,59 1,602), 540(591,602), 546(602), 583(602), 728, 735 Rosenberg, N., 338(150), 348 Rosenberger, S., 595(788), 741 Rosenblum, M., 60(696,697), 174 Rosenfeld, J. J., 70(797), 71(797), 176 Rosich, R. S., 10(69), 154 Rosmus, P., 636(1149), 755 Rosnati, V., 509(536c), 51 1(536c), 570(536c), 573(536c), 732 Rosner, P.. 210(73), 252(73), 255(255), 272, 277 Rosowsky, A , , 198(3), 270 Ross, A . M., 235(190), 241(190), 275 Rossa, L., 499(513b), 731 Rosseau, G., 358(163), 429 Rossert, M., 658(1398), 763 Rossi, J. C . , 11(98), 19(183), 44(183), 155, 158 Rossiter, B. E., 18(177), 32(177), 33(420b), 158, 165 Rossmanith, E., 638(1166), 755 Rosowsky, A , , 3(1), 4(1), 9(1), 10(1), 84(1), 85(1), 152 Roth, B., 657(1384), 762 Rothstein, E., 615(924), 746 Rouchaud, J., 34(448), 36(448), 167 Rouessac, F., 69(789), 70(789), 176 Roulet, R., 210(74), 212(74), 272 Rourke, W., 614(897b), 616(897b), 617(897b), 745 Roussi, G., 129(1296), 191 Roux, A., 48(598,599), 171 Roux, D., 312(172), 333(172), 348 Roux-Schmitt, M. C., 13(124), 48(598,599), 156, 171 Rowland, J. R., 625(999a), 626(999a), 627(999a), 628(999a), 629(999a), 749 Rozenberg, B. A , , 125(1243), 189 Roznov, V. V., 438(4c), 714 Rubailo, V. L., 34(443), 35(443), 166

83 1

Rubinson, K. A , , 629( 1039), 751 Rubottom, G. M., 325(88), 346 Rucktachel, R., 418(37), 424 Rudel, M., 34(447), 36(447), 166 Rudzik, A. D., 311(198), 349 Ruecker, Ch., 22(203), 158 Ruediger, R., 497(506), 542(506), 731 Ruehter, G., 642(1273c), 643(1273c), 759 Ruf, H., 674(1576), 768 Ruff, F., 461(275), 463(275), 482(275), 487(275), 723 Ruggeri, M. V., 545(618), 735 Rundel, W., 284(5), 343 Ruppel, R. F., 639(1186), 756 Rus, M. E., 32(385), 164 Rusche, J., 307(25), 309(25), 344 Rus Martinez, E., 32(371), 164 Russel, R. A,, 69(790), 176 Russell, D. R., 476(381), 477(381), 480(381), 492(381), 61 1(875), 613(875), 617(875), 630(1047c), 635(1047c), 727, 745, 751 Russell, G. A., 25(246), 160, 628( 1019a), 750 Russo, P. J., 658(1401), 659(1401), 660( 1401), 763 Rusznak, I., 120(1188), I88 Rutledge, R. L., 10(66), 154, 439(57b), 440(57b), 716 Ruzicka, L., 354(11), 378(11a), 381(11a), 407( 1I), 414( 1 I), 415( 1 la), 416( 1 I ) , 4 17( 1 I), 423 Ruzicka, V., 16(156), 157 Ryan, D., 250(309,312), 269(374,378), 279, 281, 282 Ryan, D. E., 214(80), 217(105), 272, 256(260,263,264,266,272,275,276), 258(80,277), 261(271,275), 262(275,277,338), 263(264), 264(277), 266(266,271,275), 268(360,362-365), 272, 273, 277, 278, 280, 281 Ryan, M. D., 633(1134a), 754 Ryang, H.-S., 34(462), 36(462), 167 Rykowski, Z., 45(577), 170 Rylander, P. N., 78(869), 178 Ryntz, R. A ,, 25(244), 159 Ryzhenkov, A. M., 92(992,993), 119( 1178), 182. 187 Rzhevskaya, N. N., 32(375,396), 164, 165 Saalfeld, F. E., 370(20), 424 Saalfrank, R. W . ,519(568), 525(568), 561(568), 562(568), 734 Sabatino, E. C., 127(1286), 141(1286), 191 Sabin, J. R., 514(550b), 520(550b), 733

832

Author Index

Sable, H. Z . , 61(708), 77(708), 115(708), 174 Saborault, B., 113(1102), 185 Sabourin, R., 57(672), 173 Saboz, J. A,, 139(1360), 193 Sacerdoti, M., 564(689), 566(689), 738 Sachs, L., 262(337), 280 Sachtler, W. M. H., 34(466a), 36(466a), 167 Sackmann, E., 12(101), 155 Sadri, E., 458(261b), 511(261b), 723 Sadykh-Zade, S. I., 27(264,265), 160 Saeed, M. A., 509(531f), 531(531Q, 732 Saegusa, T., 151(1460), 195 Safarik, I., 469(322), 725 Saidi, M. R., 60(697), 174 Sainoto, H., 33(42Of), 166 St. Clair Gantz, E., 9(60), 154 Saito, H., 128(1294), 191 Saito, I., 15(8a), 153, 352(1), 360(165), 418(137), 422, 428, 429 Saito, L., 419(138), 428 Saito, M., 629(1046v), 751 Saito, T., 629(1046v), 751 Saiz, E., 458(264c), 472(264c), 473(264c), 511(264c), 723 Sajus, L., 29(293-295,297,298), 32(298), 161 Saka, H., 441(76), 717 Sakai, J., 87(938b), 180, 458(264d), 472(264), 5 11(264d), 723 Sakaki, K., 289(55), 297(55), 298(55), 299(55), 345 Sakakibara, T., 447(162), 720 Sakamoto, M., 595(790), 741 Sakamoto, T., 53(644), I72 Sakanishi, K., 355(31), 374(31), 378(31), 386(56,57f), 387(57f), 390(57f), 392(30b), 403(83), 420(142), 424, 425, 426, 428 Saksena, A. K., 120(1183), 188 Sakurai, H., 215(91), 216(91), 233(180), 272, 2 75 Salbeck, G., 663(1448), 764 Salimov, M. A,, 449(183), 720 Sallai, P., 120(1188), 188 Salmond, W. G., 22(206), 158 Salornon, K. E., 469(319b), 484(402c), 725, 728 Salvatori, T., 67(762), 176 Salzmann, T. N., 26(258), 160 Samel, A. M., 370(15a), 423 Sarnitou, Yu., 439(26b), 715 Samitov, Y. Y., 622(972a,973a), 748 Samitov, Y . Yu., 439(54c), 716 Sammes, M. P., 492(460), 495(460), 730 Sammes, P. G., 233(178), 275, 360(175), 429 Samsa, M., 550(643), 556(643), 736

Samson, M., 44(575), 170 Samter, L. N . , 32(394), 164 Samuel, C. J., 135(1343), 192 Samuelsson, B., 61(703), 174 Sander, M., 437(2a), 443(2a), 449(181,182), 462( 18 1,277), 476(277), 480( 18 1,277), 488(277), 491(181,277), 511(2), 714, 720, 721, 723 Sandmeier, D., 564(691b), 578(691b), 738 Sandorfy, C., 9(59), 154 Sandstroem, J.. 664(1479), 765 Sandstrom, G., 232(166), 275 Sandstrom, J., 642(1254a), 759 Sandu, A . F., 9(55), 154 Sannicolo, F., 561(679c), 579(679c), 738 Sansone, E. B., 476(380c), 727 Santambrogio, A ., 29(296), I61 Santelli, M., 43(565), 170 Santiago, C . , 145(1410), 194 Santos, A,, 67(763), 176 Santosusso, T. M., 117(1147), 186 Santry, D. P., 669(1545), 767 Sanz e Carreras, E., 330(106), 347 Sapunov, V. N., 29(283), 31(345,348,362), 32(348,368,375,379,383,387,388,397), 161, 163, 164, 165 Saran, M. S., 658(1400), 658(1401), 660(1400,1401), 763 Sargeson, A. M., 6(26), 153 Sarkar, I., 142(1385), 144(1407), 193 Sarnowski, R., 82(917a), 180 Sarpotdar, A. S., 142(1396), 194 Sasaki, T., 37(510a), 169 Sasoon, Y., 216(97), 244(97), 273 Sasse, H. E., 489(421), 729 Satgk, J., 89(967), 96(1018), 181, 183, 327(196), 341(160), 348, 349, 624(986a,b), 749 Sato, K., 629(10460), 751 Sato, M. A,, 285(45), 289(45), 290(45), 341(45), 342(45), 344 Sato, N., 329(188), 349 Sato, T., 20(189), 158 Satra, S. K., 215(94), 216(94), 239(94), 254(248), 273, 277 Sattar, A , , 69(781), 176 Satti, A. M., 63(733), I75 Sauer, J., 312(171), 333(171), 348 Sauleau, J., 123(1219), 124(1235), 189 Saunders, A. D., 103(1056), 184 Saunders, J. K., 11(94), 155 Saunders, W. J., 548(626), 549(626), 555(626), 556(626), 736 Saupe, A, , 439(48), 440(48), 716

Author Index Sauter, F. J., 502(522a), 732 Sauter, H., 664(1478,1483), 765 Savignac, P., 24(224), 50(615), 55(668), 159, 172, 173 Saville, B., 620(947), 747 Saviotti, P. P., 439(46), 716 Savitsky, G. B., 439(55a), 716 Savost’yanova, I. A,, 492(493), 495(493), 731 Sawada, H., 54(640), 172 Sawahata, T., 206(43), 207(43), 271 Sawaki, Y., 37(511a,h), 76(857), 169, 178, 305(14), 306(18), 344 Sayer, J. M., 256(274), 257(275), 261(275), 262(275), 266(275), 278 Sayigh, A . A. R., 602(813), 603(813,816,817), 604(813,8 16,817), 606(835), 608(835a), 609(835a), 652(835a), 742, 743 Saykowski, F., 663(1442), 764 Scala, A . A,, 442(98), 479(98), 491(98), 614(897h), 616(897h), 617(897h), 718, 745 Scandola, F., 415(120), 427 Scartoni, V., 70(796), 71(796), 90(796), 176 Schaal, C., 447(159), 720 Schaap, A., 99(1028), 183, 355(30b,156), 357(162), 362(48), 363(32a), 364(30), 367(32h), 374(32a,h), 379(30,39b), 380(30), 382(30), 388(48h), 392(30b), 396(58e), 407(48a,h), 413(58), 414(58e), 415(48a,b), 424, 425, 429 Schacht, E., 671(1557), 768 Schack, C. J., 634(1138), 754 Schade, W., 120(1185), 123(1185), 188 Schaefer, A., 667(1513a), 766 Schaefer, F. C . , 312(174), 339(174), 349 Schaefer, R., 120(1188a), 188 Schaefer-Ridder, M., 219( 125), 227( 143), 228(143), 249(233), 268(361,362), 269(378), 273, 274, 277, 281, 282 Schaffner, H., 131(1315), 133(1315), 191 Schaffner, K . , 13 1( 13 18,1319), 132( 13 18,1319,1323,1324), 139( 1360,1361), 140(1367), 192, 193, 400(81), 426 Schalk, W., 458(263), 509(263), 51 1(263), 723 Scharf, H. D., 11(91), 155 Schauhle, J. H., 553(657,660), 556(657), 737 Schaumann, E., 437(2d), 5 16(562c), 562(683h,c), 564(683h,c), 565(693), 566(693), 578(562c), 582(562c), 602(810,81 la,h), 604(822a,e), 606(822a,e,831a,837), 607(822a), 608(831a), 622(81 la), 638( 1162,1166), 1276), 642(8 1 la,h, 1 162,1259,1273~, 643(811h,1162,1273c), 645(1162), 646(1162), 647( 1162), 714, 733, 738, 742, 743, 755, 759

833

Scheeren, J. W., 91(974), 181 Scheffer, A,, 25(254), 160 Scheffold, R., 97(1020), 183 Scheihye, S. , 630(1077), 651( 1340,1341a), 661(1077), 663(1452a,1457), 664( lO77,1452a,1473,1474,1447b,1480, 1483-1485), 752, 762, 765, 766 Scheinhaum, M. L., 338(142), 348 Scheithauer, S., 630( 1070), 632(1070), 752 Schelling, B., 333(120), 347 Schempp, H., 452(206), 468(206), 492(206,494b), 495(206,494h), 498(206), 506(494b), 534(494h,600), 583(600), 721, 731, 735 Scherer, 0. J., 656(1376), 657(1385), 662(1376,1438), 663(1376), 672(1438), 762, 764 Schermann, J. P., 285(36), 286(36), 313(36), 336(36), 344 Schemer, V., 140(1376), 193 Scheurs, H., 99(1034), 783 Scheutzkow, D., 490(425b), 729 Schiebye, S., 665(1340), 761 Schiess, P., 146(1422), 194 Schiess, P. W., 376(34), 424 Schijima, S., 342(162), 348 Schiketanz, I. I., 61(711), 174 Schildknecht, H., 438(3a,10e), 452(3a), 489(421), 492(3a), 497(3a), 498(3a), 505(3a), 531(3a), 532(3a), 540(3a), 714, 729 Schindler, N . , 661(1420), 666(1420), 764 Schinkel, H., 578(732), 739 Schinski, W. L., 439(52), 442(52), 446(52,147), 456(52,147), 49 1(52), 499(52), 509(52,147), 51 1(52,147), 716, 719 Schirmann, J. P., 29(279,284), 30(30&308,311), 161, 162 Schiwek, H. J., 497(506), 542(506), 731 Schiwy, W., 668(1527), 767 Schlessinger, R. H., 75(851), 112(1096), 178, 185

Schloezer, R., 36(485), 168 Schlogl, G., 370(17), 424 Schlosser, M., 114(1109), 185 Schmalstieg, G., 393(63), 425 Schmalstieg, H., 365(63a), 380(63a), 391(123), 428(123), 425, 428 Schmeisser, M., 667(1505c), 668(1505c, 1524), 766, 767 Schmid, G., 551(655a), 561(655a), 564(655,69lb), 578(691h), 737, 738 Schmidhauer, E., 240(131), 274 Schmidhauer, H., 94(101CL1012), 182 Schmid-Baumherger, R., 8(39), 154

834

Author Index

Schmidpeter, A,, 651(1339), 663(1458,1459), 761, 765 Schmidt, A,, 622(968), 748 Schmidt, E., 360(125), 428 Schmidt, K . D., 660(1407), 763 Schmidt, M., 674(1576), 768 Schmidt, P., 509(533), 732 Schmidt, R., 413(108), 427, 642(1260,1261), 759 Schmidt, R. R., 227(145), 274 Schmidt, S . P., 352(1), 382(50a,b), 386(60), 387(61a,b), 414(116), 415(116), 417(116), 417(132), 423, 425, 427, 428 Schmidt, U., 46(588), 171, 625(994b-d), 666(1491), 749, 766 Schmiedel, D., 630(1033), 642(1309), 644(1309), 647(1316), 752, 760 Schmitz, E., 284( 1,2), 307(2,23-26), 308(27a,28), 309(24,25,27a,28), 325(27a), 327(97), 328(2,97,98), 329(2,94), 335( 129), 338(2), 343, 344, 346, 347 Schmeuser, W., 630(1067), 752 Schneider, E., 632(1116,1117), 754 Schneider, Gy., 123(1218), 189 Schneider, K. A., 364(169b), 429 Schnockel, H., 672(1562), 768 Schnurpfeil, D., 25(253), 32(380), 120(1188a), 160, 164, 188 Schoellkopf, U., 97(1021), 183 Schoentag, W., 609(854c,e), 744 Scholl, M. J., 206(49), 21 1(49), 271 Schollkopf, K., 106(1064), 184 Schomberg, D., 634(1139b), 635(1139b), 754 Schonberg, A,, 622(966b), 630(1069), 632(1 I20d,f), 635(1069), 638(1069), 640( 1069), 642(966b,1272-1274), 643(966b,1272-1274), 748, 752, 754, 759 Schonberg, K., 625(994e), 632(994e), 650(994e), 749 Schonberger, N., 590(756) 591(756), 740 Schonecker, B., 123(1218), 189 Schonefeld, J., 328(100), 346 Schonfelder, L., 660( 1408), 763 Schore, N. E., 352(1), 422 Schotte, L., 440(70), 444(70), 569(706), 570(706), 574(706), 717, 739 Schrader, G., 661(1421c), 662(1421c), 764 Schrader, O., 353(6), 423 Schram, C. W. A., 31(336), 163 Schramm, S., 307(24-28), 309(24,25,27a,28), 325(27a), 327(97), 328(97), 329(94), 344, 346 Schreurs, A. M. M., 525(545c), 733 Schroder, G., 11(89), 155

Schroeck, C. W., 54(647,648), 172 Schroeder, H., 77(861), 79(892), 178, 179 Schroth, W., 642(1309), 644(1309), 647(1316), 760 Schubart, R., 209(61), 272 Schubert, G., 121(1205), I88 Schubert, R. M., 80(902), 179 Schuckmann, W., 605(824), 608(846), 743 Schulten, H., 642(1274), 643(1274), 759 Schultz, A. J., 629(1035), 750 Schulz, R., 514(551), 515(551), 516(551), 625(998b), 626(998b), 638(1165) 733, 749, 755 Schumaker, R. R., 601(803b), 742 Schurig, V., 33(415), 46(593a-d), 165, 171 Schuster, G., 352(1), 422 Schuster, G. B., 352(1), 355(30b,51), 360(89), 364(30), 379(30), 380(30), 381(la), 382(30,50a-b,51), 387(61a,b), 392(30b), 396(68), 405(51), 408(51), 413(89), 414( 113,116), 415( 116,ll8), 417( 116,132), 423, 424, 425, 426, 427, 428 Schutyser, J., 584(743a), 585(743a), 740 Schwartz, A , , 642(1289), 643(1289), 644(1289), 760 Schwartz, R. H., 68(774), 118(1167), 122(1167), 176, 187 Schwarz, W., 656(1375), 762 Schweig, A,, 514(551), 515(551), 516(551), 625(998b), 626(998b), 638(1165), 733, 749, 755 Schweikert, O., 224(137), 274 Schweinsberg, F., 492(469), 730 Schweisinger, R., 240(135), 274 Schwesinger, R., 224(134,137), 274 Schwenker, G., 606(831b), 743 Schwobel, A., 658(1398), 763 Scorrano, G., 441(81c), 465(81c), 483(399), 717, 728 Scott, A. I., 550(644), 555(644), 736 Scott, D. W., 441(84,93), 717 Scott, G., 260(316), 280 Scott, H., 615(922), 746 Scovell, E. G., 67(763-765), 176 Scribner, J. E., 269(371), 281 Scrocco, E., 5(17), 118(1161), 153, 187 Scrowston, R. M., 472(330g), 725 Scullard, P. W., 599(800c), 742 Scuncia, G . , 570(710), 739 Searles, S., 10(66), 254, 439(57b), 450( 194), 465(301), 716, 721, 724 Searles, S., Jr., 444(132), 450(132c,195), 457(132), 462(280a), 464(292), 468(13c), 480(280a), 719, 721, 724

Author Index Sedergran, T. C., 293(58c), 294(58c), 295(58c), 345, 497(505a,b), 505(505b,c), 506(505b), 521(582a), 524(584b), 527(582), 533(505b,c), 536( 505b,c), 54 1(50Sc), 542(505b ,c), 587(505c), 731, 734 Sederholm, C . H., 439(54a), 716 Sedmera, P., 445(124), 449(124), 718 Sedzik-Hihner, D., 45(577), 170 Seebach, D., 54(655), 112(1099), i26(1276,1277), 173. 185, 190 Seefelder, M., 603(815), 604(815), 742 Seel, F., 662(1435), 663(1435), 764 Seeley, D. A,, 41(549), 170 Seelinger, R., 633(1132), 636(1132), 637(1132), 754 Segal, G. M., 121(1205), 188 Segiet-Kujawa, W., 82(919,921,922), 180 Sehgal, R., 570(708), 578(708), 739 Seidler M. D., 76(855a), 178 Seidner, R. T.. 130(1310), 191 Seifried, H. E., 220(115), 221(115), 232(169), 246( 1 1 3 , 262( 1 15), 266( 1 15), 273, 275 Seino, Y., 215(109), 217(109), 218(109), 273 Seip, R., 630(1048), 751 Seitz, G., 250(235), 277, 445(143,144), 446( 143,144), 456(254e), 465(299d), 572(254e,7 17), 574(720), 575(254e), 577(254e), 579(717a,720), 580(254e), 58 1(254e,738), 586(254e), 630(1083), 636(1157b), 646(1157b), 719, 723, 724, 739, 740, 752, 755 Seki, E., 514(559), 516(559), 525(559), 529(559), 531(559), 733 Sekiya, M., 38(526), 169, 329(102), 346 Selander, H. G., 206(56), 207(56), 208(56), 231(56), 234( 189). 235(56), 241(189,201), 272, 2 75, 276 Selegue, J. P., 561(564c), 734 Seliger, H. H., 354(13), 395(64,65), 396(64b), 397(64b,65), 417(130,13la,b), 423, 425, 426, 428 Selim, M., 441(79), 717 Selivanova, A. S . , 622(967), 748 Selkirk, J. K., 259(303), 279 Sellars, P. J., 24(218), 159 Selling, H. A., 605(825a), 743 Selve, C., 117(1130), 186 Semashko, V. N., 622(969), 748 Semenov, L. V., 488(415), 728 Semple, J., 589(755a), 591(755a), 740 Semsel, A . M., 414(15a), 423 Semtner, P. J., 639(1193), 756 Sen, B., 509(531b), 511(531b), 732 Senda, Y . , 85(943), 181

