Compendium of Organic Synthetic Methods Volume 2

Compendium of Organic Synthetic Methods Volume 2 IAN T. HARRISON and SHUYEN HARRISON SYNTEX RESEARCH PAL0 ALTO, CALIFO...

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Compendium of Organic Synthetic Methods Volume 2 IAN T. HARRISON

and SHUYEN HARRISON SYNTEX RESEARCH PAL0 ALTO, CALIFORNIA

A Wiley-lnterscience Publication JOHN WILEY & SONS, New York

Chichester

Brisbane

Toronto

ANOTETOTHEREADER

This book has been electronically reproduced from digital We arc information stored at John Wiley & Sons, Inc. pleased that the use of this new technology will enable us to keep works of enduring scholarly value in print as long as there is a reasonable demand for them. The content of this book is identical to previous printings.

Copyright @ 1974, 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 Sections 107 or 108 of the 1976 United States Copyright Act without the permission of the copyright owner IS unlawful. Requests for permission or further information should be addressed to the Permissions Department, John Wiley & Sons, Inc. Library of Congress Cataloging in Publication Data:

Harrison, Ian T Compendium of organic synthetic methods.

1. Chemistry, Organic-Synthesis. Shuyen, joint author. 11. Title QD262.H32 547’.2 ISBN 0-471-35551-8

71-162800

I. Harrison,

PREFACE Compendiun? of Organic Synthetic Methods, Volume 2 presents the early 1971 to early 1974 crop of published functional group transformations, plus the gleanings from previous years. It is in part a supplement to Volume 7 and in addition contains a new chapter on the preparation of difunctional compounds. Previous reviewers and abstractors have tended to avoid difunctional compounds, having found the data particularly well concealed in the literature. Addition of this new chapter increases the complexity of the classification schemes, requiring more instruction in the use of the book. However, the system used is still simple enough that those who wish to just jump in will do well with no more guidance than that offered by the indexes. The task of abstracting the approx. 90 journals covered by Volume 7 and 2 of the Compendium becomes ever more difficult as chemical publications continue t o appear in increasing numbers. Within a few more years it will not be possible for a team of two to continue as sole abstractors, writers, artists, typists and proofreaders for the Compendium. Perhaps a fully organized abstracting service, responsive to the needs of the synthetic chemist, will someday be set up. It would help, of course, if chemists would learn to write orderly, concise papers that can actually be read rather than deciphered. Ian T. Harrison Shuyen Harrison Palo Alto, California May 1974

iii

CONTENTS AB B REVIAT10 NS INDEX, MONOFUNCTIONAL COMPOUNDS IN DEX, DI FUNCTIONAL COMPOUNDS HOW TO USE THE COMPENDIUM I NTRODUCT ION 1 PREPARATION OF ACETYLENES 2 PREPARATION OF CARBOXYLIC ACIDS, ACID HALIDES, AND ANHYDRIDES 3 PREPARATION OF ALCOHOLS AND PHENOLS 4 PREPARATION OF ALDEHYDES 5 PREPARATION OF ALKYLS, METHYLENES, AND ARYLS 6 PREPARATION OF AMIDES 7 PREPARATION OF AMINES 8 PREPARATION OF ESTERS 9 PREPARATION OF ETHERS AND EPOXIDES 10 PREPARATION OF HALIDES AND SULFONATES 11 PREPARATION OF HYDRIDES 12 PREPARATION OF KETONES 13 PREPARATION OF NITRILES 14 PREPARATION OF OLEFINS 15 PREPARATION OF DIFUNCTIONAL COMPOUNDS

V

vii ix xi xiii xv

1

7

28 53 70

82 92

108 127 136

146 155 185

193 214

ABBREVIATIONS Ac 9-BBN

acetyl 9-borabicyclo[3.3. llnonane butyl

DCC

dicyclohexplcarbodiimide

DDQ DMA DMF Et HMPA Me

2,3-dichloro-5,6-dicyanobenzoquinone d imethylaceta m ide di methy I f or ma m ide ethyl hexa met hy Ip h o sp ho ram ide ( hexa met hy I ph0spho r ic t r iamide) methyl methanesulfonyl N-bromoacetam ide N-bromosuccinimide N-c hIo r o w cc inim ide Raney nickel N-iodosucci ni m ide phenyl

Bu

Ms N BA NBS NCS Ni NIS Ph Pr PYr TH F TH P Ts

ProPYl pyridine tetrahyd rof u ran tetra hydropyra nyl p-toluenesulfonyl

vii

-.X

3

2

12 4

5 Miscellaneous compounds 15 5

Olefins 14

Nitriles

Ketones

Hydrides (RH)

Halides,sulfonates,sulfates 10

Ethers, epoxides

Esters

Amines

Amides

Alkyls, methylenes, aryls

Aldehydes 4

acid halides,anhydrides 1 Alcohols, phenols

Acetylenes

1 1 Carboxylicacids, 2

Sections-heavy type Pages-light type

29 23 30 24

23 13 24 15 25 16 26 18 27 20

16 7 17 8 18 10 19 11 20 12 21 13

45 45 46

4.4

41

37 32 38 32 39 34 40 36 41 38 42

31 28 32 29 33 30 34 31

58 65 59 66 60 66

64

54 61 55 61 56 63 57

46 53 47 53 48 55 49 57 50 59 51 59 52 60

76

74 79

72 77

69 73 70 73 71

71 65 72

64

62 70 63 71 84

88 89 89 90

88

85

81 85 82 86 83 87

79 84

77 82 78

99 98 100 99 101 101 102 101 103 102 104 103 105 104

114 118 115 119 116 121 117 122 118 124 119 124 120 125

117

106 108 107 108 108 113 109 115

96 95 97 112 96 117 113

91 92 92 92 93 92 94 94

INDEX, MONOFUNCTIONAL COMPOUNDS

152 146 153 146 154 148

156 149 142 157 141 149 158 150 129 144 159 131 141 150 130 145 160 132 141 151 131 146 132 142 132 162 132 152 163 153 134 149 133 144 135 150 165 135 145 154

137 136 123 138 127 137 124 130

166 155 167 156 168 157 169 159 170 160 171 161 172 161 173 162 174 162 175 163 176 167 177 168 178 174 179 175 180 178

199

200

Blanks in the table correspond to sections for which no additional examples were found in the literature.

Sect. Acetylenes 15A Carboxylic acids 30A Alcohols, phenols 45A Aldehydes 60A Amides 90A Amines 105A Esters 120A Ketones 180A Olefins 210A

1-1

186 187 187 202 188 199 203 200 204 200 190 205 188 201 191 206 189 204 192 207 189 204 193 190 209 208 195 210 191 211

184 186

182 185

196 193 197 194 198 195 199 197

67 90 105 126 181 211

47

5 26

Pg.

INDEX, DIFUNCTIONAL COMPOUNDS Sections-heavy Pages-light

302 218 303 220 304 222

313 241 314 246 315 248

type

type

323 276 324 333 284 317 325 287

225 256 298 322 336 346 358 382

309 320 330 339 347 354 360 365 369 372 228 260 302 324 337 348 362 384 394 405 231 269 311 327 340 352 372 387 400 414 428 311 322 332 341 349 356 362 367 371 374 376 377 231 270 312 328 340 353 374 388 400 417 430 432

Blanks in the table correspond to sections for which no examples were found in the literature.

xi

HOW TO USE THE COMPENDIUM Preparation of Monofunctional Monofunctional ComDounds

1

Compendi u m Volume 1

Protection of Monofunctional Compounds

1 I

page xi

1

-

1

Compendium Volume 2

rn

Section and page with examples

1 I

Section

and page

with examples

=t

Basic details

References

literature Original L

Index page ix

page xi

I)

Preparation of Difunctional Compounds

details

I$Authors

I

Further references

B Perform reaction

I

I

INTRODUCTION Relationship Between Volume 1 and Volume 2. Compendium of Organic Synthetic Methods, Volume 2, presents more than 1000 examples of published methods for the preparation of monofunctional compounds, updating the 3000 or so in Volume 1. I n addition Volume 2 presents a new chapter with about 1000 examples of the preparation of difunctional compounds. Methods for the protection of carboxylic acids, alcohols, phenols, aldehydes, amines, and ketones were included in Volume 1. I n Volume 2 protective methods for acetylenes, amides, esters, and olefins are also covered. The same systems of section and chapter numbering are used in the two volumes. Classification and Organization of Reactions Forming Monofunctional Compounds. Examples of published chemical transformations are classified according t o the reacting functional group of the starting material and the functional group formed. Those reactions that give products with the same functional group form a chapter. The reactions in each chapter are further classified into sections on the basis of the functional group of the starting material. Within each section reactions are listed in a somewhat arbitrary order, although an effort has been made t o put chain-lengthening processes before degradations. The classification is unaffected by allylic, vinylic, or acetylenic unsaturation, which appears in both starting material and product, or increases or decreases i n the length of carbon chains: for example, the reactions t-BuOH + f-BuCOOH, PhCHzOH --z PhCOOH and PhCH = CHCHzOH -+ PhCH =CHCOOH would all be considered as preparations of carboxylic acids from alcohols. The terms hydrides, alkyls, and aryls classify compounds containing react. ing hydrogens, alkyl groups, and aryl groups, respectively: for example, RCHz-H-+ RCH,COOH (carboxylic acids from hydrides), RMe -+ RCOOH (carboxylic acids from alkyls), RPh -+ RCOOH (carboxylic acids from aryls). Note the distinction between R2C0 + R2CH2 (methylenes from ketones) and RCOR’ 3 RH (hydrides from ketones). The following examples illustrate the application of the classification scheme t o some potentially confusing cases: RCH = CHCOOH RCH =CH, ArH

(hydrides from carboxylic acids) (carboxylic acids from hydrides) (carboxylic acids from hydrides)

RCH = CH2 RCH = CHCOOH + ArCOOH

4

4

xv

INTRODUCTION

xvi

ArH + ArOAc RCHO -+ RH RCH = CHCHO + RCH = CH, RCHO + RCH, R2CH2 + R2CO RCH2COR+ R,CHCOR RCH 5: CH2+ RCH,CH, RBr+RC=CH+RC=CR ROH

+ RCOOH + RCOOR

(esters from hydrides) (hydrides from aldehydes) (hydrides from aldehydes) (alkyls from aldehydes) (ketones from methylenes) (ketones from ketones) (alkyls from olefins) (acetylenes from halides; also acety. lenes from acetylenes) (esters from alcohols: also esters from carboxylic acids)

Yields quoted are overall; they are reduced to allow for incomplete conversion and impurities in the product. Reactions not described in the given references, but required to complete a sequence, are indicated by a dashed arrow. Reactions are included even when full experimental details are lacking in the given reference. In some cases the quoted reaction is a minor part of a paper or may have been investigated from a purely mechanistic aspect. When several references are given, the first refers to the reaction illustrated: others give further examples, related reactions, or reviews.

How to Use the Book to Locate Examples of the Preparation or Protection of Monofunctional Compounds. Examples of the preparation of one functional group from another are located via the monofunctional index on p. ix. which lists the corresponding section and page. Thus Section 1 contains examples of the preparation of acetylenes from other acetylenes: Section 2, acetylenes from carboxylic acids: and so forth. Sections that contain examples of the reactions of a functional group are found in the horizontal rows of the index. Thus Section 1 gives examples of the reactions of acetylenes that form other acetylenes; Section 16, reactions of acetylenes that form carboxylic acids: and Section 31, reactions of acety. lenes that form alcohols. Examples of alkylation, dealkylation, homologation, isomerization, transposition are found in Sections 1, 17, 33, and so on, which lie close t o a diagonal of the index. These sections correspond to such topics as the prepara. tion of acetylenes from acetylenes, carboxylic acids from carboxylic acids, and alcohols and phenols from alcohols and phenols. Examples of name reactions can be found by first considering the nature of the starting material and product. The Wittig reaction, for instance, is in Sec. tion 199 on olefins from aldehydes and Section 207 on olefins from ketones. Examples of the protection of acetylenes, carboxylic acids, alcohols, phenols, aldehydes, amides, amines, esters, ketones, and olefins are also indexed on p. ix.

INTRODUCTION

xvii

The pairs of functional groups alcohol, ester: carboxylic acid, ester: amine, amide; carboxylic acid, amide can be interconverted by quite trivial reactions. When a member of these groups is the desired product or starting material, the other member should, of course, also be consulted i n the text. A few reactions already presented i n Volume 1 are given again in Volume 2 when significant new publications have appeared. In such cases the starting material and product are shown in a contracted form: for example, ROH instead of PhCH2CH20H. The original literature must be used t o determine the generality of reactions. A reaction given i n this book for a primary aliphatic substrate may also be applicable t o tertiary or aromatic compounds. The references usually yield a further set of references t o previous work. Subsequent publications can be found by consulting the Science Citation Index. Classification and Organization of Reactions forming Difunctional Compounds. This new chapter considers all possible difunctional compounds formed from the groups acetylene, carboxylic acid, alcohol, aldehyde, amide, amine, ester, ether, epoxide. halide, ketone, nitrile, and olefin. Reactions that form difunctional compounds are classified into sections on the basis of the two functional groups of the product. The relative positions of the groups do not affect the classification. Thus preparations of 1,2-arninoalcohols, 1,3aminoalcohols and 1,4-aminoalcohols are included i n a single section. It is recommended that the following illustrative examples of the classification of difunctional compounds be scrutinized closely. Difunctional Product

Section Title

RC E C-C CR RCH(0H)COOH RCH(COOH)CH,COOMe RCH(0Ac)COOH RCH = CHOMe R CH (0Me) RCHF2 RCH (Br) C H?F RCH(OAc) CH,OH RCH(0H)COOMe RCOCOOEt RCOCH,OAc RCH = CHCH,COOMe RCH = CHOAC RCH(Br)COOEt RCH(Br)CH,OAc RCH = CHCHzCH= CH2

Acetylene-Acetylene Carboxylic Acid-Alcohol Carboxylic Acid-Ester Carboxylic Acid-Ester Ether-0 lef in Ether-Ether Halide-Halide Halide-Halide Alcohol-Ester Alcohol-Ester Ester-Ketone Ester-Ketone Ester-Olefi n Ester-Olefi n Ester-Halide Ester-Halide Olefi n-0 lef i n

,

xviii

INTRODUCTION

How to Use the Book to Locate Examples of the Preparation of Difunctional Compounds. The difunctional index on p. xi gives the section and page corresponding to each difunctional product. Thus Section 327 (Alcohol-Esterj contains examples of the preparation of hydroxyesters; Section 323 (Alcohol -Alcohol) contains examples of the preparation of diols. Some preparations of olefinic and acetylenic compounds from olefinic and acetylenic starting materials can, in principle, be classified in either the monofunctional or difunctional sections; for example, RCH =CHBr + RCH = CHCOOH, Carboxylic acids from Halides (monofunctional sections) or Carboxylic acid-Olefin (difunctional sections). In such cases both sections should be consulted. Reactions applicable to both aldehyde and ketone starting materials are in many cases illustrated by an example that uses only one of them. Many literature preparations of difunctional compounds are extensions of the methods applicable to monofunctional compounds. Thus the reaction RCI + ROH can clearly be extended to the preparation of diols by using the corresponding dichloro compound as a starting material Such methods are not fully covered in the difunctional sections. The user should bear in mind that the pairs of functional groups alcohol, ester; carboxylic acid, ester; amine, amide; carboxylic acid, amide can be interconverted by quite trivial reactions. Compounds of the type RCH(OAc)CH,OAc (Ester-Ester) would thus be of interest to anyone preparing the dial RCH(OH)CH?OH (Alcohol-Alcohol).

Compendium of Organic Synthetic Methods, Volume2 Edited by Ian T. Harrison, Shuyen Harrison Copyright 0 1974 by John Wiley & Sons, Inc.

PR E PARATIO N

Chapter 1

OF

AC ETY LE N ES

Section 1

t-BUCECH

Section 2

FOOMe (CH2)4COOH

Section 3

Acetylenes from Acetylenes

00000000000000000000000000

1 Ph3B

BuLi

2 I2 Et2O

THF

*

83%

t-BUCECPh JACS (1973)

95 3080

Acetylenes from Carboxylic Acids

P 000

C8H17CEC(CH2)3COOH e l e c t r o l y s i s MeOH

COOMe I

*

( C H ~ ) ~ C - C C ~7H I JCS (1955) 2218

Acetylenes from Alcohols

P

No additional examples

1

24%

2 Section 4

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 8

Acetylenes from Aldehydes

000000000000000000000000

CfCH

or BuLi T e t r L e t t (1972) 3769

CH=CH2

Br2 cc14 2 NaNH2 NH3

Et20

CECH

*

J Med Chem (1972)

Section 5

Acetylenes from Alkyls, Methylenes and Aryls

00000000000000000000000000000000000000000000

No examples

Section 6

Acetylenes from Amides

0000000000000000000000

Yo examples

Section 7

Acetylenes from Arnines 0000000000000000000000

140 a d d i t i o n a l examples

Section 8

Acetylenes

%ram Esters

P

No a d d i t i o n a l examples

Me

2 1262

48%

SECTION 10 Section 9

ACETYLENES FROM HALIDES

3

Acetylenes from Ethers 0000000000000000000000

No examples

Section 10

Acetylenes from Halides

P

Examples o f the conversion o f dibromides into acetylenes are included in section 14 (Acetylenes from Olefins)

1 Mg E t 2 O THF

OMe

2 coc12 3 ClCH=CC12

8 bMe

55%

c-c Me6

Synthesis (1972) 38

1 Li

Me

THF

4 Base

RBr

NaCXH NH3

<48%

2 CuBr E t e O 3 ICXSiMe3 Tetr Lett (1972) 5209

RCXH Org Synth (1963) Coll Vol 4 117 Angew (1959) 71245

Rec Trav Chim (1965)

84 31

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

4 Section 11

SECTION 13

Acetylenes from Hydrides 000000000000000000000000

No examples

For examples o f the reaction R C I C H + R C I C - C X R ' see section 300 (Acetylene

Section 1 2

PhCOCH2Me

-

Acetylene)

Acetylenes from Ketones

oooeooooooooooooooooooo

1 NH2CONHNH2 _____t

2 Se02 HOAc

P hC ICMe

3A

49%

Angew (1970) 484 Internat Ed 9 464 Chem Comm (1971) 1059

-7%

Section 13

No examples

Acetylenes from Nitriles

OOooOOOoOoOOooOoOOOOoooo

S e c t i o n 14

5

PROTECTION OF ACETYLENES

S E C T I O N 15A

Acetylenes f r o m O l e f i n s

00000000000000000000000

Tetrahedron (1970)

S e c t i o n 15

2637

Acetylenes f r o m M i s c e l l a n e o u s Compounds 000000000000000000000000000000000000000

CrS04

PhC = CPh I 1 Br B r

26 2127

DkIF

PhCXPh

H20

JACS (1964)

CH20Ms

86

4603

CH

I

111

c=o

C

TsNHNH2

KOAc

50%

HOAC CHzC12 Helv (1970)

AcO

S e c t i o n 15A

RCXCHZfHMe OH

53 171

Protection o f Acetylenes 000000000000000000000000

c02 (C0)g

7:CCHZFHMe OH Co (CO)3

u (CO)3Co

Fe( N0)3-9H20

96%

***,.

l ~ t l l l l

( S t a b l e t o B2H6, d i i m i d e and a c i d )

EtOH

Tetr Lett (1971) 3475

COMPENDIUM O F ORGANIC S Y N T H E T I C METHODS VOL 2

6 Me I CCH2C=CHCZCH ill CCHz:=CHCXH Me *

1 EtMgBr THF Me3SiCl * 1 AgN03 EtOH 2 KCN

H20

Me I C C H 2 C = C H C X S i Me3 ill C C H 2 IC = C H C X S i M e 3 Me ( S t a b l e t o a c i d , NaH Wittig reagents and H 2 / P d ) Rec Trav Chin (1967) 1138 JCS Perkin I (1972) 3 6 1 JACS (1968)

90 5618

Tetrahedron (1972)

I

\

.

j

+

Acid

I

NaOH

S E C T I O N 15A

C:CCHO

MeOH JCS

C

(1969) 2173

8 4591

4601 5221

Compendium of Organic Synthetic Methods, Volume2 Edited by Ian T. Harrison, Shuyen Harrison Copyright 0 1974 by John Wiley & Sons, Inc.

PR E PARATIO N OF CARBOXYLIC ACIDS ACID HALIDES AND ANHYDRIDES

Chapter 2

Section 16

Carboxylic Acids from Acetylenes

00000000000000000000000000000000

92% 3 ti2

-

t BLICr C ti

Pd-C

Ru02 NaOCl CC14

H20

EtOH

*

JCS (1963) 775

(1965) 894

60%

t-BuCOOH Tetr Lett (1971) 2941

80%

JACS (1973)

7

95 1296

a Also v i a :

Section 17

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 17

Section 106 76 320 360 322 362 301

Esters Amides Ketoacids Ketoesters Olefinic acids Olefinic esters Acetylenic a c i d s

Carboxyl i c Acids, Acid Halides and Anhydrides 000000000000000000000000000000000000000000000

f r o m Carboxylic Acids 000000000000000000000

RCH2COOH

1 NaH 2 RBr

(i-Pr)zNLi

THF

w

RFHCOOH R Org Synth (1970) 50 5 8 JOC (1972) 3 4.51-

Carboxylic Acids may be a l k y l a t e d and homologated v i a ketoacid, k e t o e s t e r and o l e f i n i c a c i d i n t e r m e d i a t e s . See s e c t i o n 320 (Carboxylic Acid Ketone), s e c t i o n 360 (Ester - Ketone) and s e c t i o n 322 (Carboxylic Acid Olefin)

Chem Comm (1971) 10

SECTION 17

CARBOXYLIC ACIDS, ACID HALIDES AND ANHYDRIDES FROM CARBOXYLIC ACIDS

C14H2gCH2COOH

1 SOC12 2 PhH ~1 CI 3

C14H2gCH2COPh

1 i-PrCH2CH20NO HC1 dioxane 2 TsCl NaOH 3 KOH PrOH

C14H2gCOOH

9

63%

JACS (1953) 2347 J O C (1961) 2 3507

C7H15COOH

M e C X H Hg(@Ac)2 BF3-Et20 CHzC12

* C7H15COO:=CH2

tiF 4

Me

J O C (1969)

C7H15COF

35%

2 2486

70%

RCOOK

PhCOOH

SDC12 Pyr

RCOCl

CH2C12

Can J Chem (1968) 46 2549 JACS (1963) 85 643-

(MezN)3P CCl4

t

(PhC0)zO

90% B u l l Soc Chim F r (1971) 3034

65% T e t r L e t t (1972) 3281

10

Section 18

Me

PrOH

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

Carboxylic Acids from Alcohols

000000000000000000000000000000

2 Hydrolysis

Ele

HO

Chem Comm (1970) 1513 1512

CN NCOOEt bH2COOEt k O O E t

CN PrLHCOOEt

Ph3P THF

Hydrolysis ---------+ PrCH2COOH

C6H6

*

C6H13COOH

JACS (1972)

JOC (1972)

KOH

245-255'

< 52%

Tetr Lett (1972) 1279

KMn04 dicyclohexyl-18-crown-6

CgH13CH20H

RCH20H

SECTION 18

*

94 4024

37

1947

RCOOH JACS (1948)

70 3485

70%

SECTION 19

f;1 e t-BUCHCHOH I Et

Br2 NaOH H20

t-BufHCOOH Et

*

38%

JACS (1950)

Section 19 CgH13CHO

11

CARBOXYLIC ACIDS AND ANHYDRIDES FROM ALDEHYDES

12 3701

Carboxylic Acids and Anhydrides from Aldehydes

!

CHz=CH(CH2)8COOEt

* CgH13CO(CH2)10COOEt

dibenzoyl peroxide

N2H4 KOH

diethylene glycol

CgHl3(CH2)11 COOH

Rec Trav Chim (1953)

2 84

Chem Corn (1972) 526 Ber (1973) 106 2277

CgH11CHO

m-Chloroperbenzoic acid THF

C5h'11COOH

2 291

JACS (1967)

PhCHZCHCHO

- - +PhCH=CHC\H

S

1 BuLi 2

WeSSMe

PhCH=CHC:Me>

-

/s

HgC12 HgO

Me2CO H20

S

PhCH=CHCOOH J O C (1972)

37

2757

< 86%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

12

K1Y1nO4 dicyclohexyl-18-crown-6

PhCHO

SECTION 20

PhCOOH

k

C6H6 JACS (1972)

94 4 0 2 4

Related methods: Carboxylic Acids from Ketones (Section 27)

Also v i a :

Esters Ani des Ketoacids Ke t o e s t e r s Olefinic acids Olefinic e s t e r s O l e f i n i c amides Acetylenic acids

PhCOO2Bu-t

PhCHO

Section 109 79 320 360 322 362 349 301

CuBr

(PhC0)zO

/

70% J O C (1960)

Section 20

25

899

Carboxylic Acids from Alkyls

0000000000000000000000000000

CH3 KMn04 dicyclohexyl-18-crown4 Me

Me JACS (1972)

CH3

02 Co(0Ac)p HBr

Br

HOAC

94 4 0 2 4

*

91 I Can J Chem (1965) 5 1306 Chem Corn (1971) 1166 J O C (1972)

31 2 5 6 4

13

CARBOXYLIC ACIDS FROM ESTERS

SECTION 23

80% JOC (1965) 2 3520 JACS (1965) 2523

Section 21 Et3CCONH2

Carboxylic Acids from Amides 00000000000000000000 0 0 0 0 0 0 0 0 rial402 H2SO4 H20

t

Et3CCOOH

>80%

M. S. Newman, S t e r i c E f f e c t s i n Organic Chemistry (J. Wiley 1956) 228 f o o t n o t e 73

Section 22

Carboxylic Acids, Acid Halides and Anhydrides from Amines

D a O D o O O O O D O O O O O O O D D o o o o o o o o o o o ~ o o o o o ~ ~ o o o o o o o ~ o0o0o0 0 0 0 0

No additional examples

NaHCO1-NaOH

(PH 1 1 )

92% Ber (1972)

105 1778

14

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

(i-Pr)3CCOOMe

1,5-Diazabicycl0[4.3.O]nonene

xyl ene

*

SECTION 23

( i-Pr)3CCOOH

94%

T e t r L e t t (1972) 3987 J O C (1973) 38 1223

LiI

PhCOOMe

NaCN DMF

*

PhCOOH

Me

Synth C o r n (1972)

2

389

Me 91 % J Am Oil Chem SOC (1956) J O C (1964) 2 1252

(CH2)6COOEt OH

CH=CHyHC5H11 OH

317

- b

(CH2)6COOH

Baker's yeast pH 7.0

33

01.1

JACS (1972)

CH=CHyHC5H11 OH

94 3643

90%

Chem Corn (1971) 667

15

CARBOXYLIC ACIDS FROM ETHERS

SECTION 24

COOH

COOMe MeS03H HCOOH

+

99% COOH

COOMe

Chem Ind (1964) 193

C17H35COOMe

Ph3P.HBr

170-180"

62%

C17H35COOH Annalen (1967)

RCH2COOEt

1 PhMgBr

Et20

t

2 220-230'

RCH=CPh2

709

Cr03

HOAc

H20

JCS (1957) 1622 (1953) 1785

S e c t i o n 24

COOH (LHz)$H2@Et

Carboxyl i c A c i d s f r o m E t h e r s

O00O000000000000000000000000

KOH

360'

COOH (LH2)$OOH JCS

(1971) 1840

105

RCOOH

COWPENDIUN OF ORGANIC SYNTHETIC METHODS VOL 2

16 Section 25

fr

Carboxylic Acids from Halides

OOOOOOOOOOOOOOOOOOOOODOOOOOOO

1 Mg

c

(FH2)9 Br

~ ~~0 s ~(CH2) , ~ 4COOH * ( y 9

1 H

FO(CH2)3CONHMe

EtzO

($H2)9

C)ONMe

N2H4 (CH2)4COOH Na-ethyl ene glycol Chem Listy (1958) 52 1926 (Chem Abs 53 3055)-

\*'

CH(C00Et)2 2 A

W

JOC (1971) (1972)

fi

1 LiCH7CXN'

2 Acid alumina

c

BuCH~CH~CON

36

37

ethylene glycol

C

O

O

H

35%

3260 825

KOH

z

OMe

OMe

) - - Y

N12%

CO( CH2)3CONHMe

CH2C1 21 Mg Me2C=C(COOEtYZ Et20

Bu I

SECTION 25

B u C H ~ C H ~ C O O H -20%

JOC (1970) 35 3405

CH2=CC12 H2SO4

RC1

BF3

*

RCH2COOH

Ber (1967)

(3ryI

BuBr

NaCECOEt

NH3

BuCXOEt

1 HgO H2SO4 2 NaOH E t O H

EtOH

*

100 978

17%

BuCH2COOH

JCS (1954) 1860 Advances in Org Chem (1960)

2

117

CARBOXYLIC A C I D S FROM HALIDES

SECTION 25 PhCH2C1

decal i n

NaCH2COONa

PhCH2CH2COOH

*

34%

Annalen (1966)

Rar

CH2(COOEt)2

EtONa

EtOH

*

RCH(C0OEt)z

1 KOH

EtOH

2 HC1 H20

CH2( COOEt ) 2 EtONa

EtOH

PhCH=CHCHzCH(C0OEt)p

691 61

RCH2COOH

a 3944

JOC (1971)

PhCH=CHCH$l

17

1 C5H11ONO EtONa 2 Ac20

PhCH4HCH2COOH

3 KOH JCS (1950) 926

C12H25Br

1 Na2Fe(C0)4 o2 THF *

C12H25COOH

84%

95 249

JACS (1973)

PhF

L i t h i u m d i hydronaphthyl i d e

*

co2

PhLi

PhCOOH

Chem Conm (1972) 752

CH2C1 RS02

1 (NH4)2S, 2 HC1 H20

H20

180"

*

RS02

Ber (1971)

104 1697

48%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2 Section Esters 115 85 Ami des Ketoacids 320 Ketoesters 360 Olefinic acids 322 Olefinic esters 362 Acetylenic a c i d s 301 Acetylenic e s t e r s 306

18

Also v i a :

SECTION 26

Carboxylic Acids from Hydrides

Section 26

000000000000000000000000000000

Reactions in which a hydrogen i s replaced by carboxyl or a carboxyl c o n t a i n i n g chain a r e included i n t h i s s e c t i o n . For r e a c t i o n s i n which alkyl groups a r e oxidised t o carboxyl s e e s e c t i o n 20 (Carboxylic Acids from A1 kyl s )

ye

i-PrCH

tie

1 (CN)p

Me

dibenzoyl peroxide

*

2 H2SO4 H20 3 NaOH H20

i -PrkOOH

Me JACS (1969)

CH3

* j y CH2COOH

1 BuLi .Me2NCH2CH2NMe2 2 co2

Me

Me

JACS (1972)

Me PhH

91 3028

c i ~ = C H C O O H ~1CI 3

*

94 4298

Me Ph2kH2COOH JACS (1943)

36%

65 59

19

CARBOXYLIC ACIDS FROM HYDRIDES

SECTION 26

Me

T e t r a h e d r o n (1967)

LUL I

\cocooH

1 6OOEt AlC13

*

2 NaOH

~ 2 ~ 4QCH2cooH

OH

CS2

KOH

2 1029

COCH2C1

H*O'/

1 Pyr.

m C O O H OH

2 NaOH H20 T e t r a h e d r o n (1970)

26

44%

201

Me

Me (COCl)*

Me

75%

d

J Med Chem (1972)

C1 CH2COC1 A l C13

2 2481

AlC13

Cs2

65-76%

Me Org S y n t h (1964)

5 69

20 PhH

COMPENDIUM

C1 COSEt

A l C13

t

-

OF ORGANIC SYNTHETIC METHODS VOL 2

PhCOSEt

Hydro1y s is

PtiCOOH

Annalen (1972)

JOC (1962)

PhH

T1C14-4H20

CCl4

PhCOOH

SECTION 27

76177

-

49%

3578

JCS Perkin I (1972) 2268

10%

A l s o via: E s t e r s ( S e c t i o n 116)

S e c t i o n 27

Me2CO

C a r b o x y l i c A c i d s f r o m Ketones 000000000000000000000006000000

1 CH2(COOEt)2

L Me3CCH(COOEt)2

ZnC12 Ac20

&' 2 MeMgI Et2O

\

----------- + 2 A

Ke3CCH2COOH

Org Synth (1970)

CuCl

;ttIcN c1

1 Hydrolysis

t-BuOK

38

0-0: 1 Bc13 Et20

\

2 A1203

3 KOH

\ Et2O

JOC (1967) 3 2 689

14%

21

CARBOXYLIC A C I D S FROM KETONES

SECTION 27

03 0

HO

1 0

CN

COOH

1 N a H S 0 3 1 0 1 SOC12 P y r

112 P c C l o /

___)

2 KOH 1129 d i e t h y l ene glycol JOC (1970)

2 KCW

COOH

EtOH

35

2376

.bCHCHo Me I

co

1 Ph3P=CHOMe E t 2 0

cr03

2 H2SO4

Me2CO

dioxane

J Med Chem

COMe

--

~ 2 ~ 0 4\ Y t H C O O &

2 1337

(1972)

COCH2COOEt

(Et0)zCO

A

CH2CH2COOH

1 H2

NaH CgHg

1s,s TH F 2 TSOH

BuLi CgHg

Pt02

A

r__

*

HOAc 2 NaOH E t O H H20

JOC (1972)

0

Me

. If)

c

37

2055

HC1

HOAc

H20

J Med Chem (1972)

15 1297

COOH

54%

COMPENDIUM

22

OF ORGANIC SYNTHETIC METHODS VOL 2

n ss

PhCO

MegSi K L i

I

*

Hg2+

----- +

PhC4f-J 1

PhCHCOOH I

s

Me

Me

SECTION 27

Me Chem Corn (1972) 526 Ber (1973) 2277

106

NH40H \ b N HoocJF;- j !2; ; ;N 2

NOH NaOCl NaOH

MeOH JACS (1972)

RCOMe

Brp

NaOH

dioxane

< 22%

94 1282

RCOOH JOC (1972) 37 25 Annalen (1971) 747 14 T e t r a h e d r o n (1972) 28 3381

"20

Na2Cr207'2H20 HOAc

Org Synth (1960) C o l l Vol 3 420

&

-

AcO."'

H

PhCHO

1 03

EtOAc +

2 Zn

HOAc

JACS (1956)

78 1414

/fi56%

RCOPh

-

OLEFINS

CARBOXYLIC ACIDS FROM

SECTION 29 t-BuOK

H20 a n i s o l e

150"

C14H2gCH2COPh

RCOOH

i-PrCH2CH20NO HC1

dioxane

H20

Eer (1971)

C14H2gCCOPh

'' NOH

104 2637

1 TsCl

S e c t i o n 28

NaOH H20

2 KOH PrOH

JACS (1953)

Also via:

23

2 2347

Section 117 320 360 347

Esters Ketoacids Ketoesters Ketoamides O l e f i n i c acids Olefinic esters O l e f i n i c amides

322

362 349

Carboxylic Acids from N i t r i l e s

OOOOOOOOOOOOOOO0OOOOODOOOOOOOOO

No a d d i t i o n a l examples

S e c t i o n 29

RCH=CH2

Carboxylic Acids from O l e f i n s

00000000000000000000000000000

CH3COOH di-t-butyl

RzC=CHz

CH2=CC12

*

R ( CH2)3COOH

peroxide

BF3

H2SO4

+

Synthesis (1970) 99 Chem Comm (1973) 694

R2CCH2COOH Me

Eer (1967)

100 978

C14H2gCOOH

24

COMPENDIUM

CsH13CH=CH2

1 CH(N02)3

OF ORGANIC SYNTHETIC METHODS VOL 2 H g ( N 0 3 ) ~ HClO4

CgH13CHCOOH i Me

MeOCH2CH20Me H20

2 NaBH4 NaOH THF

3 KMnO4 NaOH H20

SECTION 30

A c t a Chem Scand (1970)

2 550

63%

JOC (1973)

R2C=CH2

1 NaBH4 A l C l 3

diglyme t

2 H202 NaOH H20

PhCH=CHPh

S e c t i o n 30

MeCH=CHCOOH

CrO3 H2SO4 _____f

HOAc

H20

JACS (1960)

KMnO4 d i c y c l o h e x y l -la-crown-6 CgH6

Also via:

R2CHCH20H

2 2016

*

Esters Olefinic esters

53%

2498

100%

PhCOOH

JACS (1972)

R2CHCOOH

2 4024

Section 119 362

C a r b o x y l i c A c i d s f r o m M i s c e l l a n e o u s Compounds 000000000000000000000000000000000000000000000

EtMgBr

Et20

+

MeCHCH2COOH I Et J A C S (1953)

40%

75 6342

SECTION 30

1 Li

PhCH=CHCOOH

HMPA

PhCH2CHCOOH

2 Me1

63%

I

Me Compt Rend (1969)

-

R2C=yCOOH

R

J O C (1971)

WaI04

Me2S04

3

1151

J Med Chem (1965)

NiClz-KCN-NaBH4

N2H4

C 268 640

R2CHFHCOOH R

Li-NH3 Na-Hg

PhCXCOOH

25

CARBOXYLIC ACIDS FROM MISCELLANEOUS COMPOUNDS

S

598

T e t r L e t t (1968) 1821

CuSO4

HOAc

H20

*

85%

PhCH2CH2COOH Chem Corn (1971) 1245

J O C (1971)

1151

80-85%

CgH1 3CH=CHCOOH

KOH 3 6 0 '

CsH13COOH Tetrahedron (1960)

N

8

221

80%

COMPENDIUM

26 S e c t i o n 30A

RCOOH

OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 30A

P r o t e c t i o n of C a r b o x y l i c A c i d s

~00000000000000000000000000.a00

DCC

CC13CH20H

u Zn HOAc

RCOOCH2CC13

L

H20

JOC (1970)

J

35 36

2430 1259 Med Chem (1971) (1971)

S e l e c t i v e removal o f h a l o e t h o x y groups by e l e c t r o l y s i s

JACS (1972)

RNH 0 f i 2 C O O ‘2 K

MezSiClp CH2C12

14 420

426

2 5139

[/r2coj

PhNMe2

SiMe2

2 I

H20

Rec Trav Chim (1970)

1 C1 COOEt RNH 0’f13cOOK

2 PhCH-NOH

Me$O

*

‘ T \ NEt3

NaI

( o r PhSH)

Me2CO

JCS C (1971) 1917

89 1081

27

PROTECTION OF CARSOXYLIC ACIDS

SECTION 30A

Me

Tetr Lett (1973) 2205

C15H31COOH

--+

C15H31COC1

i-PrNHNHPr-i +

c6 H6 Pb(OAc)4 Pyr

RCOOH

.

k.

1 HN

DCC

2 H2SO4 Et2O

.

_-_-_-____----_Acid

C15H31 C0P;INHPr-i i -Pr /

JCS Perkin I (1972) 929

( S t a b l e t o RMgX and LiAlH4) Tetr Lett (1972) 3031

Other r e a c t i o n s useful f o r t h e p r o t e c t i o n o f carboxylic a c i d s a r e included i n s e c t i o n 107 ( E s t e r s from Carboxylic Acids and Acid Halides) and s e c t i o n 23 (Carboxyl i c Acids from Esters)

Compendium of Organic Synthetic Methods, Volume2 Edited by Ian T. Harrison, Shuyen Harrison Copyright 0 1974 by John Wiley & Sons, Inc.

PRE PARATIO N OF ALCOHOLS AND PHENOLS

Chapter 3

Section 31

PrCXH

Alcohols from Acetylenes

000000000000000000000000

1 Me

THF

t

2 MeLi Et20 3 CH2=CHCH2Br

OH Synthesis (1973) 37

4 NaOH H202 H20

Et:HCXH Me

1 NaOBr CuC12 EtNH2

Also via:

* EtCH(CX)2CH20H

2 HCiCCH20H

NH2OH

84%

PrCH2yHCH2CH=CH2

he

Acetylenic alcohols Olefinic alcohols

H2 Pt02

EtOH J O C (1971)

Section 302 332

28

EtCH(CH2)4CH20H Me

36

2902

55%

SECTION 32 Section 32 BuCOOH

ALCOHOLS FROM CARBOXYLIC ACIDS Alcohols from Carboxylic Acids 000000000000000000000000000000

C5H11MgBr Et20 CgH6

*

YgH1l BuFOH

40-60%

‘SH1 1 J A C S (1946)

Ph(CH2)2COOH

CF3CH20H

(cF3co)20

Ph(CH2)2COOCH2CF3

CH2CooH 1 ClCOOEt Et3N

RCOOH

RCOOH

OMe

B2Hg THF

2 EtOMgCH(COOEt)2*

68 1382

NaBHq

MeOCH2CH20Me

J O C (1970)

Me0

29

\’

35

Ph(CH2)2CH20H

1505

CH2COCH(COOEt)2 baBH4 MeOH

v- 98

3040

38

2786

CH2CH20H

Ber (1965)

RCH20H

Electrolysis H2SO4 EtOH H20

Also via: Esters (Section 38)

J O C (1973)

RCH201-I

Synthesis (1971) 285

66%

30

COMPENDIUM

S e c t i o n 33

OF ORGANIC SYNTHETIC METHODS VOL2

SECTION 33

A l c o h o l s f r o m A l c o h o l s and Phenols J 52%

JOC (1950) JACS (1954)

54

76 52

Meoa +

JCS

-

C (1971)

3047

Tetr Lett (1973) 1619

PrCH20H

PhOH

--+

--+

PrCH200H

PhOPO(OEt)2

H2SO4

H20

CH2C12

MeCOCH2K K

NH3

< 60%

PrOH J O C (1970) jS 3080

< 42%

PhCH2:HMe OH JACS (1972)

94 683

Section 34

RCHO

Alcohols from Aldehydes

aoooo000o00000o0~0oo000

MeBr

PhCHO

31

ALCOHOLS AND PHENOLS FROM AMIDES

SECTION 36

1

Li THF

*

(One-step procedure)

RCHOH I Me

J C S Perkin I (1972) 1655

MeSooMe EtpNLi

2 Ni

THF

*

PhCHOH I

Me T e t r Lett (1972) 4605

Me i-PrCBH2

Me

C5H11 CHO

THF

*

C5H11CH2OH J O C (1972)

Related methods:

Also v i a :

Section 35

37

2942

Alcohols from Ketones (Section 4 2 )

Acetylenic a l c o h o l s Olefinic alcohols

Section 302

332

Alcohols and Phenols from Alkyls, Methylenes and Aryls

Y

No examples o f t h e r e a c t i o n RR' ---t ROH ( R ' = a l k y l , a r y l e t c . ) occur i n the l i t e r a t u r e . For r e a c t i o n s o f t h e t y p e RH --+. ROH (R=alkyl o r a r y l ) s e e s e c t i o n 41 (Alcohols and Phenols from Hydrides)

Section 36

Alcohols and Phenols from Amides 00000000000000000000000000000000

No a d d i t i o n a l examDles

50%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

32 S e c t i o n 37

ArNH2

SECTION 38

A l c o h o l s and Phenols f r o m Amines

D o o o o o o O o o o o0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

-

1 NaN02 HC1 H20

2 HPF6

CH2NMe2

5

t

-

1 Me2NCONMe2

ArN2 PF6

2 NaOH JOC (1963)

-

;t @CHzNMei t

Br

*

1 NaOAc

ArOH 568

HOAc

2 NaOH MeOH

Me

Org Synth (1963) C o l l Vol 4 582 w80%

Also v i a :

S e c t i o n 38

PhCH2COOEt

E s t e r s ( S e c t i o n 112)

A l c o h o l s from E s t e r s

-

00000000000000000000

Na

NH3

PhCH2CH20H

CaCl2-NaBH4 Me

Compt Rend (1913) 156 1020

THF

76%

COOEt

CH20H Chem Pharm Bull (1970)

NaB ( OMe ) 3H

CH20H t

MeOCHZCHzOMe

Can J Chem (1969) 47 2099

1908

SECTION 38 Pry=CHCOOEt Me

AlH3

THF

ALCOHOLS FROM ESTERS

33

PrC=CHCH20H rlte

74% T e t r L e t t (1973) 1277

92%

62%

Synthesis (1972) 391

Pd-C

200'

HC00C8H17

ROAc

HC1

MeOH

R e l a t e d methods:

ROH

'gH170H

JOC (1970) (1973)

Acta Chem Scand (1952)

C a r b o x y l i c Acids f r o m E s t e r s Protection o f Alcohols

94%

35 1694 2 3954

Section 23 45A

1127

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

34 Section 39

SECTION 39

Alcohols and Phenols from Ethers and Epoxides 000000000000000000000000000000000000000000000

OMe PPh3-HBr 170-180"

74% Annalen (1967)

EtSNa

ArOMe

DMF

ArOH

709 105

Tetr Lett (1972) 241

PhSK PhSH C5Hll

l b C s H I 1

d i e t h y l e n e glycol

(Applicable t o compounds with l a b i l e double bonds) JOC (1971)

:HZ

EI t

y 2

@$ Me 0

FOOH (CH2)gCH20Et

OMe

:;ylene 224"

KOH

200"

721

Et

< 55% HO

glycol+

-

36

JACS (1943)

COOH I (CH2)gCH20H

OH

9 11

26 %

ALCOHOLS AND PHENOLS FROM ETHERS AND EPOXIDES

SECTION 39

35

OCH2Ph

Na-K

pet ether

P

J O C (1965)

NH3 Et20

OH Me

JOC (1971)

,0- CH2 \

Me2CuLi

1610

CH20H

Na

RCH

30

-m

CH20CH2Ph

Related methods:

75%

&;:H2),,CH=CHR

36

70%

2035

Protection o f Alcohols and Phenols (section 45A)

EtpO

c

?H

RCHCHZMe J A C S (1970) 9 2 3813 JOC (1973) 3 8 4 2 6 3 4346

-44% Tetr Lett (1972) 4605

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

36

-

0

Na

/ \

MeCH- CHMe

NH3

-

0

Li

/ \

RCH-CHR

?H MeCHCHZMe JOC (1971)

36

SECTION 40

55%

330

OH

EtNH2

I

RCHCH2R

Synthesis (1972) 391

L i A l (OBu-t)3H

EtgB 100%

t e t r a hydropyra n JACS (1972)

Section 40

2 1750

Alcohols and Phenols from Halides and Sulfonates 00000000000000000000000000000 OOOOOOOOOOOOOOODOOO

C5H11B r

Mg --c C5H11MgBr

PrCOOH Et20

*

C6H6

f5H1 1 PrCOH I

JACS (1946)

ocl Li

PhCHO THF

40-60%

C5H11

68 1382

doH (One-step procedure)

JCS Perkin I (1972) 1655

60%

SECTION 40 i-PrCHzBr

ALCOHOLS AND PHENOLS FROM HALIDES AND SULFONATES

(y 1 Mg Et20

2

i-PrCHzCH=CH(CH2)30H

0 c1 3 Na Eta0

EtCHCH2Br 1 Mg Et20 I

Me

3 Na

C7H1gBr

1 Mg

Et20

--* g H g c l

Me

Me

HZ

14 236

Et$HCH2(CH2)40H

Pt02

Me

36%

JCS (1950) 2685

*

2 c02 3 NaAl (OCH2CHzOMe)2H2

gBr

HZ i-PrCHz(CH2)50H catalyst

JCS (1953) 98 J Med Chem (1971)

EtCHCH2CH=CH( CH2)zOH

Et20

-

37

C7H15CHzOH

85%

Coll Czech (1971) 2 2394

70%

21 Base BzH6 THF H202 H20 Me

Chem Corn (1971) 1475

51%

JACS (1969)

91 3544

38

SECTION 41

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

ArCH2C1

AgN03 Me2CO H20

*

ArCH20H

J O C (1971)

-

CF3COONa CI~H~~~H-FHCH~FH-FH(CH~)~B~ PhBr EtOH Br Br Br Br

2

79%

1765

C5H11:H-FHCH2:H-FH(CH2)70H Br Br Br Br

39%

Acta Chem Scand (1953) 1 1 0 0 1

78%

TsO T e t r Lett (1971) 4555 4559 B u l l Chem SOC J a p (1968)

41 3025

Also via:

01 ef inic alcohols

Acetylenic alcohols

Section 41

Secti on 332 302

Alcohols and.Phenols from Hydrides

y 2 ?H CCH2CHCH2Pr-i

0000000000000000000000000000000000

2 i-PrCH2CHO 0

/ \

2 CH2-CH2 MezNCHzCHzNMe2

Me 2 02

4 H20

JACS (1972) 2 4298 JOC (1972) 37 3543

SECTION 41

CH3, Me'

C=CHCHzMe

ALCOHOLS AND PHENOLS FROM HYDRIDES

K3Cr-08

MeOH

H20

OH

OH

+

CH2=CiHCH2Me

Me&CH=CHMe

Me JACS (1972)

c1

Ci

@

94 4348

c1

c1

c'@:;-

39

c,c1

u91%

CH20H c1

c1

JACS (1971)

93 3538

48% Me0 Tetr Lett (1968) 2917

@h9 MeC002H

HO

HOAc

10% HO

t-BuOH

JACS (1972)

94 6228

40

0

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2 PhNO2

SECTION 41

hy

____t

Chem Comm (1970) 1390

2 2

Me

Me

Me I CHCH20H

/O\

MeCH -CH2

AlCl3

CHzC12

Me

Me

6JMe H202

H202

HF

H20 AlC13

*

JACS (1972)

94 4241

@:; JOC (1971)

2 3184

H20

15% JOC (1970)

2 4028

SECTION 42 Also v i a :

Section 42

41

ALCOHOLS FROM KETONES Esters (Section 116)

Alcohols from Ketones 000000000000000000000

Conversion o f Ketones t o alcohols w i t h longer carbon chains.page 41-42 Reduction o f Ketones t o alcohols . . . . . . . . . . . . . . . 42-45

.