835

Senechal, G., 73(825), 84(825,936), 85(825,936), 177, 180 Sengal, R. K., 96(1016), 183 Seng-neon Gan, 124(1234), 189 Senichar, Yu. N., 37(505), 168 Seno, M., 16(158), 157 Sepulchre, M., 151(1468), 196 Sequin, U., 13(120), 156 Serebryakov, B. R., 32(383,397), 164, 165 Seree de Roch, I . , 29(293-295,297,298), 32(298), 34(452), 36(452), 161. 166 Sergeichuk, V. V., 492(449-451), 495(449,450), 503449-45 1,525), 506(525), 53 l(525), 532(525), 730, 732 Serkiz, B., 364(174), 429 Serra-Errante, G., 233(178), 275 Serve, M. P., 206(55), 208(55), 271, 632(1120b), 754 Servis, K. L., 12(113), 156 Serzyho, J., 101(1050), 184 Sethi, S., 34(433), 166 Sethi, S. C . , 129(1297,1298), 191 Seto, S., 232(170), 275 Sevin, A,, 7(35), 145(35,1409), 154, 194, 312(172), 333(172), 348 Sevrin, M., 89(961), 181 Sewell, M. J., 630( 1063), 633(1063), 636( 1063), 752 Seybold, G., 561(678b), 579(678), 638(1164), 642(1164), 643(678b,1164), 646(1164), 738, 755 Seyden-Penne, J., 48(597-599), 171 Seyfert, D., 55(666), 173 Scyferth, D., 114( 1 1 14), 185, 667( 1499). 766 Seyferth, K., 32(380), 164 Seykens, D., 516(562a), 525(562a), 733 Sgorabotto, P., 297(63), 317(63b), 320(63b), 345, 489(418a,419,420,423a,b), 492(467), 495(467), 729, 730 Shaap, A. P., 373(30), 386(58), 390(48b), 396(58), 424, 425 Shabana, R., 65 I ( l340,134la), 664( 1466-1469,1480), 665(1340,1341a), 666(1491b), 669(1341a), 761, 765, 766 Shabanov, A . L., 88(958), 98(1026), 128( 1291), 181. 183, 191 Shabarov, Yu. S., 24(235), 159 Shackelford, S. A . , 39(529), 169 Shagidullin, R. R., 622(970,971), 748 Shahak, I., 121(1199), 188, 244(214), 276 Shaik, S., 514(560a), 529(560a), 733 Shakirov, I. Kh., 622(971), 748 Shanah, I.. 87(953), 181 Shani, A., 223(129), 239(129), 273

836

Author Index

Shanklin, J. R., 54(654), 173 Shanzer, A., 635(1144b), 642(1144b), 646(1144b), 649(1144b), 754 Shapiro, A. L., 92(991-993), 119( 1178), 182, 187 Shapiro, M. J., 360(134c), 418(134), 428 Shapiro, Yu. E., 32(403), 165 Sharkey, W. H., 630(1075,1085,1088), 632(1075,1088), 633(1075), 635( 1075,1085,1088), 752, 753 Sharma, C . , 34(433), 166 Sharma, N. D., 204(29,30), 218(30), 221(29,30), 222(29,30,33), 261(271), 264(328,335,336), 265(30), 266(271), 271, 278, 280, 323(185), 349 Sharma, N. K., 613(892), 616(892), 617(892), 745 Sharma, R. D., 264(29,33), 271 Sharman, S. H., 62(724), 175 Sharpless, K., 30(301), 161 Sharpless, K. B., 18(177), 30(333), 32(177,333,399,407), 33(414,420a-c,g,h), 52(631), 58(675), 75(848), 158, 162, 165, 166, 172, 173, 178, 233(183), 275 Sharykin, V. G., 32(379), 164 Shashkov, A. J., 81(905a), 179 Shashkov, A. S., 19(181), 158 Shawl, E. T., 672(1560,1561), 768 Shchenikova, M. K., 34(456), I67 Shearer, G. O., 16(165), 157 Sheehan, J. C., 549(638), 555(638), 736 Sheeran, P. J., 535(603), 540(603), 735 Sheeto, J., 353(10), 423 Sheinson, R. S ., 372(24a,b), 382(24b), 386(57), 412(24b), 424, 425 Sheldon, R. A,, 29(275), 30(275,332,333a), 3 1(335,336,338,344), 32(333a,335,344,366), 34(275), 161, 162, 163 Sheldrick, G. M., 658(1395), 763 Shell, P. S., 59(684), 174 Shelton, G., 74(837), 75(837), 177 Shen, M., 630(1080), 752 Shen, Q., 625(998a), 749 Sheng, M. N., 30(316,321,325), 31(337), 32(325,367,400), 162, 163, 164, 165 Sheppard, C . , 48 1(397a), 482(397a), 728 Sheppard, N., 11(87), 155 Sheppard, W. A , , 642(1301a), 644(1301), 760 Sherman, S., 151(1475), 196 Shermergorn, I. M., 622(973,974,977,979), 748 Sherwin, P. F., 484(402a), 630( 1057b), 631(1057b,1113a), 632(1057b), 633(402a,1057b,I 113a), 635(1057b,1113a), 636(402a,1057b,1113a), 728, 752, 753

Shevchenko, Z. A , , 11 1(1090), 185 Shevliri, P. B., 59(681), 173, 469(309), 725 Shibahara, S., 331(108), 347 Shibanuma, T., 641( 1234,1235), 642( 1235), 646( 1234), 758 Shibata, T., 214(80), 258(80), 272 Shibayama, S., 639(1207), 640(1207), 757 Shibaya, S., 45(580), 170 Shigemune, T., 439(31), 440(31), 715 Shigesato, H., 19(182), 158 Shih, E.-M., 139(1363-1365), 193, 194 Shih, J., 355(38), 424 Shih, L., 379(38), 424 Shih, L. S . , 418(134), 428, 628(1022), 750 Shih, N. Y . , 125(1262), 190 Shil’nikova, L. N., 93(996), 182 Shilov, A. E., 34(428), 166 Shilton, R., 615(922), 746 Shimagaki, M., 69(793), 176 Shimizu, H., 76(857), 178, 516(565b), 734 Shimizu, K., 441(77), 717 Shimizu, N., 37(511), 169 Shimizu, Y . , 421(149), 428 Shimomura, O., 354(14b,c,e), 420(14b,c,e), 423 Shimozato, Y . , 16(158), 157 Shimozawa, T., 439(24), 443(24), 479(24), 480(24), 491(24), 715 Shin, K., 36(483), 168 Shing, A. C . , 439(43), 440(43), 716 Shingaki, T., 492(446), 494(446), 495(446), 496(446,447), 594(784), 597(784), 729, 741 Shinohara, Y . , 73(821), 177 Shioiri, T., 25(251a), 160 Shioyama, I., 642(1263), 759 Shioyama, O., 641(1243), 758 Shipov, A. G., 492(452,493), 495(452,493), 506(526b), 534(526b), 730, 731, 732 Shippey, M. A , , 60(699), 174 Shiraga, T., 255(252), 277 Shirai, N., 264(334), 280 Shirota, Y., 492(488,489), 494(488,489), 495(488,489), 506(488,489), 534(488,489), 731 Shirrell, C. D., 578(727), 739 Shizuka, H., 453(219), 456(219), 722 Shode, L. G., 120(1187), 188 Shostakovskii, M. F., 445(142), 719 Shostokovskii, S. M., 441(80), 717 Showiman, Al- S., 296(60), 315(60), 345 Shreeve, J. M., 472(331c), 634( 1 135- 1 137,1139- 1141,1143), 635( 1 139b), 674(1578), 725, 754, 768 Shreeve, R. W., 634(1139a), 754

Author Index Shreve, 0. D., 9(48), 154 Shridhar, D. R., 664(1481), 765 Shroeck, C. W., 52(628,629), 53(528,529), 172 Shteinman, A., 34(428), 166 Shudo, K., 12(114), 156, 215(109), 217(109), 2 18( 109), 2 19( 11I), 239( 197), 241( 197,198), 2 73, 2 76 Shuikin, N. I., 83(929), 180 Shushunov, V. A,, 34(456), 167 Shuster, G. B., 373(30), 386(51), 389(51), 424, 425 Shvets, V. F., 119(11741176), 120(1186), 121(1196), 123(1220,1221), 187, 188, 189 Sianesi, D., 612(890a,b), 615(890a,b), 745 Siddiqui, I. A,, 117(1126), 186 Sidebottom, H. W., 612(889), 617(889), 745 Sideridu, A. Ya., 631( 1113d), 753 Sieber, W., 537(612,613), 545(613), 546(612,6 13), 735 Siegl, W. O., 452(207b), 461(276), 462(207b,276,28 la), 463(207b), 465(207b), 476(276), 477(207b,28 la,388,389), 479(207b,276,389), 480(207b,276,281a,389), 48 1(207b), 482(389), 484(207b,276), 487(276), 490(276), 491(207b,276), 492(207b,388), 497(207b), 498(207b,389), 502(207b), 505(207b,389), 506(207b), 508(276), 509(276), 512(276), 529(207), 53 1(207b), 532(207b), 538(207b), 540(207b), 544(207b), 721, 723, 724, 726, 727 Sieveking, S.,562(683c), 564(683c), 565(693), 566(693), 738 Siewinszky, A , , 131(1315), 133(1315), 191 Sigwalt, P., 151(1468,1469), 196 Sih, J. C . , 106(1068), 184 Sill, A. D., 509(534), 732 Silvon, M. P., 553(659a), 555(659a), 561(659a), 562(659a), 579(659a), 737 Simalty, M., 664( 1489), 766 Simkin, R. D., 136(1348), 192 Simmons, H. E., 625(999a), 626(999a,1003), 627(999a, 10 12), 628(999a), 629(999a, 1012), 642(1258), 647(1258), 749, 750, 759 Simo, I., 413(111), 427 Simonet, J., 545(617), 637(1158), 735, 755 Simons, G., 4(10), 5(10), 153 Simonsen, S. H., 558(674), 582(674), 583(674), 737 Simpson, G. A., 386(57), 387(57c), 395(57d), 414(57d), 425 Simpson, W. T., 441(73), 717 Sims, P., 215(82), 216(99,101), 2 17( 102,103,106), 220( 121- 123), 22 1( 122), 236( 122), 255(251,257), 264(327),

837

267(257,355), 269(257,369,370,372), 273, 277, 280, 281 Sineokov, A . P., 449(180), 475(180), 491(180), 720 Singer, E., 625(994e), 632(994e,l12Of), 749, 754 Singer, F., 650(994e), 749 Singer, L. A,, 366(129), 388(129), 415(129), 428 Singh, B., 311(131), 335(131), 347 Singh, H., 509(532), 511(532), 732 Singh, H. K., 639(1197), 756 Singh, S., 516(565c), 734 Singh, S. P., 66(753,748), 129(1300), 140(1377), 141(1378), 175, 191, 193 Singleton, D. M., 58(674), 173 Sirat, H. M., 18(172), 157 Sitz, G. E., 438(14), 474(14,371), 476(14), 714, 727 Sivade, A,, 117(1130), 186 Sivaramakrishnan, R., 131(1313), 191 Sjoberg, B., 449(167), 720 Skakovskii, E. D., 92(980), 182 Skancke, P. N., 439(23b), 630(23b), 715 Skanke, P. N., 477(387c), 727 Skau, E. L., 353(9), 423 Skell, P. S.,469(310), 725 Skladnev, A. A,, 630(1097), 753 Skotnicki, J. S.,97(1023), 183 Skowronska, A,, 656(1378), 762 Skuballa, W., 569(697), 574(697), 577(697), 579(697), 581(697), 738 Slack, W. E., 570(707,708), 574(707), 578(707,708), 579(707), 739 Slade, S. W., 656(1370), 762 Slaga, T. J., 256(268), 261(268), 278 Slagel, R. C., 438(15a), 474(15a), 476(15a), 714 Slagle, I. R., 633(1131a), 754 Slater, R., 413(112), 427 Sleath, P. R., 215(92), 216(92), 232(92), 233(92), 272 Slessor, K. N., 439(50), 478(50), 490(50), 716 Sletzinger, M., 29(290), 161 Sloan, R., 34(458), 36(458), 167 Sloane, R. B., 129(1302), 191 Slopianka, M., 123(1217), 189 Slusser, P., 400(78), 413(109), 426, 427 Smagin, V. M., 32(383,397), 164, 165 Smalley, R. K., 336(132,133), 347 Smart, B. E., 614(903), 616(903), 653(1361), 746, 762 Smets, G., 312(183), 342(162), 348, 349 h i t , W. A,, 450( 187), 721

838

Author Index

Smith, A. B., 111, 327(194), 349 Smith, B. R., 245(221), 266(221), 276 Smith, C. W., 61 1(862c), 614(862c), 616(862c), 744 Smith, C. W., Jr., 99(1032), 183 Smith, D., 444(136), 505(136d), 506(136d), 533(136d), 719 Smith, D. J. H., 439(55b), 443(125b), 445(141), 452(141b), 462(141b), 476(381), 477(55b,141b,381), 478(55b,141b), 480(141b,381), 481(141b), 482(141b), 489(55b), 490(55b), 491( 126b, 14 lb), 492(141b,381), 495(495), 497(141b,495c), 498( 141b), 499(495c,513e), 501(125b), 502(495e), 505( 125b,495c), 506(495c), 508(495c), 53 1(495c), 532(495c), 534(495c), 540( 141b,495c), 541(495c), 545(495c,513e), 546(621b), 583(495c), 584(495c), 585(495c), 61 1(875), 613(875), 614(875), 617(875), 630(55b), 635(55b), 716, 719, 727, 731, 735, 745 Smith, G., 473(336a), 725 Smith, H. A , , 509(531g), 511(531g), 732 Smith, J. P., 387(61), 425 Smith, J. R. L., 93(999), I82 Smith, J. W., 83(925), 180 Smith, K. K., 414(113), 427 Smith, M., 77(868), 178 Smith, R. H., 336(132,133), 347 Smith, R. L., 141(1379), 193 Smith, R. V., 231(164), 259(164), 275 Smith, S.,486(406b), 502(406b), 728 Smith, Z . , 630(1048,1055b), 751 Smithers, R. H., 124(1234), 189 Smithson, T. L., 439(30), 440(30), 715 Smizewski, M., 232(168), 275 Smolinski, S . , 476(379), 727 Smythe, G. A , , 576(724), 578(724), 739 Snider, B. B., 632(1130), 754 Snohle, K. A. J., 114(1110), 185 Snowden, B. S . , Jr., 464(290), 724 Snyder, D. M., 541(614b), 735 Snyder, J. P., 333(120), 347, 514(549), 611(873,874), 624(873), 635(1146), 733, 744, 745, 749, 755 Snyder, L. C., 12(101), 155 Snyder, L. R., 443(109), 475(109), 718 Soai, K., 78(874a), 179 S o b a h , M. C., 22(206), 158 S o b c ~ a kJ., , 30(333b), 31(360,361), 32(333b,384), 162, 163, 164 Soccolini, F., 47(596a), 171, 509(536c), 51 1(536c), 570(536c), 573(536c), 732

Soderhall, S., 267(359), 281 Sohma, A., 84(940), 85(940), 180 Sojka, S. A., 24(220), 159 Sokolov, A . G., 32(394), 164 Sokolov, V. E., 438(4c), 714 Sokolova, G. D., 661(1429b), 662( 1429b,1436), 764 Sokolova, V. M., 624(985b), 749 Sokol’skii, G. A,, 93(1004), 182, 61 1(860,865,868-870,876,882), 6 14(898f,h,i,899-902,905a,908,916), 615(876,89Xf,h,X99,905,908,9 16,925,926a,b), 616(868-870,898f,h,i,900,902,908,925,926a,b, 927-929,930~,93l), 617(882,926b,934-937), 618(937-942), 619(934,935), 636(1157d), 637(1157d), 653(1362-1364), 654(908,1365-1367), 655(1157d,1367), 744, 745, 746, 747, 755, 762 Sokovishina, I. F., 91(975), 181 Solar, J. P., 34(460a), 36(460a), 167 Solouki, B., 630(1057b), 631(1057b), 632(1057h), 633( l057b), 635( 1057b), 636(l057b,1149,1150), 752, 755 Solov’yanov, A. A,, 151(1461), 195 Soloway, A. H., 76(859), 178, 212(69), 272 Sommerfeld, C.-D., 224(133), 240(133), 248(133), 274 Son, P., 495(487), 731 Son, P. N., 492(486,487), 495(486), 730, 731 Sonawane, H. R., 129(1297,1298), 191 Sondheimer, F., 223(129), 239(129), 273 Sone, T., 246(226), 277 Song, P. S., 421(153), 429 Sonnet, P. E., 60(698), 126(1271,1272), 174, 190 Sonoda, A ,, 81(904), 179 Sonoda, N., 24(232), 114( 11 17), 159, 186 Sont, W. N., 439(29d), 715 Sorarrain, 0. M., 439(29e), 715 Sorgeloos, D., 605(825b), 608(825b,c), 743 Sorochinskikh, S. A ,, 24(233), 159 Sorokin, M. F., 21(190), 120(1187), 158, 188 Sorriso, S . , 13(134), 156 Sotiropoulos, J., 642(1256), 759 Sotoya, K., 447(162), 720 Sodas, R., 437(1), 443(1), 472(1), 511(1), 714 Soysa, H. S. D., 668(1533), 669(1534), 767 Spadlo, M., 38(523), 169 Spagnolo, P., 520(581c), 598(792), 734, 741 Sparke, M. B., 30(314), 162 Spassky, N., 151(1467), 196 Spath, E., 653(1360), 762 Spear, K. L., 458(261a), 51 1(26la), 723

Author Index Spence, G. G., 284(7), 307(7), 309(7), 343 Spirikin, L. V., 33(41 I ) , 165 Splitter, J., 336(135), 348 Splitter, J. S . , 307(80,1 IX), 312(119), 322(80), 333(118,119), 346, 347 Spratt, R., 297(64), 298(64), 303(64), 322(64), 345 Squire, R . H . , 337(140), 348 Squires, T. S . , 120( 1190), 188 Srednev, S. S . , 32(365), 72(817-820), 163, 177 Srinivasan, V., 64(737), 175 Stace, A . J., 442(99), 718 Stamos, I., 452(208), 492(208), 498(208), 513(548), 515(208), 516(208), 520(208), 521(208), 522(548), 524(584a), 525(208), 529(208), 531(208), 721, 733 Staninets, V. I., 670(1555), 768 Stanishevskii, L. S . , 98(1025), 183 Stanley, H.-K. J., 614(898b), 616(898b), 617(898b), 619(898b), 745 Staral, J. S . , 661(1414), 666(1414), 763 Starcher, P. S., 16(163), 157 Stark, B., 13(123), 156 Stark, C. J . , 33(424a), 166 Starling, K . E., 443(105b), 718 Staroscik, J., 107( 1073), 110( 1073), 184 Starr, J . E., 137(1353), 192 Stasevich, G. Z . , 92(980), 182 Staudinger, H., 354(11), 378(11a), 381(11a), 407(11), 414(11), 415(11a), 416(11), 417(11), 423, 551(649), 555(649), 556(649), 594(787c), 612(787c), 617(787c), 65 I ( 1314c), 656(1341c), 655(787c), 737, 741. 761, 762 Stauff, J., 370( 17), 413(11 I), 424, 427 Stautienberger, A . L., 30(320), 162 Steele, A . E., 639(1187), 756 Steele, K . , 667(1501), 766 Steer, M., 620(947), 747 Steer, R. P., 469(312-315,318,319a), 470(315), 725 Steffen, M., l99( 13), 270 Stegelmcier, H., 224( 136), 274 Stein, C. A., 465(299c), 724 Stein, U., 628(1019b), 750 Stein, W., 67(768), 176 Steiner, E. C . , 490(429), 504(429), 729 Steinfeld, A . S . , 307(166), 348 Steinrnetzer, H. C . , 352(1), 355(30b), 364(30), 369(42), 373(30), 379(30), 380(30), 382(30,49a), 386(58), 387(53c), 389(107), 392(30b), 396(58c,d,68), 413(58c,d,108), 422, 424, 425, 427 Stempel, K . , 354( l4d), 420( 14d), 423

839

Stendel, W., 605(823), 606(823), 742 Stenzowski, J. J., 575(721,722a), 739 Stepanov, I. P., 142(1389,1390), 193, 194 Stepanova, N. V., 81(905a), 179 Stepanyants, A . U., 492(494a,496), 495(494a), 506(496a), 534(496a), 731 Stephen, J. F., 492(476), 502(522b), 730 Stephens, H. N., 353(6), 423 Stephens, P. J., 669(1545), 674(1545b), 767 Stephens, T. B., 470(326), 725 Stephens, W. D., 626(101 la), 750 Stephenson, A , , 630(1069), 635( 1069), 638( 1069), 640( 1069), 642( 1274), 643( 1274), 752 Stephenson, R . A , , 105(1062), 184 Steppel, R. N., 150(1450), 195 Sterlin, S. R., 630(1098,1102a,1103a,1105), 642(1103a,l105), 644( 1105), 753 Stern, E. W., 34(425), 166 Sternbach, L. A , , 311(30), 325(30), 344 Sternbach, L. H., 309(29,30), 31 1(29), 324(84), 331( 11 I ) , 344, 346, 347 Sternhell, S . , 10(67), 11(67), 154 Stevens, H. C., 29(282), 161 Stevenson, C. D., 117(1128), 186 Steward, J. M., 464(287), 471(287), 724 Stezowski, J . J., 569(699), 738 Stiefel, F. J., 445( 140), 446( 140), 719 Stiggall, D. L., 353(5), 423 Stiles, D. A , , 469(322), 725 Still, W. C . , 54(651a), 173 Stille, J. K . , 441(78b,c), 473(78b,c,337,342), 474(342), 5 1 1(78c), 717, 726 Stillings, M . R . , 93(999), 182 Stillwell, W. G . , 230(150,151), 274 Stogeryn, E. L., 10(73), 155 Stogryn, E. L., 147(1432), 151(1454), 195 Stoher, W. D., 199(15), 200(15), 270 Stojaneva-Antoszczynszyn, M., 46(587), I71 Stokozenko, V. N., 120(1187), 188 Stolle, R . , 621(959), 630(959,l loo), 748, 753 Storning, J. A , , 268(263), 281 Stoodley, R. J., 509(531e), 5 1 1(531e), 520(574), 529(574), 549(636,637,641b), 550(637), 558(636,637), 644(574), 734, 736, 738 Stork, G., 101(1046), 183. 452(204), 492(204), 498(203), 721 Story, P. R., 39(530), 169 Stothers, J. B . , 584(742), 614(742), 740 Stotskaya, L. L., 473(353-355), 474(354), 726 Stout, D. M . , 12(193), 158 Stovakova, I . , 32(381), 164