H20 JACS (1967)

R2CO

BuBr Li

THF

t

R2COH Bu

561

(One-step procedure) JCS P e r k i n I (1972) 1655

57% Chem Corn (1971) 351

53%

Ber (1972)

105 1978

42

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 42

-68% Tetr Lett (1972) 4605

@ @ -"

t

-

. vt=CH2 1le

Ph3PMe Br

F;1'

1 NaBH4 BF3.Et20* b C H C H 2 0 H

2 NaOH H202

NaH Me2SO

JACS (1972)

0

94 4 2 4 1

OH 1 Li

NH3 THF

2 PhCOONa Tetr Lett (1971) 1853

K-graphite

- OH

THF

Can J Chem (1972)

PhCO I

Me

NaAl (OCH2CH20Me)2H2

.

C6Hg

92% 3058

PhCHOH

90%

,

Me C o l l Czech (1969)

2 118

ALCOHOLS FROM KETONES

SECTION 4 2

L i A l (OMe)3H

0

clo

NaBH2S3 T H F *

PhCO he

NaBH3CN MeOH

pH

t

+&

43

THF

80%

Synthesis (1972) 217

UoH

Can J Chem (1970) 48 2366 Synthesis (1972) 526

93%

PhCHOH I

Me

90%

J.4CS (1971)

93 2897

OH

,@Jc o ~ ~ ~ ~ 2 0 NaBH4-CaC12 H

' P

NO2

EtOH

,@

~HFHCH~OH

NO2 Ber (1960) 3 387

NHAc

70%

44

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

JACS (1971)

SECTION 42

93 7319

Me LiB(hHEt)3H

THF

+

100% JACS (1972)

R2CO

R ' 2 S n H 2 or R ' 3 S n H

(99% c i s )

94 7159

R2CHOH S y n t h e s i s (1970) 499

[MeHsio]~

bis ( d i b u t y l a c e t o x y t i n )

t-Bu

R2CO

EtOH

IrCl4 i-PrOH

(Me0)3P

e

t

H20

65%

OH

t-Bu JOC (1973)

HC1

0 2 162

R2CHOH Org Synth (1970)

13

+ C9H19p Me

y 2 NH2=CS02-

EtOH H 2 0

NaOH c

CgH1gFHOH Me

74% T e t r L e t t (1972) 343 JCS P e r k i n I (1973) 2633

Related methods: Also via:

Section 43

45

ALCOHOLS FROM OLEFINS

SECTION 44

Alcohols from Aldehydes (section 34) Section 332 302

Olefinic alcohols Acetylenic alcohols

Alcohols and Phenols from Nitriles 0000000000000000000000000000000000

No examples

Section 44

Alcohols from Olefins 000000000000000000000

for the preparation o f diols from olefins see section 323 (Alcohol-Alcohol)

75%

3 (CF3C0)20 4 H202 NaOH

Chem Comm (1971) 1048

H20

JACS (1971) J O C (1973)

AlH3 THF

2 CO (70 atmos)

93 2070

38

3968

CSu-t

w

60%

Synthesis (1972) 197

EtCH=CH2

1 B2Hg THF

*

2 Br2 hV CH2C12 H20 3 H202 NaOH H20

76%

(EtCH2CH2)2FOH EtCH2 JACS (1971)

93 1 0 2 5

Synthesis (1972) 699

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

46

1 B2Hg THF

MezC=CHMe

3 Brp H2°2

hv

Me Me2CHFOH

b

2 MeOH CH2C12

Synthesis (1972) 303 304 699

H2°

1 BugB hv p - x y l e n e

8 2%

Me2CHCHMe

H20

EtoH

NaoH

C6H6

2 H202 base

*

80%

Tetrahedron (1973)

1 BH2Cl

29 2365

EtpO

2 NaOH H202 EtOH

H20

*

QMe

OH

JOC (1973)

Me

SECTION 45

38

182

1 NOCl 2 NaBH4

i-PrOH

H20 Aust J Chem (1971)

S e c t i o n 45

PhCH=CHCH20H

24 1089

A l c o h o l s f r o m M i s c e l l a n e o u s Compounds

0000D00000000000000000Do00000000000000

H2

nickel boride

EtOH

*

Ph( CH2)30H J O C (1971)

a 2018

100%

47

PROTECTION OF ALCOHOLS AND PHENOLS

SECTION 45A

OH

MeOH

HO

li

JOC (1971)

@QJs03H

2 2730

NaOH

Me

_L

M e

280-300"

Ber (1925) 58B 1211 JACS (1949) 21 3889

Ph2S

MeCOCH2K K NH3

*

I

JACS (1972)

Me

Electrolysis

Et CH2

S e c t i o n 45A

71 %

PhCH2CHOH

dioxane MeOH

t

Me4N OTs

94 683

-

*

47%

JACS (1971)

Me

2 5284

P r o t e c t i o n o f Alcohols and Phenols

OOOOOOOoOOOOOOOOOOOOooaooooooooooo

E s t e r s o f o r g a n i c and inorganic a c i d s . . . . . . Ethers . . . . . . . . . . . . . . . . . . . . . Tetrahydropyranyl e t h e r s , a c e t a l s a n d o r t h o e s t e r s

. . . page 48-49 .. .. .. .. .. 49-51 51-52

COMPENDIUM OF ORGANIC SYNTHETIC ClETHODS VOL 2

48

SECTION 45A

C8H17 C1 COOEt Pyr

*----------------

HO

RO H

Acid or base

C1 COOCH2CC13 Pyr

*

f

c1 OH210H

Ur I

CH2 HO~H

HO

-

ROCOOCH2CC13

El ec trol ysi s

94 5139

JACS (1972)

C1 COOCH2CH=CH2 Pyr

t

N i (CO)4

2 3309

J A C S (1952)

MezNCH2CH2NMe2 DMF

(PhCH2CH2CO)zO

Pyr

*

a-Chymotrypsin pH 7.8

C10H21 OCOOCH$H=CH2 JOC (1973)

38

3223 3575

Ur I

FH2 PhCH2CHzCOOCH PhCH2CH2COObH2

JOC (1973)

2 977

Zn NHqCl THF HzO J C S P e r k i n I (1973) 599

(Applicable to phenols)

SECTION 45A

W

HO HZ 0 HO

49

PROTECTION OF ALCOHOLS AND PHENOLS r

Ph3COCHzCOONa Pyr

Ph3COCH2COOCH2

*

GI

chloride tri isopropylbenzenesulfonyl

OTHP 4

NH3 MeOH

Can J Chem (1972)

1283

sc1 NO2 4

C1 CH2CH2C1

HO

>

A1-Hg MeOH or Ni EtOH

0s

'

l

*

Me2NCH2CH2NMe2 (Stable to MeLi, LiAl H4 KOH and d i 1 HC1)

JACS (1972)

ooH Me

2 301

BuLi THF

BuLi Me2NCH2CH2NMe2

i-Pr

NO2

'v

Carbohydrate Res (1972)

I

d

QNO2

94 5098

5 i -Pr

CHz=CHCHzBr NaH

>

*1 RhCl (PPh3)3

diazabicyclo[2.2. 2loctane EtOH H20 2 pH 2

JOC (1973)

Me

38

3224

OCHzCH=CH2

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

50 ROH

NaH PhCH2Br CgHg

SECTION 45A

ROCH2Ph

w

4

H2

EtOH

Pd-C

JACS (1971)

93 1746

+-

Cleavage o f benzyl ethers with Ph3C BF3 JCS Perkin I (1972) 542 Further examples of the cleavage o f benzyl ethers a r e included in Section 39 (Alcohols and Phenols from Ethers and Epoxides)

%

PhCH20CH2

0

t-Bu ClSiMe2 imidazole

*

THF

OH

t -

BuqN F THF o r HOAc H20

t-Bu (More stable than OSiMej. Stable t o base, Wittig reagents, (i-Bu)zAlH and H2/Pd)

JACS (1972) 94 6190 T e t r L e t t (1973) 317 JACS (1972) 94 3651

Preparation o f ROSiMe3 using MegSiNEt2 I/ ,I I1 I' MegSiCl Synth Comm (1971) 1 8 1 I, I, II 'I MeCON(SiMe3)z J Med Chem (1973) la 54 ,I 'I ROSi(Me2)Pr-i using i-Pr(Me2)SiCl JACS (1971) 93 7319 Cleavage o f silyl ethers with H2/Pd JACS (1972) 94 6190 f o o t n o t e 4

OMe

c1 6H330 TSOH

c1 6H330H

4

t

03-( Ph0)3P CH2C12 J O C (1971)

3 4134

Ph3CC1

ROH

,

Pyr

CgHg

t

4

H2

51

PROTECTION OF ALCOHOLS AND PHENOLS

SECTION 45A

Pd-C

EtOH

ROCPh3 J O C (1972)

37

2877

Cleavage o f t r i t y l e t h e r s w i t h Na/NH3 T e t r Lett (1972) 2349 Preparation o f s u b s t i t u t e d t r i t y l e t h e r s J O C (1972) 31 956 Polymer-bound t r i t y l e t h e r s Annalen (1972) 766 6

HO Ph

0

C16H330H N2H4

TSOH

CgHg

t

0

NaOH t r i e t h y l e n e glycol T e t r a h e d r o n (1972)

ROH

<

Q

2 419

catalyst

RO

acid Catalyst :

TsOH

Cone HC1 POC13 BF3.Et20 Picric acid Ion exch resin (Acid)

S y n t h e s i s (1973) 169 S t e r o i d s (1964) 5 229 JCS P e r k i n I (1973) 720 JCS (1950) 3646

Synthesis (1972) 81 T e t r Lett (1972) 3333 J C S (1956) 4665

Cleavage o f tetrahydropyranyl e t h e r s with Ph& EFq Chem Corn (1971) 1109

ROH

MeOCH2C1 ( 2 equiv) CHCl3

PhNEt2 ( 2 equiv)

t

ROCH20Me

Acid

V. F l e t c h e r (Columbia Univ) ,

unpub 1ished

52

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 45A

HocwTh >s

OMe

mesitylenesulfonic acid d i oxane

RO

Acid H20 dioxane

/

RO

6

Chem Corn (1972) 766

Goti

EtOCH=CH2 TsOH EQO

4

Me

HOAc dioxane H20

.-

OfHMe OEt

Me JCS

Acid

C

(Stable t o LiAlH4 and base)

(1971) 2944

Ber (1970)

103 643

Related methods: Alcohols and Phenols from Ethers and Epoxides Ethers from Alcohols and Phenols

Section 39

123

Compendium of Organic Synthetic Methods, Volume2 Edited by Ian T. Harrison, Shuyen Harrison Copyright 0 1974 by John Wiley & Sons, Inc.

PR E PA RAT10 N OF ALDEHYDES

Chapter 4

Section 46

EtCXH

Aldehydes from Acetylenes OOOOOOOOoOOOOOOOOOOOooooo

CO

H2 HRh ( C O ) (Ph3P)3

t

to1 uene

< 75%

EtFHMe

CHO Tetr Lett (1972) 3455

CsHi3CECH

1 Et3SiH H2PtC16

*

C6H13CH2CHO

2 m-Chloroperbenzoic acid

N

60%

3 H2SO4 MeOH

4 HOAc H20

Section 47

JACS (1971)

93 2080

Aldehydes from Carboxylic Acids a n d Acid Halides 00000000000000O000000000000000000000000000000000

Ye

C5H11 COOH

i-PrCBH2 I Me

THF

*

98%

C5H11CHO JOC (1972)

53

31 2942

54

COMPENDIUM

OF

1 NapFe(CO)4

PhCH2COCl

2 HOAc

w

ORGANIC SYNTHETIC METHODS VOL 2

*

JACS (1972) 2 2516 B u l l Chem SOC Jap (1971) Tetr Lett (1973) 3535

Rec Trav Chim (1971)

Et3SiH

RCOCl

Pd-C

L i A l (OBu-t)3H

b

C7H15CHO

diglyrne

t

44 2569

78%

v

(i-Pr)*NEt

C7H1 gCOC1

-59%

PhCH2CHO

H20

EtOH

SECTION 47

90 1323

51 %

JOC (1969) 34 1977 Chem Comm (1970) 1703

RCHO

Synthesis (1972) 217

PhCH=CHCOCl

COCl

1 (Et0)3P _____t

2 NaBH4 3 NaOH

MeOH

Ber (1970)

HO OMS MehHiHMe

100%

PhCHzCHCHO

Pyr

COO OMS MeiHbHF.,e

103 2984

1 NaBH4

Pyr

H2S04 H2° DMF

Org Synth (1971)

; 11

O

C

H

O -25%

PrCH2COOH

PhCH2COOH

Section 48

55

ALDEHYDES FROM ALCOHOLS AND PHENOLS

SECTION 48

---t

PrCHCOOH Br

Na2S208 AgN03

P y r i d i n e N-oxide .

H20

*

< 67%

PrCHO

t

xyl ene

J O C (1966)

2 3058

48%

PhCHO

JCS (1960) 1332

Aldehydes from Alcohols and Phenols 0000000O000000000000000000000000000

Me @OH

FW;1H2Cl

K2CO3 i- PMe@ocHr

i-Pr

j-pr Me QCHo1

7%

Bull SOC Chim Fr (1960) 278 JOC (1961) 26 4308

CH20H CH2=CHCH20H Hg ( O A C ) ~ BF3.Et20

540-545'

C6H6

(Vapor phase)

CH20H

CH20CH2CH=CH2

JCS

C (1971)

-

CHO 2730

+-

C7H15CH20H --+ C7H15CH20CPh3

Ph3C ASF6 CH2C12

C7H15CHO

JOC (1973)

38

625

<56%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

56

t

-

FHZC? N-SMe2 C1 CHzCO

C7H15CH20H

SECTION 48

*

Et3N to1 uene

C7H15CHO

96%

JACS (1972)

fiCHZoH

1 Me2SOsC12 CH2C12

LJ

2 Et3N

+

94

7586

rv YH0

> 95%

T e t r L e t t (1973) 919

CgH13CH20H

Resin-CHpN=C=NPr-7 H3P04 Me2SO C6H6

CfjH13CHO T e t r L e t t (1972) 3285

NO2

RCH20H

A r g e n t i c p i c o l i n a t e H20

Synthesis (1971) 655

RCHO Tetrahedron (1973)

CrO3-graphi t e c15H31CH20H

to1 uene

*

2 751

95%

c15H31 CHo Can J Chem (1972)

2 3058

SECTION 49

ALDEHYDES FROM ALDEHYDES

C U ~ O 250-300°

C7H15CH20H

98%

C7H15CHO

( v a p o r phase)

T e t r Lett (1972) 257

H202 FeS04

CH20H

57

H20

37%

F C H O

+

Can J Chem (1965)

Related methods:

Section 49

-

43

2924

Ketones from Alcohols and Phenols ( S e c t i o n 168)

Aldehydes from Aldehydes

3

Fe(C0)s HCHO C~OH~~CH~CHO * KOH EtOH

55%

C 1 OH21CHCHO he T e t r Lett (1973) 2491

+*

PhCH2C1 NaOH Bu4N I

Me2CHCHO

C6H6 H2°

Me2CC HO

75%

PhiH2 T e t r L e t t (1973) 1273

PhCHO

1 MeSOCH2SMe THF

MeOH

2 LiA1H4

+

-

PhCH2NMe3 OH

*

PhCH$H(SMe)z

--+

PhCHZCHO

T e t r Lett (1972) 1383

58

COMPENDIUM

1

QCHO

OF

VOL 2

ORGANIC SYNTHETIC METHODS

( M e 0 13 P=Cf

S

7>

SECTION 49

CH~CHO

*

2 CF3COOH CHZC12 3 PhgSiH

EtCHO

BrCH2COOEt

JOC (1971)

0

( M e 3 S i )2 N L i

TH F

1 Base

I \

EtCHCHCOOEt

+

3 2731

-----t EtCH2CHO

2 A

T e t r Lett (1972) 3761

*g

Pr-i

1 Ph3CNa

DMF

2 Me1 CHO

Et2CHCHO

66%

Me CHO

Chem Corn (1971) 10

1 BujSnOMe MeCOOMe

--+ E~~CICHOAC

C5H11 CH2CHO

1 ClSiMe3 DMF 2 CH212

-D

2 Me1

Et3N

t

Zn-Ag

< 82%

Et2CCHO I

Me Compt Rend (1970)

A C5H11 CH-CHOSiMe3

C 270

NaOH

EtOH

100

C5H11 CHCHO >53%

H20

T e t r L e t t (1973) 2767

I

Me

3

1 CH2N2

MeCH2CHO --+ MeCH=CHN

R e l a t e d methods: Also v i a :

S e c t i o n 50

Me

59

ALDEHYDES FROM AMIDES

SECTION 51

2 Pd-C

CuCl

Et20

H20

EtOH

i

Me2CHCHO

J O C (1973)

38

304

Aldehydes from Ketones ( S e c t i o n 5 7 )

O l e f i n i c aldehydes ( S e c t i o n 341)

Aldehydes from A l k y l s 000000000000000000000

@Me

MnOp HpSOf

Me@cHo Me

Me J A C S (1946)

S e c t i o n 51

RCONMe2

68 1085

Aldehydes from Amides OOOOOoOOOOOoOOOOoOOoa

L i A l (OEt)3H E t 2 0

b

RCHO

Synthesis (1972) 217

< 28%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS

60

VOL 2

SECTION 53

Aldehydes from Amines

S e c t i o n 52

oOOOoOOooOOOdoOOOOOOO

69%

[ (T-CgHg ) 2Mo (SMe2) B r I+ PFS

PrCH2NH2

+

H20

C5H11 CH2NH2

hv

PrCHO

Chem Corn (1971) 1274

cycl

Ohexane,

C5H1 ICH=NCH~C~H~ 1 --+ Cgti11CHO Chem Corn (1971) 1430

PrCHzNH2

S e c t i o n 53

PhCOCH2Br

PrCH2NHCH2COPh

Aldehydes f r o m E s t e r s

000000000000000000000

No a d d i t i o n a l examples

hv

MeOH H20

JOC (1972)

PrCHO

2 1254

<57%

SECTION 55 Section 54

61

ALDEHYDES FROM HALIDES Aldehydes from Ethers and Epoxides

)

+-

PhCH2OMe

Ph3C BF4

0°C" 0

I\

Bu~C-CH~

PhCHO

LiBr HMPA C6H6

+

HF MeCN

-I

PhBr

?H OH -CH-;Me2

JACS (1971)

93 1693

2 Chem (1967)

229

~ a 1 0 ~fOOMe CH=TCH2CH2CHO THF Me

94 5374

Aldehydes . f r o m Halides 0000000000000000000000

Et20

2 MeCOCH2Cl 3 EtONa

0

I \

PhC-CH2

HC1

74%

-

JACS (1972)

- he 1 Mg

75%

OCHO

BUZCHCHO

110"

I0 \ HC104 CH=fCH2CH2CHCMe2 THF Me H20

Section 55

Chem Corn (1971) 1109

PhCHCHO Me JACS (1939) (1946)

2383

9 2339

5379

62

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

1

2 A1-Hg

Et20

H20

*

2 BuLi

3 EtI 4 A1-Hg 5 HgC12

t-BuC1

1

--+ t - B u L i

Et20

THF

Me

NaH DMF

2 NaBH4 EtOH 3 Acid

1

l2 N

CH2Li

2 NaBH4 THF 3 (C0OH)p

H20

t-BuCH2:HCHO

38 2136

51 %

Ph(CH2)3CH2CHO (1972)

94 3243

RCH2CHO

8uLi THF hexane

THF

Et

Tetrahedron (1971) JOC (1973) 38 36

2 HgCl2 HgO MeOH 3 TsOH

50%

J O C (1973)

H20

I sI

1s,S

*

EtOH

PhCH2FHCHO

Me

JACS

THF

60%

EtOH THF

(CooH)2 H20

1

PhCH7CHQCHO

MeCN H20 T e t r L e t t (1972) 3929

&& .

2 NaBH4

H20

SECTION 55

*

27 5979

47-55%

C14H29CH0

Org Synth (1971)

2 39

SECTION 56

BuI

MeSOCH2SMe NaH THF

-

63

ALDEHYDES FROM HYDRIDES H20

HC1

BuFHSOMe

THF

SMe

BuCHO

Tetr Lett (1971) 3151

66%

(1973) 3267

*

75% Chem Ind (1972) 380

RBr

Li

Et20

___t

Me I t-BuFNC RLi

Me

RCHO

hexane

Me HCOiPh

C7H15Br

Also v i a :

Section 56

ArH

THF

Li

C7H1SCH0

Org Synth (1971)

31

(One-step procedure) Synthesis (1973) 160

O l e f i n i c aldehydes ( S e c t i o n 341)

Aldehydes from Hydrides

00000000000000000000000

C12CHOMe Tic14 CHZC12 Z-

ArCtlO Org Synth (1967)

41 1

73%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

64

Hexamethylenetetramine

CF3COOH

t-BU

*

75%

t-Bu

J O C (1972)

N

~

SECTION 57

31 3972

N

1 b ~ )AlCl3 HC1

+ & @I@ 2 H20

Me

J O C (1973)

PhCXH

HC(OEt)3

Section 57

Me

Arch Pharm (1971)

ZnI2

* PhCECCH(OEt)2

38

304 362

2915

--+ PhCrCCHO

Org S y n t h (1963) C o l l Vol 4 801

Aldehydes from Ketones 00000D0000000000000000

Me

Re 1

PhCHCHO he

+----

PhCHCC Me

:)

I

i

!

PhCCHO I Me

Chem Comm (1972) 526

75%

SECTION 58

ALDEHYDES FROM NITRILES

Li 1 Ph2P(O)bHNMe2 Et20

Ph2CO

2 H2SO4

Ph2CHCHO

H20

44%

JACS (1971)

*

BrCH2COOEt (Me39 )2NLi

65

93 4027

O C H o

- - ~

JC% ,lO,tOH

THF T e t r L e t t (1972) 3761

F u r t h e r methods f o r t h e p r e p a r a t i o n o f g l y c i d i c e s t e r s a r e i n c l u d e d i n s e c t i o n 358 (Ester - Ether, Epoxide) Also v i a :

O l e f i n i c aldehydes (Section 341)

Section 58

ArCN

RCN

Aldehydes from N i t r i l e s 00000000000000000000000

Ni-A1

HCOOH

H20 +r

L i A l (OEt)3H

Et20

t

ArCHO

RCHO

Org Synth (1971)

Synthesis (1972) 217

20

c 53%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

66 Section 59

EtCH=CH2

Aldehydes from Olefins 0000000000000000000000

?B!

(EtCH2CH2)3B

NZCHCHO

Et(CHz)$HO

Can J Chem (1970)

RzC'CH2

Section 60

1 Cr02Cl2 CH2C12 2 Zn

P

H20

SECTION 60

-77%

48 868

R2CHCHO Org Synth (1971)

4

A1 dehydes from Miscellaneous Compounds

oooooooooooooooooooooooooooooDooooooooo

1 Et3SiH (Ph3P13RhC1 2 K2CO3 Me2CO MeOH H20 T e t r L e t t (1972) 5035

EtCH2N02

1 Zn

HOAc

2 H2S04

H20

43%

EtCHO J A C S (1939)

MeONa, 03 J O C (1974)

2 3194 2 259

75%

PROTECTION OF ALDEHYDES

SECTION 60A

67

P r o t e c t i o n o f Aldehydes

Section 60A

00000000000000000000000

MeCHCHO

- 0

MeCHCH(0Me)z

MeOH HC1

+-----------

Acid

Ac 0

H20

JCS (1953) 3864

FH20H CH20H I

CH2Br c1 1H23CH0

%

Zn

TSOH MeOH

CgH6

*

c11 H 2 3 C t 0

CH2Br

(Stable t o NH3, NaBH4, peracids,

MeLi and Cr03-HzS04)

JOC (1973) 38 834 T r i c h l o r o e t h y l a c e t a l s JOC (1973) 38 554

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

68

SECTION 60A

gH0 ---__+

Me1 Me2CO H20

H

Thioacetal cleavage with NBS chloramine-T HgO, BF3.Et20 CuC12, Cuo 12, Me2SO

-OR .OR

--+

OR

HgO CaS04

He

Pd-C

MeOH

Chem Corn (1972) 382 Synthesis (1969) 17

T e t r L e t t (1971) 3445 3449

JOC (1971)

2 366

Bull Chem Soc Jap (1972) 45 3724

Tetr Lett (1973) 3735

OR OR

JOC (1963)

2 1395

(EtS)gB Pet ether

PhCHO

.....................*

PhCH(SEt)2

(Neutral conditions) Can J Chem (1965) 43 307 (1969) 41 859

Tic13 NH40Ac HOAc dioxane H20

PhCHO

Ph3CONH2

----------

T e t r L e t t (1971) 195

PhCH=NOCPh3 JOC (1971) 2 3835

m N

69

PROTECTION OF ALDEHYDES

SECTION 60A

CH=NNH2

N2H4 -----* NaN02 HC1

NH2NEt2

PhCHO

H20

JOC (1961)

4465

PhCHzNNEt7

MeC002H CHCl3

Ber (1961)

94

712

occ;I Me

OCHO

MeNHCHzCHzNHMe

I

.-’

*

)

( S t a b l e t o Na-NH3)

h

..a

Acid

Aust

Me

J Chem (1955) 8 512

_-----_+ H

CHo

O C H O

NaOH H20

H

CH=C (CN)2 Angew (1960) 72 6 5 1

Me3SiCN Acid or base

Related methods: P r o t e c t i o n of Ketones Enol ethers Acetal s

Chem Corn (1973) 55 T e t r Lett (1973) 4929

Section 180A 367 363

Compendium of Organic Synthetic Methods, Volume2 Edited by Ian T. Harrison, Shuyen Harrison Copyright 0 1974 by John Wiley & Sons, Inc.

Chapter 5

PREPARATION OF ALKYLS METHYLEN ES AND ARYLS

This chapter l i s t s the conversion of functional groups into Me, E t a - . , CH2, Ph e t c . Section 61

Alkyls, Methylenes and Aryls from Acetylenes 00000000000000000000000000000000000000000000

No additional examples

Section 62

Alkyls and Aryls from Carboxylic Acids oooooooooooooooooooooooooooooooaoooooo

Reactions in which carboxyl groups are converted into alkyl or a r y l , e.g. RCOOH --L RR' are included i n t h i s section. For the conversion RCOOH --f RH see section 152 (Hydrides from Carboxylic Acids)

MeO.,/@COCl

ORp\y

1 LiAlH4

SnCl4 C6H6

~ 1 ~ 1 3 2 Ni E t O H

OMe

MeOQ(CH215R

OMe R=H or Bu

Aust J Chem (1971) 2 2655

70

&Me3A1

PhCOOH

--+

CgHg

PhCONHNHCOPh

75% Chem Corn (1972) 595

Ago C6H6 ____+

Ph-Ph J O C (1972)

Section 63

71

ALKYLS FROM ALDEHYDES

SECTION 64

37

< 37% 2748

Alkyls from Alcohols

00000000000000000000

Reactions in which hydroxyl groups a r e replaced by alkyl e.g. ROH +RMe, are included in t h i s section. For the conversion ROH + R H see section 153 (Hydrides from Alcohols and Phenols)

Me3A1

200"

83%

t

Chem Comm (1972) 595

Section 64

Alkyls from Aldehydes

000000000000000000000

Reactions which convert t h e group CHO into CH3 o r larger alkyl groups are included in t h i s section. For the conversion RCHO + R H see section 154 (Hydrides from Aldehydes)

C& 3CHO

C1@02CHzPO(OEt base

12

*

-

0

CgH13CH=CHS02

1 Me2CuLi

2 Na-Hg

c1

Tetr Lett (1973) 935

(1972) 2 9 3

CsH13CHMe2 52%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

72

CHO i-Pr

Et20 + 2 L i NH3 3 NH4C1

NH3 THF,

Me2N

RCHO

i-Pr

aCHo Li

i-Pr

CH2Me

1 MeLi

SECTION 65 96%

Chem Corn (1971) 1242

90%

i-Pr

JOC (1972)

31 760

Mep

T e t r L e t t (1967) 1849

1 TsNHNH2 TsOH

sulfolane 2 NaBH3CN

DMF .r

RMe JACS (1971)

93

1793

Related methods: A1 kyls and Methylenes from Ketones (Section 72)

Section 65

Et

Alkyls from Alkyls oooooooooooooo.aooo

2 H20 140-150°

Et

Et

Et

Org React (1942) 1 3 7 0

91 %

SECTION 70

ALKYLS AND ARYLS FROM HALIDES

Section 66

Alkyls, Methylenes and Aryls from Amides

73

0000000000000000000000000000000000000000

No a d d i t i o n a l examples

Alkyls, Methylenes and Aryls from Amines

Section 67

0000000000000000000000000000000000000000

No a d d i t i o n a l examples

Alkyls, Methylenes and Aryls from E s t e r s

Section 68

0000000000000000000000000000000000000000

No a d d i t i o n a l examples

Alkyls from Ethers

Section 69

000000000000000000'

The conversion ROR +RR' ( R ' = a l k y l ) i s included i n t h i s s e c t i o n . For the hydrogenolysis of e t h e r s (ROR + R H ) see s e c t i o n 159 (Hydrides from Ethers)

MeMgI xylene*

OMe

0"'

16%

Gazz (1970) 100 939

Section 70

Alkyls and Aryls from Halides

~ ~ O ~ O O O O O O ~ ~ O ~ O O O O O O O O O O ~ O O O O

The replacement of halogen by a l k y l o r aryl groups i s included i n t h i s s e c t i o n . For t h e conversion RX + R H (X=halo) see s e c t i o n 160 (Hydrides from Hal ides and S u l f o n a t e s )

@

Br Bis (1,5-cyclooctadiene)nickel

Me0

DMF

Me0,MO" JACS (1971) 93 5908

83%

74

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

Br

1 Mg

BH3 THF

2 AgN03-KOH

t

52%

MeOH

OMe

PhI

OMe OMe T e t r Lett (1972) 2193

a-ally1 n i c k e l bromide

*

OMF

PhCH2CH4H2

JOC (1972)

82%

7 462

Org React (1972)

CH2=CHCH2I

PhCH2I

Et3B

02

*

Br

19 115

PhCH2CH2CH=CH2 JACS (1971)

64%

93 1508

MeRh(PPh3)g DMF

*

Ph

65% Ph Tetr Lett (1973) 2967

Zn-Ag

c115~2.3~

BuBr

SECTION 70

BuMgBr Ag C&

3MgBr

H20

THF

t

LiCl

c16H33-C16H33

C o l l Czech (1964)

2 597

79%

Bu-BU CuC12

*

70%

BU-C6H13 Synthesis (1971) 303

78%

ALKYLS AND ARYLS FROM HALIDES

SECTION 70

1 Mg BH3 THF

-

PhCH2Br

90%

C8H1 7-CgH17

2 AgN03-KOH MeOH)

C8H17Br

75

T e t r L e t t (1972) 2193 JACS (1938) 3 105

1 BuLi

>(-SzHChP

2 Me1 3 Ni

PhCH2Me

<60%

T e t r Lett (1971) 4359

Br

PhCl

1

Et20

2 Me2S04

BuMgBr [NiClz(dpe)]

Also v i a :

BuLi

.-

58% JACS (1969)

EtzO

*

PhBu

JACS (1972)

Acetylenes Olefins

Section 10

205

91 3544

2 4374

76%

COMPENDIUM

76 Section 71

OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 71

A l k y l s and A r y l s from Hydrides

000000000000000D00000000000000

This s e c t i o n l i s t s examples o f t h e r e a c t i o n RH + RR' (R,R'=alkyl or (R=alkyl o r a r y l ) see s e c t i o n a r y l ) . For t h e r e a c t i o n C=CH +C=CR 209 ( O l e f i n s from O l e f i n s )

1 TeC14

160'

74%

f

Me0

2 Ni

MeOCH2CH20Et

Me0 Tetrahedron (1972)

2 3323

n

27%

Synthesis (1971) 203

+a CH2Me

1 C1H j 11 Na -Me2NCHzCH2NMe2 hexane 2 Me1

CH3

CH2Me

3 2152

JACS (1972)

0

o g 3 i :

%2CH2CH=CMe2

1 BuLi mMe2NCHzCH2NMe2

Me

2 Me$=CHCHzBr

Me JACS (1972)

3 4298

77

ALKYLS AND METHYLENES FROM KETONES

SECTION 72

Alkyls and Methylenes from Ketones

Section 72

0000000000000000000000000000000000

The conversions R2CO + R R , R2CH2, RzCHR, e t c . are l i s t e d in t h i s section. For the conversion R2CO + R H see section 162 (Hydrides from Ketones)

-3 Decane

1 H202 HClo4 MeCN

(ref1 u x )

(CH2)14

S y n t h e s i s (1970) 181 Advances i n Org Chem (1972)

8 67

24% B u l l SOC Chim F r (1966) 2253

PhZCO

NaAl H ~ ( O C H ~ C H ~ O M PhPr ~)Z

h

162"

PhpCMez

71 %

T e t r L e t t (1972) 691

Me3Al

p-dichl orobenzene

43%

Chem Corn (1972) 595

JCS

C

(1971) 2294

78

Ph2C0

Ph2CO

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

1 MeLi

Et20

2 L i NH3 3 NH4C1

--+

CgH19COMe

Ph2C:’J

95%

Ph2CHMe JOC (1973)

LiAlH4

ZnClp

S

CuC12

THF

1738

Ph2CH2

Bull Chem SOC Jap (1971)

1 TsNHNH2 TsOH s u l f o l a n e DMF

2 2285

CgHl gCH2Me

w

2 NaBH3CN

2 1735

JACS (1971)

PhCOMe

SECTION 72

93 1793

-

2,4-Dini trophenyl hydrazine

H2

ph-;@ :! N02

Pd

HOAc

PhCH2Me

NO2

JOC (1971)

&

1 Li

2 737

NH3 THF

‘2 NH4C1

96%

* JOC (1971)

2 2588

SECTION 74

1 0 -1 0

1 LiAlH4

Li

P

2 BuLi Et3N C1 PO(NM~Z)~

Related methods:

Section 73

EtNH2

OPO (NMe2 )2

JACS (1972)

Also v i a :

79

ALKYLS, METHYLENES AND ARYLS FROM OLEFINS

c.,

69%

2 5098

Alkyls from Aldehydes ( S e c t i o n 6 4 )

O l e f i n s (Section 207)

Alkyls, Methylenes and Aryls from N i t r i l e s <

No a d d i t i o n a l examples

Section 74

Alkyls, Methrlenes and Aryls from O l e f i n s

b

b

The hydrogenation, a l k y l a t i o n and a r y l a t i o n o f o l e f i n s forming alkanes o r a r y l - s u b s t i t u t e d a l k a n e s , a r e included i n this s e c t i o n . 1 B2H6 THF 2 Ph-jAsCHPh

Bu(CH2)3Ph

t -

0

J A C S (1967)

6804

benzoyl peroxide

*

C6H13CH2CH2 JCS (1965) 1939

42%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

80

a

c

H

2 CH212 Zn-C;

SECTION 74

\p H2 P t

HOAc

C h e m C o r n (1968) 569

C$l7CH=CH (CH2 )7COOH

+ QN"3

NaBH4 NiC12

C h e m P h a r m Bull (1971) J O C (1971) 2 2018

0:

-

+

Br Br2 CHC13,

Br

[MeHSiOIli Pd-C

CgH13CH=CH2

E t CH CMe2

EtOH

Hp

b

2 817

+

-

NMe3 Br

H2 Pd-Bas04

Br

H20

-

NMe3 Br

J A C S (1947) 69 2555

(1948) 70 2517

CgH13CH2Me J O C (1973)

BuLi-cobal t 2-ethylhexanoate

cyclohexane

92%

CgH17 (CH2)gCOOH

MeOH

b

38

162

EtCHzCHWe2

J O C (1971)

2 1445

Polymer-supported Rh( I ) c a t a l y s t J A C S (1971) 93 3062 "Hydrogenation o f Organic Compounds using Homogeneous C a t a l y s t s " C h e m R e v (1973)

73 21

92%

81

ALKYLS, METHYLENES AND ARYLS FROM MISCELLANEOUS COMPOUNDS

SECTION 75

77% JCS (1957) 1969

Na

HMPA

91 I

t-BUOH J O C (1970)

a-

35

3565

Pr-i

i-Pr

PhCH=CHPh

0

S021IHNH2

Pr-i

THF

*

PhCH2CH2Ph

N

60%

Chem Corn (1972) 1132

W-QQQ HI

CH2

CHZNMe2

P4

94%

Me

CH2NMe2

J Med Chem (1971)

Section 75

14 982

Alkyls, Methylenes and Awls from Miscellaneous Compounds

OOOOOOOOoOoooOOOoDoOooooooooooooooooooooooooooooooooooooo

No a d d i t i o n a l examples

Compendium of Organic Synthetic Methods, Volume2 Edited by Ian T. Harrison, Shuyen Harrison Copyright 0 1974 by John Wiley & Sons, Inc.

Chapter 6

Section 76

PREPARATION OF AMIDES

Amides f r o m Acetylenes

0000000000000000000000

No additional examples

Section 77

Amides from Carboxylic acids and Acid Halides

000000000000000000000000000000000000000000000

I1 Farmaco Ed Sc (1971) (Chem Abs 75 4874)

PhCOOH

PhCOOH

1 Ph3P CCl4 THF 2 BuNH2

1 (Me2N)3P

2 Et2NH

PhCONHBu

*

CCl4 Et20

b

26

153

85%

JOC (1971)

36

1305

PhCONEt2 Bull SOC Chim Fr (1971) 3034

SECTION 77

AMIDES FROM CARBOXYLIC ACIDS AND A C I D HALIDES

BuNH2 C5H11 COOH

Ph3P

Q-c1

CQSS E t 3 N CUC12

CH2C12

83

C5H11 CONHBu

t

62%

B u l l Chem SOC Jap (1971)

B u N H ~ NCP(O)(OEt)2

PhCOOH

E t 3 N DMF

44 1373

PhCONHBu

t

94%

Tetr Lett (1973) 1595

PhCOOH

- 3 1 ClCOOMe

2 H

O

N

1 ClCOOEt RCOOH

PhCOON

BuNH~

~

Et3N

PhCONHBu

__+

T e t r L e t t (1971) 2697

CH2C12 t

2 t-BuNH2

RCONHBU-t

JCS

(t-Bu)2CHCOCl

NH3

NaNH2

Et20

C

(1971) 3540

( t - B u ) 2CHCONH2 JACS (1960)

FOOMe (CH2)4COOH

FOOH

(CH2 )5NHAc MeONa

MeOH

e l e c t r o lysis h

81 % 2498

FOOMe ( C H ) 9~~~~ ~ 2 N a t u r f o r s c h (1947)

2

185

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

84

Electrolysis MeCN H20

t-BUCOOK

SECTION 79

t-BuNHAc Acta Chem Scand (1964) 18 1567 Bull SOC Chim F r (1968) 3657 Angew (1971) 579

b

(Internat Ed

40%

2 557)

Related methods: Amides from Amines (Section 82) Also via: Esters (Section 83)

Section 78

Amides from Alcohols

P

CH20H

GrT"'

OMe MeCH=tNMeZ xylene

*

JCS

88%

CHCONMe2 Me

C (1971) 2950 Ber (1971) 104 3689

t -

Ph2CHOH --* Ph2CHN3

Section 79 PhCHO

NO BF4 MeCN

Ph2CHNHAc

JACS (1970)

92

4999

-53%

Amides from Aldehydes 000000000000000000000

Li [MezNCONi (CO)g]

Et20

t

PhCONMe2 JOC (1971) 36 2721

< 84%

85

AMIDES FROM AMIDES

SECTION 81

1 NaCN

Et2NH

i-PrOH

98%

o C O N H 2

2 Mn02

Chem Comm (1971) 733

(Ar and ccB-unsaturated only)

-

PhNH2 PhCHO -----+ PhCH=NPh

Cr02C12 CCl4

80%

PhCONHPh

Chem Ind (1970) 1297

Also via:

Olefinic amides (Section 349)

Section 80

Arnides from Alkyls, Methylenes and Aryls 0000000000000000000000000000000000000000

No additional examples

Section 81

Arnides from Amides

a o o o ~ ~ ~ ~ o o o o o o o o o o

CH20R

7

CH20R

NaH Me1

ROQOMe

NHAc

RO@OMe

89% YAc Me

Carbohydrate Res (1972)

MeCO;Me CH3

MeC002Bu-t

hu

>

cupric 2-ethylhexanoate C6Hg

23 251

MeCOvMe --+ MeCONHMe CH20Ac Synthesis (1972) 1

<67%

COMPENDIUM OF ORGANIC SYNTHETIC METHOOS VOL 2

86

Related methods:

Section 82

BuNH~

PRNHZ

PhNH2

HOAC

SECTION 82

Amides from Halides (Section 85)

Amides from Amines OOOOOOOOOOOOOOOOOO

Ph3P

P

CCl4 THF

Resin-CO-0-COPh

to1 uene

BuNHAc

*

J O C (1971)

2 1305

91 %

PhCONHPh T e t r Lett (1973) 1627

C17H35COOH Sic1 4

Pyr

t

PhNHCOCl7H35 JOC (1969)

70%

34

2766

Further examples of the reaction RNH2 + R ' C O O H --tRNHCOR' are included i n section 77 (Amides from Carboxylic Acids and Acid Halides)

PhNH2

PhNH2

MeCOOEt NaH Me2SO

*

PhCOSCSNMe2

PhNHAc

85% T e t r L e t t (1971) 321

PhCONHPh

80% T e t r Lett (1972) 4785

c1

87

AMIDES FROM ETHERS AND EPOXIDES

SECTION 84

@ NH2

HCOOPh

95%

OH

JOC (1971)

2 3238

45% I

I

H

CHo

Related methods:

Section 83

D

COOEt

Chem Corn (1971) 1482

Protection o f Amines (Section 105A)

Amides from E s t e r s

000000000000000000

o

H

2 NaH

Me2SO

CONH

t

68%

Tetr Lett (1971) 3 2 1

58% J Med Chem (1973)

Section 84

Amides from Ethers and Epoxides

O O O e O O O O O O O O D D D O D O O O o o ~ ~ ~ ~ ~ o ~ ~ ~

No a d d i t i o n a l examples

16 1

88

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

Section 85

CgH11Br

SECTION 85

Amides from Halides

0000000000000000000

1 Na2Fe(C0)4 2 I2

C5H11 CONEt2

+

E t 2 N H THF

80%

JACS (1973)

95 249

99% (Applicable t o aromatic and vinyl ha1 i d e s )

J O C (1971)

C7H15Br

Et2NCOOEt L i

THF

C7H15CONEt2

2 2721

70%

(One-step procedure)

Synthesis (1973) 360

c1 8H37C1

PhNHAc KOH

Me2SO

90%

c18H37;Ac Ph Synthesis (1971) 266

E l e c t r o l y s i s MeCN H20

*

cJNHA 85%

Compt Rend (1970)

C E

324

AMIDES FROM NITRILES

SECTION 88

89

MeNHAc YAc Me J Med Chem (1971)

Section 86

14 535

Amides from Hydrides 00000000000000000000

No a d d i t i o n a l examples

Section 87

Amides from Ketones

0000000000000000000

No a d d i t i o n a l examples

Section 88

Amides from N i t r i l e s

acN OcoNH2 00000000000000000000

HC1

HCOOH,

Annalen (1971)

PhCN

1 BBr3

2 H20

PhCONH2

JCS

C (1969)

749 198

739

92%

90

COMPENDIUM

H202

FN CH2$H(CH2)2CN OMe

Also v i a :

OF ORGANIC SYNTHETIC METHODS VOL 2

Na2C03

CONH2 bH2CH(CH2)2CONH2 OMe

Helv (1956) 2 1233 Chem Ind (1961) 987

Amines ( S e c t i o n 103)

Section 89

Amides f r o m O l e f i n s 0000000000000000000

Electrolysis

MeCN

*

0

NHAc Compt Rend (1970)

Also v i a :

SECTION 90A

80%

C

Z

324

Amines ( S e c t i o n 104)

S e c t i o n 90

Amides f r o m M i s c e l l a n e o u s Compounds

00000000000000000000000000000000000

No a d d i t i o n a l examples

S e c t i o n 90A

P r o t e c t i o n o f Amides

~ ~ ~ O O O O ~ O O O ~ O O ~ O O O O ~

Q N M e EtCONHR

HC1

EtOH

(or

H20

R

Bull SOC Chim Fr (1964) 292

91

PROTECTION OF AMIDES

SECTION 90A

( S t a b l e t o NBS)

Na2C03 H20

Can J Chem (1955)

2 1819

SiMeg

NHAc

MeCON(SiMe3)2

MeCN

+------------------

HC1

H20

n02 JACS (1966)

3390

OH MeO@-iHoOMe RCH2CH2CONH2 -k

RCHzCH2CONH

H2S04 CF3COOH

Me0

anisole

@-

AH QoMe

( S t a b l e t o H2/Pd)

Ber (1970)

RCHzCONH2

POCl3

o r HBr

Pyr

HOAc

CH2C12

*

2 2041

RCH2CN

Chem Ind (1961) 987

Compendium of Organic Synthetic Methods, Volume2 Edited by Ian T. Harrison, Shuyen Harrison Copyright 0 1974 by John Wiley & Sons, Inc.