840

Author Index

Stoyanov, A,, 125(1255), 190 Stozhkova, G. A, , 31(349), 32(349), 163 Strait, L. A . , 10(65), 154 Stransky, W., 22(198), 158 Strating, J., 364(30), 379(30), 380(30), 382(30), 424, 623(980), 653(1354), 748, 762 Stratonova, E. I., 21(190), 158 Straub, H., 99(1031), 183 Straws, H. L., 439(35), 440(35), 715 Strausz, 0. P., 4(9), 37(506,508), 128(1288), 153, 168, 191, 469(322), 725 Streinz, L., 45(576), I70 Streith, J., 284(6), 331(6), 339(6,200), 343, 349 Strickmann, G., 642(1297), 645(1297), 760 Striegler, H., 307(25), 309(25), 335(129), 344, 347 Stringer, 0. D., 305(167), 326(193), 327(193), 348, 349 Strom, E. T., 464(290), 724 Strow, C. B., 130(1309), 191 Stubbs, M. E., 202(24,25), 204(24-26), 22 1(24,26), 222(24-26), 256(25), 264(24-26), 271, 323(82), 346 Stuche, D., 209(65), 210(65), 251(65), 272 Stucki, H., 492(445c), 495(445c), 497(445c), 506(445), 53 1(445c), 532(445c), 536(445c), 540(445c), 544(445c), 545(445c), 729 Studner, Y. N . , 114(1115), 185, 630( 1097), 753 Stumbreviciute, Z . , 449( 183), 720 Sturm, W., 668(1528,1530), 669(1542), 767 Sturtz, G., 96(1019), 112(1097), 125(1257), 183, 185. 190 Stylianopoulou, F. L., 259(297), 279 Su, C., 32(369), 164 Su, S. R . , 498(512,513a), 503(512,513a), 731 SU, T.-M., 312(119), 333(119), 347 Suan, R., 609(856b), 744 Suarez, J. Q., 647(1333,1334), 761 Subramanyam, A. V. D. V., 212(69), 272 Subramamyam, V., 76(859), 178 Suchomelova, L., 480(394), 728 Sucrow, W., 123(1217), 189 Sudoh, R., 447(162), 720 Suffolk, R . J., 630(1060), 752 Suga, K., 92(978), 181 %a, S.,126(1266), 190 Sugawara, S.,629(1046t), 751 Sugawara, T., 13(125), 156 Sugi, Y . , 84(937), 86(945,947), 180, 181 Sugihara, Y . , 239(200), 241(200), 276 Sugimura, T., 215(109), 217(109), 218(109), 2 73 Suginome, H., 329(188), 338(151), 348, 349

Sugishita, M., 99(1030), 183 Sugita, T., 118(1154), 125(1263), 126(1267,1268), 187, 190 Sugiura, M., 255(253,254), 277 Sugiura, S., 16(153), 157 Sugiyama, N., 453(211,212), 426(211,212), 468(21 I), 491(211,212), 630(1093), 632(1093), 721, 723 Suhara, Y., 331(108), 347 Sukornick, B., 632(1121d), 754 Sulaimanov, A. S., 662(1434), 663(1434,1454), 764, 765 Sullivan, G. A ,, 36(489), 168 Sulser, U., 124(1233), I89 Sumegi, L., 30(327), 32(386), 162, I64 Sumoto, K., 53(640,641), 172, 461(272,273), 487(272), 509(272,273), 723 Sunaga, M., 52(626), 172 Sunami, M., 653(1355), 762 Sundermeyer, W., 114(1116), 185, 633(1132), 636(1132,1156), 637(1132,1156), 754, 755 Sunner, S., 441(86), 717 Sunshine, W. L., 120(1191), 188 Surzur, J. M., 456(254a), 723 Sus, O., 595(788), 741 Suschitzky, H., 336(132,133), 347 Suslova, E. N., 623(98 1,982), 624(98 1,982), 748 Susse, P., 575(705b), 739 Sutcliffe, L. H., 612(883), 745 Sutherland, B. L. S . , 66(746), 175 Sutherland, J. K., 67(763-765), 176 Sutherland, J. O., 638(1167), 755 Sutherland, R. G . , 133(1332), 192 Suto, N., 456(252), 571(716b), 572(716b), 723, 739 Suwita, A , , 569(698b), 571(698b), 574(698b), 577(698b), 738 Suzuki, A. , 86(946), 114(1107), 129(1299), 181, 185, 191 Suzuki, H., 61(701), 174, 312(182), 349 Suzuki, J., 372(26c), 424, 461(271a), 474(271a), 723 Suzuki, K., 38(526), 169, 312(173), 349, 629( 1046v), 751 Suzuki, M., 71(804), 73(804), 74(839), 76(854a,b), 176, 178 Suzuki, N., 379(40), 424 Suzuki, S . , 83(931), 180 Suzuki, S-i, 630(1090), 632(1090), 753 Suzuki, T., 18(177a), 33(420f), 158, 166 Suzumato, G., 11 1(1089a), 185 Svahn, C. M., 44(573), 170

Author Index Svanholt, H., 672(1569), 768 Svetlik, J., 606(838b), 743 Svitych, R. B . , 32(375,396), 164, 165 Svoboda, M., 124(1230), 189 Swain, C. G., 43(560), 170 Swanson, D. D., 633(1134a), 754 Sweeney, A., 74(838), 75(838), 177 Sweeney, R. F., 632( 1121d), 754 Sweeney, W., 548(627), 550(627), 556(627), 736 Sweeny, W., 473(338), 474(338) 726 Swern, D., 9(48), 15(149), 77(860), 117(1146,1147), 154. 157, 178. 186 Swift, H. E., 31(346), 163 Swinton, P . F., 440(64), 716 Sydnes, J. K., 453(240b), 552(240b), 578(240), 722 Sydykov, Zh. S . , 121(1205), 188 Symeonides, K., 570(709), 575(709), 578(709), 582(709), 739 Symmes, C., Jr., 24(213,214), 159 Synder, J. P., 627(1016), 750 Syrov, A . A., 34(429), 166 Sytilin, M. S., 16(159), 157 Sytin, V. N., 28(268,269), 160 Szabo, I . , 73(824), 177 Szabo, J., 9(57), 154 Szakacs, S . , 34(466c), 36(466c), 167 Szakacs, S . , 92(989a), 182 Szalkiewicz, A , , 34(460a), 36(460a), 167 Szelcjewski, W., 38(523), 169 Szilagy, P. J., 441(81a), 464(81a), 510(81a), 717 Tabacchi, R., 520(577), 529(577), 734 Tabasaranskaya, T . Z . , 663(1444), 764 Tabata, T., 338(149), 348 Tabushi, I., 439(19), 447(152), 449(179a), 450(179a), 499(152), 717, 719, 720 Tachibana, A., 629(1046e,p), 630( 1046e), 633( 1046e), 635(1046e), 751 Tack, D., 671(1557), 768 Tada, M., 257(276), 264(329), 278 Taddei, F., 440(62), 489(62), 716 Tadokoro, H., 474(374a), 727 Taeger, T., 669(1535), 767 Taffer, I. M., 78(878a), 179 Tagaki, M., 452(202b), 499(202b), 721 Tagaki, T., 631(1112), 753 Tagaki, W., 52(626), 172 Taguchi, H., 312(33), 336(33), 344, 613(895), 617(895), 745 Taguchi, M., 592(767), 741

84 1

Taguchi, Y., 118(1154), 187, 638(1160), 755 Tahara, A., 69(793), 176 Tai, K., 474(374a), 727 Tajima, M., 629(1046i), 751 Takada, S., 130(1310), 191 Takahashi, H., 338(151), 348 Takahashi, K., 49(604a,b), 171, 452(208), 492(208), 498(208), 513(548), 515(208), 5 16(208,561), 520(208), 521(208,561), 522(548), 524(583,584a), 525(208), 529(208,561), 530(208), 721, 733, 734 Takai, K . , 33(421), 166 Takaku, M., 230( 150), 274 Takamizawa, A,, 580(736,737), 739, 740 Takamoto, T., 447(162), 720 Takamubu, S. , 233(180), 275 Takamuku, S., 215(91), 216(91), 272 Takao, I., 123(1222), 189 Takase, M., 78(874a), 179 Takashina, N., 491(430), 497(502,503), 499(503), 506(502), 537(502), 538(502), 539(502), 542(502,503), 545(619), 546(502,519), 729, 731, 735 Takasugi, H., 438(6), 714 Takata, T., 576(716c), 577(716c), 582(716c), 739 Takaya, T., 438(6), 714 Takayama, K., 357(125), 360(125), 428 Takeda, T., 16(154), 92(976a), 122(1214), 157, 181. 189 Takehira, K., 31(353), 163 Takei, R., 453(243), 466(243), 472(243), 474(243), 632(243), 722 Takeno, N., 34(466e), 36(466e), 167 Takeshima, T., 631(1107), 642( 1295,1303,1304), 643( 1303,1304). 645(1295,1314), 753, 760 Takeshita, H., 37(498), 168 Takimoto, F., 589(752c), 652(752c), 740 Talaty, E. R . , 4(10), 5(10), 153, 628(1019a), 750 Talbiersky, J., 46(588), 171 Taliani, L., 548(623), 549(623), 559(623), 736 Tamagaki, S., 289(55), 297(55), 298(55), 299(55), 345, 461(270), 463(285), 479(391), 480(391,392c), 48 1(285), 483(392c), 510(258a), 653(1356), 723, 724, 728, 762 Tamura, K., 461(270-274), 723 Tamura, Y . , 53(640,641), 125(1261), 172, 190, 439(19), 447(152), 449(179a), 450(179a), 499(152), 612(886), 715, 719, 720, 745 Tamarawa, K., 641(1234,1235), 642(1235), 646(1234), 758

842

Author Index

Tarnres, M., 10(66), 154, 439(57b), 440(57b), 462(280a), 464(292), 465(301), 480(280a), 716, 724 Tarnsma, A . F., 444(131), 457(131), 465(131), 480(131), 484(131), 511(131), 719 Tamura, M., 11 1(1089a), 185 Tamura, Y., 487(272), 509(272-274), 616(930a), 723, 747 Tan, Y. S. R., 69(790), 176 Tanabe, K., 72(805-810,812-815), 177 Tanabe, T., 492(446,447), 494(446,447), 495(446,447), 496(446,447), 505(447), 729 Tanaka, H., 40(544a), 170, 639(1207,1224), 640( 1207), 641( 1238,1242), 642( 1238,1242), 757, 758 Tanaka, I., 312(182), 349 Tanaka, K., 669(1543), 674(1543), 767 Tanaka, M., 584(741), 614(741), 740 Tanaka, S . , 64(742), 175, 338(145), 348 Tanaka, Y., 151(1464), 196, 615(924b), 746 Tancrede, J., 60(696), 174 Tang, F. Y. N., 13(116), 156 Tang, I. Y. N., 129(1302), 191 Tang, R., 462(282), 480(282), 484(282), 509(282), 51 1(282), 512(282), 724 Tangari, N., 55(663), 173 Tani, H., 151(1463), 196 Tani, K., 33(416), 163 Tanielyan, S . , 31(358,359), 125(1255), 163, 190 Taniguchi, E., 642(1277,1278), 643(1277,1278), 759 Taniguchi, K., 642(1263), 759 Tanikaga, R., 628(1019a), 750 Taninaka, K., 641(1238,1239,1241-1243, 1245,1246), 642( 1238,1241,1242,1246), 758 Tanino, H., 16(153), 157 Tappen, W. A , , 356(106a), 364(106b), 412(106), 427 Tarasenko, N. A,, 624(985a), 749 Tark, S . Y., 20(184), 158 Taschner, M. J . , 56(669), 173 Tasevski, M., 17(168), 157 Tashiro, M., 551(651), 571(713), 599(797), 737, 739, 741 Tatikolov, A. S . , 36(480), 168 Tau, K. D., 465(306b), 724 Taube, H., 465(299c), 724 Taube, R . , 32(380), 164 Tavares, D. F., 49(606,609), 171 Taylor, E. C., 97(1023), 183, 198(3), 270, 284(7), 307(7), 309(7), 343 Taylor, M. J., 630(1057a), 752 Taylor, N. J., 629(1038), 751

Taylor, S . K . , 99(1033), 103(1057), 110(1033), 126(1265a), 183. 184, 190 Taylor, W . C., 536(610), 735 Tazaki, M., 452(202b), 499(202b), 721 Tazawa, H., 40(544), I70 Te, L. B., 480(395), 728 Teeninga, H., 593(765d), 741 Teichteil, Ch., 333(126), 347 Telly, V. Yu., 520(578), 529(578), 734 Temkin, M. I., 34(472), 36(472), 39(472), 167 Ternnikova, T . I., 87(952), 93(997), 142(1389,1390), 181, 182, 193, 194 Tempel, E., 492(470,471), 730 Tempesti, E., 612(888), 616(888), 745 Temple, R. D., 26(256), I60 Tenma, S . , 87(949), I 8 1 Tennent, N. H., 656(1377), 762 Terada, Y . , 109(1083), 184 Terama-e, H., 669(1543), 674(1543), 767 Teranishi, H., 34(431), 166 Teranishi, S . , 18(174), 32(174,409), 34(430,453), 35(430), 36(453), 38(430), 58(676), 165, 166, 167, 173 Terao, S . , 358(39i), 359(39i), 424 Terasawa, H., 144(1406), 194 Terashima, Sh., 33(412,413,419), 165 Terent’ev, P. B., 492(468c), 502(468c), 730 Tereshchenko, G. F., 125(1241), 189 Terlouw, J. K., 8(36), 154, 442(102a), 718 Terwiel, J . , 28(274), 160 Tesky, F. M., 651(1342-1344), 652( 1342,1343,1346~),656( 1346c), 658(1344), 659(1346c), 660(1344,1346~),761, 762 Testa, E., 593(774,775,778), 595(774,775,789), 596(774,789), 599(789), 741 Teutch, J.-G., 33(424), 166 Teyssie, P., 36(486), 168 Thakker, D. R., 204(27), 217(105), 218(27), 221(120), 230( 157), 256(27,264,265,268,270, 272-274), 257(276), 258(277), 259(270,304,306), 261(268,322), 262(265,270, 277,322,331,338), 263(264,270,331), 264(277,329), 265(33 1-335), 268(363,367), 269( 157,374,375,378,379), 271, 273, 274, 278, 279, 280, 281 Thalen, A,, 569(703,705a,706), 570(706), 574(706), 738, 739 T h a p Do-minh, 142(1394), 194 Thayer, A . L., 362(48), 382(48), 388(48b), 390(48b), 407(48a,b), 4 15(48a,b), 416(48b), 425 Theonot, J.-P., 230(150), 274

Author Index Thewalt, U., 659(1402b), 660( 1402b), 763 Thize, M., loo( l042), 183 Thiel, W., 37(491,492), 168 Thiem, J . , 78(870), 115(1120), 178, 186 Thies, R. V., 63(729), 175 Thijs, L., 66(756), 74(836), 90(756), 135(1340), 177, 192 Thimm, K., 630(1066,1067), 752 Thio, J., 11(89), 155 Thomas, A . H., 354(13), 423 Thomas, D., 286(49a,b), 287(49a,b), 33 l(49), 345 Thomas, E. J., 18(172), 157 Thomas, M. J., 24(219), 159 Thomas, P. E., 214(80), 217(105), 256(260,263, 264,266,272), 257(275,276), 258(80,277), 260(3 12), 261(27 1,275), 262(275,277,338), 263(264), 264(277), 266(266,271,275), 268(360,362-365), 269(374), 272, 273, 277, 278, 279, 280, 281 Thomas, T. W., 444(117), 718 Thomas, W. A., 11(85), 155, 440(63), 716 Thomasi, J . , 330( 105), 347 Thompson, H. W., 8(44), 154 Thompson, J . C., 668(1520), 767 Thompson, J. W., 90(968), 181 Thompson, M. H., 267(351), 281 Thompson, N. J., 297(66), 298(66), 301(66), 315(66), 320(66), 345 Thompson, N. T., 323(82), 346 Thomson, I., 664( 1477b,l487), 766 Thomson, R. H., 336(206), 350 Thomson, T . W., 468(117), 718 Thorsen, M., 664(1486), 766 Thorstad, O., 333(121), 347 Thorton, E. K., 413(1 lo), 427 Thosar, V. B., 582(739), 740 Throckmorton, P. E., 438(14,15a), 450(196a), 474( 14,15a,369-37 l), 476( 14,15a,370), 714, 721, 727 Thummel, R. P., 62(719-722), 174 Thyagarajan, B. S., 61(708,712), 77(708), 115(708), 150(712), 174 Tiffany, B. D., 62(713), 174 Tigelgaar, H. L., 443( 108a), 718 Tijhuis, M. W., 245(217), 276 Tilak, B. D., 520(571a), 527(587c,588a,b), 529(571a,588a), 644(571a), 734, 735 Tilford, C. H., 492(463), 495(463), 730 Tilichenko, M. N., 97( 1024), 183 Timmons, R. J., 640(1227b), 758 Timoshchuk, T., 30(300), 161 Tin, K.-C., 613(893,894), 616(893,894), 745

843

Tinker, A. C., 233(178), 275 Tinsley, S. W., 16(163), 157 Tishchenko, I. G., 28(268,269), 92(980), 93(1000-1001a), 98(1025), 124(1228), 160, 182, 183, 189, 305(184), 349 Tishenkov, A. A , , 624(985a), 749 Times, P., 477(390c), 728 Tits-Skvortsova, 1. N., 440(66), 716 Tkatchenko, I., 59(684), 173 Tochtermann, W., 199(12), 210(73), 252(73), 255(255), 270, 272, 277 Toda, M., 629(1046i,v), 751 Todesco, P. E., 447(151), 462(151), 480(151), 719 Toffoli, P., 661(1427), 764 Togashi, S., 59(685), 114(685), I73 Tohma, M., 30(304), 161 Toi, H., 81(904), 179 Tokuda, M., 129(1299), 191 Tokumaru, K., 129(1295), 191 Tokumura, K., 239(197), 241(197), 276, 339(202), 350 Tokura, N., 492(477,488-490), 494(488,489), 495(477,488,489,490), 502(490), 506(488,489), 534(489), 584(741), 641(741), 655( 1369), 730, 731, 740, 762 Tolstikov, G . A , , 30(302,328), 32(328,401,402), 33(401,41 I ) , 78(886), 101(1051), 161, 162, 165, 179, 184, 285(38), 286(38), 290(38), 313(38), 344 Tomasi, J., 5(17), 118(l161,1162), 153, 187 Tomasic, V., 548(629a), 549(640), 550(629a,642,643), 555(629a,642), 556(629a,640,643), 558(642). 736 Tomaszewski, J. E., 232(165), 235( 191), 236(191), 237(191), 241(191), 275 Tomer, K. B., 442(101), 520(580), 529(580), 718. 734 Tomimatsu, Y . , 595(790), 741 Tomioka, H., 18(177a), 34(420f), 158, 166 Tompson, R. B., 353(4), 423 Tonosaki, F., 642(1303), 643(1303), 760 Tontapanish, N., 357(162), 429 Topfl, W . , 642(1294), 645(1294), 760 Toppet, S . , 342(162), 348, 562(684b), 563(684b), 564(684b), 566(684b), 567(695,696), 577(695,696), 605(825b), 608(825b,c), 738, 743 Toren, P. E., 12(102), 155 Tori, K . , 10(70), 13(125), 155. 156 Torii, S., 40(544,544a), 112(1098), 170, 185 Torok, I., 73(824), 177 Torre, G., 11(81), 24(215,216), 155, 284(11),

844

Author Index

Torre, G., (Continued) 287(50), 296(50,53), 297(63), 307(21), 3 14(50,7 l), 3 15(21,50,63a), 3 17(21,63), 319(11,21,178), 320(50,63b), 321(53), 343, 344, 345 T o m , T., 32(408), 165 Toupance, G., 443(1 I I), 718 Townsend, J. M., 30(301), 52(631), 161, 172 Toyama, T., 461(271a), 474(271a), 723 Tozune, S . , 461(271a), 474(271a), 723 Tracey, A . S . , 439(50), 478(50), 490(50), 716 Tramp, D., 83(925), 180 Trautluft, M., 502(521), 506(521), 534(521), 546(521), 583(521), 732 Trefonas, L. M., 229(148), 274 Treger, Yu. A., 32(370), 164 Trifiro, F., 31(351,352,357), 32(389), 163, 164 Trindle, C., 41 1(45), 425, 630( 1053), 751 Trippett, S . , 64(651), 172, 492(433), 495(433a), 502(433a), 503(433a), 535(433), 628( 1025), 729, 750 Trofimov, B. A , , 442(97), 623(984a), 718, 749 Trofimov, N. N., 449(179b), 462(179b), 480(179b), 491(179b), 508(179b), 720, 721 Troisi, L., 25(253a), 160 Trost, B. M., 26(258), 52(623), 53(635,636), 69(788), 70(788), 160, 172, 176, 439(52), 442(52), 446(52,147), 456(52,147), 459(269), 466(269), 467(269), 471(269), 476(269), 491(52), 499(52), 509(52,147,269), 511(52,147), 612(886), 716, 719, 723 Trostmann, U., 148(1441), 149(1442, 1444,1446a-b), 195 Trozzolo, A. M., 142(1383,1385,1394,1396), 193, 194 Truce, W. E., 46(583), 171, 492(432,439,440, 483,484,486,487), 495(440,483,486,487), 496(440), 499(5 14), 503(514), 505(439,440), 506(440,514), 508(484,5 14), 53 1(439), 532(439), 534(440,514), 535(606), 538(514), 54 l(6 14a), 544(5 14), 546(440,606), 583(440,484,5 14,606), 584(484,5 14), 585(514), 61 1(880), 614(880), 729, 730, 731, 735, 745 Trumbull, E. R., 62(714), 174 Trumbull, P. A , , 62(714), 174 Trybulski, E. J., 328(187), 349 Tsai, A. I., 480(396), 520(396), 524(583,584), 529(396), 531(396), 728, 734 Tsang, W., 499(513c,d), 731 Tsang, W.-S., 230(151,155), 269(155), 274 Tsaroom, S . , 216(97), 244(97), 273 Tsay, Y.-H., 224(137), 274

Tse, M.-W., 151(1458), 195 Tseitlina, E. O., 623(984c), 749 Tseng, C.-Y., 131(1317), 132(1317), 191 Tseng, K.-S., 628(1022b), 750 Tsnitsugu, S . , 79(895), 179 Tsuchida, T., 92(986), I82 Tsuchihashi, G., 453(213-215,220,223), 462(2 13,214), 721 Tsuchitani, K., 128(1294), 191 Tsuchiya, F., 38(520), 169 Tsuge, O., 492(448), 495(448), 594(448,785-787), 596(448), 599(448,787), 729, 741 Tsuji, T., 77(862), 178 Tsujimoto, N., 630(1076), 752 Tsunokawa, Y., 25(244a), 160 Tsuruta, H., 456(251,252), 723 Tsuruta, T., 46(591), 151(1470), 171, 196 Tsutsumi, S . , 24(232), 159 Tsyskovskii, V. K., 34(441), 35(441), 166 Tuan, G., 593(769), 741 Tuck, D. G., 625(998a), 629(1044), 749, 751 Tucker, B., 603(816), 604(816), 606(835a), 608(835a), 609(835a), 652(835a), 742, 743 Tucker, J. N., 339(207), 350 Tuddenham, D., 33(420g), 166 Tukaev, I. Kh., 622(970), 748 Tukumura, K., 339(154), 348 Tuleen, D. L., 470(326), 725 Tulp, M. T. M . , 232(166), 275 Tulupov, V. A . , 34(449), 36(449), 167 Tundo, A, , 520(581c), 734 Turcant, A , , 95(1013), 182 Turchi, I. J., 37(492), 168, 293(58c), 294(58c), 295(58c), 345 Turnbull, S. A ., 639(1185), 756 Turner, A. G., 658(1393), 659(1393), 660(1406), 669(1393), 763 Turner, D. W., 14(146), 157 Turner, E., 264(325), 280 Turner, J. H. W., 8(20), 153 Turner, J. J., 11(87), 155 Turner, J. O., 34(444), 36(444), 166 Turro, N. J., 37(499), 168, 352(1), 354(11), 355(30b), 364(30), 369( 1 lb,59), 373(30), 379(30), 380(30), 381(1 lb,c), 382(30,49a), 386(56,58,59), 387(58a,c,59), 389( 1 lb,59), 392(30b), 396(58,67,68), 399(56,67), 400(59), 403(67), 407( 1 lb,c), 410(58b), 41 1(58b,67,104), 413(58,112), 4 14( 1 I , 104,115), 4 15( 1 1b,c), 416( 1 l ) , 4 17( 1 1 ), 418(136), 422, 423, 424, 425, 426, 427, 428, 452(210c), 453(241), 630(210c), 721, 722

Author Index Turujman, S . , 217(105), 221(120), 262(331), 263(331), 264(331), 273, 280 Tyerman, W. J. R., 469(322), 725 Tyukova, 0. A., 120(1186), 188 Tyurin, V. D., 631(1113d), 753 Tyutchenkova, L. D., 32(378), 164 Tzeng, D., 130(1311), 191 Uchida, K . , 114(1106), 185 Uchimaru, T., 76(852), 178 Udenfriend, S . , 260(308), 261(161), 262(161), 2 79 Udre, V. E., 520(581a), 529(581a), 734 Udupa, M. R., 651(1342), 652(1342), 761 Uebel, J . J., 445(141b), 452(141b), 462(141b), 476(384,385), 477(141b), 478(141b), 480( 141b), 48 1( 141b), 482( 141b), 484(384,385), 49 1( 141b), 492( 14 1b), 497(141b), 498(141b), 540(141b), 719, 727 Ueda, M., 592(760-765), 593(762,764), 596(761-765), 597(761,762,764,765), 740 Uemura, S . , 125(1260), 190 Ueno, N. Y . ,631(113e), 753 Ueno, Y., 450(193c), 606(830b), 613(896b), 640(830b), 721, 743, 745 Ugo, R., 34(435,461), 36(461,484), 166, 167, I68 Uhing, E . H., 622(978), 748 Uhlemann, E., 647(1323c), 761 Uhlig, H. F., 647(1316), 760 Ujikawa, N . , 31(340), 163 Ukai, Sh., 121(1194), 188 Ulanova, V. N., 31(354), 163 Ullman, E. F., 136(1345-1347), 192 Ullmann, R., 34(458), 36(458), 167 Ulrich, H.. 602(8 13), 603(8 13,8 16,817), 604(813,8 16), 606(835a,b), 607(835b), 608(835a), 609(835a,b), 652(835a), 742, 743 Ultvary, K . , 667(1518), 668(1518), 767 Umaki, N., 126(1265), 190 Umbreit, M. A., 58(875), 173, 356(88), 362(88), 426 Umezawa, H., 331(108), 347 Ummat, P. K., 669(1544), 767 Undefriend, S., 231(160-162), 231 Undeman, O., 267(353), 281 Undheim, K . , 46(582), 171, 333(121), 347, 438(7g), 475(7g), 714 Uneyama, K., 40(544,544a), 170 Unmat, P. K . , 674(1580), 768 Unrau, A. M., 118(1170), 187 Unterberger, V. K., 661(1416,1417), 662(1416), 663(1416,1417), 763

845

Unterstenhoefer, G . , 438( lOa), 462(10a), 480(10a), 488(10a), 491(10a), 714 Uppenkamp, R., 663(1460), 765 Urbel, H., 126(1264), 190 Urhahn, G., 589(753), 590(753), 740 Uriarte, R., 465(306b), 724 Uring, N. A , , 125(1241), 189 Urry, W. H., 353(10), 423 Ushio, S . , 79(895), 179 Utabaev, U. U., 449(183), 720 Utimoto, K., 68(772,773), 114(1105,1106), 176 Uyegaki, M., 239(200), 241(200), 276 Uzarewicz, A., 82(916-922), 180 Vadasz, A., 70(798), 71(798), 176 Vadi, H., 267(352), 281 Vaganoescu, M., 619(921d), 746 Vaidya, 0. C., 669(1544), 767 Vakratsas, T., 663(1441), 764 Vakul'skaya, T. I., 642(1306,1308a), 644(1306,1308a), 760 Valentin, E., 492(454,455), 502(454,455), 730 Valentino, D. S . , 128(1292), 191 Valov, P. I., 38(521,522), 169 Van Anda, J., 245(224), 246(224), 266(224), 2 76 Van Asch, A., 589(752b), 595(752b), 652(752b), 740 Van Auken, T. V., 130(1309), 191 van Bladeren, P. J., 219(113,114), 256(274), 257(275), 261(271,275), 262(275), 266(271,275), 273, 278 Vance, R . F., 465(301), 724 Van de Graaf, B., 464(295a), 724 Vandenberg, E. J., 474(365), 727 van den Elzen, R., 54(653), 173 Van der Jagt, D. L., 241(204), 245(204), 276 van der Leij, M . , 653(1351), 761 van der Plas, C., 339(201), 349 Van der Plas, H. C., 87(951), 181 van der Puy, M., 630(1078h,1130b), 632(1078h,1121d), 752, 753, 754 Vandervorst, D., 232(173), 275 Van de Sande, C. C., 14(144), 157 Vandewalle, M., 44(575), 170 Van Doorn, J. A., 31(335,336,338), 32(335), 162 Van Duuren, B. L., 216(98), 230(153,154), 239(98), 239, 273, 274 Van Eenoo, M., 61(702), 174 Van Ende, D., 54(657,658,660,661), 173 Van Epp, J. E., Jr., 205(38), 206(38), 209(38), 21 1(38), 231(38), 236(38), 237(38), 271

846

Author Index

Van Gemert, B., 541(614a), 735 Van Haard, P. M. M., 135(1340), 192 Van Leusen, A . M., 623(980), 748 Van Meersseke, M., 333(205), 350. 562(684a,685), 563(684a,685), 564(684a,685), 566(684a), 567(696), 576(685), 577(696), 666(1492), 738, 766 Van Meervelt, L., 605(825b,826b), 608(825b), 743 Van Ootgehem, D., 441(78e), 473(78e,348), 717, 726 Van Santer, R. A,, 34(466a,b), 36(466a,b), 167 Van Saun, W. A,, Jr., 553(660), 737 van Tamelen, E. E., 130(1307), 191, 205(42), 2 71 Van Tilborg, W. J. M., 514(556,557), 515(557), 521(557), 525(556,557), 531(557), 529(557), 733 Van Voightlander, P. F., 311(198), 349 Van Wazer, J. R., 667(1502,1503), 668(1502,1503), 766 Varenne, P., 14(142), 157 Varescon, F., 31(335a), 32(335a), 163 Vargha, L. V., 642(1272), 643(1272), 759 Varshavskii, S. L.. 661(1417), 663(1417), 763 Vasilcnko, I. V., 31(342), 163 Vasil’ev, V. V., 121(1197), 188 Vasil’eva, I. P., 548(629e), 552(629e,656a,c), 553(629e), 555(629e,670), 624(987), 736, 737, 749 Vasilevich, L. A,, 34(466,467), 36(466,467), 167 Vasilieva, V. S . , 438(4c), 714 Vasquez, E. M., 13(116), 156 Vassil’ev, R. F., 398(73), 426 Vatsis, K. P., 258(278,279), 278 Vatteroni, A., 122(1212), 188 Vedejs, E., 59(688), 114(1110), 174, 185, 457(260), 458(260,26Ia), 51 1(269,26la), 653(1352), 723, 761 Veenstra, L., 49(612), 171 Vegas, A,, 669(1546), 767 Veh, G . V., 443(127a), 570(127a), 572(127a), 575(127a), 719 Veillard, A., 320(7a), 346 Veksli, Z . , 556(673a), 737 Vcnier, C. G., 653(1351), 761 Venkatesan, K . , 516(565c), 734 Venzo, A . , 54(695), 172 Vereshchagin, A . N., 9(54), 154, 439(26a,b,d,f) 442(26a,d,f), 443(26f), 462(26a), 475(26a), 479(26a,f), 480(26a), 622(975,976), 715, 748

Verhoeckx, G. J., 513(545a), 516(545a), 733 Verhoeren, T. R., 18(177), 32(177), 158 Verhoeven, T. R . , 30(333), 32(333), 162 Vcrma, H., 21(194), 133(194), 158 Verma, S. K., 639(1192), 756 Vermeer, P., 99(1034), 183 Verweij, A . B., 605(825a), 743 Vessiere, R . , 650(1336), 761 Vest, R . D., 625(999a), 626(999a,1003), 627(999a, 1012), 628(999a), 629(999a,1012), 749, 750 Veysoglua, T., 16(155), 157 Viala, J., 43(565), 170 Vialle, J., 55 1(650), 556(650), 558(650), 571(650), 630(650), 737, 752 Viau, R., 54(653), 173 Vibet, A., 630(1073,1078), 752 Vidal, J. D., 11(98), 19(183), 44(183), 155 Vidigal, C. C . C.,421(149,151), 428 Vidigal-Martinelli, C., 421(147,150), 428 Viehe, H. G., 251(236), 277 Vigny, P., 267(355), 281 Vij, V. K., 509(532), 51 1(532), 732 Viktorova, E. A ,, 472(254b,329,330a,c,e), 723, 725 Villa, P., 67(766), 68(766), 77(863), 79(890,891,893), 176, 178, 179 Villani, A. J., 656(1370). 762 Villieras, J., 48(601-603), 55(667), 56(670-671), 171, 173, 183 Vilsmaier, E., 458(263), 509(263), 51 1(263), 723 Vincent, E., 520(576), 529(576), 734 Vincent, M., 150(1448), 195 Vioque, E., 125(1252), 190 Virgili, A , , 92(983), 182 Vishwakarma, C . V., 664(1481), 765 Visser, J. P., 546(620a), 735 Visser, R. G., 516(562d), 519(567b), 525(562e), 564(691a), 566(691a), 568(691a), 578(691c,733a,b), 581(733a), 582(733b), 733, 734, 738, 739 Vistocco, R . , 543(616), 735 Viti, S. M., 33(420h), 166 Vlasova, N. N., 623(984d), 749 Vlasuk, G . P., 256(260), 277 Vogel, A. I., 442(103), 443(105), 491(103), 718 Vogel, E., 147(1433), 195, 198(1), 205(1), 206(1), 209(1,61,64,66), 219(125), 220(1), 221( I), 222( I), 223( 130), 224( 13 1-133,136, 139,141), 227(143), 228(143), 236(64), 237(192), 238(192), 239(1,66,132), 240(13 1,133), 241( 192), 247( l), 248( 133), 254( I), 270, 271, 272, 273, 274, 276

A u t h o r Index Vogel, P.. 81(905), 179. 210(72.74), 212(74), 2 72

Vogt, P. F., 49(606), 171 Vogtle, F., 499(513b), 731 Voigt. E., 514(554,555), 515(555), 516(554,555). 529(555), 733 Volger, H. C . , 254(250), 277 Volkov, N. D., 614(904), 615(904), 746 Volkova, V. V., 624(985a), 749 Volnina, E. A , , 624(985b), 749 Von Criegern, T., 650(1339), 761 Von Schnering, H. G., 661(1426), 663(1426), 764 Vorob'ev, B. I,., 119(1178), 187 Voronenkov, V. V., 32(403), 165 Voronkov, M . G . , 114(1113), 185, 520(581a), 529(581a), 623(981-984d), 624(98 I ,982,985a,b), 642( 1306- 1308a), 644( I306,1307,1308a), 734, 748, 749, 760 Vose, C. W., 214(79), 272 Voss, B., 224(141), 274 Voss, J., 561(680a), 575(722b), 579(680a,b), 582(680b), 626(101 Ib), 630(1066,1067), 664( l465), 738. 739, 750, 752, 765 Vostrowsky, O., 22( 198), 158 Vovsi, B. A , , 61 1(881), 614(881), 616(932), 745, 747 Vrain, T. C., 639(1169,1171), 755 Vranesic, B., 32(404), 165 Vreugdenhil, A. D., 38(524), 169 Vukov, V., 148(1436), 195 Vul'fson, S . G., 622(975,976), 748 Vyalykh, E. P., 442(97), 718 Vyas, K . P., 214(80), 256(272-274), 257(275), 258(80,277), 261(275), 262(275,277), 263(264), 264(277,329,330), 266(275), 269(374), 272, 278. 280, 281 Vyazinkin, N. S., 668(1525), 767 Vystrcil, A , , 45(576), 170 Wachter, W., 642(1287), 644(1287), 646(3287), 647(1287), 759 Waddington, D. J., 38(518), 169 Waddington, G., 441(92,93), 717 Wadia, M. S . , 39(535), 169 Wadl, F., 625(999b), 626(999h), 642(999b), 749 Waegell, B., 34(460c), 36(460c), 167 Wagenaar, A , , 653(1354), 762 Wagner, G., 630(1061), 752 Wagner, H. G., 128(1290), 191 Wagner, W. R., 323(197), 349 Wahib. I.. Al-. 123(1220.12211. 189

847

Waiser, A , , 327(187), 349 Waisser, K., 45(576), 170 Wake, S., 499(515), 731 Wakefield, B. J., 112(1095), 185 Wakita, Y., 250(234), 277 Wakselmann, C., 11 1(1089), 185 Wald, H. J., 657(1388,1390), 762, 763 Waldrop, M., 629(1027), 750 Walker, E. R. H., 438(7a), 714 Walker, F. J., 33(420g), 166 Walker, M., 245(221), 266(221), 276 Walker, M. A . , 54(651), 172 Walker, M. P., 266(342), 280 Walling, C., 415(121), 427 Walsh, J . P., 492(439), 505(439), 531(439), 532(439), 729 Walter, W., 565(693), 566(693), 606(837), 664( 1470), 738, 743, 765 Walz, F. G., 256(260), 277 Walz, G., 492(437), 495(437), 729 Warnpler, J. E., 395(64), 425 Wan, C. N., 150(1452), 151(1453), 195 Wang, I., 21(194), 133(194), 158 Wannlund, J., 354(14a), 420(14), 423 Warasziewicz, S. M., 207(59,60), 235(59,60), 242(60), 272 Ward, D. L . , 140(1366), 193 Ware, W. R., 398(75), 399(75), 426 Waring, L. C., 303(69), 345 Warnhoff, E. W., 8(40), 13(40), 64(737), 154,

I75

Warrener, R. N., 23(211), 69(790), 159, 176 Warsop, P. A ,, 439(45), 441(45), 716 Wartburg, B. R., 139(1362), 140(1362,1373), I93 Wasilewski, J., 34(463), 36(463), 167 Wasserman, H. H., 3S2( I), 358(39i), 359(39i), 373(28,29), 378(28,29), 379(39i), 419( 138), 423, 424, 428 Wasserman, S. R., 625(999b), 626(999b), 630(999b), 642(999b), 659(999c), 749 Watahe, T., 206(43), 207(43), 246(226), 262(324), 271, 277, 280 Watanabe, K., 372(26c), 424 Watanabe, M., 287(165), 327(95), 329(195), 342(95), 346, 348, 349 Watanabe, N., 125(1260), I90 Watanabe, S . , 92(976a,978), 122(1214), 181, I89 Watanabe, W. H., 7(31,32), 153 Watanahe, Y., 29(291), 126(1270), 161, 190 Waterfall, J. F., 220(122), 221(122), 236(122), 2 73 Waters, J. A . , 131(1314), 191

848

Author Index

Watkins, R. J., 145(1421), 194 Watsky, R. P., 120(1190), 188 Watson, C. G., 232(167), 258(167,296), 275, 287(20), 288(20), 289(20), 290(20), 291(20), 293(20), 299(20), 300(20), 307(20), 344 Watson, H. R., 453(245a), 474(245a), 722 Watson, K. G., 285(41), 298(41), 299(41), 327(41), 340(157), 344, 348 Watson, S . C., 105(1060), 184 Watson, T. R., 70(798), 71(798), 176 Watson, W. H., 293(58c), 294(58c), 295(58c), 326(193), 327(193), 345, 349 Watt, D. S.,323(83), 331(83), 346 Wawzonek, S., 627(1015), 750 Webb, T. R., 469(309), 725 Weber, G., 395(66), 397(66), 426 Weber, H., 657(1388,1389), 762 Weber, R., 46(593b,593d), 171 Weber, W. P . , 114(1116a), 130(1311), 185, 191, 668(1533), 669(1534), 767 Weedon, A. C., 620(948), 626(948,1004), 627(948,1004), 628(948,1004), 629( 1004), 747, 749 Weese, G. M., 442(102a), 718 Wege, H., 642(1286), 644(1286), 759 Wegler, R., 611(861), 614(861,92la), 638(1163), 642(1163), 646(1163), 744, 746, 755 Wehner, R., 199(9), 270 Wehrli, H., 131(1318,1319), 132(1318,1319,1323,1324), 139(1360), 191, 192, 193 Wehrung, T., 672(1558), 768 Wei, C. C., 355(18b), 370(18), 379(18b,39), 398(18b), 403(39a), 424 Weichsel, C., 520(572), 644(572), 734 Weidenbruch, M., 667(1513a,b), 766 Weidenhammer, K., 636(1155), 755 Weidinger, H., 603(815), 604(815), 742 Weiler, H., 336(134), 348 Weiler, L. S . , 642(1255), 759 Weinert, J., 94(1007,1008), 182 Weinges, K., 22(208), 158 Weinstein, I. B., 258(281), 267(350), 278, 281 Weinstein, J., 339(168), 348 Weintraub, P. M., 509(534), 732 Weiss, E., 630(1099b), 633(1099b), 753 Weiss, F., 285(36), 286(36), 313(36), 336(36), 344 Weiss, J., 489(421), 729 Weiss, L. B., 206(53,54), 208(53), 211(53,54), 271 Weissberger, A , , 198(3), 270

Weissenberg, M., 118(1165), 120(1182), 187, I88 Weissman, P. M., 78(871-873), I78 Weitz, E., 25(254) 160 Welch, S. C., 89(962), 181 Welchman, N., 672(1558,1565,1567), 768 Weller, A , , 414(117), 415(117), 427 Wellman, G. R., 39(538), 169 Wells, D. V., 604(822b), 606(822b), 742 Wells, J. N., 492(464), 495(464), 502(464), 504(464), 506(464), 53 1(464), 544(464), 730 Welsh, W. J., 474(374b), 727 Wemple, J., 49(608), 66(754,755,757), 171. 175 Wenksa, G., 453(240b), 552(240b), 578(240b), 722 Wennerbeck, I., 642(1254a), 759 Went, C. W., 124(1232), 189 Wentz, F. G., 575(705b), 739 Wenzel, G., 644(1308c), 760 Wepplo, P. J . , 11(95), 18(95), 44(95), 155 Weringa, W. D., 464(295b), 509(295b), 724 Werner, W., 100(1044), 183 Weser, U., 674(1577), 768 West, S. B., 256(259), 277 Westkaemper, R. B., 120(1189), 188 Wetter, F., 625(993a), 749 Weuger, J., 210(74), 212(74), 272 Weyerstahl, P., 55(664), 90(971), 91(973), 173, 181 Whalen, D. L., 123(1223), 189, 235(190), 241(190), 275 Whalley, E., 630( 1057a), 752 Wharry, S. M., 439(55b), 477(55b), 478(55b), 489(55b,423), 630(55b), 635(55b), 716, 729 Wheatley, P. J., 661(1424), 764 Wheeler, J. E., 269(371), 281 Wheland, R., 377(36), 424 White, D. E., 10(69), 154 White, D. R., 49(613), 172 White, E. H., 353(10), 354(13), 356(88), 362(88), 370(18), 379(18b,39a,40), 398(18b), 403(39a), 423, 424, 426 White, E. M., 90(972), 181 White, E. V., 39(538), 169 White, F. H., 417(131a,b), 428 White, J. C . , 330(103), 347 White, J. D., 22(202), 158 White, J. E., 548(626), 549(626), 555(626), 556(626), 736 White, M. S., 439(29a), 715 White, P. D., 63(727), 175 White, R. E., 256(262), 278 Whitehouse, K. C., 661(1431), 666(1431), 764