Chapter 7

Section 91 PhCECC6H13

Section 92 C7H15COOH

Section 93 C5H1 loH

PREPARATION OF AMINES

Amines f r o m Acetylenes 0000000000000000000000

-

1 NaNHNH2 N2H4 Et20

2 H2 Ni

NaOH MeOH

PhCH2CHC6H13 I NH2

71 %

Ber (1966) 99 1843

Amines from Carboxylic Acids

0000000000000000000000000000

1 N3PO(OPh)2

2 t-BuOH

Et3N DMF

* C ~ H ~ ~ N H C O O B U ---+ t C7H15NH2 JACS (1972) 94 6203

-67%

Amines from Alcohols and Phenols

00000000000000000000000000000000

0

1 (Me2N)3P CCl4 CHzC12

0""'

NHC5H11

MeCN

Bull SOC Chim Fr (1971) 4368

92

58%

M I N E S FROM ALCOHOLS

SECTION 93

PhCHOH I

Me

1 C1 S02NCO hexane

*

AND

93

PHENOLS

PhCHNH2

52%

I

2 NH~NHCOOBU-t 3 Pb(0Ac)q CH2C12

Me JACS (1973)

95 4083

rJCOOEt

1 Phthalimide

C6H13FHOH

2 N2H4

Me

Ph3P NCOOEt THF

*

EtOH

C6H13:HNH2 Me

JACS (1972)

94 679

Carbohydrate Res (1972)

0

CH20H

c1

( Me 2 N ) 3 PO+ 230-240'

oc''2NMe 68%

c1

1 NaH

HO

23 460

Chem Corn (1971) 1018

&iPh

2 330-335' 3 NaOH

@I

NH2

J Med Chem (1966)

9

249

Steroids (1968) LI_ 1 5 1

58%

94

COMPENDIUM

Amines from Aldehydes

S e c t i o n 94

RCHO

OF ORGANIC SYNTHETIC METHODS VOL 2

000000000000000000000

CH3NO2

FIH40Ac

*

HOAc

RCHzCHN02

SECTION 95

LiA1H4 THF

RCH2CH2NH2 Ber (1971) 104 2517 JCS (1965) 3645 (1957) 2926

RCHO

R'NH2

NaBH3CN

*

RCH2NHR'

MeOH pH 6-8

CHO

p 2 EtCCOOH 1 he

c1

2 HC1

DMF

70%

H20

( A r aldehydes o n l y )

CgH13CHO

NH20H

----+

JOC (1971)

CgH13CH'NOH

H2

Pt02

S e c t i o n 95 No examples

36

1710

EtOH

CHCl3

JOC (1972) R e l a t e d methods:

93 2897

JACS (1971)

t

31 335

Amines f r o m Ketones ( S e c t i o n 102)

Amines f r o m A l k y l s , Methylenes and A r y l s

0000000000000000000000000000000000000000

C6H13CH2NH2

SECTION 96 Section 96

C5H11 CONR2

AMINES FROM AMIDES

95

Amines from h i d e s 000000000000000000

B2Hg THF

C5H11 CH2NR2

87% R=H 95% R=Me J O C (1973)

-

38 912

NaBH2S3 THF

PhCONH2

NCOPh

PhCH2NH2

Can J Chem (1971)

49 2990

(i-Bu)ZAlH toluene JACS

(1970)

92 204

Tetr Lett (1971) 1935

PhCH2CONH

-=(2 1 PCl5

H-methylmorpholine

COON=CHPh

F,eOH J C S C (1971) 1917 Rec Trav C h i m (1970) JOC (1971) 2 1259

1081

46%

96

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

S e c t i o n 97

Me PhCHNH2

A r n i n e s from Arnines

-

OOOOODOOeooOOOOOOO

Me

BuLi

I

PhCNH2 Bu

+ -

t-BuYCHg Me

BuNH~

SECTION 97

1 Ph3C C l O 4

2 PhMgBr

25% T e t r Lett (1971) 2187

CHzC12

Et20

Me1 B u 3 L OMF w

*

+

t-BuNCH2Ph ie Annalen (1971)

BuNMeg I

75%

752 86

J O C (1971)

36

+

NMe3

92%

824

-

BF4

100% Chem Corn (1972) 315

ClCHZCOOH H20 NH2

NaOH

KI

* N(CH2COOH)2 J O C (1964)

9 488

NMe2

SECTION 97

97

AMINES FROM AWINES

33%

PhCH2NH

HCHO NaBH3CN

it

BuNH2

MeCN H 2 0

PhBr

NaNH2

w

PhCH2;Me Et

BuNHPh

JOC (1972)

31 1673

JOC (1973)

38 1348

72%

JOC (1971) 36 1841

59% Tetrahedron (1961) fi 208 Tetr Lett (1971) 4661 4665

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

-

98

1 03 CH2Clp

PhNMep

f'r v

2 HC1

H20

41 %

PhNHMe

K3Fe(CN)6 KOH

NMe2

JCS

H20

*

C

(1971) 1369

nNHMe v 93%

OH

OH

16 1303

J O C (1951)

+

c1 ZH25NMe3I

-

SECTION 99

1,4-Diazabicyclo[2.2.2]octane

DMF

*

c1 2H25NF'e2

68%

S y n t h e s i s (1972) 702

Dealkylation with LiI J O C (1963) PrSLi J O C (1973) OAc-

28 2407 2 1961

T e t r a h e d r o n (1968)

Ph3P, (NH2)pCO or NaN3 Synth Comm (1973)

Section 98

2 5493

2 99

Amines from Esters 000000000000000000

No additional examples

Section 99

Amines from Epoxides

P

17%

SECTION 100 S e c t i o n 100

AMINES FROM HALIDES Amines f r o m H a l i d e s

P

1 Mg

BuBr

Et20

Bu3CNEt2

2 Et2NCC13

Me2C=NOH EtMgBr

RX

99

Synthesis (1972) 611

t o 1 uene

F

37%

62% (R=Ph) 48% (R.PhCH2CH2)

RNH2

Tetr Lett (1972) 1007

1 Mg

RBr

R2CHNHS02Ph

>

Bu I

Me2NN0

Ber (1969)

(i-Pr)2NLi

*

BuCH2YNO Me

< 92% (R=Ph) (74% (R=Pr)

R2CHNH2

--+

2 EtOCH=NS02Ph

--+

3 1641

BuCHzNHMe

Angew (1972) (Internat Ed

350

2 301)

Et

PhCH2C1

Et'-NEt

"1

MeOH H20 >

65%

PhCH2yE t Me Synthesis (1971) 89

EtNMe2

C12H25I

-----+

+

-

C12H25l;Me2 I Et

PrSLi

HMPA

JOC (1973)

38

C12H25yMe Et 1961

-

100

COMPENDIUM

1 (PhCH2)zNMe

CH2=CHCH2I

EtOH

DMF

1 (PhS)2NLi

THF

2 HCl

H20

H20

+

Et20

t

PhCH2NHSOzCF3

base

X

2 Na-Hg

CH2=CHCHzNPr I Me

249

111

RNH2

-

fooEt

NaOH

TsNBu

_ I

6

1 PrI

SECTION 100

Bull SOC Chim Fr (1970) 1938

COOEt I TsNNa

C7H1 5 B r

Me

-

Arch Pharm (1911)

2 NaOH

BuBr

RBr

CH2=CHCH2yCH2Ph

2 Na-Hg

1 (NH2)2C=NH

RBr

OF ORGANIC SYNTHETIC METHODS VOL 2

< 60%

--+ BuNH2

JOC (1971)

36

4102

RNH2 Bull Chem SOC Jap (1971)

C7H15vSO2CF3 CH2Ph

0

TsNHBu

1 NaH

DMF

2 HC1

H 2 0 THF

*

C7H15NH2

T e t r L e t t (1973) 3839

JOC (1972)

31 335

44 2797

80%

S e c t i o n 101

ArH

R2CO

Amines f r o m H y d r i a e s

00000000000000000000

Me2NC1

H2SO4 Na2S04 b

S e c t i o n 102

ArNMe2

Synthesis (1973) 1

Amines f r o m Ketones

0000000000000000000

Me2NH NaBH3CN MeOH

101

AMINES FROM KETONES

SECTION 102

pH 6-8

*

R2CHNMe2 JACS (1971)

93 2897

Chem Corn (1971) 1433

R2CO

--+

R2C=NOH

Na

R'OH

R2CHNH2 Chem Ind (1972) 683

Chem Ind (1969) 260 R e l a t e d methods:

Amines f r o m Aldehydes ( S e c t i o n 94)

102

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

S e c t i o n 103

Amines f r o m N i t r i l e s OOOOOOOOOOOODOOOOOOO

EtMgBr

PhCN

toluene

60%

PhCEtp

w

I

NH2

H2

c1 2H25CN

Ni

Ac20

NaOAc

*

Tetr Lett (1973) 1057

C1 ~ H ~ ~ C H ~ N H A--+ C

JOC (1960)

PrCN

PrCN

H2

Pt02

N2H4.H20

EtOH

Ni

CHC13

*

EtOH

*

PrCH2NH2 J O C (1972)

PrCH2NH2 JOC (1971)

PhCHZCHCN

SECTION 103

AlH3

THF

HOCH2:HaCN

A

2 1658

2 335

36

JACS (1968)

NaBH4

MeOH

Ni

96%

75% 3539

78%

PhCH=CHCHZNHz

-

C ~ ~ H ~ ~ C H ~ N H Z -100%

90

2927

HOCHZ:~?

A

A n n a l e n (1972)

756 1 4

103

AMINES FROM OLEFINS

SECTION 104

NaBH2S3 THF

40% Can J Chem (1971)

2990

63%

S e c t i o n 104

Amines from O l e f i n s

a o ~ o o ~ ~ o o o o ~ o o o o o ~ ~

FH2NMe2 Me2NH CO

((CH2) CH=CH) 10

Rh2O3

140 atrnos

170"

1 LiBH4 BCl3

3 KOH

B2H6

---+

H20

(CH'CH)

F

(CH2)lO

Helv (1971)

90%

54 1440

- 0

Et20

2 BUN^

EtCHICHZ

Fe(C0)5

N-rnethylpyrrol i d i n e

64 %

NHBu

H20

(EtCH$H2)3B

94 2114 (1971) 93 4329 (1973) 95 2394 2396

JACS (1972)

Me2NC1

EtCHzCHzNMe2

J Organometallic Chem (1970) 23 C11

1 04

-

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

PrNH2 Na

PhCH=CH2

1 03 MeOH

Ni 3 Me2NH

2 H2

NaN3 H2S04

18% Ber (1950) J O C (1972)

-

C14H2gCH=CH2

PhzC=CHEt

PhCH2CH2NHPr

2

65%

T e t r Lett (1971) 3591

PhNH2

12 5777

57%

Amides ( S e c t i o n 8 9 )

S e c t i o n 105

N3

Amines f r o m M i s c e l l a n e o u s Compounds 00000000000000000000000000000000000

LiAlHq J O C (1962)

Me

ArN02

1 4243

C14HzgCH2NMe2

JACS (1950)

Also via:

SECTION 105

Ber (1972)

-

It

ArNHZ

J O C (1972)

I,

Sn, HC1 JACS

(1969)

27 2925 105 1524

37

335

91 3544

H2/Pd JOC (1972) 3,J 335 NaBH4, CoC12 T e t r L e t t (1969) 4555 NaBH2S3 C a n J Chem (1971)

2 2990

CO, RhC13 T e t r L e t t (1971) 3385

Fe3(C0)12 JOC (1972) Fe(C0)S

37 930

Can J Chem (1970)

2 1543

34 %

105A

SECTION

105

PROTECTION OF AMINES P r o t e c t i o n o f Amines

S e c t i o n lO5A

a o o o ~ o o ~ ~ ~ ~ o ~ o o o o o o o

Q HCOOH H20

NH2

CF3

PIHCHO

hu MeCN

ONH O '

cF3 C h e m C o r n (1972) 758

C1 COOCH2CH=CH2 liji (CO)4

DMF

Pyr

*

Me2NCH2CH2NMe2 H20

OQ

COOCH2CH=CH2

38

J O C (1973)

RNH7 -

C1 COOCH2CC13

3

Zn

MeCN

HC1

3223

RNHCOOCH2CC13

H20

a 1259

J O C (1971)

S e l e c t i v e removal o f h a l o e t h o x y c a r b o n y l groups by e l e c t r o l y s i s J A C S (1972) 94 5139

Ph 1 Ph

PhCHzCH2NH2

"\ H2

KO. co d

2 CF3COOH

DMF

*

PhCH2CH2N

/

/

co\

0

H Ph Ph

Pd-C

o r m-chloroperbenzoic a c i d C F3 COOH o r NaHH2

J A C S (1972)

94 6561

COHPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

106

EtOOC

COOEt

EtOOC

+

Ph3CC1

RNH2

Pyr

+

T e t r Lett (1971) 3165

RNHCPh3

HOAc H20

Me

COOEt (Stable t o HC1, Ac20, KOH and CdMe2) CIi20CH2Ph

1 H2 Pd-C 2 PhCH2NNe3 OH

H

SECTION 105A

J Med Chem (1973)

QNH2

16 959

*

+---------------

Me @JNyI:lective

f o r NH in presence o f O H )

Chem Corn (1972) 1148

PhCH2CHNH2 - 1

Me

~

TsCl

Pyr

Et20

*

*NaAlH2(0CH2CH2OMe)2 to1 uene

PhCH7CHNHTs - 1

Me

J O C (1972)

37

2208

Cleavage of sulfonamides with h v T e t r Lett (1971) 4555 4559 Chem Pharm Bull (1970)

H2SO4, HOAC Chem Corn (1973) 664

182

SECTION 105A

PROTECTION

CNH

(CF3S02)20

4

LiAlH4

107

-c

CH2C12 C6Hg

OF AMINES

NS02CF3

( S t a b l e t o Zn/acid)

Tetr Lett (1973) 3839

CH=N

MeOH HC1

Me2C0

H20

Can J Chem (1968) JCS (1971) 3864

46 2549

Compendium of Organic Synthetic Methods, Volume2 Edited by Ian T. Harrison, Shuyen Harrison Copyright 0 1974 by John Wiley & Sons, Inc.

Chapter 8

Section 106

Esters from Acetylenes

P

T1 (NO3)3 MeOH

PhCXEt

PREPARATION OF ESTERS

Et I PhCHCOOMe

JACS (1973)

95

82%

1296

Also via: Carboxylic Acids (Section 16)

Section 107

Esters from Carboxylic Acids and Acid Halides 000000000000000000000000000000000000000000000

...

Homologation of carboxylic acids. . . . ..... Esters by reaction of carboxylic acids, acid halides etc. with alcohols . Esters by reaction o f carboxylic acids with halides, sulfates and sulfites . Esters by reaction of carboxylic acids and acid halides with miscellaneous reagents .

RCOCl

1 CH2N2 Et3N Et20

b

2 PhCOOAg Et3N EtOH

. page 108 . . . . 109-110 . . . . 110-111 . . . . 111-112

85-92%

RCH2COOEt Org Synth (1970) 108

77

BCooH

SECTION 107

ESTERS FROM CARBOXYLIC ACIDS AND ACID HALIDES

$'JcoMe

conc MeOH HC1

____t

T e t r a h e d r o n (1971)

R'OH

RCOOH

D

COOH

BF3.Et20

*

RCOOR'

BuOH resin-A1C13

*

109

44%

2 4845

S y n t h e s i s (1971) 316

D

COOBu

56%

T e t r Lett (1973) 1823

67%

110

COMPENDIUM

cocl

t-BuOLi

OF ORGANIC SYNTHETIC METHOOS VOL 2

t-BuOH

Me

*

Me

SECTION 107

@cooBu-t Org Synth (1971)

79-82% 96

F u r t h e r examples of t h e r e a c t i o n RCOOH + ROH +RCOOR are included i n s e c t i o n 108 ( E s t e r s f r o m A l c o h o l s and Phenols) and s e c t i o n 30A ( P r o t e c t i o n of C a r b o x y l i c A c i d s )

HO

HO

mcH2 100%

RX=MeI a t 25" RX=C,jH13Br a t 90" J . R i e g l , I . T . Harrison (Syntex Research) unpublished

EtI

K2CO3 CHzCOOE t Me T e t r L e t t (1972) 1853 J O C (1969) 2 3717

Me

91 % Synthesis (1972) 262

Me

@: Me

Me 1 NaOH HMPA

2 i-PrI

H20 Me T e t r L e t t (1973) 689 (1972) 4063

100%

SECTION 107

ESTERS FROM CARBOXYLIC ACIDS AND A C I D HALIDES

PhCH2Br

RCOOK

DMF

BuBr PhCH2COOH

RCOOCH2Ph

J O C (1962)

111

3 1381

ONC *

86%

PhCH2COOBu

Synth Corn (1972) 2 1 JOC (1973) 38 1753-

@ CF3

Me2CO

PhCH=CHCOOH

SH !

Me2CFHCOOH

,+90%

CF3 Chem Ind (1972) 691 Tetr Lett (1972) 757

Et2S04-HCONMe2 f

150'

Me2S03 HC1

COOEt

PhCH=CHCOOEt

Ber (1971)

MeOH

*

SH

83%

M~~~CHCOOM~ NH2

NH2

J Med Chem (1971)

1:

@

94%

104 3711

14 868

COOBU-t

t-BuOAc

22% COOBU- t

NO2 Annalen (1961)

646

119 134

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

-

112

Et3SiH

BuCOF

BuCOOCH~BU

Me

JOC (1971)

36

SECTION 107

2547

-@N-NNHMe 70-90%

NO2

*

Et.20

No2@cooMe NO2 Org Synth (1968)

48 102

NO MekONH2 Et3N MeOCH2CH20Me

*

100%

@JCOOMe NO2

Tetr Lett (1973) 1397

c -

Et30 BF4

E t 3 C COOH

+

C13H27COOH

RCOOH

(i-Pr)ZNEt

*

*

2 Toluene ( r e f l u x )

Pb (O A C ) ~

Tetr Lett (1971) 4741

90%

-

1 PhNMe3 OH MeOH

-

Et3CCOOEt

C13H27COOMe

> 90%

Synthesis (1973) 494

ROAc Org React (1972)

279

SECTION 108 S e c t i o n 108

ESTERS FROM ALCOHOLS AND PHENOLS

113

E s t e r s from A l c o h o l s and P h e n o l s

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 00 0 0 0 0 0 0

NDNMez

(PhC0)ZO ROH

PhCOOR

t

Synthesis (1972) 619

Hocwr C

l

o OCHZCOC1

2,6-lutidine

C

78% (1971) 3230

&COOi:CHzPh

w

Et

C6H6

*

MeCN

JCS

PhCHZCHOH I Ph

Cl@

Et J A C S (1953)

PhCO,

EtOH

Resin-CO'

0

to1uene

i-Pr , A Y MP .-

7$ 6011

EtCOCl

PhCOOEt Tetr Lett (1973) 1627

SO2

EtCOO

*

2

U Me

Synthesis (1971) 639

92%

114

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

MeOCH2COOH Pyr

ROH

'.c[

t

Can J Chem (1971)

-

MeCOCl

MeOCH2COOCH2

t r i isopropyl benzenesul fonyl chloride

O x 0 Me OMe

Mg

SECTION 108

49 493

ROAc

92% T e t r a h e d r o n (1971)

2

753

'''oh phcoo C:PN,:

Bu3N

PhCOO

OH

T e t r Lett (1971) 185

&

' ___t YNCooEt COOH

HO

phC0O.s'&ocoph

NCOOEt Ph3P

T e t r L e t t (1973) 1619

(EtC0)ZO NaOH H20 Ph

*

EtCo@g3Jph 73%

JACS (1942)

3

2271 3163

ESTERS FROM ALDEHYDES

SECTION 109

115

i-PrCOO

i-PrCOOH H3B03

58%

\

H2SO4 xylene T e t r L e t t (1971) 3453

Further examples of the reaction ROH + R'COOR are included in section 107 (Esters from Carboxylic Acids a n d Acid Halides) and section 45A (Protection of Alcohols and Phenols)

Mn02

(CH=CHC=CH)2CH20H

(CH=CHy=CH)$OOMe

52%

_____t

MeOH HOAc pet ether

C5H11CH20H

Section 109

02 C O ( O A C ) ~ HOAC

:

CoBr2

C5H1 iCOOCH2CgH11 Can J Chem (1965)

43 1306

Esters from Aldehydes oOOOOOOOOOoooOoOooOOo

dHo (EtO)*POCHCOOEt Na+ Me

Chem Ind (1971) 1016

MeOCH2CH20Me

O : f . C H C ~ ~ ~ ~ ~

@CHZCH2COOEt

t

Ele J O C (1971)

2 1040

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

116

CHo Me 0

PhCH=CHCHO

1 MeSOCH2SMe Triton B 2 HC1 EtOH * Me0 @cH2CooEt

SECTION 109

93%

Tetr Lett (1972) 1383

1 BuLi

--+ PhCH=CHCH

2 Me2S2 3 HgO HgC12

PhCH=CHCOOEt

J O C (1972)

37

c 84%

2757

< 90%

NBS

PhCHO --+ PhCH(OEt)2

Bu$HCHO Et

H3BO3 heptane 250'

*

PhCOOEt JACS (1951)

BuCHCOOCH~FHBU I Et Et J O C (1973)

Related methods: Also via:

2 973

Esters from Ketones (Section 117)

O l e f i n i c e s t e r s (Section 362)

47%

38

1433

ESTERS FROM ESTERS

SECTION 113 Section 110

117

Esters from Alkyls, Methylenes and Aryls 0000000000000000000000000000000000000000

No examples of the reaction RR -+ RCOOR' or R ' C O O R (R,R'=alkyl, aryl e t c . ) occur in the l i t e r a t u r e . For the reaction RH --F RCOOR' or R'COOR see section 116 (Esters from Hydrides)

Section 112

Section 113

Esters from Amines

D00000000000000000

Esters from Esters

0D0000000000000000

1

BuCH~COOBU-t

:rRro

2 Me1 , Me2SO

THF

*

BuFHCOOBu-t

Me JACS

(1971)

83%

93 2318

T e t r Lett (1973) 2425

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

118

EtOH Bu3SnOEt

*

PrCOOPr

PrCOOEt

SECTION 114

Bull SOC Chim Fr (1969) 262

KCN Synthesis (1973) 790

BuOH C02

PrCOOEt

C1 lli23COOMe

P q C ( COOEt)2

Section 114 i-PrCH20R

R20

PrCOOBu

Bull Chem SOC Jap ( 1 9 7 1 ) , s 852

1 (i-Bu)zAlH octane

C11 H23CH20Ac

w

2 Ac20

Synthesis (1971) 309

NaCl Me2SO H20 178-183"

Pr2CHCOOEt

w

Tetr Lett (1973) 957

Esters from Ethers

P

Trichloroisocyanuric acid

*

H20

TsOAc MeCN

i - Pr COOR

Tetrahedron (1971)

ROAC

JOC (1971)

36

27

532 540

2671

271

SECTION 115 S e c t i o n 115

E s t e r s from H a l i d e s

OOOOOOOOOOOOOOQOOOO

1 NaCXOEt

BuBr

NH3

*

BuCH2COOEt

HgO EtOH

2 H2SO4

JCS (1954) 1860 Advances i n Org Chem (1960)

oBr

Tetr Lett (1972) 1163

BrCH2COOEt

2 CdC12

PhCHZC1

ArZCd

1 (s:CHCooEt s

2 Ni

RI

69%

b

- 1 Mg

2 117

CH2COOE t

CuCH2COOEt THF

ArBr

119

ESTERS FROM tiALIDES

NaH

DMF

t

EtOH

ArCH2COOEt JOC (1973) 38 3189

PhCH2CH2COOEt JOC (1972)

CH2 ( C O O E t ) 2

NaCl

Me2SO

EtONa

H20

178-183'

----------+ R$(COOEt)2

t

37

48% 505

R2CHCOOEt

Tetr Lett (1973) 957

oCHZBr

COMPENDIUN OF ORGANIC SYNTHETIC METHODS VOL 2

120

t

RI~I:

SECTION 115

-

0 c H 2 p p h 3Br

2 ClCOOEt

Annalen (1964) 674 11

1 Na2Fe(CO)4 C8H17C1

2 I 2 N-methylpyrrol idone

+

EtOH

CgH17COOEt

JACS (1973)

CO SbC15 EtOli

t-BuC1

RBr

SO2 CH2C12

CuOAc Pyr

Related methods:

Also via:

+

89%

249

t-BuCOOEt

66% Synthesis (1971) 639 Bull Chem Soc Jap (1971)

ROAc

( R i s l r y , 2ry or 3ry, a l k y l , a l l y l i c or v i ny 1 i c ) Tetr Lett (1972) 491

Carboxylic Acids from Halides (Section 25)

Acetylenic e s t e r s Olefinic e s t e r s

44 2001

Section 306 362

ESTERS FROH HYDRIDES

SECTION 116 Section 116

121

Esters from Hydrides

P

T h i s s e c t i o n contains examples of the r e a c t i o n RH + RCOOR' or R'COOR (R=alkyl, a l l y l , a r y l e t c . ) and ArH + Ar-X-COOR (X=alkyl c h a i n )