Author Index Whitehouse, R. D., 509(531f), 511(531f), 732 Whitesell, J. K . , 63(727), 175 Whiteside, J. A. B., 439(45), 441(45), 716 Whitesides, G. M . , 11(93), 155 Whiteham, G. H, 12(113), 18(173,175), 59(689), 68(779), 1 18(1168), 122(1168), 156, 157, 174, 176, 187, 238(195), 241(195), 252(238), 276, 277 Whitman, R. H., 370(15a,b,d), 414(15a,b,d), 423 Whitney, W. K . , 639(1190), 756 Whittaker, N., 217(105), 273 Whittle, P. J . , 628(1025), 750 Wiberg, E., 668(1528,1530), 669(1543), 767 Widmer, J., 124(1233), 189, 291(56), 293(56), 331(56), 345 Wiebe, H. A,, 469(316), 725 Wiechmann, C., 643(1270), 647(1270), 759 Wiecko, J . , 355(18b), 370(18b), 379(18b,39), 398( 18b), 403(39a), 424 Wieland, D. M., 106(1067), 107(1072), 110(1067,1072), 184 Wiering, J. S., 28(270), 160 Wieringa, J. H., 373(30), 379(30), 380(30,63b), 382(30), 424, 425 Wieser, H., 439(29d,30,32,33,42), 440(30,32,33,42), 715, 716 Wijens, H., 444(115), 718 Wijsman, T. C. M., 578(732), 739 Wilbur, R. D., 639(1225,1226) 757 Wilcox, E. J . , 339(207), 350 Wild, J., 46(588), 171 Wild, S. B . , 64(652), 173 Wildes, P. D., 355(18b), 370(18), 379(18b), 398(18b), 424 Wiles, R. A,, 632(1121d), 754 Wilhelm, M., 509(533), 732 Wilhelm, R. S., 110( l085a), 184 Wilkens, W. F., 635(1147,1148), 755 Wilkins, C., 25(245), 160 Wilkins, C. J., 667(1517), 668(1517), 766 Wilkinson, J . B., 118(1163,1164), I87 Wilkinson, S. G., 3(5), 15(5), 41(5), 47(5), 153 Will, W., 603(814), 604(814), 742 Willett, J. A , , 630(1091), 632(1091), 753 Willi, A. V . , 117(1127), 186 Williams, B. K., 95(1015), 183 Williams, D., 14(138,139), 156 Williams, D. E., 578(727), 739 Williams, D. H . , 7(33), 153 Williams, D. J . , 13(127), 131(1313), 156, 191 Williams, D . R., 30(301), 161, 441(75), 630(75), 638(1167), 717, 755

849

Williams, F. W., 372(24a,b), 382(24b), 386(57), 412(24b), 424, 425 Williams, G. R. J., 625(999b), 626(999b), 630(999b), 642(999b), 659(999c), 749 Williams, H. B., 604(822b), 606(822b), 742 Williams, J . D., 553(657,660), 556(657), 737 Williams, J. W., 25(243), 159 Williams, M. A,, 642(1254a), 759 Williams, P. H . , 24(237), 159 Williams, R. P., 432(12), 714 Williams, T. E., 418(134), 428 Williams, T. H., 604(821), 742 Williams, T. R., 599(798,799), 741 Williams, W. M . , 594(782,783), 741 Williamson, A. D., 8(37), 154 Williamson, K. L., 10(76), 155, 612(883), 745 Williams-Smith, D. L., 59(687), 174, 469(3 lo), 725 Willcott, M. R., 11(89), 155 Willis, C. L., 17(167), 157 Willmes, A,, 589(753), 590(753), 740 Willner, H., 672(1562), 768 Wilske, A., 639(1175), 640( 1175), 756 Wilson, A. G. E., 267(356), 281 Wilson, C. W., 23(210), 159 Wilson, D. A., 296(59), 309(31), 311(31), 328(98), 344, 345, 346 Wilson, E . B., 385(52), 425 Wilson, G. S.,633(1134a), 754 Wilson, J. G., 593(771), 741 Wilson, J. M . , 361(167), 429 Wilson, J. W., 131(1317), 132(1317), 191 Wilson, R. D . , 22(205), 63(734), 158, 175 Wilson, T . , 352(1), 355(127), 359(90b), 360(90a), 361( 166), 362( 166), 386(58), 387(86), 389(127), 391(90,90b,125), 392( 127), 396(58,58e), 398(77a,b), 412(86), 413(58,90,90b,109), 414(114), 422, 425, 426, 427, 428, 429 Wilz, I., 438(3a), 492(3a), 497(3a), 498(3a), 505(3a), 531(3a), 532(3a), 540(3a), 714 Wing, R. M., 476(384,385), 484(384), 727 Winicov, H., 447(149), 457(149), 511(149), 719, 762 Winkler, D., 123(1217), 189 Winkler, T., 664(1478,1483), 765 Winter, H. J . , 670(1552), 671(1552), 767 Winter, W., 622(966), 748 Winternitz, F., 13(130), 156 Wise, L. D . , 509(531d), 511(531d), 732 Wislocki, P. G., 269(375,376), 282 Wisnik, I., 46(587), 171 Wisson, M., l46( 1422), 194

850

Author Index

Withers, C. P., 61(705), 174 Withers, G. P., 61(700), 64(741), 68(771), 150(1432) 174, 175, 176, 195 Witkop, B., 131(1314), 191, 205(35), 207(57), 231(35), 233(177,182), 237(192), 238(192), 239(39), 241( 192), 245(39), 246(35), 260(308), 261(161), 262(161), 271, 275, 276, 2 79 Witte, G., 77(861), 79(892), 178, 179 Wittenhrook, J . S . , 491(163), 720 Wittenhrook, L. S . , 448(163), 449(163), 475(163), 640(1227b), 720 Wittig, F., 548(631), 736 Witz, G., 216(98), 239(98), 273 Wohig, D., 606(832), 743 Woessner, D. E., 464(290), 724 Wohl, R., 117(1131), 186 Wohl, R. A , , 93(998), 123(998), 182 Wojcicki, A , , 498(512,5 13a), 503(512,513a), 731 Wojnowska, M., 667( 1494b), 668(1494h,1522,1523), 674(1494h), 766, 767 Wojnowski, W., 668(1521-1523), 669(1540), 767 Wolak, R., 33(422), 166 Wolf, H. R., 139(1362), 140( 1362,1369,1370,1371,1373-1376), 193 Wolf, M., 488(41 l), 728 Wolf, S. F., 24(240,241), 159 Wolff, C., 255(255), 277 Wolff, S . , 138(1358), 193 Wolinsky, J., 90(972), 181 Wollowitz, S., 210(71), 212(71), 272 Wolnij, S., 639( 1175), 640(1175), 756 Wolz, G., 492(492), 495(492), 731 Wong, E., 361(167), 429 Wong, G. S . K., 620(948), 626(948), 627(948), 628(948), 747 Wong, J. P. K., 144(1406a), 194 Wong, S. S., 639(1202), 757 Wood, A. W., 204(27), 217(105), 218(27), 230(156,157), 256(27,268,270), 259(270,306). 261(268), 262(270), 263(270), 268(360-367), 269( 157,373,374,376,378,379),271, 273, 274, 279, 281, 282 Woodard, S. S . , 33(420a), 165 Woodford, D. E., 9(46), 154 Woodhams, R. T., 443(15e), 715 Woodward, R. B . , 142(1393), 146(1393), 194 Woolhouse, A. D., 339(204), 350 Woolsey, N. F., 49(605), 171 Worman, J. J., 569(702), 630(1080), 738, 752 Worsfold, D. J., 151(1479,1480), 196

Worther, H., 417(131), 428 Wortmann, J., 638(1161), 755 Wray, V., 117(1122-1125), 186 Wriede, U., 642(1259,1273~),643(1273c), 759 Wright, M. J., 60(693), 174 Wu, C. Y., 31(346), 163 Wu, G. S . , 119(1180), 187 Wu., K. C., 398(75), 399(75), 426 Wu, R., 614(909h), 619(909h), 746 Wu, Y., 42(554,555), 170 Wucherpfennig, W., 439(51), 443(51), 449(51), 462(51), 477(51), 479(51), 480(51), 490(51), 491(51), 589(749), 716, 740 Wudl, F., 630(999h), 642(1253), 646(1253), 659(999c), 672(1570), 672(157 l), 749, 759, 768 Wuest, H., 355(33), 424 Wunderlich, H., 199(13), 270 Wunderwald, M., 120(1185), 123(1185), 188 Wurrey, C. J., 9(52), 13(52), 154 Wuthrich, H. J., 131(1315), 133(1315), I91 Wylde, J., 117(1130), 186 Wylie, C. M., 492(460), 495(460), 730 Wynherg, H., 28(270,271), 40(540), 160, 169, 358(164), 359(164), 364(30), 365(171), 373(30), 379(30), 380(30,63h), 382(30), 424, 425, 429, 509(535,536a), 51 1(536a), 554(664), 732, 737 Wyvratt, M. J., 497(500), 504(500), 506(500), 537(500), 541(500), 542(500), 731

Xu, B., 619(909h), 746 Yagi, H., 198(20), 204(26,28), 217(105), 220(116,117), 221(2,26,28,116,117,120), 222(26,28), 230(156,157), 231(2), 233(187,188), 234(187-189), 235(191), 236(117,191), 237(191,193), 238(2,193,194), 241( 188,189,19 1,193,194,201,205), 245(223), 256(264,267-270,272-274,276), 258(277), 259(270,302,304,306), 26 1(268,322), 262(270,277,322,33 l), 263(264,270,33 I), 264(26,269,277,329,330,335), 265(28), 267(2,350), 268(360,362,364-366), 269(1.57,373-376,378,379), 346(2), 270, 271, 273, 274, 278, 280, 281 Yagihara, T., 461(271a), 474(271a), 723 Yagihashi, F., 338(153), 348 Yagisawa, N., 331(108), 347 Yaguchi, K., 614(912,913), 615(912), 6 16(9 12,9 13), 618(9 13), 746 Yagupol’skii, L. M., 614(904), 615(904), 746 Yahav, G., 413(1122h), 427

Author Index Yakubovich, L. S., 124(1227), 189 Yamabe, S., 118(1158), 187 Yamabc, T., 441(76), 669(1543), 674(1543), 717, 767 Yamada, C., 439(31), 440(31), 715 Yamada, K . , 60(695), 453(211,212), 462(21 I ) , 468(21 I ) , 491(211,212), 721 Yamada, M., 447(162), 720 Yamada, S., 33(412,413,419), 165, 331(112), 347 Yamada, T., 72(805), 177 Yamada, Y., 33(420a), 165, 338( 145), 348, 369(79a), 388(79h), 400(79), 426 Yamaguchi, K . , 37(507), 168, 41 1(45), 425 Yamaguchi, S . , 642(1303), 643( 1303), 742 Yamakawa, H., 41 1(45), 425 Yamaki, T., 571(716b), 572(716b), 739 Yamamis, J., 125(1253), 190 Yamamoto, C., 121(1194), I88 Yamamoto, H., 64(742-744). 65(744), 69(782), 122(1207), 175. 176, 188, 254(246,247), 277 Yamamoto, K., 644(1312), 646(1312), 760 Yamamoto, M., 338(145), 348 Yamamoto, N., 27(267), 160 Yamamoto, T., 30(303), 161, 592(767), 642(1303), 643(1303), 741, 760 Yamamoto, Y., 81(904), 179, 613(895), 617(895), 745 Yamamura, S., 369(79a), 388(79h), 400(79), 426 Yamanaka, T., 40(544a), 170 Yamasaki, H., 27(267), 160. 258(281), 278 Yamasaki, K., 69(794), 176, 667(1493), 766 Yamashita, Y., 92(984), 99(1035), 182, 183 Yamataka, N., 588(745), 590(745), 591(745), 740 Yamaya, M., 114(1106), 185 Yamazaki, A,, 641(1234-1237), 642(1235), 646(1234), 758 Yamazaki, K . , 667(1505), 766 Yamamki, M., 629(1046t,x), 751 Yamazaki, S . , 254(247), 277 Yamazoe, Y., 255(253,254), 277 Yanagida, Y., 19(182), 158 Yanai, I . , 639(1207), 640(1207), 757 Yandovskii, V. N., 61(710), 87(710,952), 92(981), 93(997), I74, 181, 182 Yanez, M . , 1 18(1160), 187 Yang, F., 369( 1 lb), 423 Yang, K. H., 24(231), 159 Yang. S. K., 232(174), 258(278), 259( 174,305), 261(323), 262(337), 263(339), 275, 278, 279, 280

85 1

Yano, A,, 642(1295), 645(1295), 760 Yano, K . , 629(1046e,p,v), 630(1046e), 633( 1046e). 6 3 3 1046e), 636( 1046e), 637(1046e), 641(1234), 646(1234), 751, 758 Yano, S., 254(246), 277 Yano, Y., 52(626), 99(1029), 172, 183 Yany, F., 354(1 lh,12b), 362(35,92), 363(92), 369(12b,99), 375(12b), 377(12h,35), 378(12b), 381(11h,12b), 386(57), 389(1 lb,12b), 392(92), 395(57d), 407(1 Ib), 413(57e), 414(11,57d,l16), 415(1 lb,l16), 416(11), 417(11,116), 423, 424, 425, 426, 427 Yarbrough, K. N., 604(822b), 606(822b), 742 Yasnikov, A . A,, 119(1177), 125(1240), 187, I89 Yasuda, A,, 64(742,744), 65(744), 175 Yasuda, K., 342(164), 348 Yasuda, T., 40(544a), 170 Yasuda, Y., 285(44), 289(44), 290(44), 344 Yasuhara, S.,92(976a), 122(1214), 181, 189 Yasuoka, N., 588(745), 590(745), 591(745), 740 Yatabe, S. , 47(596), I71 Yates, K., 118(1159), 187 Yates, P., 136(1344), 192, 641(1251), 642( 1254,1255,1281,1282), 644( 1254h,131 I ) , 6 4 3 1254b), 646( 1281,1282), 647( 1281,1282), 649(1281,1282), 759, 760 Yatsimirskii, K . B., 32(391), 164 Yavari, I., 13(118,119), 156 Yazdanbakhch, H. R., 3 8 ( 5 2 5 ) , 169 Yardanbakhsch, M., 630( 1089), 635( 1089), 638(1089), 640(1089), 753 Yeargin, G. S., 103 1060), I84 Yeh, H. J., 214(80), 258(80), 272 Yeh, H. J. C., 228(146), 230(146), 242(40), 243(40), 244(40), 247(40), 254(40), 271, 274 Yekta, A,, 352(1), 382(49a), 386(58,58c), 387(58c), 396(58c), 422, 425 Yelvington, M. B., 353(5), 360(57a), 362(57a), 386(57), 412(57a,106), 413(109), 425, 427 Yen, H. J. C., 131(1312), 191 Yeong, Y. C . , 68(777), 176 Yocklovich, S . G., 326(93), 327(191), 346, 463(286a), 481(286a), 724 Yoishikawa, K., 262(324), 280 Yokoe, I . , 331(112), 347 Yokoi, M., 667(1493,1494a,1505a), 766 Yokomatsu, T., 45(580), I70 Yokoo, K., 86(945), 181 Yokoohji, K., 21 I(%), 217(86), 219(86), 272 Yokoya, H . , 369(79a), 388(79a), 400(79), 426 Yokoyama, M . , 497(505c), 505(505c), 533(505c). 536(505c), 541(505c), 542(505c),

852

Author Index

Yokoyama, M. (Continued) 587(505c), 606(830a), 607(830a), 608(830a), 631(1107) 642(1305), 643(1298,1305), 731, 743, 753, 760 Yokoyama, Y., 25(248), 160 Yolitz, P., 229( 147), 274 Yona, I., 216(97), 244(97), 273 Yoneda, G. S., 121(1198), 188 Yoneda, S., 561(678a), 579(678a), 738 Yonemoto, H., 445(120), 449(124), 472(120), 476( 120,124b), 578(124b,730a), 580(124b), 581(124b), 586(124b), 718, 719, 739 Yonezawa, T., 441(77), 453(234), 717 Yoon, N. M., 78(879-883), 81(903), 82(879,880,909,915), 179, 180 Yoshida, H., 480(392c), 483(392c), 728 Yoshida, K., 445(122), 476(122), 718 Yoshida, Y., 125(1244,1245), 189, 604(822d), 606(822d), 742 Yoshida, Z., 439(19), 447(152), 449(179a), 450(179a), 499(152), 561(678a), 579(678a), 715, 719, 720, 738 Yoshiha, M., 227(144), 274 Yoshioka, M., 453(211,212), 462(211,212), 468(2 1l), 49 l(2 11,212), 630( 1093), 632(1093), 721, 753 Yoshishu, K., 9(56), I54 Yotsuji, 629( 1046m), 752 Young, A., 338(144), 348 Young, D., 59(684), 173 Young, D. W., 550(644), 555(644), 602(81 lc), 736, 742 Young, F. K., 443(105b), 718 Young, R. N., 115(1117a), 286 Youssetyeh, R. D., 39(530), 169 Yu, P.-Sb., 49(608), 171 Yu, S.-L., 575(723), 577(723), 739 Yuen, G. U., 39(529), 169 Yukawa, Y., 625(995d), 749 Yukowa, H., 441(82), 717 Yun, S. S., 469(309), 725 Yur’ev, V. P., 30(302,328), 32(328,401,402), 33(401,411), 78(886), 101(1051), 161, 162, 165, 179, 184 Yur’ev, Yu. K., 440(66-68), 458(264a), 466(264a), 472(264,33la), 473(264a), 511(264a), 716, 717, 723 Yurlova, M. N., 661(1416,1417), 662(1416), 663(1416,1417), 763 Yurugi, S., 445(120,121), 450(120), 472(120), 476(120,121), 718 Yus’kovich, A. K., 472(330a,c,e), 725 Yustratov, V. P., 465(297), 484(401), 724, 728

Zabransky, J., 445(124), 449(124), 718 Zacharias, D. E., 199(10,11), 270 Zachariasse, K. A ,, 414(117), 415(117), 427 Zahradnik, R., 513(546,547), 514(546), 733 Zaidi, S. Al-, 549(641b), 555(641b), 579(641b), 736 Zaidlewicz, M., 82(916-917a), 180 Zaikin, V. G., 624(985a,b), 749 Zainalov, S. B., 151(1459), 195 Zaitseva, G. S., 492(293), 495(493), 506(526b), 534(526b), 731, 732 Zajacek, J. G., 30(316,325), 31(337), 32(325,367,400), 162, 164, 165 Zakhar’eva, T. N., 34(449), 36(419), 167 Zakharov, A . P., 480(395), 728 Zakharov, V. Yu., 59(686), 173 Zaklika, K. A ,, 362(48), 363(32a), 364(87a), 367(32b,87a), 374(32a,b), 382(48a), 388(48b), 390(48b), 407(48a,b,87), 416(32b,48b), 424, 425, 426 Zalkov, L. H., 21(191), 158 Zaltzman-Nirenberg, P., 23 I ( 160,161), 260(308), 261(161), 262(161), 275, 279 Zarnbri, P. M., 30(310), 162 Zanderighi, G., 36(484), 168 Zanderighi, G. M., 34(461), 36(461), 167 Zankowska-Jasinka, W., 603(820), 742 Zapelov, A . Ya., 43(566), 170 Zapevalov, A. Ya., 67(767), 176 Zapevalov, A. Yu., 80(899), 179 Zauli, C., 440(62), 489(62), 716 Zdero, C., 569(698c), 577(698c), 738 Zefirov, N. S., 19(181), 81(905a), 158, 179, 450(187), 657(1380), 672(1574), 721, 762, 768 Zehavi, U., 630(1078a), 752 Zeiss, W., 656(1375), 663(1458), 762, 765 Zelinsky, N. D., 353(6), 423 Zepp, C. M., 601(801c), 742 Zhavnerko, K. A ,, 124(1227), 189 Zhdanov, Yu. A., 652(1348), 761 Zhemchuzhin, S. G., 661(1429b), 662(1429b), 764 Zhirenbaev, A. N., 38(517), 44(517), 169 Zhuravkova, L. G., 630(1098,1103a,l105), 642(1103a,l105), 644(1105), 753 Ziegler, G. R., 222(126), 273 Ziegler, K., 101(1049), 183 Ziegler, M., 438(3a), 452(3a), 492(3a), 497(3a), 498(3a), 505(3a), 53 1(3a), 532(3a), 540(3a), 714 Ziegler, M. L., 489(421), 636(1155), 729, 755

Author Index Ziffer, H., 21(196), 158, 237(192), 238(192), 241(192), 276 Zika, R. G., 254(245), 254 Zilch, H., 622(966a), 748 Ziman, S. D., 459(269), 466(269), 467(269), 47 1(269), 476(269), 509(269), 723 Zimmerman, H. E., 126(1279), 190, 131(1317), 132(1317), 136(1348), 190, 191, 192, 365(39f), 366(39f), 367(39f), 379(39f), 400(80), 407(80), 424, 426 Zimmermann, D., 13(122), 156 Zirnmermann, W. D., 312(174), 339(174), 349 Zindler, G., 662(1435), 663(1435), 764 Zinger, B., 74(843), 178 Zinkevich, E. P., 438(4c), 714 Zinner, K., 361(126), 366(126), 390(126),

853

391(123), 397(69), 398(69,74), 403(83), 421(147,149,150,151), 428(123), 426, 428 Ziolkowski, J. J., 30(333b,c), 31(361,362), 32(333b,c,384), 162. 163, 164 Zoltai, A , , 9(57), 154 Zubiani, G., 55(662), 59(677), 173 Zubovics, Z., 571(712), 572(712), 573(712), 575(712), 632(712), 739 Zuman, P., 480(394), 728 Zwanenburg, B., 28(274), 66(756), 74(836), 135(1340), 160, 175, 177, 190, 590(755c), 591(755c), 595(755c), 653(1351,1354), 740, 761 Zwart, Z., 509(536d), 511(536d), 732 Zyablikova, T. A,, 622(972-974,979), 748 Zyka, J., 480(394), 728

Chemistry of Heterocyclic Compounds, Volume42 Edited by Alfred Hassner Copyright 0 1985 by John Wiley & Sons, Ltd.

Subject Index Acenaphthylene, 514 I-Acetylcyclohexene oxide, reaction with amines, 124 N-Acetylcysteine, 266 Acetylenic oxirane, reaction with Grignard compounds, 99 a-Acetylenoxirane, reaction with lithiumdiorganocopper compounds, 107 Acid-catalyzed rearrangement, 65 3-Acinitrocamphor, 338 Acridine, 379 Acyclic sulfones acidity, 490 2, 2-Acycloxaziridines, 308 3-Acyloxaziridines, 310, 337 Adamantathione, 453 Aldimines, stereoselectivity in conversion to oxaziridines, 314 Aldol condensation, 544, 574 1,4-Aldadienols, 107 Alkenes oxidation, 15-40 with alkaline hydrogen peroxide, 25 with hydrogen peroxide, 25-30 with hydrogen peroxide and catalyst, 29-30 with molecular oxygen, 34 molybdenum catalyzed, 31 with organic hydroperoxides, 30-33 with organic peracids, 15 with oxygen and metal complexes, 34 oxygen without catalyst, 36 and polar solvents, 31 reaction mechanism, 16, 32 reaction rate, 31 solid catalysts, 31 stereochemistry of reaction, 17 stereoselectivity, 32 with thallium acetate, 40 Alkenyloxirane, and lithiumdiorganocopper compounds, 107 with thallium acetate, 40 trans-Alkenyltrialkylaluminate, 1 13 Alkoxyaluminohydrides, 78 Alkoxy radicals, 470 S-Alkoxythietanium salts, displacement reactions, 5 11 Alkylaluminium compounds, reactions with oxiranes, 101-105

Alkylaminocrotonates, 62 1 Alkylation, 101 a-Alkylketones, from acetoxyoxirane, 109 Alkylmagnesium compounds, reactions with oxiranes, 101- I05 Alkyl-substituted oxiranes, 9 Alkyl thietes, oxidation, 520 1-Alkynyloxirane, stereospecific synthesis, 43 Allene epoxidation, 24 Allenemonooxirane derivative rearrangement, 67 a-Allenoxiranes, 24 Ally1 alcohols: acyclic, epoxidation, 18 chiral epoxides from, 33 epoxidation with organoaluminum peroxides, 33 trimethylsilyl substituted, 18 1,2-Aminoalcohols, from oxiranes, 123 3-Aminopropanethiol, 466 a-Amino-8-propiothiolactone, 548 reaction with nicotinyl chloride, 559 Aminothietane, as monoamine oxidase inhibitor, 438 3,4-Anhydropyranoside, I 1 Aniline, conversion to phenylhydrazine, 328 Anisotropy, 10 trans-Anthracene dioxide, 227 9,lO-Anthracene endoperoxide, photochemical isomerization, 229 9,10-Anthraquinone, 227 Antibiotics, containing benzene dioxide, 230 Antihypertensive agents, 476 Arene amines, synthesis from azide and arene oxides, 244 Arene dioxides, production during metabolism of polycyclic aromatic hydrocarbons, 230 Arene oxide isomerization: effect of substituents, 235 oxygen-walk mechanism, 238 p H dependence, 233 Arene-oxide metabolites, 214 from a-naphthoflavone, 214 Arene oxide-oxepin synethesis from pyrylium salt, 212

855

856

Subject I n d e x

Arene oxide-oxepin equilibrium: double bond localization, 202 effect of substituents, 200 molecular orbital calculations, 199 solvent dependent, 199, 200 structure determination in crystalline state, 199 temperature dependence, 199 Arene oxide reactions, 230-255 aromatization, 231-237 Arene oxide rearrangement, carbonium ion involvement, 233-235 Arene oxides, 197-282 addition reactions, 241-251 biochemistry, 255-269 enzymatic formation, 255-259 hydration to trans-dihydrodiols, 259 reaction with glutathione, 266 Arene oxides: in body, 255 as carcinogens, 267, 269 catalytic hydrogenation, 254 from chlorohydrin acetates, 218 decomposition in acidic medium, 215 deoxygenation, 254 by pyridine, 254 from 3-diphenylisobenzofuran oxide, 21 1 dipole moment, 200 dynamic equilibrium with oxepin, 198 epoxidation, 252 formation of dihydrodiols on hydration, 24 1 hydration by epoxide hydrolase, 260 hydroxide anion addition, 242 isomerization to non-phenolic products, 238-240 nucleophilic addition reaction, 343 optically active, racemization, 202 oxidation-reduction reactions, 252-255 from phenanthrene, 214 of polycyclic aromatic hydrocarbons, 198, 2 13-223 polymethylated, arornatization, 236 reactions: with amines, 243 with azides, 244 with diene, 247 with dimethyl magnesium, 247 with methyl lithium, 247 with thiolate anion, 245 with thiol glutathione, 246 rearrangement to phenols, 231, 233 reduction reactions, 254

structure, 198-204 substituted, 201 aromatization, 236 synthesis, 204-230 from bromohydrin ester, 220-222 by direct oxidation of polycylic aromatic hydrocarbons, 214 from halogenoepoxide, 220 by ring closure of biphenyl dialdehydes, 215 trimethylamine addition, 244 Arene oxides and cancer, 266-269 Arene polyoxides synthesis, 223-230 from bromohydrins, 223 P-Aroylacrylic acid oxirane, reaction with Grignard reagents, 101 Arylation, 101 3-Arylazo-2,1-benzisoxazolethermal rearrangement, 336 Arylglycidic acids, 140 C-Aryloxaziridines, isomerization by irradiation, 333 N-Aryloxaziridines, Schmidt rearrangement, 33 1 Aryloxiranes: photocatalytic reactions, 141 reaction with arylcarboxylates, 122 substituents’ effect on hydrolysis, 117 Aryloxirane synthesis, 45 3-Arloxythietane 1-oxide, as herbicides, 476 3-Aryloxythietane sulfones, 488 N-Arylsulfonyl oxaziridines, 48 1 3-Arylthiete 1,l-dioxides, 532 Atomix oxygen, 37 Azaarene oxides, 215 synthesis from halogenoepoxide, 220 Azaphospholes, 95, 651 Azetidine, 335 Azidooxirane, 95 Aziridines, 52, 244, 328 synthesis from oxiranes, 87 Azirine peroxidation, 307 Azomethane, 327

Base-catalyzed rearrangements, 62-71 Basicity, 14 Backmann rearrangement, 338 Benzaldehyde phenylhydrazone, 328 Benz(a)anthracene, 214 cis-Benzene dioxide: synthesis by Diels-Alder reaction, 224 valence tautomerization to 1,4-dioxocin, 239

Subject Index trans-Benzene dioxide, synthesis from p benzoquinone, 224 Benzene oxides: addition reaction with diazomethane, 251 cycloaddition reaction with singlet oxygen, 248 ethanol solvent addition, 242 molecular geometry, 200 monosubstituted, 205-213 synthesis from halogenepoxide, 205 and oxepin as valence tautomers, 198 polysubstituted, 205-213 reaction: with n-butylamine, 243 with 3,4-diazacyclopeutadienone,247 with thiocyanate, 254 synthesis, 205 Benzene sulfide-thiepin, 254 Benzenesulfonate, 445 2-Benzenesulfonyl-3-phenyloxaziridine, reaction with Grignard reagent, 326 Benzenethiazole-2-thione, 88 cis-Benzene trioxide, isomerization to 1,4,7,trioxonin, 240 truns-Benzene trioxide, synthesis by thermal rearrangement of endoperoxide, 224 Benzodiazepine N-oxides, phototoxicity, 309 Benzodithiete, 626 Benzofuran, 90 Benzoisofuran, water elimination, 506 Benzooxathiete, 620 Benzophenone, 37, 307 Benzo(a)pyrene, 214 metabolism, 258 Benzo(a)pyrene 4,5-oxide, binding to nucleic acid, 267 Benzo(a)pyrene 7,8-oxide, hydration catalyzed by epoxide hydrolase, 261 Benzo(a)pyrene 9,10-oxide, 236 p-Benzoquinone, 224 Benzo-1,2-thiazete, 598 Benzothiete, 514 nmr spectrum, 515 oxidation to sulfone, 521 photoelectron spectra, 515 ring expansion, 525 Benzothiete sulfones, 531 electrolysis of, 545 reduction, 539 Benzothiete synthesis, 5 I 6 5 17

3,4-Benz-2-oxabicyclo(3.2.0)hepta-3,6diene, 239 Benzoxathiete, 620

857

Benzoxepin, 239 reaction: with singlet oxygen, 248 with tetracyanoethylene, 247 synthesis: via bromoepoxide, 223 from 1,4-epoxy-l,4dihydronaphthalene, 222 by pyrolysis of 1,2dihydronaphthalene 2hydroperoxide, 223 3-Benzoyl-2-phenylthietane, 452 Benzylidenecyclohexanone oxide, 13 Benzylmercaptan, reaction with cis-benzene trioxide, 121 Bicyclic phosphine oxides, 24 Bicycloheptadienes, 455 Bicyclo(2.2.l)heptane-iodolactone, conversion to oxirane, 44 Bicyclo(2.2.l)heptane oxirane, I3C spectra, 13 Bicycloheptenyl vinyl ketone, nucleophilic oxidation, 27 Bioluminescence, 352, 417 Bis(benzoy1dioxyiodo) benzene, 25 Boron hydrides, 78 reducing properties, 82 Borthiin, 668 Bromine substituted dioxetanes heavy atom substitution, 409 Brominolysis, 374 Bromoepoxide, dehydrohalogenation, 222 Bromohydrin ester, 220 Bromohydrins, for synthesis of arene polyoxides, 223 Bromohydroperoxides, 37 1 Bromo-P-lactone epoxide, 21 1 P-Bromoxirane, 43 I-p-Bromophenyl oxirane, x-ray diffraction studies, 13 N-Bromosuccinimide, 371 3-Bromothietane 1 ,I-dioxide, 533 Brucine, reaction with oxaziridine, 325 Brucine N-oxide, 325 Butadiene dioxide, 38 Butadienylmagnesium chloride, 99 2,3-Butanedione, phosphorescence, 382 Butenal, 147 3-tert-Butyl-4-cyanocyclohexene oxidation, 17 terr-Butylhydroperoxide, 33 Butylketene, 378 4-tert-Butyl-methylenecyclohexane, 87 2-t-Butyl-3-phenyloxaziridine, reaction with phenyllithium, 326

858

Subject Index

trans-3-t-Butylthietane 1-oxide, heat of oxidation, 480 y-Butyrolactone, 113 Camphanic acid, 123 Cancer, and arene oxides, 266-269 t-Caprolactam, 335 Carbenes, 459 Carbodiimide, 93, 215 Carbonium ion, 66 arene oxide rearrangement and, 233-235 Carbonyl compounds, 47-57 reaction with diazoalkanes, 51-52 Carbonylditriazole, 24 Cephalosporin, 629 Cephamycin, 629 Chalcones, 50 Chemical shift, in styrene oxides, 11 Chemiluminescence, 382-417 bioluminescence, 417 direct, 394 energy transfer and, 382-414 electron exchange, 397, 414-417 energy balance, 382 enhanced, 394, 396 excitation yields determination, 394 intermolecular electron exchange, 414 Chiral shift reagents, 11 Chloramine-T, 461 Chloroalcohols, 40 a-Chloroepoxycarboxylic acid, 100 a-Chlorethanol, ring closure mechanism, 43 Chlorohydrin, 125 Chlorohydrin acetates, 218 Chloronitrosobenzene, 251 a-Chlorooxiranes reaction: with Grignard reagent, 100 with phenyllithium, 110 m-Chloroperbenzoic acid, 16 in oxaziridine synthesis, 305 Chloroperoxybenzoic acid, 215 P-Chlorosulfones, 6 13 3-Chlorothietane, reaction with sodium thiocyanate, 474 3-Chlorothietane 1,l-dioxide, 533 3-Chlorothietane 1-oxide: conformation study, 477 dipole moment, 479 P-Chlorothiol acid, 550 Chlorpromazine oxidation, 421 Cholestatrienone, 27 Cholesterol, stereoselective epoxidation, 22 Chromic acid oxidation, 39

Chromone oxiranes, conversion into 1,2-diols, 118 Chrysene, 256 Chrysene-5,6-oxide, 219 Complex metal hydrides, 78 Configurational isomerization, 75 Conformational energy, of oxirane ring, 8 Cope rearrangement, 253 Corey synthesis, 52 Coupling constant, 10, 11 Crotoxirane, 22 Cumulene, 129 reactions with oxaziridines, 341 Cyanine dyes, 488, 583 6-Cyanophenanthridine 5-oxide, photolysis, 339 Cyclic orthoesters, from oxiranes, 91 Cycloalkene oxide, reaction with Grignard compounds, 99 2-Cycloalkenol, transformation to chlorooxirane, 44 Cyclobutane-l,3-dithiones,electrochemical reduction, 561 Cyclobutene-butadiene, valence tautomerism, 514 Cyclodisilanthianes, 667 reactions, 668 Cyclododecanone, synthesis from epoxycyclododecane, 73 Cycloheptene oxide, conformation, 12 Cyclohexadienemonooxirane, reaction with lithiumdiorganocopper compounds, 107 Cyclohexadienonemonooxirane,photochemical reactions, 133 Cyclohexene: hydroxyethylation, 114 oxidation, 9 Cyclohexene oxide reaction: with amines, 124 with lithium alkyl amide, 62 with monochloracetic acid, 122 with trans-neopentylallyllithium, 111 with phenylmagnesium chloride, 100 with phosphodiesters, 125 Cyclohexenes- 1,4-dienes, epoxidation, 18 Cyclooctatetraene oxide, 62 photoinduced valence isomerization, 130 Cyclopentadienemonooxirane, stereoselective ring opening, 105 Cyclopentenone oxide, photochemical conversion to 2-pyrone derivatives, 135

Subject Index Cyclopropyloxiranes, production from chalcones, 53 Cytochrome P450, 231 arene oxides formation a n d , 255 benzo(2)pyrene metabolism a n d , 258 binding sites, 256 formation of naphthalene 1,2-oxide, 257 isozymes, 256 stereoselectivity in forming anthracene 1,2oxide, 257

Darzen’s reaction, 47-50 glycidyl thioester synthesis, 49 mechanism, 47 retroaldolization, 48 stereochemistry, 47 Decarboxylation, 414 Dehydrobromination, 372 Deoxygenation, 58-61, 254 Diacetylenic oxiranes, reaction with amines, 93 Diadamantylidene-l,2-dioxetane,379 1,5-Dialkadiencs, 100 Dialkylamino-aryloxosulfonium alkylides, 54 Dialkyl sulfoxide, 52 Dianthryldioxenedioxetane,chemiluminescent catalysis, 416 trans-Diaxial bromohydrins, transformation to oxirane, 44 Diaza-L-oxathietanes, 657 Diazathiaphosphetane, 657 Diaiepine, 324 Diazepinone, 331 Diazoalkanes, 51 Diazoketoxirane, 49 Diazomethane, 51 Diazothiaphosphetane, 657 Dibenzoxazepine, conversion to 2-(2hydroxyphenyl)benzoxazole, 332 Dibromoselenetane, 670 3,3-Di-f-butyl-oxaziridine, 307 3,3-Dicyanostilbene oxide, photolysis, 143 Dicyclohexylcarbodiimide, 375 Dicyclohexylurea, 376 Dicyclopentadienes, 20 3,6-Dideuteriobenzene oxide: azide addition, 244 photolysis, 239 Dielectric constant, 13 Diels-Alder reaction, 224 activation energy, 412 7,7-Diethoxynorbornadiene, 253

859

2-( Diethoxyphosphinylimino)-l,3-diethietane, 639 3,3-Diethoxythietane l,l-dioxide, 506 ethanol elimination, 506 Diethyldiazomalonate, 461 3,4-DiethyI-l,2-dithietane1 ,I-dioxide, 625 1,2-Difluorooxirane, structure determination, 8 Dihydrodiols, 218, 241 4,5-Dihydrofuran, 91 Dihydrooxepines, 149 Dihydrooxepino(4,5d)pyridazine, 250 p-Dihydroxyethylbenzene synthesis, by oxirane Grignard reaction, 101 Diiodoselenuranes, 670 Diisobutyl-aluminium hydride, reduction of vinyloxirane, 81 3,3-Dimethoxythietane, 57 1 Dimethylazodicarboxylate, 247 1,4-Dimethylbenzene oxide, formation of dihydrodiols, 241 2,3-Dimethyl-2-butene, allylic hydroperoxide on singlet oxygenation, 373 Dimethylcyclohexene, 22 Dimethyl-l,2-dioxetane: purification by column chromatography, 378 reaction with dimethyl sulfooxylate, 419 1,4-DimethyIenecyclohexane, 20 1,4-Dimethylnaphthalene endoperoxide, 373 Dimethylsulfonium methylide, 52 Dimethylsulfoxonium methylide, 52 Dimethylthietane, 438, 446 2,2-Dimethyl-3-thietanone, reaction with potassium ferricyanide, 575 Dinitrophenylhydrazones, 522 Diol epoxides, 269 p-Dioxene- 1,2-dioxetane: activation energy, 412 reaction with diphenylsulfide, 419 1,2-Dioxetanes, 37, 351-429 from acridine, 379 activation parameters, 386 biological implications, 420 chemical methods of identification, 380 chemical transformations, 417-420 chemiluminescence, 382 chemiluminescence mechanism, 4 10-4 14 combination analysis, 380 deoxygenation to oxirane, 40 electron exchange chemiluminescence, 414 excitation parameters, 393 excited state energy, 407 explosive nature, 380

860

Subject Index

1,2-Dioxetanes (Continued) heteroatom substitution, 409 identification, 378-382 melting points for, 380 by nmr, 380 spectroscopic methods of, 380-382 by x-ray structure analysis, 380 infrared spectra, 381 intermolecular transformations, 402-403 intramolecular transformations, 399-402 iodometric titration, 380 mass spectra, 382 nature of excited states, 405 phosphorescence, 382 photoelectron spectra, 381 physical methods of identification, 379 potassium iodide detection, 379 purification by recrystallization, 378 reactions: with electrophiles, 420 with nucleophiles, 418 with phosphines, 418 substitution patterns, 408 thermal decomposition energetics, 385 thermal decomposition kinetics, 386 thermal decomposition mechanism, 410-414 triplet excitation yield, 406 volatile crystalline, 378 1,2-Dioxetanes decomposition, 379 1,2-Dioxetanes synthesis, 370-375 by dehydrohalogenation of 8bromohydroperoxides, 371 effect of temperature, 372 by endoperoxides rearrangement, 374 by intramolecular peroxymercuration, 374 Kopecky method, 371 by ozonization of vinyl silanes, 375 side reactions, 373 silver ion catalyzed cyclization, 372 singlet oxygenation, 372-373 Dioxetanes, aryl substituted, 374 Dioxetanyl ring protons, chemical shifts, 381 trans-Dioxirane, 20 1,4-Dioxocin, 239 1,3-Dioxolanes, 146 from oxirane condensation, 92 1,3-Dioxolanones, synthesis from oxiranes, 92 Dioxygenases reactions, dioxetane role, 421 9,lO-Diphenyl anthracene, epoxidation, 227 1,2-Diphenylcyclopropene,rate-strain relationship, 21 2,3-Diphenyl-2,3-epoxybutanehydrogenolysis, 85

5,5-Diphenylhydantoin, 212 Diphenylisobenzofuran, 542 3-Diphenylisobenzofuran oxide, isomerization, 21 1 N-Diphenylmethylene a-methylbenzylamine, oxidation to oxaziridines, 319 C,N-Diphenylnitrone, photolysis, 332 3,3-Diphenyloxaziridine,307 conversion into benzophenone, 307 4,6-Diphenylpyridine I-oxide, photolysis, 339 2,4-Diphenylthietane, reaction with potassium-t-butoxide, 467 2,4-Diphenylthietane 1,l-dioxide: nmr spectrum, 490 reaction with t-butoxymagnesium bromide, 502 2,3-Diphenylthiirene 1,l-dioxide, 536 Dipole moment: measurement, 8 via dielectric constant, 13 of thietane-I-oxides, 479 1,3-Diselenetanes, 672 1,6-Disubstituted cyclohexenes, 19 2,4-Disubstituted-6-hydroxymethylphenols, 38 5,6-Disubstituted norbornene, 19 Disuccinoyl peroxide, 25 Disulfur dinitride, 658 thermal decomposition, 660 1,3-Ditelluretanes, 672 Dithiadiboretanes, 668 reactions, 669 1,3-Dithietane-2-0nes, 638-639 1,3-Dithietane-l-oxide, thermolysis, 636 1,3-Dithietanes, 629-637 oxidation of sulfur atom, 633 properties, 629-630 reactions, 632-635 with antimony trifluoride, 635 ring opening, 632 synthesis, 630-632 by dimerization of thiocarbonyl compounds, 630 by reduction of 1,3-dithietane-l-oxide, 63 1 uses, 629 1,2-Dithietes, 625-629 properties, 625 reactions, 628 ring-opening, 629 synthesis, 626 P-Dithiolactones, 516, 561-562 1,2-DithioIanes, photolysis, 452 1,2-Dithiolium ion, 514