FH2COC1

\y(CH2)3COOMe

1 CH2COOMe AlCl3

COOEt

h

2 H2 Pd-C JACS (1955)

1 CH2CO ?2C!j&

AlC13

2 MeOH acid 3 H2 Pd-C

1

*

3 0 C (1972)

@ -

3856

a

(CH2)3COOMe

37

3687

BrCH2COOEt

Me

0

N2CHCOOEt

Me @cH2cooEt Tetrahedron (1972)

hV

CH2COOEt J A C S (1956)

78 4947

2 211

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

122

Me

Benzoyl peroxide

PhH

Pd(OAc)2

K2Cr207

t

LiOAc HOAc

RzCzCHCHR2

*

CuCl CuC12 MeCN

Me

-

PhOAc

kJMe

Me

OCOPh

C1 (CH2)3COI Me

24%

S y n t h e s i s (1972) 1

J O C (1971) 36 1886 S y n t h e s i s ( 1 9 7 3 ) 567

R,C=CH?R2 OAc

Hg(0Ac)z S y n t h e s i s (1971) 527 PhC002Bu-t or MeC002Bu-ty CuX S y n t h e s i s (1972) 1 Mn02, HOAc JCS 4. (1971) 2355 Co(OAc)2, 02 Can J Chem (1965) 43 HOAc, electrolysis JACS (1972) 94 7892

Section 117

SECTION 117

1306

Esters from Ketones 0000000000000000000 1 C5H11MgBr Et2O 2 ACZO

OAc C1 ( C H ~ ) ~ { C ~ H I ~ Me JOC (1948)

13 239

> 75%

SECTION 117

ESTERS FROM KETONES

123

Me COOMe 1 Br2

2 MeONa

3 AgNO3

MeOH

4 Acid

5 (Ph3P)3RhC1

JACS (1973)

PhCOMe

Tl(N03)3

HClO4

MeOH

95 2038

84 %

PhCH2COOMe JACS (1971)

76%

93 4919

T e t r Lett (1968) 5405

124

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

PhCOCHj

Also v i a :

Section 118

RCN

1 i-PrCH2CH20NO

Et20

Compt Rend (1942)

214

113

Section 27 360 362

Carboxylic a c i d s Ketoesters O l e f i n i c esters

Esters from N i t r i l e s 0000000000000000000

w

RCOOMe

Ber (1972)

1778

84 %

Esters from O l e f i n s

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0O O O T

1 BH2C1 *Et20

JACS (1972)

Carboxyl i c a c i d s O l e f i n i c esters

78%

CH2COOEt

2 N2CHCOOEt

Also v i a :

> 90%

PhCOOMe

b

2 Me2S04 NaOH H20

HC1 MeOH Et20

Section 119

HC1

SECTION 119

Section 29 362

94 3662

Section 120

E s t e r s from Fliscel laneous Compounds

Me

-

00000000000000000000000000000000000

MeCH=CHCOOCHEt I

125

ESTERS FROM MISCELLANEOUS COMPOUNDS

SECTION 120

BuMgBr CuCl

Et2O

MeCHCH2COOCHEt

85%

I

I

Me

BU

Acta Chem Scand (1961) Org React (1972) 19 1

PhCH=CHCOOMe

NaBH4

NiC12 MeOH

PhCH2CH2COOMe Chem Pharm B u l l (1971)

BuCHCOOEt

WaBH3CN HMPA ____f

271

19 817

BuCH2COOEt

Br

100%

90%

Chem Corn (1971) 1097

OcooEt0 OCH20Me

C1 CH20Me NaH HMPA )r

t-Bu

COOEt

::2f4H3b

t-BU

J O C (1970) (1971)

JACS (1950)

35 36

t-Bu

2601 2597 1151

2 4296

32%

126

CONPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

Section 120A

Protection o f Esters

SECTION 120A

00000000000000000000

HgO BF3 THF H20

(Stable t o HOAc, KOH and L i A l H 4 ) JACS (1973)

95 5829

Compendium of Organic Synthetic Methods, Volume2 Edited by Ian T. Harrison, Shuyen Harrison Copyright 0 1974 by John Wiley & Sons, Inc.

Chapter 9

PREPARATION

OF

ETHERS AND EPOXIDES

S e c t i o n 121

E t h e r s and Epoxides f r o m A c e t y l e n e s

0000000000000D000000000000000000000

No examples

S e c t i o n 122

E t h e r s and Epoxides f r o m C a r b o x y l i c A c i d s

00000000000000000000000000000000000000000

No a d d i t i o n a l examples

S e c t i o n 123

HO

E t h e r s and Epoxides f r o m A l c o h o l s and Phenols OOOOOOOOoOooOOOOOOOOOODOODOODOOOOOOOOOOOooooo

&';;wmlL

J O C (1972)

127

~ 6 0 %(R=Me) 50% (R=Ph)

RO

37

912

128

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2 1 K

t-BuOH

Me2SO

Me1

C7HI50H

“

w

2 (i-Pr)$COOMe

O

c

NaH THF

W

C7H150Me

SECTION 123

50%

t-BuOMe Tetr Lett (1964) 2969

Tetr Lett (1973) 21

PhCHN2 S n C 1 2 MeOCH2CH20Me MeOH

401

38% PhCH20

OH

JOC (1972) 2 3398

CH2N2

HBF4

CH2C12

t

ROH

+-

E t 3 O BF4

RoMe

Org Synth (1961)

41 9

CH2Cl2

95% Tetr L e t t (1971) 1999

COMe

Me2S04

K2CO3

_____)

&OH

Me2CO

c & k C O M eOMe

Chem Pharm Bull (1964) 11 312

SECTION 123

Me

ETHERS AND EPOXIDES FROM ALCOHOLS AND PHENOLS

&I:-t

Me1 NaH THF +

&I::;" 86%

Me

T e t r L e t t (1973) 21

w

2 MeNNO

MeOCH2CHzOMe

T e t r Lett (1973) 1397

t

ArOH

-

PhNMej OH A

ArOMe

(Gas chrom scale)

J Pharm Sci (1969) 2 370

Related methods: Protection o f Alcohols and Phenols (Section 45A)

NaOCl CgH, 1 OH ----+ C5H11OC1 HOAc

CHCl =CHC1 hg

Freon-113

129

MeFH(CH2)30H

c1

Luti d i ne

J O C (1972) 31 3514

Synthesis (1971) 501

130

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

Q!

SECTION 124

PhCH

HoI OH 1

PhCHO

----*MeCHCHMe

MeCHCHMe

0

1 NBS cc14 2 NaOH HOCH2CH20H

JOC (1973)

MeiiCHMe

80%

2 1691

MeCCOOH I \

Ho OH MebHbHMe

MeCOCOOH

I

1

i o n exch r e s i n C6H6

2 Base

JOC (1973)

MeiiCHMe

38

Chimia (1969)

S e c t i o n 124

1173

2 267

E t h e r s and Epoxides f r o m Aldehydes

0 0 0 0 0 0 0 0 0 0 0 0 0 00 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

Ph2PONa PhCHO

C7H15CHO

0

1 PCl5 CH2C12

MeCHCHMe

t

0

180'

*

Ph

LtkHP h

MeCHBr2 BuLi (or L i ) THF

*

JCS Perkin I (1972) 1113

0

I \

C7H15CHCHMe

88%

80%

Tetrahedron (1972) (1971)

27

3009 6109

SECTION 129 Section 125

ETHERS AND EPOXIDES FROM ETHERS AND EPOXIDES

131

Ethers and Epoxides from Alkyls, Methylenes and Aryls

!

No examples of the preparation o f ethers and epoxides by replacement of alkyl, 'methylene and aryl groups occur in the l i t e r a t u r e . For the conversion RH + ROR' (R,R'=alkyl) see section 131 (Ethers from Hydrides)

Section 126

Ethers and Epoxides from Amides 0000000000000000000000000000000

No additional examples

Section 127

Ethers and Epoxides from Amines 0000000000000000O00000000000000

No additional examples

Section 128

Ethers and Epoxides from Esters

boooooooooooooooooooooooooooooo

No additional examples

Section 129

Ethers and Epoxides from Ethers and Epoxides 00000000000000000000000000000000000000000000

PhOEt

PhoMe

@2

Chem Comm (1972) 315

C8H17

AcO

AcO&

0."

Synthesis (1971) 32

48%

COMPENDIUM OF ORGANIC SYNTHETIC HETHODS VOL 2

132 S e c t i o n 130

PhBr

Ethers f r o m H a l i d e s

-

aoooooooooo0 ~000000

1 Mg Et20

2 CdC12

PhCH20Me

3 ClCHzOMe

PhBr

1 Mg Et2O 2 (BuO)~P(O)OOBU-~

S e c t i o n 131

J O C (1973)

38

3189

J O C (1972)

37

2267

PhOBu-t

95%

Ethers f r o m H y d r i d e s

00000000000000000000

T h i s s e c t i o n l i s t s examples o f t h e r e a c t i o n RH Electrolysis

RzbCHCH2R

--t

ROR

+ -

Et4N OTs

P

MeOH

RzC=CHCHR 1

OMe J A C S (1972)

CH3 02 methylene b l u e M~

Me

hv

MeOH CgHg

Me

S e c t i o n 132 R2CO

SECTION 132

*

94 7892

CH20Me Me

Me Me J O C (1971)

36

Ber (1973)

106 2620

1765

Epoxides f r o m Ketones

000000000000000000000

1 LiCHC12 E t 2 0 > 2 BuLi

0 R2C-CHBu I t

31 %

SECTION 134 R2CO

133

ETHERS AND EPOXIDES FROM OLEFINS 0

MeCHBr2 BuLi THF

I \

R2C-CHMe

+

2 3009

Tetrahedron (1972)

2 6109

(1971)

(t-Bu)zCO

1 PhSCH2Li THF t -

2 Me30 BF4 CH2C12

3 NaOH H20

Section 133

*

0

(~ - B u ) ~ C - C H ~ I \

JACS (1973)

2 3429

Ethers and Epoxides f r o m Nitriles 000000000000000000000000000000000

No examples

Section 134

Ethers and Epoxides from Olefins

00000000000000000000000000000000

0

OMe

Synthesis (1972) 483

JCS

(1971) 1174

42%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

134

MezC=CH2

T1( OAC ) 3 HOAc H20 THF

0

I \

< 82%

MezC-CH2 J O C (1971)

(40 AgOAc

t-Bu

SECTION 134

36

1154

KOH

t-Bu

t-Bu T e t r a h e d r o n (1972)

2 3475

74% MeCN H20

0 T e t r Lett (1973) 4359

[Mo (02)20] *HMPA

*

0 I \ CgH13CHCHMe T e t r a h e d r o n (1970) 26- 37

0

m-Chl oroperbenzoi c a c i d

I !

t

C~H~~CHCHZ

4,4 ' - t h i o b i s - (6-t-butyl-3-methyl phenol) C1CH2CH2C1 (Applicable t o unreactive o l e f i n s )

Chem Comm (1972) 64

*e

EPOXIDES FROM MISCELLANEOUS COMPOUNDS

SECTION 135

m-Chloroperbenzoic acid NaHC03 CH2C12 H20 OAc

135

86%

OAc (Method f o r a c i d s e n s i t i v e compounds) J O C (1973)

Peracid

R2CzCR2

___t

2 2267

0 I \ RzC-CRz

p-Methoxycarbonylperbenzoic a c i d J O C

(1972)

37

4210

disuccinoyl peroxide S y n t h e s i s (1973) 156 o-Sulfoperbenzoic a c i d T e t r Lett (1971) 691 P r e p a r a t i o n o f RC002H from RCOCl + (EtO)zP(O)OAg J O C (1971) 36 2162

S e c t i o n 135

Epoxides from Miscellaneous Compounds

0000000000000000000000000000000000000

J O C (1968)

33 4045

Compendium of Organic Synthetic Methods, Volume2 Edited by Ian T. Harrison, Shuyen Harrison Copyright 0 1974 by John Wiley & Sons, Inc.

Chapter 10

Section 136

PREPARATION OF HALIDES AND SULFONATES

Halides and Sulfonatss from Acetylenes 00000000000000000000000000000000000000

No additional examples

Section 137

Br2

RCOOH

00000000000000000000000000008

HgO CCl4 b

n

(CH2)7

Halides from Carboxylic Acids

C=CHCOONa

W

a

RBr

6r2 DMF

O r g Synth (1971) 106 J O C (1972) 31 669 664

n

(CH2)7

C=Ch’Br

u

45%

J O C (1965) 30 2208 JCS (1971) 2352

ocooH NCS Pb(OAc)4*

EMF HOAc

Synthesis (1973) 493 136

83%

RCOOH

I2

Pb(OAc)4

1 TlOEt

CgHigCOOH

2 Br2

Section 138

RI

pet

Org React (1972)

ether f

CCl4

2 279

89%

C9H19Br J O C (1969)

34

1172

Halides and Sulfonates from Alcohols 000000000000000000000000000000000000

Halides from a l c o h o l s . . Sulfonates from a l c o h o l s .

ROH

137

HALIDES AND SULFONATES FROM ALCOHOLS

SECTION 138

(Ph0)3P.MeI

. . . . . . . . . . . . . . . . . page ....................

RI

Org S y n t h (1971)

(PhO)QP*PhCH2C1 0

xo

ROH

Ph3P CCl4

DMF

RC1

137-139 140

44

70% 0

xo

JOC (1972)

37

2289

JOC (1972)

37

1466

138

8uOH

ROH

Ph3P *C12

BuCl

NBS Ph3P

+

[)CH20H

JACS (1964)

RBr

CH@ ;H2c5N-SMe2

Ph2CHOH

OF ORGANIC SYNTHETIC METHODS VOL 2

COMPENDIUM

2 342

-

C1

> 95%

Ph2CHC1

( S p e c i f i c f o r a l l y l i c and b e n z y l i c a l c o h o l s ) Tetr Lett (1972) 4339

.

Me2S B r 2

D

CH2Br

Chem Comm (1973) 212

T r i c h l o r o i socyanuric a c i d

*

CSHlloH

0°”

CHC13 NaOH H20 t

-

PhCHzNEt3 C1

*

JOC (1970) 2 3967 Chem Ind (1971) 1416

ocl Me

JACS (1971)

78%

44%

%H11 c1

i-Pr

i-Pr

Me

99%

964

Chem Corn (1970) 602 Carbohydrate Res (1971) Tetr Lett (1973) 3937

t

CH2C12

SECTION 138

93

1820

139

HALIDES AND SULFONATES FROM ALCOHOLS

SECTION 138

Me

83% Angew (1972) ( I n t e r n a t Ed

OCONHW

84 158

11 229)

NBS Pyr

42% (t38% di bromide)

Chem Comm (1971) 1112

i-PrOH

51-2 SO2

%N

38%

i-PrBr

S y n t h e s i s (1971) 639

CH20H

N'

Me

68%

Me Org Prep and Procedures (1970)

1. 189

NO2

Pr2C=CHCH20H

MsC1' LiCl

DMF

*

93%

Pr2C=CIICH$l T e t r a h e d r o n (1971) JOC (1971) 36 3044

21 5979

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

140

SECTION 141

100%

JCS (1953) 1225 Chem Ind (1971) 702

MsCl C F3

Et3N

92%

CF3 JOC (1970) 2 3195

Section 139

Halides and Sulfonates from Aldehydes

0000000000000000000000000000000000000

No a d d i t i o n a l examples

Section 140

Halides and Sulfonates from A l k y l s 0000000000000000000000000000000000

No a d d i t i o n a l examples For t h e conversion RH

Section 141

4

Rlial see s e c t i o n 146 (Halides from Hydrides)

Halides and Sulfonates from Amides

0000000000000000000000000000 000000

No a d d i t i o n a l examples

Section 142

NHZ

Ha,',~d,e,s,of~",oZ~~;~

CgHgONO CIiBrg

53%

NO2

NO2

1 ClCOOEt CgHg

RNMe2

t

2 KOH propylene glycol

Section 143

141

HALIDES FROM HALIDES AND SULFONATES

SECTION 145

JCS

C

(1966) 1249

RC1 J Med Chem (1971)

5 982

Halides and Sulfonates from Esters 0000000000000000000000000000000000

No additional examples

Section 144

Halides from Ethers 0000000000000000000

PhgP-Brp R20

Section 145

PhCN

t

RBr

JOC

(1972)

37

626

Halides from Halides and Sulfonates 00000000000000000000000000000000000

S L~CHZS~~]

PhCH2CHzBr

2 Me1 DMF

*

Ph(CH2131 T e t r L e t t (1972) 2743

C 70%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

142

SECTION 146

50%

ROMs

liar EtCOMe

RI

0'' 1 Li

Et20

T e t r a h e d r o n (1971)

ox

~

2 Xp pentane

ArBr

CuCl

OH

picoline

ArCl

JACS (1958)

80

1716

Halides from Hydrides

P

MeCHCHzC1 I

PhH

57% (X=Br) 692 (X.1)

T e t r a h e d r o n (1972) 28 4883 Ber (1971) 104 2412-

____j

Section 146

11 5987

BF3 P2O5

*

Me PhCHCHzC1 JACS (1948)

37% 1772

p HpH s HALIDES FROM HYDRIDES

SECTION 146

143

53%

J Pled Chem (1972) 15_ 1297

JACS (1958)

Me

4327

NBS H2SO4 H20

t

95%

Other Ar brominating agents: IBr Br2-SO2 Br2-AgzS04 T1 (OAc)3-Br2 Ar chlorinating agents: TiC14-CF3C002H Ar iodinating agents: T1 (OCOCF~)Q-KI 12-HI04

t-BuOC1

dibenzoyl peroxide

30

J O C (1965)

304

JACS (1938) 60 256 B u l l SOC Chim F r (1971) 1785

Rec Trav Chim (1960)

31 88

J O C (1972)

Can J Chem (1972)

2 1022 1233

93 4841 (1971) 2 94

JACS (1971)

Org Synth

OC’ Helv (1957)

40 130

77%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

144

HO (CHz)&HzMe

( i - P r )2NC1 hv H2SO4 H20

*

SECTION 149

tiO(CH2)6FHMe

6040%

c1

JACS (1971) 93 438 Synthesis (1973) 1

FH3 t-BuCMe2

Br2 HgO CCl4

*

CH2Br t- Bu ;Me 2 Can J Chem (1972)

Section 147

32% 3109

Hal ides from Ketones 00000000000000000000

No a d d i t i o n a l examples

For the r e a c t i o n C=O + C(Hal12 see s e c t i o n 368 (Halide-Halide)

Section 148

Halides and Sulfonates from N i t r i l e s 000000000000000000000000000000000000

No examples

Section 149

Halides from Olefins 00000000000000000000

For t h e conversion of o l e f i n s t o d i h a l i d e s s e e s e c t i o n 368 (Halide-Halide) For a l l y l i c halogenation s e e s e c t i o n 146 (Halides from Hydrides)

SECTION 150

HALIDES FROM MISCELLANEOUS COMPOUNDS

NBA

145

(I -Br

HF

Bu3SnH

Synthesis (1971) 255

i-PrCH=CHMe

BuCHSCH~

S e c t i o n 150

CH24HCH2Cl MeCH=CHCl

C7H1gSH

1 9-BBN

2 By2

THF

CHzC12

1 B2Hg THF 2 CH2=CHCHzI

*

air

i-PrCHeFHMe Br 3 Organometallic Chem (1971)

74%

2 C51

BuCH2CH2I JACS (1971)

93 1508

H a l i d e s from M i s c e l l a n e o u s Compounds

2

H2 (500 p s i )

Rh-Al2O3

ClCOSCl

Ph3P

*

*

MeCHzCH2Cl JOC (1964) 9 194

C7H15c1 Chem Corn (1972) 773

42-58%

Compendium of Organic Synthetic Methods, Volume2 Edited by Ian T. Harrison, Shuyen Harrison Copyright 0 1974 by John Wiley & Sons, Inc.

Chapter 11

PREPARATION OF HYD R I D ES

This chapter 1 ists hydrogenolysis and related reactions by which functional groups are replaced by hydrogen, e.g. RCH2X + RCH2-H or R-H

Section 151

Hydrides from Acetylenes

O O O O O O O O O O O O O O O O O O O O O O ~ ~

No examples of the reaction R C 3 R + RH occur in the literature

Section 152

Hydrides from Carboxylic Acids 000000000000000000000000000000

This section lists examples of the decarboxylation o f acids, RCOOH

CCOOH

-

---f

RH

Soda-1 ime

230'

Ph

JCS (1962) 1445

JACS (1950)

Section 153

72 1849

Hydrides from Alcohols and Phenols

0000000000000000000000000000000000

This section lists examples o f the hydrogenolysis of alcohols and phenols, ROH + RIi 146

SECTION 153

HYDRIDES FROM ALCOHOLS AND PHENOLS PhgSiH CF3COOH

Et3COH

*

CH2C12 (3ry only)

JOC (1971)

( PhO) 3P * Me1

ClOH210H

Et3CH

HMPA

NaBH3CN

b

147

a 758

c1 OH22

78%

99%

Chem Corn (1971) 1097

-G d j

1 BuLi MeOCH2CH20Me 2 (Me2N)zPOCl 3 Li EtNH2 t-BuOH THF

JACS (1972)

OH

1 Li

89%

94

5098

NH3 THF

2 NH4C1

Tetr Lett (1971) 1853

OH

@ OH

PhNCO

OCONHPh

OCONHPh Chem Ind (1973) 187

70%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

148

ArOH

?h N -N 1 ‘lgN-;;

K2C03 Me2CO

2 H2 Pd-C

SECTION 154

ArH 0rg Synth (1971)

82

-

@@OH

2 A

3 NaOH MeOH

JOC (1966)

Also via:

Halides and Sulfonates Ethers

Section 154

31 3980

Section 160 159

Hydrides from Aldehydes 00000000000000000000000

This s e c t i o n l i s t s examples o f the decarbonylation of aldehydes, RCHO 3 RH. For the conversion RCHO + RMe e t c . s e e s e c t i o n 64 (Alkyls from Aldehydes)

RCHO

C6Hl 3CH0

Pd-C

‘190’

hl/

RH

JOC

PhCH2SH PhCOMe

t

(1968)

33 923

CtiH14 JACS (1963)

85 4010

HYDRIDES FROM AMINES

SECTION 157

CHo

Fe(C0)5 Bu2CO

*

i-Pr

i-Pr

149

36%

Tetr Lett (1973) 447

Section 155

Hydrides from Alkyls, Meth,ylenes a n d Aryls 000000000000000000000000000000000000000000

No additional examples

Section 156

Hydrides from Amides

~ ~ ~ O C O C O O O O O O O O C ~ O ~ ~

-

This section l i s t s examples of the conversion RCONH2 -+ RH

t-BuCiCCONH2

Also via:

Section 157

NaNH2 NH3

t-BuCXH

JCS (1963) 4402

Carboxylic acids (Section 152)

Hydrides from Amines 00000000000000000000

This section l i s t s examples o f the conversion RNH2 -+ RH

66% JCS Perkin I (1973) 5 4 1

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

150

SECTION 159

gJNH2 +.a COOEt

i-PrCH2CH20NO hydroquinone

H2SO4 dioxane

COOEt

ArNH2

-

Section 158

COOEt

COOEt

Chem Comm (1973) 605

+ -

ArM2

X

Y

ArH

Y=RhCl (PPh)3 J O C (1971) 36 1725 Bu3SnH T e t r a h e d r o n (1970)

4609

Hydrides from Esters 00000000000000000000

This section lists examples of the reaction RCOOR' + R'H PhCOOCHPh2

Bu202 Bu3SnH

*

Ph2CH2 T e t r L e t t (1968) 4351

Section 159 PhONe

Hydrides from Ethers

Ni MeOH

PhH

A u s t J Chem (1963)

16 20

62%

HYDRIDES FROM HALIDES AND SULFONATES

SECTION 160

151

Hydrides from Hal i d e s and Sulfonates

Section 160

000000000000000000000000000000000000

This s e c t i o n l i s t s t h e r e d u c t i o n o f h a l i d e s and s u l f o n a t e s RX

NaBH3CN HMPA

c12H25X

--f

RH

96% (X=I) 97% (X=Br) 78% (X=OTs )

c12H26

C h e m Corn (1971) 1097 J O C (1971) 1568 J A C S (1973) 95 6 1 3 1

a

C8H17x

Cu I- L i A1 H (OMe ) 3 THF

b

C8H18 J A C S (1973)

95 6452

98% (X=Br) 95% (X=OMs)

99% J A C S (1973)

PhCH=CHCH2Cl

NaH TsNHNH2

Me2SO

95

1669

HOAc

PhCHzCHCH2NHNHTs + PhCHzCH'CH2

60%

T e t r L e t t (1969) 8 7 1

99% J A C S (1973)

95 6452

152

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 162

30% Tetr Lett (1973) 447

PhFHCH2Br Br

NaBH4 Me2SO

64%

PhCH2Me Tetr Lett (1969) 3495

JACS (1948) (1947)

Section 161

2 2517 2 2555

Hydrides from Hydrides

dOOOOOOOIIOOOOOOOODb000

No additional examles

Section 162

Hydrides from Ketones 000000000000000000000-

This section lists examples of the conversion R2CO ---t RH. For the conversion R CO --t R2CH2 or RzCHR' see section 72 (Alkyls and Methylenes from Ketones?