Subject Index m-Dithiophosphonates, 66 1 Divinylketone monooxirane, reaction with hydrogen sulfide, 98 Divinyloxirane synthesis, from diols, 42 DNA damage, 421 Dopastin, 331 Dypnone oxide, photolysis, 133 Electrochemical oxidation, 40 Electrochemistry of thietane I-oxide, 480 Electrolytic reaction, disrotatory, 198 Electron-transfer theory, 415 Enaminoketone, 502 Energy balance in chemiluminescence, 382, 384 Energy transfer chemiluminescence, see Chemiluminescence, enhanced Emethials, 522 Enethiones, 522 a-Enolate carboxylates, autoxidation, 377 Epichlorohydrin, 533 Epicrotoxirane, 22 Epipolythiopiperazinedione, 245 Epoxidation, asymmetric, 24 Epoxidation agents, 24 Epoxide hydrolase, 214, 259 regiospecificity, 261 stereospecificity, 261 2,3-Epoxybutane, deuterolysis, 85 a-3,4-Epoxycarane, 12 1 hydrogenolysis, 79 Epoxycarboxamide, 28 1,2-a-Epoxycholestadienone,27 Epoxycholestanes, reaction with methanol, 120 trans-Epoxycyclododecane, isomerization, 64 1,2-Epoxydecane, hydrogenolysis, 84 a$-Epoxydiazoketones rearrangement, 90 cis-Epoxyepimino-1,3-cyclohexadiene,251 Epoxyethylphosphonates, photolysis, 144 Epoxy imine, oxidation by p-nitroperbenzoic acid, 305 2,3-Epoxyindanone, 46 Epoxyketones: photochemical reactions, 131 rearrangement, 64 reduction t o epoxyalcohols, 81 unsaturated, photochemistry, 139 7,8-Epoxy-2-methyloctadecane,22 Epoxynaphtoquinones, photochemical behavior, 134 Epoxynitriles reactions: with alkyllithium, 112

86 1

with alkylmagnesium compounds, 103 with Grignard reagents, 100 exo-Epoxynorbornene, intramolecular photocycloaddition, 130 1,2-Epoxyoctane, 68 2P,3P-Epoxypinane, 45 Epoxypropelladiene, 22 a$-Epoxysilanes, 64 reactions: with Grignard regents, 101 with hydrobromic acid, 122 with methanol, 119 Epoxysuccinic acid, deuterolysis, 85 trans-Epoxysulfone, 49 3,4-Epoxytetrahydropyran, study of inductive effect, 117 Ergosterol, photooxygenation, 353 Ethanesulfonamide, 597 3-Ethoxythiete 1,I-dioxides, 534 Ethyl diazoacetate, 535 trans-a-Ethylene-a-acetylenoxirane, thermolysis, 150 Ethylthiostyrenes, 246 2-Ethynylcycloalkano1, synthesis by oxirane reduction, 83 Exothermic thermal decomposition, 383 Flavin oxaziridine, as oxygen transfer agents, 325 Flavoprotein reductase, 256 Fluorooxiranes, 43 Formyloxirane, reaction with alkylaluminium compounds, 105 Fungal enzymes and arene oxides metabolism, 258 Germadioxolanes, 96 Germaoxetanes, 89 Gliotoxin, 245 Glutathione, reaction with arene oxides, 266 Glutathione-S-epoxide transferase, 246 Glutathione S-transferase, 266 Glycidic esters, 47 Glycidic nitriles, 48 Glycidonitriles, 97 Glycidyl thioesters, 49 Grignard compounds, 99 Grignard reactions, copper catalysis, 100 Halogenated oxiranes, reduction with lithium aluminium hydride, 80 a-Haloglycidates, 48 Halohydrin, 43

862

Subject Index

3-Halomercaptans, conversion to thietanes, 446 a-Halooxirane: formation, 56, 57 thermal rearrangement, 150 a-Halosulfones, 505 3-Halothietane 1 ,I-dioxide, dehydrohalogenation, 506 Hammett correlation, 28 Heats of combustion, oxiranes, 6, 7 Heats of formation, oxiranes, 7 Herbicides, 476 2,4-Hexadienemonooxirane, photochemical isomerization, 129 Hexamethylcyclotrisilazane, 667 n-Hexyl P-alkylvinyl ketone epoxidation, 28 n-Hexyloxirane rearrangement, 66 Homopropargyllic alcohols, 111 Horse radish peroxidase, 421 Hydrazones, 91 Hydrogen peroxide: as oxidation agent, 25-30 reaction with thietanes, 462 Hydrogenolysis, catalytic, 83-87 a-Hydroperoxy acids, 375 by a-lactones and hydrogen peroxide, 377 as precursors to a-peroxylactones, 376 synthesis via a-lactones, 377 a-Hydroperoxyamines, reaction with hydrogen peroxide and imines, 306 Hydrosilation reaction, 623 a-Hydroxyacetate, transformation to oxiranes, 42 a-Hydroxyalkyloxirane rearrangement, 64 a-Hydroxyhydroperoxide, 29 4-Hydroxyindaq 237 3-Hydroxythietane: 446 from 3-chloro-l-mercapto-2-propanol, as flavoring substances, 438 from monothiolcarbonate, 448 oxidation, 462 polymers, 472 reaction with aminophosphine, 474-475 Hypochlorous acid, 39 h i n e oxidation: with m-chloroperbenzoic acid, 305 dichloromethane as solvent, 284 with peroxy acids, 284-307 production of nitrone and oxaziridine mixture, 305 product selectivity, 305 reaction mechanism, 305 reaction temperature, 284

Imines, reaction with monopercamphoric acid, 3 14 1,6-Imino( IO)annulene, photooxidation, 228 Iminodioxetane: activation energy, 393 reaction with triphenylphosphine, 4 18 Imino-l,3-dithietanes, 639-641 synthesis, 640 uses, 639 Iminophosphorane, 88 Iminothiazetidines, 604-609 properties, 605 reactions, 607 synthesis, 605-607 2-Iminothietanes, 562-568 alkylation, 568 from isonitriles and iminothiiranes, 564 mass spectra, 563 nmr spectra, 563 nucleophilic ring opening, 567 photochemical rearrangement, 566 properties, 562-563 reactions, 566-568 ring opening reactions, 566 synthesis, 563-566 cycloaddition to thiocarbonyl group, 563 by intramolecular cyclization, 565 from ketenimines and thiobenzophenone, 564 from p-lactones and phenylisothiocyanate, 565 thermolysis, 566 x-ray analysis, 562 3-Iminothietanes, 575-577 reactions, 577 Indan oxide, 237 formation of dihydrodiols, 241 reaction with singlet oxygen, 248 Indene oxide, reaction with benzoic acid, 122 Intermolecular transformations, in dioxetanes, 402-403 Intramolecular electron transfer, in bioluminescence, 417 Intromolecular transformations, in dioxetanes, 399-402 Iodohydrins, 44 Iodosulfonium compounds, 483 Ionization potential, 14, 381 of oxiranes, 7 IR frequency, of oxiranes, 9 IR spectroscopy, of oxiranes, 8 Isocrotoxirane, 22 Isomerization, photocatalytic, 136

Subject Index Ketene acetals, 91 dioxetane production by reaction with singlet oxygen, 372 Ketenimines, 341 cycloaddition to thiocarbonyls, 563 a-Keto-a-cyanooxirane, thermal rearrangement, 146 P-Ketoesters, 21 cis-Ketoglycols, from ketooxiranes, 118 Ketone alkylation, by Grignard reagents, 101 Ketone oxidation, and bioxirane formation, 21 Ketones, unsaturated, 26 3-Ketothietane I,l-dioxide, 546 Lactones, 89, 377 Lanthanide shift reagents, 1 1 Limonene, 20 d-Limonene oxide rearrangement, 72 Limonenol, 68 Linear Taft correlation, 12 a-Lipoamide, 451 Liquid crystals, 12 use in oxaziridine configuration determination, 318 Lithium aluminium hydride, 78 Lithium 9,9-di-n-butyl-9borabicyclo(3.3.l)nonate, 8 1 Lithium vinylcuprate, 108 Luciferin, 417 Manganese acetylacetonate, 35 Manganese porphyrin, 39 Mass spectrometry, 14 p-Mentadiene dioxide, 121 Menthenone, 27 Mercaptoacetaldehyde, 617 3-Mercaptothietane sulfones, as insecticides, 488 y-Mercaptothiuronium salt, 450 Mercuric chloride complexes, of thietane 1oxides, 484 o-Mesitylenesulfonylhydroxylamine,461 Metal hydrides, as reducing agents, 77 Methanesulfonyl chloride, 492 2.4-Methanesulfonylimino-lJdithietane, 640 4-Methoxyazobenzene, 332 p-Methoxy-carbonylperbenzoic acid, 24 I-Methoxy-3,3-dimethylthietaniumsalts, nmr spectra, 512 Methylamine, conversion to azomethane by oxaziridines, 327 Methyldichlorosilane, 667 N-Methyldihydroacridinylidenyl, 415

863

Methylene blue, 373 Methlenecyclohexane, stereoselective epoxidation, 44 Methylene-l,3-dithietanes,641-650 as antibiotics, 641 desulfurization, 646 nucleophilic reactions, 647-649 oxidation, 647 properties, 641-642 reactions, 646-650 reduction, 646 synthesis, 642-646 thermolysis, 646 2-Methylene-3-iminothietane, 576 Methylene sulfone, 506 Methylenethietane I-oxides, 586-588 reactions, 587 synthesis, 586 Methylene thietanes, 577-582 occurence, 577 properties, 577 reactions, 580-582 Diels-Alder reaction, 581 isomerization to thietes, 582 with nucleophiles, 580 oxidation, 581 photochemical, 581 with tetrazine, 581 synthesis, 578-580 from bis-(trifluoromethyl)thioketene, 579 by cycloaddition of cumulenes to thiocarbonyl group, 579 from cyclobutanedione and thiones, 579 by desulfurization of thiirane, 580 intermolecular cyclization, 578 intramolecular cyclization, 578 by thioenolate cyclization, 578 by Wittig reaction of, 579 x-ray crystallography, 577 Methylene-3-thietanone: reaction with thionyl chloride, 575 by thermal rearrangement of adiazoketones, 580 I-Methyl-2,3-epoxycyclohexane, hydrogenolysis, 86 2-Methyl-3-isopropyloxirane, isomerization regioselectivity, 72 2-Methyl-2-methoxy-l,3-dioxolanes, 21 8 Methyloxirane: hydrogenolysis, 73, 84 photochemical behavior, 127 photochemical bromination, 128 reaction: with dibutylamine, I25

864

Subject Index

Methyloxirane (Continued) with Grignard compounds, 99 solvolysis in acidic medium, 117 thermal gas-phase reactions, 145 3-Methyl-3-phenylthietane 1-oxide, mass spectra, 479 2-Methyl-3-piperidinothietane 1,l-oxide, 494 Methylpyrazole, 543 Methylspirothiete, 525 Methylstyrene, 36 a-Methylthietane, Raman spectra, 440 tmns-2-Methylthietane synthesis: by 4-t-butylsulfinyl-1-butenethermolysis, 48 1 from cyclization of .I-mercaptopropene, 456 2-Methyl-3-trimethylsilyl-2-butene, ozonization, 375 Methyltriphenoxyphosphoniumiodide, 60 Metiamide, 656 Michael reaction, 245, 447 Microwave spectroscopy, of oxiranes, 8 Molecular geometry, of oxiranes, 5-6 Molecular orbital calculations, for arene oxideoxepin equilibration, 199 Molecular oxygen, 34 Moller-Plesset perturbation theory, 4 Molybdenum oxide, 29 Monoepoxyalcohols, 26 Monoterpene oxiranes, hydrogenolysis, 86 Monothiobenzil, 619 cis-Monotosylbornane, oxirane formation from, 45 Morpholine, 97, 492 3-Morpholinothiete 1,I-dioxide, 544 Muconaldehyde, 252 Mutagenesis, 268 Naphthaldehyde, 538 Naphthalene, arene oxide formation, 213 cis-Naphthalene dioxide synthesis by benzyne and butadiene, 227 Naphthalene 1,4-endoperoxide, 219 Naphthalene oxide, 202 existence as oxepin, 202 Naphthalene 1,4-quinone reduction, 228 Naphthoflavone, 214 as inducer of cytochrome P450, 256 1-Naphthol, 242 Naphthothiete: oxidation, 520 photoelectron spectra, 515 reaction: with methyllithium, 522

with trimethyloxonium tetrafluoroborate, 521 sulfoxide, 529 Naphthothiete 1,l-dioxides, 506 exomethylene derivatives, 536 production in hepatic metabolism of naphthalene, 230 reduction, 538 Naphthothiete sulfone, 516 hydrogen-deuterium exchange, 540 photolysis, 546 thermolysis, 546 Nitriles, unsaturated, epoxidation, 28 2-@ -Nitrobenzoyl)-3-phenyloxaziridines, reaction with cyclohexylamine, 325 Nitrogen stability in oxaziridines, 322 Nitroimidazo-oxazole, synthesis from oxiranes, 96 Nitrones: mass spectra, 333 photolysis of, 309-312 production during imine oxidation, 305 Nitroolefins, epoxidation with hypochlorous acid, 39 p-Nitroperbenzoic acid, 305 trans-a-Nitrostilbene, 28 Norbornane diepoxides reduction, 81 Octalin, 22 Octene 1,2-oxide hydration, 261 1-n-Octenoxirane, rearrangement to aldehyde, 67 Olefins: chromic acid oxidation, 39 substituted, 24 transformation to oxiranes by ozone, 39 Optical rotatory dispersion, 14 Orbital hybridization, 5 Oxadiazolidinone, 341 Oxadithietane-2,3,3-trioxide, 655 7-Oxanorbornadiene, 21 1 Oxaphosphetanes, 622 3-Oxaquadricyclane isomerization, 205 Oxaspiropentanes, 53 l-Oxa-3-thia-2,4-diphosphetanes,656 Oxa-2,3-thiazete-2-oxides, 650 1,2-Oxathietane 2-oxides, 610 from P-hydroxysulfoxides, 613 1,2-Oxathietanes, 610-619 decomposition to mercaptoacetaldehyde, 617 nucleophilic ring opening reaction, 615 properties, 61 1

Subject Index reactions, 615-619 synthesis, 6 12-615 thermolysis, 619 uses, 61 1 1,3-Oxathietanes, 621 1,2-Oxathiete derivatives, 619-620 Oxathiol S-oxide, 619 1,3-Oxazines, 97 Oxaziridine-amide, photochemical rearrangement, 333 Oxaziridine isomerization: nitrogen inversion mechanism, 320 and racemization, 321 Oxaziridine reactions, 322-343 acid-catalyzed, 329-332 with amines, 327 with r-butylcyanoketene, 342 with carbodiimides, 341 with cumulenes, 341 cycloaddition reactions, 341-343 deoxygenation, 325 with enamines, 326 with episulfides, 329 with hexafluoroacetone, 343 hydrolysis, 329 with ketenimines, 341 metal ion catalyzed, 340-341 with nucleophiles, 322-329 nucleophilic attack at nitrogen, 327-329 nucleophilic p elimination, 322-325 oxidation to oximino ketones, 332 with phosphines, 327 photochemical, 333-340 thermal, 333-340 with thiocyanates, 342 with thiols, 327 with thiourea, 327 Oxaziridines, 283-350 asymmetric synthesis in chiral media, 319 chiroptical properties, 322 configuration determination, 318 from a-hydroperoxyamines, 306 isomerization on heating, 333 mass spectra, 333 nitrogen stability, 322 optically active, 313 from N-diphenlymethylenemethylamine, 314 monopercamphoric acid as peroxy acid, 314 optical yield dependence on chiral solvent, 319

865

preparation using chiral peroxy acids, 314-315 synthesis, 314 as product of photochemical autoxidation of amines, 312 ring-opening reactions, 340 stability, 309 thermal amide formation, 333 thermal rearrangement: to azetidine, 335 to keto anil, 335 Oxaziridine stereochemistry, 3 13-322 Oxaziridine stereoisomers: interconversion, 320-322 thermal epimerization, 320 Oxaziridine synthesis, 284-313 imine oxidation with peraceticacid, 305 by oxidation of chiral imines with achiral peracids, 316-319 by oxidation of imines with peroxy acids, 284-307 by photolysis: of diphenyldiazomethane, 322 of ethylazidoformate, 312 of nitrones, 309-312 of oximes, 312 by reaction of chloramines with ketones, 307 Oxazoles synthesis from oxiranes, 93 Oxazolidine synthesis from oxirane, 93 Oxazolines, 113, 123 Oxepins, 197-282 cycloaddition with tetrazine, 250 dipole moment, 20 molecular geometry, 200 photochemical rearrangement to cyclobutene, 239 of polycyclic aromatic hydrocarbons, 213 reduction reaction, 255 Oxepin structure, 198 Oxetanes synthesis from oxiranes, 88-89 Oxidation: as electrophilic addition, 16 and olefin structure, 36 of oxiranes, 76-77 reaction mechanism, 35 Oximes, photochemical rearrangement, 338 Oximino ketones, 332 Oxirane alkynylation, by organoaluminium compounds, 105 Oxirane-carboxaldehyde, steric structure, 9 Oxirane deoxygenation, 58-61 with lithium alkyls, 61

866

Subject Index

Oxirane deoxygenation (Continued) with methyltriphenoxyphosphonium iodide, 60 and nucleophilic reagents, 59 and olefins production, 58 as organic synthesis, 58 with transition metal atoms, 59 with trimethylsilylpotassium, 60 by triphenylphosphine, 59 Oxirane enantiomers, determination by nmr, 12 Oxirane fragmentation, 14 Oxirane hydrogenolysis, 83-87 catalyst’s role in regioselectivity, 84 kinetic investigation, 87 mechanism, 85 stereochemistry, 85 Oxirane hydrolysis, 118-1 19 epoxy-oxygen participation, 119 Oxirane isomerizations, 61-76 base-catalyzed, 63 reaction mechanism, 73 ring contraction, 68 ring expansion reactions, 69 role of metals, 73 stereochemistry, 66 Oxirane-nucleophile interaction, 118 Oxirane oxidation, 76-77 with alkaline hydrogen peroxide, 76 Oxirane photochemistry, 125-145 Oxirane reactions, 57-152 with alcohols, 119 with alkylaluminium compounds, 101-105 with alkyllithium, 110-113 with alkylmagnesium compounds, 101-105 with amines, 123 with ammonia, 123 with aryllithium, 110-1 13 with carboxylic acids, 122 cationic polymerization, 151 conversion into olefins, 59 deoxygenation, 58-61 with diphenylphosphine, 125 with enamines, 124 with tris(ethylthio)borane, 114 with Grignard reagents, 99-101 with halogen acids, 121-122 heterolytic C - 0 bond opening, 57 with 8-hydroxydiphenylphosphine oxide, 59 with isothiocyanatosilane, 114 kinetics of alkylmagnesium compounds reactions, 102

with lithiumdiorgano copper compounds, 106-1 10 with lithium trialkylalkynylborate, 114 with lithium triphenylphosphine, 114 mechanism of ring opening in acidic medium, 116 with organometallic compounds, 98-1 15 oxidation, 76-77 with phenols, 119 polymerization, 151 reduction, 77-87 ring basicity, 57 ring opening, 115-126 stereochemistry of, 116 ring opening regioselectivity, 118 ring strain, 57 with sodium dialkyl phosphite, 125 stereospecific deoxygenation, 59 with sulfurated borohydrides, 121 thermally induced, 145 with thiols, 120 with triazoles, 125 with trimethylchlorosilane, 114 Oxirane rearrangements, 61-76 acid catalyzed, 65 to ally1 alcohols, 62 base-catalyzed, 62-7 1 carbenoid insertion, 62 containing acetylenic sidechain, 63 a-elimination, 62 induced by catalysts, 71-75 and Lewis acids’ strength, 67 in presence of solid acids, 72 silica-gel-induced, 71 Oxirane reduction, 77-87 catalytic hydrogenolysis, 83 dissolving metal reduction, 83 with lithium aluminum hydride, 79 mechanism, 78 with metal hydrides, 78-82 stereochemistry, 78 Oxirane ring: anisotropic shielding effect, 10 characteristic overlapping band, 8-9 conformational effect, 11 conformational energy, 8 opening by diethylmagnesium, 103 stereochemistry of hydrogenolysis, 85 terminal, 9 transformation into other heterocyclic compounds, 87-98 Oxiranes, 1-196 absorption maximum, 9

Subject Index aliphatic, oxidation by nitric acid into oxalic acid, 77 alkylation by sodium tetraethylaluminate, 113 aryl substituted, 81 base-catalyzed oxidation, 77 bent bond chemical nature of, 5 from bicycloheptane derivatives, 27 b o n d angle, 6 catalytic hydrogenolysis, 83 C-C bond distance, 6 cleavage of C-C bond, 7 concentration determination by IR bands, 9 condensation with carbonyl compounds, 92 configurations derived from prostaglandin, 10 conversions: t o ally1 alcohols by selenium, 75 into dialdehydes, 77 into fluorohydrin, 121 into germaoxetanes, 89 C - 0 ring-opening, 7 cyclic: isomerization, 69 polyoxirane isomers, 24 degree of bond bending, 5 diazoketoxirane, 49 diffraction measurements, 13 dipole moment measurements, 8, 13 electron affinity, 4 energetics, 6-8 excitation energy, 4 ground state, 4 heats of combustion, 6, 7 heats of formation, 6, 7 hydroxyalkylation, 112 from indenedione, 26 inductive a n d hyperconjugative effects, 15 ionization energy, 4 ionization potential, 7 IR bands, 8 IR frequency, 9 IR spectroscopy, 8 kinetics of reactions with amines, 125 low excited state, 4 mass spectrometry, 7, 14 microwave spectroscopy, 8 molecular geometry, 5-6, 8 monosubstituted, oxidation to glycols, 76 from naphthalenone, 26 n m r in oriented phase, 12 nmr studies, 10-13 nomenclature, 3

867

optically active, synthesis from alkaloids, 28 optical rotatory dispersion, 14 phenyl substituted, 62 photoadditions, 129 photoelectron spectra, 14 physical properties, 4-15 proton abstraction by phenyllithium, 11 1 proton chemical shifts, 10 quantum-chemical calculations, 4 Raman spectroscopy, 13 reactions: with carboxylic acid, 123 with iron chloride, 125 with isocyanates, 9 4 refractive index, 9 regioselective rearrangement to ally1 alcohols, 76 ring expansion, 88-98 ring strain, 7 ring transformation, 87-98 rotational spectra, 9 shift techniques, 11 spectroscopic properties, 8-13 spirooxirane derivatives, 38 structure calculation via STO-3G programmes, 4 substituent effect on electronic structure, 5 substituted, 5 bond angle measurements, 8 bond length measurements, 8 bonding energy, 5 chemical shift, 10 conjugative effects, 10 dipole moment, 5 inductive effect determination, 12 IR frequencies, 9 nmr spectroscopy, 12 theoretical models, 4-5 thioether oxiranes, 49 transformation into carbonyl compounds, 65 unsaturated, photochemical behavior, 129 UV spectroscopy, 9-10 Oxirane spectrum, solvent effect, 11 Oxirane synthesis, 15-57 from acetals of 1,2-diols, 41 from aldehydes with phosphorous derivatives, 56 by alkenes oxidation, 15-40 from bromohydrin, 41 from carbonyl compounds, 47-57 with sulfonium ylides, 52 by cooxidation of aldehydes and olefins, 38

868

Subject Index

Oxirane synthesis (Continued) Corey synthesis, 52-54 from diazoalkanes, 51 from 1,2-difunctional compounds, 40-46 from dioxo compounds, 55 by electrochemical oxidation, 40 from 1,2-epoxyalkane phosphonates, 55 from glycol monotosyl ester, 41 from halohydrins, 40 from molybdenum peroxo complexes, 29 by oxidation of ethylene wtih molecular oxygen, 34-38 from oxidation of nitroolefins, 39 from 2-substituted alkanols, 40 2-Oxiranylcycloalkanone, photolysis, 138 Oxonium ion, 116 Oxygen, singlet, 372 generation by photosensitization, 373 triphenylphosphite ozonate as chemical source, 373 Ozonization, 375 Payne rearrangement, 43 Penicillamine, 548 Pentacyanocobalt complexes, as catalyst for oxirane isomerization, 74 Pentacyclododecanol, synthesis by oxirane rearrangement, 63 3,3-Pentamethylene oxaziridine: irradiation, 335 thermal rearrangement, 335 Pentamethylthiophenium ion, photochemical rearrangement, 5 10 Peracetic acid, 24 Peracetyl nitrate, 25 Peracids: imino analogues, 24 polymer-supported, 24 Peracid stablizers, 16 Perbenzoic acid, 15, 24 Performic acid, 24 Perhydropyridazine, 97 Periodate compounds, 39 Peroxomolybdenum-olefin complex, 30 S-Peroxyalkyl radical, 35 Peroxybenzimidic acid, 24 Peroxycarbamic acid, 24 Peroxycarbonic acid, 25 Peroxyimidic acids, 24, 215 a-Peroxylactones, 351-429 chemiluminescence, 382 electron-exchange chemiluminescence, 397, 414

a-hydroperoxy acids as precursors, 376 identification, 378-382 nonvolatile derivatives, 376 phosphorescence, 382 purification, 378-382 reaction with triphenylphosphine, 418 spectroscopic methods of identification, 380-382 synthesis, 375-378 by dicyclohexylcarbodiimide cyclization, 375 ketene bis(trimethylsilyl)acetal as starting point, 377 by singlet oxygenation of ketenes, 377 thermal decomposition kinetics, 386 volatility, 376 Peroxyphosphonic acid, 25 Perpropionic acid, 24 Phenanthrene, 214 Phenanthrene oxidation, 215 Phenanthrene oxides: deoxygenation, 254 solvolysis, 241 Phenolic benzene oxide, 213 Phenylacetaldehyde, 140 Phenylacetylene, 522 2-Phenyl-3,3-dibenzoyloxaziridinestability, 338 truns-2-Phenylcyclohexanol,100 Phenyldimethylglycidic acid, photolysis, 140 truns-l-Phenyl-2,3-epoxybutane,104 I-Phenyl-2,3-epoxypropane,102 Phenyl-glycidic acid: ammonolysis, 124 photochemical reactions, 140 Phenyllithium, action on chlorooxiranes, 110 Phenylmethanesulfonates, 534 Phenyl oxaziridine: isomerization t o nitrones, 331 reaction with formanilide, 328 Phenyloxiranes, 10 reactions with alkylmagnesium compounds, 102 reduction with alkali metals, 83 solvolysis in acidic medium, 117 thermal reactions, 146 l-Phenyl-3-thietanone, 527 1-Phenyl-3-thietanone perchlorate, 509 3-Phenylthiete: alkylation, 521 nmr spectrum, 515 Phenylvinyloxirane thermolysis, 148 Pheromone synthesis, 109

Subject Index Phorone, 26 Phosphates, isomerizing effects, 71 Phosphine selenide, 672 Phosphinimines, 656 Phosphobetaine, 59, 114 Phospholenes, 24 Phosphomycin, 50 Phosphonates, homoallyl, epoxidation, 24 Phosphorous pentoxide, 549 Photochemical reaction, 384 Photoelectron spectroscopy, 14 Photoionization, 7 Photomultiplier tube, 397 Photooxidation, 37 Phthalazine, 250 Phytochrome phototransformation, 421 Pinacolic rearrangement, 41 a-Pinene, 20 Piperazine, 97 Polychlorinated biphenyls, as inducers of cytochrome P450, 256 Polyepoxyalcohols, 26 Polyethers, 474 Polymerization, of oxiranes, 151 Polyurethanes, 474 Potassium iodide, as detector for dioxetanes, 379 Pregnane, 27 p-Propiolactone, 105 P-Propiothiolactone, vibrational spectra, 548 P-Propiothiolactone synthesis, from pchloropropionyl chloride, 550 Propylene, photochemical epoxidation, 37 Prostaglandin synthesis, 105 Prostaglandin synthetase, and oxidation of benzo[a]pyrene 7,8-dihydrodiol, 258 Pyrazine, 97 I-Pyrazoline, 251, 543 Pyrene oxidation, 215 Pyridine N-oxide, photolysis to form naphthalene oxide, 214 Pyridines, 326 Pyridothiones, 447 a-Pyrone, 542 Pyrroles, 93 Pyrrolidines, synthesis from epoxy aminonitriles, 92 Pyrrolinium iodide, 92 Pyruvaldehyde acetal imines, 91 Quadricyclane, 453 Quinazoline, 476 Quinoxalines, 97

869

Raman spectroscopy, of oxiranes, 13 Reduction, of oxiranes, 77-87 Rhodium carbonyl chloride, 75 Ring expansion, in thietanes, 472 Ritter reaction, 123 Rose Bengal, 373 Selenathietane sulfone, 672 Selenetane, 670 Selenium heterocyclic compounds, 670 Sensitizer-solvent system, tetraphenylporphine in methylene chloride, 373 Sesquiterpene isolongifolene, 23 Sex pheromone, 22 Silyl aminoselenurane, 674 a-Silylcarbonyl compounds, 101 Silyl thione, 667 Spectroscopic properties of oxiranes, 8-13 Spiro(benzothiete), as hypertensive agents, 5 12 Spirolactones, 97 Spirooxaziridines, photolysis, 334 Spirooxirane: from cyclic ketone derivative with diazomethane, 5 1 from 2,4-disubstituted-6hydroxyrnethylphenols, 38 isornerization, 70 thermolysis, 145 Spirosilazane, 657 Spirothietane, 444 Spirothietane synthesis, from methone and sulfur dichloride, 455 Spirothiete: bond lengths, 513 x-ray analysis, 513 Spiro thiete 1,l-dioxides, 536 Stark effect, 13 Stereochemistry of oxaziridine, 313-322 Steric effect, 11 Steroid acetate, 33 Steroid epoxyketones, photochemical rearrangement, 132 Steroid oxiranes: acid-catalyzed rearrangement, 70 alcoholysis, 120 hydrolysis to diols, 1 I8 IR investigation, 9 reactions: with acetic acid, 123 with hydrochloric acid, 121 Steroids, stereospecific oxidation, 30 Steven rearrangement, 51 1 Stilbene oxide, 11

870

Subject Index

Thiadiazetidin-3-one, 65 1 thermal cleavage, 652 Thiadiazetidin-I-oxides, 652 Thiadioxetanes, 653 Thiagermacyclobutanes, 623 Thiamin anhydride, 580 Thianaphthalenium, 527 Thiaoxaphosphetanes, 653 1,2-Thiaphosphetanes, 621 Thiasilacyclobutanes, 623 2-Thiaspiro(3.5)nonane, from benzenesulfonate ester, 446 Thiazaphosphetidine, 65 1 1,2-Thiazete derivatives, 598-601 1,2-Thiazete 1,l-dioxides, 599 1,2-Thiazete I-oxides, 599 1,3-Thiazetes, 609 1,2-Thiazetidine 1,l-dioxides, 592-597 nucleophilic reactions, 596 properties, 593 reactions, 595-597 synthesis, 593-595 Taft correlation, 63 tautomerism, 595 Tartaric acid, 33 1,2-Thiazetidine I-imines, 590 Tellurium heterocyclic compounds, 670 1,3-Thiazetidine-2-ones, 602-604 Terpene oxide, reaction with hydrochloric 1,2-Thiazetidine I-oxides, 589-592 acid, 121 reactions, 591 Terpineol, 23 synthesis, 589-590 2,2',5,5'-Tetrachlorobiphenyl, 259 thermolysis to ethanesulfonamide, 597 Tetrahydrofuran, 91, 498 Thiaziridines, 327 Tetramethylallene, 561 1,2-Thiazetidines, 588 Tetramethyl-I ,2-dioxetane, 372 1,3-Thiazetidines, 601-602 Thietane alkylation, by acetylaziridine, 457 activation energies, 386 Thietane carboxylic acid, quinazoline heat of reaction, 385 2,2,4,4-Tetramethyl-3-thietanone, reaction derivatives, 438 with diiron noncarbonyls, 575 Thietane-2,4-diones, 553 Tetramethylene sulfoxide, 480 Thietane 1,l-dioxides, 452, 488-508 Tetraphenylcyclopentenone oxides, acidity, 490 photochromic valence isomerization, amino derivatives as drugs, 488 136 anionic reactions, 504 Tetraphenyl-I-propanone,353 decomposition to methylpyrazole, 503 Tetrasulfur tetranitride, 659 desulfurization, 506 Thermal epimerization, of oxaziridine dipole moments, 491 diastereomers, 320 halogenation, 505 Thermal epoxidation, 37 mass spectra, 491 Thermal instability, of benzene oxide, 205 nmr spectra, 489 Thermal stability, of dioxetane ring, 393 photolysis, 501 I-Thia-3-aza-2,4-diphosphetane-2,4-disulfides, properties, 489-491 656 reactions, 498-507 Thiacyclobutadines, 529 with n-butyllithium, 505 conformation studies, 514 reduction, 498 Thiacyclobutenes, see Thietes ring opening reactions, 501 Thiacyclobutene sulfonium ions, 526-529 structure analysis, 489 Styrene oxidation, solvent effect, 36 Styrene oxide: chemical shift, 11 hydration, 261 reaction with ethanethiol, 246 Styryloxirane, 149 Sulfenes, 494, 535 Sulfides, oxidation to sulfonides by oxaziridine, 326 Sulfilimine, 487 Sulfinic-carboxylic acid anhydride, 558 Sulfonamide, 657 Sulfones, 635-637 Sulfonium ylides, 52 N-Sulfonyloxaziridine, 305 oxidation of enolate to hydroxyketone, 327 o-Sulfoperbenzoic acid, 22 Sulfoxides, 326, 635-637 Sulfurane, 419, 482 p-Sultams, See 1,2-Thiazetidine 1 ,I-dioxides Sultines, 502

87 1

Subject Index substitution reactions, 405 synthesis, 491-498 by aryl-substituted enamines, 492 isomer composition, 496 by oxidation of thietanes, 491 by sulfene a n d ketene acetals, 492 by sulfones cycloadditions, 492 from thiete 1,l-dioxides, 497 thermolysis, 499 uses, 488 x-ray analysis, 489 Thietane-I-oxides, 476-487 o-alkylation, 484 basicity, 480 b o n d lengths, 476 a s carcinogen absorbent, 476 dipole moment, 479 mass spectra, 479 microwave structure determination, 476 n m r chemical shifts, 478 n m r spectra, 477 photolysis, 484 polymerization, 482 properties, 476-480 reactions: with Grignard reagents, 486 isomerization, 482 with metal complexes, 484 oxidation, 483 with potassium t-butoxide, 486 with trimethylsiloxy radicals, 485 reduction, 483 ring opening, 485 solvent characteristics, 480 synthesis, 480-482 by thietanes oxidation, 480 thermochemistry, 480 thermolysis, 484 uses, 476 x-ray analysis, 476 Thietane persulfurane, 512 Thietanes, 438-476 alkoxysulfonium salts, 509 a s anti-corrosive agent, 438 anti-ulcer activity, 438 complex formation with mercury halides,

465

desulfurization, 468-470 IR spectra, 440 methylation, 509 n m r spectrum, 439 occurrences, 438 oxidation, stereochemistry of, 463

as pesticides, 438 photochemical unstability, 469 platinum complexes, 465 polymerization, 439,472 Grignard reagent’s effect, 474 Lewis acids effect, 473 reaction with tetranitromethane, 473 properties, 439-443 basicity, 441 dipole moment, 442 electron diffraction study, 439 ionization potentials, 441 mass spectrometry, 441 structure and conformations, 439 thermodynamic quantities, 441 Raman spectra, 440 reactions, 456-476 with alkoxy radicals, 470 with ally1 chloride, 458 with carbenes, 459 with carbon electrophiles, 456 with chloramine-T, 461 with a-chloroethers, 458 with N-chlorosuccinimide, 470 with diethyldiazomalonate, 461 with free radicals, 470 with halogen electrophiles, 463 with metal ions, 465 with nitrogen electrophiles, 461-462 with nucleophiles, 466 oxidation to sulfones, 462 with oxidizing agents, 462 with protons, 464 ring opening with nucleophiles, 466 ring expansions, 472 substitution, 474 with sulfur electrophiles, 464 with sulfuryl chloride, 464 with thiobenzophenone, 471 with trifuloromethyl hypofluorite, 464 with trimethyloxonium tetrafluoroborate,

456

separation by gas chromatography, 443 synthesis, 443-456 from benzene sulfonate, 445 from chloromethyloxiranes, 449 from chloromethylthiirones, 449 from cyclic carbonates, 450 from dihalopropane a n d sulfide, 443 from 1,3-disubstituted propanes, 443-448 from 1,2-dithiolanes, 451 liquid ammonia as solvent, 444 by photolysis of bicyclic enone, 456

872

Subject Index

Thietanes (Continued) by photolysis of 1,2-dithiolanes, 452 from pyridinium salt, 447 by reduction of thietane I,l-dioxide, 452 from sulfur dichloride and bicyclo(2.2. I)heptadiene, 455 from thiocarbonyl compounds, 452 thermolysis, 470 uses, 438 UV spectra, 440 Thietane sulfilimines, 487 Thietane sulfodiimide, 508 Thietane sulfones, see Thietane 1, I-dioxides Thietane sulfoximines, 508 Thietane sulfuranes, 512 Thietanium salts, 508-512 mass spectrometry, 509 reactions and properties, 510-512 ring opening reactions, 51 1 Stevens rearrangement, 51 1 synthesis, 509-510 Thietanone I,1-dioxides, 534, 583-586 alkylation, 585 photolysis, 585 reactions, 584 with benzoxazolium salts, 586 with methanol, 584 reduction, 584 synthesis, 583-584 by oxidation of thietanone, 583 thermolysis, 584 Thietanone I-oxides, 582 3-Thietanones, 569-575 in Berkheya barbata plants, 569 bond lengths, 569 IR spectrum, 569 occurrence, 569 oxidation, 574 properties, 569 reactions, 572-575 aldol condensation, 574 with hydrazines, 572 with morpholine, 573 with nucleophiles, 572 with phosphines, 573 photochemical, 574 with piperidine, 573 with sodium hydrosulfide, 573 thermal, 574 Wittig, 572 reduction, by sodium borohydride, 574 synthesis, 569-571 by cycloaddition of thiocarbonyls to ketenes, 571

from 1,3-dihaloketones and sodium hydrosulfide, 569 by hydrolysis of ketals of 3-thetanone, 57 1 by intramolecular cyclization, 569 by oxidation of 3-hydroxythietanes, 570 by photolysis of 1,3-diethian-5-ones, 57 1 in photolysis of 3-thiatetralone, 571 by 3-thietanol oxidation, 571 x-ray crystallography, 569 Thietanoprostanoids, 488 Thiete anion, electronic energies, 513 Thiete 1,l-dioxides, 530-547 additions: of benzo-isofurans, 537 to C-C double band, 541 of hydroxide ion, 544 catalytic hydrogenation, 540 Diels-Alder reaction, 497, 542 with exocyclic double bonds, 536 exomethylene derivatives, 536 hydrogen-deuterium exchange, 540 hydrolysis, 546 isomerization, 540 mass spectra, 531 microwave spectrum, 530 nmr spectrum, 531 photolysis, 545 platinum complexes, 546 properties, 530 reactions, 538-547 with diazoalkanes, 543 with nitrile oxide, 543 with potassium hydroxide, 540 reduction, 538-540 ring opening reactions, 544 synthesis, 531-538 from 3-chlorothietane 1,l-dioxide, 533 by elimination reaction of thietane I,]dioxides, 531 by Hofmann elimination method, 532 by oxidation of thietes, 531 from sulfenes and ynamines, 535 from 3-thietanone 1,l-dioxide, 535 thermolysis, 545 treatment with diazomethane, 535 x-ray analysis, 530 uses, 530 Thiete 1-oxides, 529 Thietes, 512-526 S-alkylation, 521 hydrolysis to 8-mercaptoaldehyde, 521 mass spectra, 515

Subject Index nmr spectra, 515 oxidation, 520 properties, 5 13-5 15 proton abstraction, 522 reactions, 520-526 with lithium piperidide, 522 with nucleophiles, 522 ring opening to enethials, 522 with tetracyanoquinodimethane, 526 spectroscopic properties, 515 structure, 513 synthesis, 516-519 from acetylene and thiocarbonyl, 516 from 3-N,N-dialkylaminothietane, 5 16 by isomerization of 2-methylenethietane, 516 thermal stability, 520 uses, 512 valence tautomerism, 514 Thiete sulfones, see Thiete 1,l-dioxides Thiete-2-thione, 514 Thiobenzophenone, 456, 471 addition to diphenylketene, 551 Thioctic acid, 445 Thiocyanate, 254 4-Thiocyano-2-pentanol, 446 Thioethers, 115 Thiol glutathione, addition to arene oxide, 246 P-Thiolactones, 515, 547-560 anions, 557 and n-butanethiol. 555 carbonyl group conversion to methylene group, 555 comparison to p-lactones, 547 desulfurization, 558 hypotensive activity, 548 nocardicin derivatives, 559 optically active polymers, 556 oxidation, 558 photolysis, 557 polymerization initiators, 556 properties, 548 reactions, 554-560 with acetylsulfenyl chloride, 559 with ammonia, 555 with lithium aluminium hydride, 558 nucleophilic addition, 554 polymerization, 554 ring opening, 554 with sodium methoxide, 555 reduction, 558 substitution reactions, 559 synthesis, 548-554

873

from acyl chlorides of 4-Sbenzylcarboxylic acid, 550 from carbon oxysulfide and alkenes, 551 from carboxylic-sulfonic acid anhydride, 549 by cycloaddition of thiocarbonyls to ketenes, 551 from 1,2-dithiolan-3-ones, 552 by hydrolysis of 2,2-dichlorothietanes, 552 by intramolecular cyclization, 548 from P-mercaptoacid salt, 550 by photolysis of thiocyclohexan-4-ones, 554 thermolysis, 556 uses, 548 x-ray analysis, 548 2-Thiones, 602-604 Thiophosgene, 453 Thiopyranone, 98 Thioxanthone, 564 Thromboxane, 438, 488 Titanium tetrachloride, complex formation with thietane, 466 p-Toluenesulfonate, 445 o-Toluenethiol, 539 Triazoles, 125 Trichloro(nitroso)ethane, 25 1 Tricyclic dienone, 23 Tricyclic thiiranium ion rearrangement, 509 Trimethyloxonium tetrafluoroborate, 456 Trimethylsilyloxirane, thermal rearrangement, 150 1,2,4-Trimethylthietaniumtetrafluoroborate, reaction with n-butyllithium, 510 cis-Trioxatris(u)homotropylidene,22 cis-l,4,7-Trioxonin, 240 Triphenylene triepoxide, synthesis by epoxidation of triphenylene, 229 Triphenylphosphine, in oxirane deoxygenation, 59 Triphenylphosphite ozonate, 373 Triterpene oxide, 45 Trithietane, 656 Trithiocarbonates, 96 Tungsten oxide, 29 UV spectroscopy, of oxiranes, 9-10 Valence tautomers, 198 Valerolactones, 96 Vanadium catalyst complex, geometry, 32 Vinyl ether oxiranes, 68

874

Subject Index

Vinyl ethers, dioxetane production by reaction with singlet oxygen, 372 Vinyl substituted oxiranes, Raman spectra, 13 Vinylallenes, 24 2-Vinyldihyrofuran, from trans-vinyloxirane, 147 Vinyloxiranes: deoxygenation, 6 1 photochemical reactions, 131 reaction with alkylmagnesium compounds, 102

reduction, 81 thermal rearrangement, 147 o-Vinyl thioanilides, 453 Wittig-Horner reaction, 91 Wittig reaction, 222 Ynamines, 535 1,4-Zwitterion, 37