SECTION 164

HYDRIDES FROM OLEFINS ‘OPh

153

t-BuOK H20

95%

____)

anisole

Ber (1971)

Section 163

Hydrides from Nitriles

0000000000000000000000

This section lists examples of the conversion RCN RCN

Fe(acac)3-Na

CgHg

w

-P

Li

RCN

EtNH2

Na NH3

Section 164

c12H26

RH

Hydrides from Olefins 000000000000000000000

No additional examples

RH

RH JACS (1971)

C12H25CN

104 2637

93 7113

46% (R=Ph) 100% (R’C8H17)

JACS (1969) 91 2059 Tetr Lett (1968) 1975

JOC (1972)

31 508

35%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

154 Section 165

Hydrides from Miscellaneous Compounds

a

o

~

o

o

~

~

~

~

~

~

~

~

o

~

~

~

SECTION 165 ~

~

o

o

~

This sect ion lists examples of the rep1 acement of miscellaneous functional groups by hydrogen (RX + RH)

& -

NaBH4 hv

~

60% T e t r Lett (1971) 2197

-

KOH

“2

diethylene glycol

60%

Tetr Lett (1971) 3203

’” Me

Me

Ni

EtOH Me

Me

JOC (1966)

2 3980

70%

~

o

o

~

Compendium of Organic Synthetic Methods, Volume2 Edited by Ian T. Harrison, Shuyen Harrison Copyright 0 1974 by John Wiley & Sons, Inc.

PREPARATION OF KETO N ES

Chapter 12

Ketones from A c e t y l e n e s

S e c t i o n 166

BuCXH

00000000000000000000006

1 RLi 2 (CgH17)3B

*

BuFHCOCBH17

hexane

Me

3 Me2S04 d i g l y m e 4 NaOH H202 H20

RCXR

1 BH 2 H202

NaOH

Chem Comm (1973) 544

RCH2COR BH = BH2C1

BH = c a t e c h o l borane

1 NaNHNH2

85%

N2H4

2 H2SO4

Et20

*

JOC (1973)

JACS (1972)

PhCH2COC6H13 Ber (1966)

A c e t y l e n i c ketones 01 e f i n i c ketones

38 1617 94 4370

Section 309 374

155

99 1843

76%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

156 Section 167 RCOCl

PhCOF

Ketones f r o m Acid Halides

aooooooooooooooo~ooooooo~

RiCuLi

RCOR'

BupCuLi

Et20

T e t r Lett (1971) 829 Synthesis (1972) 701

PhCOBu

94 5106

JACS (1972)

ME

Br(CH2)10COCl

SECTION 167

ide Br(CH2)10CObHEt

( t -BuOCu ;HE t ) L i

t

83%

T e t r L e t t (1973) 1815

C5H11 COCl

PhCH=CHCOCl

1 NapFe(CO)4

2 EtI

HMPA THF

Li [PhCOFe(C0)4]

h

C5H11 COEt JACS (1972)

2 1788

PhCH=CHCOPh

t

87%

22%

Synthesis (1971) 5 5

PhCH=CHCOCl

RhCl (CO) (PPh3)2 PhLi Et20 THF

t

PhCH=CHCOPh JACS (1973)

95 3040

85%

KETONES FROM ALCOHOLS AND PHENOLS

SECTION 168

~ 1 ~ 1cs2 3*

157

gCo@

NO2

50%

NO2

Organometallics in Chem Synth (1971) 1 1 5 1

Also v i a :

Olefinic ketones (Section 374)

Section 168

Ketones f r o m Alcohols and Phenols

D0D0000000000000000000000000000~0

23% JCS Perkin I (1972) 2100

0 OH

t-Bu

1 Me2SOnC12 2 Et3N

> 97%

t-Bu

Tetr Lett (1973) 919

91 % JACS (1972) 94 7586

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

158

Resin-CHzN=C=NPr-i Ph

H3P04 Me2SO C6Hg

b

SECTION 168 67%

Ph T e t r L e t t (1972) 3285

C U ~ O 250-300"

C5H11 !HOH Pr

(gas phase)

100%

C5H11F0 Pr

-+

T e t r Lett (1972) 257

68% Acta Chem Scand (1971)

Cr03-3,5-dimethyl pyrazole T e t r Lett (1973) 4499

R2CHOH

PhZCHOH

PhCHOH I

Me

RuO4

R2CO

*

Ph2C=NBr hv

C6H6

1125

T e t r Lett (1970) 4003

PhIC12 Pyr CHC13

-

25

Ph2CO

49% T e t r Lett (1973) 3635

PhTO

Me

94%

JOC (1970)

35

4245

SECTION 169

159

KETONES FROM ALDEHYDES

J O C (1973)

PhCHOH PhLHOH

HC(OEt)3

-

PhCHO;C,,oEt

BuLi

PhbHO

Et20

38

625

PhCH2

< 76%

I

PhCO

Aust J C h e m (1968)

21 2013

Me PhtOH

T1 (NO3)3

HOAc

w

PhCOH

PhCOMe

I

Me

JOC (1972)

Ye

63% 4204

Ye

PhCOCHCl

@JoH

37

@ocHcoph ___t

MeCO

K2C03

Me2CO

M~CO

JOC (1961) R e l a t e d methods:

S e c t i o n 169

26

4308

Aldehydes from A l c o h o l s and Phenols ( S e c t i o n 48)

Ketones f r o m Aldehydes

a o o D ~ ~ ~ o ~ ~ o o o o ~ o o ~ o ~ o o

P h C H 2 0 g CHO

CH3COEt NaOH MeOH

PhCH20

MeCO

320-350"

-

'+>CH=CHCOEt Cycl ohexene PhCti20QCH2CH2CO:TI Pd-C

THF

JOC (1972)

37

PhCH20 2204

< 30%

160

PhCHO

-

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

1 PhSH ZnC12 HOAc

PhC(SPh)2

2 NaH Me1 DMF

CH24HCHO

Me

HgCl2

-----+

PhCO

HgO (1971)

1 HCN

2s 961 36

3553

J Med Chem (1973)

CHz=CHCHCN I OCHMe

2 EtOCH.CH2

t

Me

JOC (1963)

-

bEt

SECTION 170

1 (i-Pr)2NLi

THF

*

la 749

CH2=CHCOC6H13

C6H13Br 3 H2SO4 MeOH 4 NaOH H20

N

75%

JACS (1971) 9 3 5286 Synthesis ( l v 3 ) 777

PhCHO --+ PhyHCN OH

- D i h y d r o p y r an

HC1

Et20

PhCHCN

1 NaH Me2SO

2 C7H15Br 3 HC1 H20

0 5

Synthesis (1973) 358

R e l a t e d methods: Also v i a :

Aldehydes from Aldehydes ( S e c t i o n 49)

O l e f i n i c Ketones ( S e c t i o n 374)

S e c t i o n 170

Ketones from A l k y l s and Methylenes

~ ~ ~ ~ ~ ~ O O O O O O O O ~ O O ~ O ~ O O O ~ O O O O O O O O O O

1 0

1 NBS h3

______f

2 Na2C03

H20

Chem Comm (1972) 350

PhCOC7H15 56%

KETONES FROM AMINES

SECTION 172 02

PhBu-t

Co(OAc)2 HC1

HOAc

Section 171

PhCONEt2

b

PhCl

161

PhCOMe

23% Chem Comm (1971) 1166

Ketones from h i d e s 0000000000000000000

EtBr Li

THF

PhCOEt (One-step procedure)

(79%)

Synthesis (1973) 160

Section 172

t

-

PhNMe3 I

EtCHNH2

Ketones from Amines

0000000000000000000

1 MeCOCH2K K

2 CrO3 HzSO4

NH3

*

JACS (1972)

(V-CgHg) 2Mo (SMez)Br]+ PF6-

I

Me

P hCH2 COMe

H20

*

56%

94 683

EtCO I Me Chem Corn (1971) 1274

1

@CCtiO

C6H6

2 MeONa 3 (COOHI2 MeOH H20

Oo

JCS Perkin I (1972) 1652

86%

OF ORGANIC SYNTHETIC METHODS VOL 2

- -

162

COMPENDIUFI

No PhCHhs

1 TsCl

PhCHNH2

2 NaN02

Me

hY MeOH

{,e

HOAc

< 25%

PhCO Me

Rec Trav Chim (1971)

0

NH2

NHCH2C0Ph h r

MeOH

31 1254

Ketones f r o m E s t e r s

0000000000000000000

PrMgCl

HMPA

1 EtCHZMgCl

w

HMPA

+

2 Me1

t - Bu COPr

98%

t -BU COCHE t

81 %

I

Me

Tetrahedron (1973)

R2CHC)R

Ketones f r o m E t h e r s and Epoxides 00000000000000000000000000000000

t - B u t y l perbenzoate

t

R2COR

--+

R2CO

PhCO6

Synthesis (1972) 1

t -

(Me2CH)zO

<71%

H20

S e c t i o n 173

S e c t i o n 174

90 9 0 1

0 -0

PhCOCH2Brp

JOC (1972)

t-BuCOOMe

SECTION 174

Ph3C BF4

Me2CO

JACS (1967)

89 3550

2 479

SECTION 175

0

HF MeCN

I\

Me2C-CHMe

lloo

KETONES FROM HALIDES

163

Me2CHCOMe

67%

2 Chem (1967)

JACS (1971) Ber (1973)

Also via:

229

93 1693

106 1365

O l e f i n i c Ketones ( S e c t i o n 374)

S e c t i o n 175

Ketones f r o m H a l i d e s

00000000000000000000

. . . . page 163 . . . . . . . 163-166 . . . . . . . . . . . . . . . . . .166-1 67 . . . . . . . . . . . . . . . . . . . . . 167

Ketones by a1 k y l a t i o n and c l e a v a g e o f B - k e t o e s t e r s Ketones f r o m G r i g n a r d t y p e and m e t a l l a t e d r e a g e n t s Ketones f r o m m e t a l c a r b o n y l s M i s c e l l a n e o u s methods

BuBr

MeCOCH2COOEt

fooEt

- - - - - - - - - - - +BuCHCOMe

base

NaCl

H20

Me2SO

BuCH2COMe

T e t r L e t t (1973) 957

Cleavage o f B - k e t o e s t e r s w i t h LiH-BuLi

T e t r L e t t (1971) 4585

B203

T e t r L e t t (1970) 3903

OEt Br

$HMe 1 MeCHCN

LiN(Pr-i)2

2 H2SO4 MeOH H20 3 NaOH E t 2 0 H20

HMPA

*

OcoMe

JACS (1971)

80%

93 5286

COMPENDIUM O F ORGANIC SYNTHETIC METHODS VOL 2

164

MeCOCHZK

K NH3

*

Me

Me @ J c H Z c o M e JACS (1972)

s

SECTION 175

57%

2 683

OSiMeg

BuBr

N=C=CMe2 P h M g B r

THF

*

BuFMe2 COPh JOC (1973)

81 %

38 2129

SOEt BuBr

1 EtSiHEt

BuLi

THF

*

2 ~ ~ 1 0 4

BuCOEt Tetr L e t t (1973) 3267

Me 1 MeSCH=CHC8H17

C8H1 7Br

HMPA T H F 2 H g C 1 2 MeCN

EthHLi

*

H20 JACS (1973)

PrBr

1 MeSOCH2COPh 2 Hg-Al

NaH

THF H 2 0

DMF

b

82%

C8H17COC9H19

95 2694

PrCHZCOPh JOC (1966) 31 2355 T e t r Lett (1974) 107

44%

SECTION 175

1 CH$OCH=PPti3

CgH11Br

165

KETONES FROM HALIDES BuLi

THF

*

2 H20 E t O H

C5H11CH2COMe

JOC (1973)

82%

2 4082

ck 0 OBrOMgBr ’

CH2fHCOMe

THFb

--*

2 MeLi E t 2 0 3 NaBH4

JOC (1973)

(C00H)2

BuBr

--+ BuzCuLi

1 Mg E t 2 0

i-PrC1

CO

F

2 EtCOOMe HMPA

Et2O

Me

2 2136

Bu2CO

70%

T e t r L e t t (1972) 2803

i-PrCOEt

43% Tetrahedron (1973)

29 479

E

PhBr

PhCONEt2

Li

THF

*

Ph2CO

(One-step p r o c e d u r e )

76%

Synthesis (1973) 160

BuBr

--*

BuMgBr

PhCH2CH2COS TH F

BuCOCH~CH~P~ JACS (1973)

95 4763

< 97%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

166

BuBr

t-BUC1

1 Mg

2

SECTION 175

BuCOPh

.t

G $ = , P h IiSMe

55% Chem Ind (1972) 380

3

--+ t-BUB

1 CHz=CHCOMe THF + 2 H202 NaOH H20

t-BuCHzCH2COMe

JACS (1971)

< 90%

93 3777

Synthesis (1971) 55

C8H17Br

1 NazFe(C0)4 EtI

N-methylpyrrol idone

b

CgH17COEt

JACS (1972)

RBr

PhCH2C1

Li[R'COFe(C0)4]

EtzO CgH6

)r

94

80%

1788 2516

RCOR'

Synthesis (1971) 55

Fez(C0)g

C6Hg

(PhCH2)zCO J Organometallic Chem (1967)

52%

2

361

SECTION 176 Fe(C0)5 BuLi

PhCHpI

167

KETONES FROM HYDRIDES EtpO

t

PhCHpCOBu

50%

Tetr L e t t (1969) 5189

MeCHpBr ---w

MeCH=PPh3

OMe I 1 PhC=W(CO)5 Etp0 2 HC1

H20

t

MeCH2COPh

3 6543

JACS (1972)

Ph!HBr Me

NaN02

MepSo

Related methods: Also via:

PhTHNOp

Me

NaNOp

PrONO

_____f

MepSO

PhCO Me JOC (1973)

39%

38

1418

Ketones from Ketones (Section 177)

Olefinic ketones (Section 374)

Section 176

Ketones from Hydrides

0000000~0000000000000

This section l i s t s Ftxamples of the replacement of hydrogen by ketonic groups, RH ---t RCOR . For the oxidation of methylenes R2CHp + RpCO see section 170 (Ketones from Alkyls and Methylenes)

(Method f o r reactive compounds) Synthesis (1972) 533

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

168 S e c t i o n 177

Ketones f r o m Ketones 00000000000000000000

.. .............. ..... ......... .... ...,. ....

A1 k y l a t i o n o f ketones . R i n g expansion o f ketones , T r a n s p o s i t i o n o f c a r b o n y l groups , , Deal k y l a t i o n and r i n g c o n t r a c t i o n o f ketones ,

PhCH2COMe

SECTION 177

. . . .

. page 168-171 . . . .171-172 . . . .172-173 . . . .173-174

+

BuBr

Et3NCH2Ph C1

PhCHCOMe

t

NaOH H20

90%

I

Bu T e t r L e t t (1971) 1351

RCOCHR2

1 BuMaBr

HMPA

*

2 BuI

RCOCR2 I

Bu

Bull SOC Chim Fr (1969) 160

ocophOPh E t 2 0 HMPA*

I:

72%

Bull SOC Chim F r (1968) 595

PhCOCH2Me

1 (i-Pr)*NLi

MeOCH2CH20Me

2 BuBr

*

I

Bu

JOC (1973)

PhCOCH2Me

HCHO KOH

75%

PhCOCHMe

Fe(C0)5

EtOH

38

2756

PhCOCHMe2 T e t r L e t t (1973) 2491

85%

SECTION 177

8

KETONES FROM KETONES

169

OMe

Chem Pharm Bull (1971) t

1 K MeaNMeg I

19 1150

-

34%

2 Na2Ct-207 H2SO4 H20 Et20

Me JACS (1972)

94 683

1 HMPA 215-220" 52%

2 PhCH2Br Tetr Lett (1972) 929

oo--+ooLi .ao BuI

o r BugSnC1

Bu

Tetr Lett (1969) 1117 50s

0

1 ClSiMeg

Et3N

DMF

NaOH MeOH -t

Me

2 CH212 Zn-Ag Tetr Lett (1973) 2767

64%

7 70

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 177

Cycl ohexylamine

0

Me -80% JACS (1971)

JCS

4 (1971)

2 5938

1047

For the preparation o f enamines f r o m ketones see section 356 (Amine Olef i n )

-

<61%

JOC (1971)

a 1790

SECTION 177

171

KETONES FROM KETONES

JACS (1973) 95 3076 Tetr Lett (1973) 4349

CHSBu

1 Li NH3 Et20* H20 2 Me1

JACS (1971)

0;: <83%

93 1027

Ketones may a l s o be a l k y l a t e d and homologated v i a o l e f i n i c ketones ( S e c t i o n 374)

172

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 177

3 H2 P t HClO4 JOC (1967) 2 926

ocHR oro 1 N3CN MeCNb

2 HC1

R = H o r Me

H20

R

JOC (1973) 38 2821 3862

3 HC1 MeOH

Angew (1971)

( I nte r na t Ed

J O C (1972)

490

2 491)

37

1639

SECTION 177

KETONES FROM KETONES

173

&

9% 2 E2H6 3 H202 NaOH

= 1 NH201-1 0

RCOCH2R

Bull SOC Chim Fr (1971) 1649

1 m-Chloroper-

benzoic acid

*

2 BF3.Et20

h9

0

0 1

~63%

JCS P e r k i n I (1973) 2076

RCOMe

Acc Chem Res (1971)

C8H17

5

168

COOH

2 E4aOC1

NH3 NaOH 1 t-Eutyl hypochlorite

NaHC03

2 EtONa E t O H 3 H2SO4 H20 J O C (1965) 30 3775 JACS (1971) 93 2786

22%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

174

SECTION 178

CSH17 1 MeMgI

2 HOAc 3 0s04

0

M e C O a j

1 m-Chloroperbenzoic acid 2 KOH MeOH 3 CrO3 H2SO4 Me2CO J O C (1971)

J-C00H HOAc HOOC

0

36

’ CH2N2 H20

PhCN

*.

2 t-BuOK 3 Na~C03 MeOH JOC (1971)

Section 178

2400

36

81

Ketones from Nitriles OOOoOOOOOooOOoOoDOOOO

(i-Bu)zBe

PhCOBu-i

C h e m Ind (1972) 689

oal 44$

t-BuCN

Na

H2S04

(t-Bu)zC=NH

pet ether

Section 179

175

KETONES FROM OLEFINS

SECTION 179

(t-Bu)eCO

H20

J A C S (1971) 93 4527 Tetr Lett (1972) 2071

Ketones from O l e f i n s 00000000000000000000

Conversion of o l e f i n s i n t o ketones w i t h longer carbon chains page 175-176 Conversion o f o l e f i n s i n t o ketones o f the same chain length . . . 176-177 . . . . . . . . . . . . . 178 Degradation of o l e f i n s t o ketones . .

.

1 B2Hg

THF

85%

2 MeOH 3 MeOCHC12 4 EtgCOLi 5 H202

EtOH

NaOH

GH 0 '

THF

2 RCH=CHCOMe

3 H202 NaOH H20

H20

J A C S (1973)

6876

0' R CHCH2COMe

J A C S (1971)

<81% ( R = H ) < 7 1 % (R=Me)

93 3777

3 NaCN

NaHC03 H20 ( o r m-chloroperbenzoic a c i d )

4 H202

Chem Corn (1971) 1048

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

176

PhCH2CHzCH2

C10H21 CH=CH2

CHR

Ph CSOMe

hu

1 :CBr2

2 MezS2 3 A g C 1 0 4 MeOH 4 MeSH CF3COOH

SECTION 179

Ph(CH2)2COPh Tetr Lett (1972) 4993

/ \

C10H21 CHCH2

CFQCOOH

H20

C10H21 CH2COMe

51 %

Tetr Lett (1973) 3509

1 N3CN MeCN MeOH 2 HC1

80% (R=H o r M e )

H20

JOC (1973)

38

2821

JOC (1973)

38

3455

JOC (1973)

38

185

- &*; NOCl

NaBH4

i -PrOH

i-PrOH

QNoH

---+

H20

Aust J Chem (1971)

C5H11 CH=CH2

02

Rh(PhsP)3Cl

CgHg

c

qo 177

KETONES FROM OLEFINS

SECTION 179

2 1089

20-25%

C5H11 COMe T e t r Lett (1972) 5273

BuCH=CH~

1 Hg(OAc)2 MeOH

*

0

PrCH-CHPr

BuCOMe

2 Li2PdClq CuC12

--+

I \

PrCHCHPr

100%

Chem Corn (1971) 818 T e t r L e t t (1972) 3595 S y n t h e s i s (1971) 527

q Bu~PO

PrCOCH2Pr

CHo

c1

JACS (1965) S;. 1405

See a l s o s e c t i o n 134 (Ethers and Epoxides from O l e f i n s ) and s e c t i o n 174 (Ketones from Ethers and Epoxides)

1 MeC002H

NaOAc 2 KOH E t O H

~

1

:la

THF

___t

OH

Tetrahedron (1971)

;o 35%

21 3013

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

178

SECTION 180

1 03 MeOH

70% JCS P e r k i n I (1972) 50

Reduction o f ozonides with E t C H O JACS (1971)

Section 180

93 3042

Ketones from Miscellaneous Compounds

000000000000000000000000000000000000

. . . . . . . . . . . . . . page 178 . . . . . . . . . . . . . . . . .178-179 . . . . . . . . 179-180 . . . . . . . . . . . . . . 180-181

Reductive a l k y l a t i o n o f enones Reduction o f enones t o ketones Reduction o f acetoxy and halo ketones t o ketones Ketones from miscellaneous compounds

RCH=CHCOR

R' ZCuLi

RCHCH2COR

(R'=alkyl o r v i n y l )

R' Org React (1972)

19 1

R ' C u C X P r JACS (1972) 94 7210 R'Li - t-BuOCu JACS (1972) 94 658 R'tuLi Chem Corn (1973) 88 CN

PhCHECHCOMe

HCOOH

Ru Cl2 (PPh3)3

t

90%

PhCH2CH2COMe T e t r L e t t (1972) 1015

CH=CHCoMe1 EtgSiH RhCl (PPh3)3

4-

CHzCH2COMe

2 K2CO3 MeOH Me2CO H2

T e t r Lett (1972) 5035

96%

Hp n i c k e l boride

MqC=CHCOMe

EtOH

Me2CHCHzCOMe

>

JOC (1971)

Bu3SnH

RCH=CHCOR

179

KETONES FROM MISCELLANEOUS COMPOUNDS

SECTION 180

RCH2CHzCOR

Organometallics in J C S C (1971) 1241

Fe(C0)5

PhCH=CHCOMe

36

MeOH H20

NaOH

CH2CH=CH(CH2)3COOMe

2018

Chem Synth (1970) L 57

PhCH2CH2COMe J O C (1972)

1 N~BH~CN

90%

31 1542

-Q

2 CrO3 H2SO4 Me2CO Tetr

OAc

OAc

Fe(C0)5

BupO

Lett (1973) 141

GZ:3

42%

Tetr Lett (1973) 447

LiCuMe2 Tetr Lett (1973) 4349

PhCOCHPh c1

EtSNa EtOH

PhCOCH2Ph

100% Bull Chem SOC Jap (1971)

5 828

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

180

0 : r

Tic13 MeCN

no

86%

2 237

Synth Corn (1973)

LiCuMe2 T e t r L e t t

CONMe2 I

(yH2)7 CHCOOMe

co I

LiI collidine

P

SECTION 180

(1973) 4349

FONMe2 (FH2)7 FH2

63%

co I

I

(FH2)8 CONMe2

(?H2)8 CONMe2

JOC (1973) 38 1424 Org Synth (1965) 2 7

oNo20'

Decarboxylation with NaCl i n Me2SO T e t r Lett NaCN in HMPA T e t r Lett NaBH2S3 THF,

(1973) 957 (1973) 3565

(+ oxime)

75%

Can J Chem (1971)

NaN02 PrONO

w -

W

88%

JOC (1973)

03 JOC

EtCX (CH2)zF.H(CH2)2COMe NO2

Tic13 H20

MeOCHzCH20Me

2 2990

(1974)

2 1418

2 259

E t C X ( CHz)2CO( CH2)zCOMe

JACS (1971)

93 5309

PROTECTION OF KETONES

SECTION 180A

181

< 73%

Me 2 CO JCS

AcO

C (1970)

1182

"' CONH2

NaOCl

40%

MeOH JACS (1960)

@OH

82 4642

Pb(OAc)4 HOAc

92%

OH

OH JCS CECH

C

(1971) 1292

Ag2C03-Cel it e

100%

to1 uene Chem Corn (1972) 468

Me 0

Section 180A

P r o t e c t i o n o f Ketones

000000000000000000000

Ketal s . . . . . . . . . . . . . . . . . . . . . . . . . . page Hemithioketals Thioketals . . . . . . . . . . . . . . . . . . . . . . . . . . . Oximes, semicarbazones, phenyl hydrazones and tosyl hydrazones . . Cyanohydrin s i l y l e t h e r s . . . . . . . . . . . . . . . . . . . .

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

182 182 183 183-184 184

See a l s o s e c t i o n 363 (Ether-Ether) f o r k e t a l s and s e c t i o n 367 (EtherO l e f i n ) for enol e t h e r s . Some of t h e methods in s e c t i o n 60A ( P r o t e c t i o n of Aldehydes) a r e a l s o a p p l i c a b l e t o ketones

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

182

CH20H CHOH

0

t-Bu

D O Y H

OFH2

LH2Br TsOH C & j

Zn MeOii

t

t-Bu

CH2Br

(Stable t o MeLi, NaBH4, NH3, CrO3 and peracids) J O C (1973)

Trichloroethyl ketals

oo

SECTION 180A

J O C (1973)

38 834 38 554

E t O H TsOH molecular sieves b

*--------------------------------Acid

Ph3C'

u

H2U

Rec Trav Chim (1971)

BF4- CHZCl2

Chloramine-T E t O H H20

90 1 1 4 1

JCS Perkin I (1972) 542

I Tetr Lett (1971) 3445 3449

Nickel boride JCS Perkin I (1973) 654

PROTECTION OF KETONES

SECTION 180A

183

----------------* PhC]:'

PhCO I

Me 1'

Et30'BFq2 NaOH

1 s

Me

CH2C12

H20

T e t r Lett (1972) 1085

The f o l l o w i n g r e a g e n t s may a l s o be used for the c l e a v a g e o f t h i o k e t a l s : cuC12-Cuo

Bull Chem SOC J a p (1972) JACS (1972) 3 8641

45

3724

Ce(NHq)z(N03)6 Chern Corn (1972) 791 MeOS02F S y n t h e s i s (1972) 561 Me1 Chern Comm (1972) 382 Ag20 Chern Comm (1972) 1323 AgN03 T e t r a h e d r o n (1968) NCS, AgN03 JOC (1968) NBS J O C (1971) Chloramine-T

33 298 36 3553

24 4249

T e t r L e t t (1971) 3445 3449

12, Me2SO T e t r L e t t (1973) 3735 T1 (OCOCF3)3 Can J Chem (1972)

+-

3740

Et3O BF4 T e t r L e t t (1974) 11 OR

1

orobenzotriazol e or m-chloroperbenzoic a c i d

Chem Comm (1971) 750

PhCO I

Me

NH20H

*1

Al(OPr-iJ3

2 HC1

PhC=NOH I

(Not a p p l i c a b l e

t o h i n d e r e d ketones)

Me

H20 Chem Ind (1972) 680

184

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

JACS (1971)

SECTION 180A

2 4918

Chem Ind (1964) 153 footnote 3

.-

Me3SiCN 21112

Acid or base

Chem Corn (1973) 55 T e t r L e t t (1973) 4929

Compendium of Organic Synthetic Methods, Volume2 Edited by Ian T. Harrison, Shuyen Harrison Copyright 0 1974 by John Wiley & Sons, Inc.

Chapter 13

PREPARATION OF N ITR ILES

No additional examples

Nitriles from Carboxylic Acids and Acid Halides

Section 182

~

~

~

O

~

O

O

~

COOH

O

O

c12H25tCN Me

C11 H23COOH

O

~

O

D

~

O

O

O

electrolysis

t

~

O

O

~

~

O

O

O

O

~

O

D

O

~

RCOOH

RCOOH

285'

RCN

t

1 ClS02NCO CH2C12

2 DMF

*

185

O

:12H25 Me

J O C (1971) 36 3050

RCN

O

c11 H'23$.CN

J Pharm SOC Jap (1944)

CW Me I I CH2CHzCHCN H3P04

O

Org Synth (1970)

18

64 25

~

O

O

O

O

O

O

~

~

~

~

~

186

COMPENDIUM

S e c t i o n 183

OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 184

N i t r i l e s from Alcohols 0000000000000000000000

No a d d i t i o n a l examples

S e c t i o n 184

PhCHO

N i t r i l e s f r o m Aldehydes

OOOOOOOOOOODOOOOOOOOOOO

NC I TsCHK

YHCHo

PhCH=CTs

MeONa __t

MeOH

PhCH2CN Angew (1973) ( I n t e r n a t Ed

RCHO

Mn02 NaCN

NH3 i - P r O H

<81%

s 402 12 407)

RCN Cheni Corn (1971) 733

Can J Chem (1971)

9 1321

NITRILES FROM AMIDES

SECTION 186

187

The following r e a g e n t s may a l s o be used for dehydration of oximes t o ni t r i l e s :

TiClq-Pyr

Tetr Lett (1971) 559

HCOONa, HCOOH JCS Ph3P, CCl4, Et3N

+

CHC13, NaOH, PhCHzNEt3 C11,1 '-dicarbonyldiimidazole DCC (190') CC13CN

(1965) 1564

Ber (1971)

104 2025

Tetr Lett (1973) 2121

Chem Corn (1973) 628 Synth Corn (1973)

J O C (1973)

2

101

2 2241

HgO Tetr Lett (1971) 361

PhCHO

--+

h v cyclohexane

F

PhCH=NN=CHPh

JACS (1963)

Related methods:

Also v i a :

85%

PhCN 2679

N i t r i l e s from Ketones (Section 192)

O l e f i n i c n i t r i l e s (Section 376)

Section 185

N i t r i l e s from Alkyls, Methylenes and Aryls 000000000000000000000000000000000000000000

No a d d i t i o n a l examples

Section 186

N i t r i l e s from Amides

~ ~ ~ O ~ ~ O O O O O O O O O O O O O O

+

PhCH=CHCONH2

CHC13 PhCH2NEt3 C1NaOH

H20

*

PhCH=CHCN Tetr Lett (1973) 2121

52%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

188

SECTION 190

The following reagents may a l s o be used f o r the conversion of amides into n i t r i l e s : CC14, Ph3P Ber (1972) 105 244 (PNC12)3 Can 3 Chem (1972) 3857 HMPA (220-240') Can J Chem (1971) 49 2897 (HNSiMe2)3 JOC (1970) 35 3253 TiCla, amine T e t r L e t t (1971) 1501

Section 187

Nitriles from Amines 00000000000000000000

Argentic picol i nate

BuCHCH~NH~

t

I

Et

H20

BuCHCN 1 Et

35%

Tetrahedron (1973)

Section 188

29

751

Nitriles from Esters 00000000000000000000

No additional examples

Section 189

Nitriles from Ethers and Epoxides

000000000000000000000000000000000

No additional examples

Nitriles from Halides

Section 190

Me 0

B

000000000000000000000

r

- - ~Me@Li

F'P:.x;:;:obenzoni

trile

+

T e t r L e t t (1972) 4169

Me

OCN

SECTION 192 Section 191

PhH

189

NITRILES FROM KETONES N i t r i l e s from Hydrides 0000000000000000000000

C1 (CH2)3CN Al C13

Ph(CH2)3CN

b

Tetr Lett (1972) 1929

ArH

ArH

--+

KCN

CuCN MeCN

ArT1C12

hl/

t-BuOH

NH2CN

H20

*

ArCN

ArCN Tetrahedron (1972)

Zs 3025

Tetrahedron (1972)

2 5081

i-PrCH2CH20NO

*

12% Acta Chem Scand (1972)

Section 192

N i t r i l e s from Ketones

~ ~ ~ O O O O O O O O O O O O O O ~ ~ O ~

ad)e

~

--.f

~

~

H

c

o1 HCN o ~MeOHe 2 Br2

H20 3 MeONa 1 HCN MeOH

NaHC03

CH2C12

MeOH

2 Br2 NaHC03 CH2C12 H20 3 Me1 MeOLi MeOCH2CH20Me JACS (1971)

2 4318

26

3870

a::

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

190

Pr2CO

1 NH2NHTs

*

2 KCN HOAc MeOH

Oecalin

PrzyNHNHTs CN

180"

SECTION 193

Pr2CHCN

Chem Ind (1972) 213

Pr2CO

TsCH~NC t-BUOK

t-BuOH

75%

Tetr Lett (1973) 1357 Angew (1973) 402 (Internat Ed 11. 407)

Nitriles from Aldehydes (Section 184)

Related methods: Also via:

Pr2CHCN

b

MeOCH2CH20Me

Olefinic n i t r i l e s (Section 376)

Section 193

Nitriles from Nitriles 0000000000000000000000

Pr-i

EttHCH2CN

Me

1

OLi

2 Me1

'

THF

*

Ye

< 66%

EtCHCHCN I Me Ber (1973)

106 1376

86%

J Med Chem (1965) S 598 JOC (1958)

(1973) 16 490 1346-

23

C7H15ONa C7H15OH

PhCH2CN

PhCHCN

PhCOOMe 21 0-220'

73%

I

C7H15 JOC (1971) (1972)

Section 194

191

NITRILES FROM MISCELLANEOUS COMPOUNDS

SECTION 195

36

37

2948 526

37

3552

N i t r i l e s from O l e f i n s 000000000000000000000

No a d d i t i o n a l examples

Section 195

PhCH=CHCN

N i t r i l e s from Miscellaneous Compounds

0000000000000000000000000000000000000

H2

nickel boride

*

PhCH2CHzCN JOC (1972)

CH2CH2N02

POCl3 DMF

85%

___.c

A c t a Chem Scand (1970)

PhCH2N02

NaBH2S3 THF

2 3424

80%

PhCN Can J Chem (1971)

2 2990

192

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 1 9 5

28% Tetr Lett (1970) 4701

Compendium of Organic Synthetic Methods, Volume2 Edited by Ian T. Harrison, Shuyen Harrison Copyright 0 1974 by John Wiley & Sons, Inc.

PREPARATION OF OLEFINS

Chapter 14

Section 196

Olefins from Acetylenes

00000000000000000000000

Reviews : Stereoselective and Stereospecific Olefin Synthesis Quart Rev (1971)

Catalytic Semihydrogenation o f the Triple Bond

25

135

Synthesis (1973) 457

BuCECH

--+ B u E C B r

1 (

*

2 MeONa 3 HOAc

BuCXH

--+ B u C X B r

1 E B H

2 NaOH H20

TH F*

3 12

EtCGCEt

1 BH2C1

EtpO

2 HOAc THF

k

Meo oMe

BuCH=CH trans

BuCH

JACS (1971) (1972)

2 6309 94 6560

Me

Synthesis (1972) 557

EtCH=CHEt cis

Catecholborane 193

81% JOC (1973)

JACS (1972)

1617

2 4370

194

RCZCR

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

Na NH3

RCH=CHR

or Li amine

Section 197

R(CH2)5COCl

Me2CHCOOH

SECTION 197

Synthesis (1972) 391

Olefins from Carboxylic Acids and Acid Halides

0000000000600060000ODOOOOOOOOOOODODODOO

1

@C7H1

5

SnC14 2 N2H4 NaOH

R(CH2)6

Nickel

C7H15

6

boride

Synth Corm (1972)

1 (i-Pr)zNLi THF

Me2C-yO

R( CH2)7CH=CHC8H17

6

,g 415

140-160;

hexane

Go

3 PhS02C1 Pyr

EtCH2CH2COOH

JACS (1972)

Electrolysis (carbon electrodes ) KOH H20 JACS

RCH2CH2COOH

Pb(OAc)4

*

94

2000

EtCH=CH2 ( + isomers)

(1964)

4686

RCH=CH2 Org React (1972)

19 279

50%

SECTION 198

OLEFINS FROM ALCOHOLS

CgH13(CH2)3COCl

PhH A l C l 3

RFHCOOH

Pb(OAc)4

R$H

RCHCOOH

___)

RC H

OH I

hr/

CeH13CH=CH2

36

J O C (1971)

<75%

1838

Org React (1972)

2

279

O l e f i n s from A l c o h o l s

S e c t i o n 198

R2CHCR2

C6H13(CH2)3COPh

195

000000000000000000000

I2

xylene

R2C=CR2

Monatsh (1968)

99 642

32%

( 2 r y and 3ry o n l y )

J A C S (1971)

(1972)

93 4327 94 5003

59% Tetr L e t t (1971) 567 J O C (1971)

(1972) 165 36 3826

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

196

OH ButHCH2Pr

(Ph0)3P*MeI HMPA

BuCHrCHPr

*

JOC (1972)

(2ry o n l y )

SECTION 198 88%

J1 4190

(yH2 OM' t

3 200-250"

OH

50%

JCS

2

11%

(1971) 582

1 NaH Me2SO

Me

3 Me1

Can J Chem (1972)

1181

Me

Chem Corn (1972) 1215

&ph:oa-lhv C8H1 7

HO

S

cyclohexane

Chem Corn (1971) 1014

*

197

OLEFINS FROM ALDEHYDES

SECTION 199

p&o'i 1 MeLi THF Et20

(CH2)10 CMe \OH

P C M e (CH2)10 M :e

u

K2WC16 3 NaOH H20

58%

Chem Comm (1972) 370

0,

Bis(l,5-cycloocta-

o/

diene)nickel

DMF

t

0

82%

T e t r L e t t (1973) 2667

RCHOH

N,N'-Thiocarbonyl

RCHOXCS

RCHoH

diimidazole

R~HO'

I

Section 199 Reviews:

tolue;

RiH RCH

Ber (1973) 106 1076 JCS (1971) 2960 Can J Chem (1970) 48 383

O l e f i n s from Aldehydes

0000000000000000000000

Stereosel e c t i ve and Stereospecif ic 01 e f i n Synthesis Quart Rev (1971) 25 135 The W i t t i g Reaction

PhCHO

(RO)3P __t

1 TsNHNH2

2 MeONa

PhCHN2

Org React (1965)

Ce(NH4) 2(N03) 6

14 270

PhCH=CHPh

MeCN pentane JACS (1971)

93 2086

74%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

198

"'O

WClg-BULi

THF

47%

Me 0

Me0 JACS (1972)

(0

'

THF

PhCH-CMe2

6 -60

hexane

2 PhS02C1

45-50%

Tetr Lett (1966) 4315

Me2CHC00H (i-Pr)2NLi THF

6538

PhCH=CHCH2BU

f

BuLi

94

) 212

Bu CH2CHD PhCHO

PhCHO

SECTION 199

Pyr

140-1 60"

+ -

JACS (1972)

94

PhCH=CMe2

29%

2000

SH PhCHO

Ph2kOOH TsOH

*

PhCHSCPh2 I

0-

C6H6

co I

150-160"

PhCH=CPh2 (Et2N)3P JCS Perkin I (1972) 305

89%

Ph PhCHO

CgH1 gCHO

1 PhSOzCLi2 2 A1-Hg

H20

NMe y e 1 PhiO-CHLi 2 Al-Hg

HOAC

< 90%

PhCH=CHPh

b

THF

Chem Comm (1973) 351

THF L

60%

CgH1 gCH=CHMe JACS (1973)

2 6462

SECTION 202

PhSCH2Li

CgH1gCHO

OLEFINS FROM AMINES

CgH19FHCH2SPh OH

1 MeLi _____c

199

CgH1gCH=CHZ

@PCl Tetr Lett (1972) 737

Related methods:

Section 200

Olefins from Ketones (Section 207)

Olefins from Aryls

000000000000000000

-

@JR

Section 201

Synthesis (1972) 3 9 1

Olefins from Amides

00OOODOO00000000000

No additional examples

Section 202

Me2N

ouo

Olefins from Amines

0000000000000000000

PhCH2Br Etp; Me2CO

i;\%& Me2N BrCH2Ph

NH3 JOC (1972)

ouo

31 2896

-

67%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

200

a C H Z N H 2

1 ClCOOMe Et20

S e c t i o n 203

CgH1 9COOMe

NaOH

H20

2 N2O4

3 KOH

NaOAc CgHg

HOAc JACS (1972)

H20

94 7771

Olefins from Esters 0000000D00000000000

1 PhSCH2Li

THF

46%

CgHig?=CHz

2 (PhC0)ZO 3 L i NH3

S e c t i o n 204

SECTION 204

Me .-

JACS (1972)

94 4758

O l e f i n s f r o m Epoxides

000000000000000000000

OAc

-0 p0c13 PYr

JCS Perkin I (1973) 91

0

I \

PrCHCHPr trans

Zn-Cu

EtOH

PrCH=CHPr trans J O C (1971)

36

1187

201

OLEFINS FROM HALIDES AND SULFONATES

SECTION 205

0

1 PhpPLi

I\

C5H11 CHCHMe

THF

*

2 Me1

cis

75%

C5H11CH=CHMe trans

J A C S (1973) 95 822 Tetr Lett (1973) 1983

WClg-BuLi

THF

*

75%

Et

Et

J A C S (1972)

I0 EtCHCH2

94 6538

1 Sodium (cyclopentadienyl ) d i c a r b o n y l f e r r a t e TH F 2 HBF4 3 NaI

0

I t

CgH13CHCH2

Section 205

Me2CO

J A C S (1972)

Ph3PSe CF3COOH

*

CH2C12

F

EtCH=CH2

94 7170

71 %

CgH13CH=CH2 C h e m Corn (1973) 253

O l e f i n s f r o a Halides and Sulfonates OOOOOODOCOOOOOOOOOOOooooooooooooooo

-

Ph3P + PhCH2C1 ---+ PhCH2PPh3 C1

BuLi to1 uene

PhCH=PPh3

-91 %

5

Ber (1970)

PhCHZCHPh

103 2995

202

COMPENDIUM

OF

ORGANIC SYNTHETIC METHODS VOL 2

SECTION 205

Organornetallics i n Chem Synth (1972) 1.375

EtCHO

PhCHZBr

/

Ph3P

0

\

CHz-CHz

PhCH=CHEt

b

Angew (1968) 535 ( I n t e r n a t Ed 1 5 3 6 )

BuBr

Me 1 BuCOiHCOOEt Na2C03

2 PhC-CHPh N

EtC\-/CHPh NH

--+ C5H11 MgBr

-

Me

Coll idine B ~ C H ~ B ~ B~CH=~B~ b-bO (reflux) T e t r Lett (1968) 4569

Ph

1 Mg \\

C5H11 B r

t

2 NaBH4 3 MsCl

EtBr

NaH

BuONO

?l

EtCcCHPh T e t r L e t t (1969) 4001

1 Me3SiCH2COMe E t z O

+

2 NaOAc

HOAc

CsH11$=CH2 Me

T e t r Lett (1972) 1785

N

76%

CgH1 3Br

BrCH=CHMe

--* CgH13MgBr

TH F

ICH2CH=CH2 Et3B

PhCH2I

203

OLEFINS FROM HALIDES AND SULFONATES

SECTION 205

air

e

THF

FeCl3

b

CgH1 3CH=CHMe

JACS (1971) 93 1487 Synthesis (1971) 303

-67%

72%

PhCH2CH2CH=CH2

( B e n z y l i c and a l l y l i c h a l i d e s o n l y )

93 1508

JACS (1971)

CH=CHPh

I PhCH=CH2 Pd(OAc)2

Et3N

COOMe

75% COOMe JOC (1972)

31 2320

95% JACS (1972)

MeCH=CHMgBr THF

t

C7H1gBr

94 4374

C7H15CH=CHMe

71 %

B u l l SOC Chim F r (1963) 1888

RI

(R' CH=CH)2CuLi

+

RCH=CHR'

Helv (1971)

1939

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

204

SECTION 207

< 94% (X=halide o r OTs)

X

I

R2CHCR2

T e t r Lett (1973) 1979

Diazabi cycl oundecene

R2C=CR2

t

or diazabicyclononene

(X=halide o r OTs)

Synthesis (1972) 591

OMS ?Ms I

ct -Dimethylaminonaphtha1 ene-Na

(-CH=CH

t

(CH2110

67%

T e t r L e t t (1973) 2097 (1972) 3447

Section 206

Olefins from Hvdrides 000000000000000000000

This section l i s t s examples of the replacement of hydrogen by olefinic groups CHzCH2CH=CHMe

Ha

CH3 CH2=CHCH=CH2

19% JOC (1965)

Section 207

Olefins from Ketones

~

~

~

~

~

O

O

O

O

~

O

O

O

O

O

O

~

~

O

30 82

O

Conversion o f ketones into olefins w i t h longer carbon chains page 205-207 Conversion of ketones into olefins of the same chain length . . . 207 Conversion of ketones into olefins with shorter carbon chains . . 208

SECTION 207 Reviews:

205

OLEFINS FROM KETONES

S t e r e o s e l e c t i v e and S t e r e o s p e c i f i c 01 e f i n S y n t h e s i s Quart Rev (1971)

Org React (1965)

The W i t t i g R e a c t i o n

EtCO

WC16-BuLi

THF

Me

N2H4 _.t_

H2S

P b ( OAc)4

RzCNHNHCR2

J C S P e r k i n I (1972) 305

SH

1 Ph2bCOOH TsOH CgH6

2 (Et2N)3P

Ph2CO

94 6538

R2C=CR2

Ph3P

'S'

oo

14 270

10%

Me Me J A C S (1972)

R2CO

135

Et,C=C,it

t

I

25

160-200"

1 Me2CHCOOH L i N ( P r - i ) 2 2 PhS02C1

+

*

OCPh2 68%

J C S P e r k i n I (1972) 305

Ph2C-FMe2 0-co

140-1 60"

PhzC=CMe2

J A C S (1972) 94 2000 J O C (1971) 36 1149

/

2 A

w S y n t h e s i s (1972) 565

47%

.

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

206 +- /

,

phyo 1 Me

Resin-Ph3P.CHPr

cis

100%

1 Resin-Ph3P=CHPr

PhF=CHPr trans

+

2 BuLi

SECTION 207

Me

59%

3 LiC104 4 HC1

Et20 Annalen (1973) 227 Chem Corn (1972) 134

5 t-BuOK

0' ;I-I-IH~C~

Ph3P

0 CH2CH2 I \

*

0'""

69%

Angew (1972) 84 1173 [Internat Ed 1041)

PhCOO CH2SPh

)c

1 PhSCH2Li THF * 2 BuLi (PhC0)20

cz"

Li

NH3

1 6

31%

JACS (1972) 94 4758

Ph2CO

PhCO ' Me

PhSCHZLi

1 MeLi Ph2CCH2SPh * Ph2C=CH2 2 o-Phenylene p h o s p h o c h l o r i d i t e OH Tetr Lett (1972) 737

t-BuSOCH2Et _.____L

MeLi

Ho ?oBu-t Phb-CHEt

Me

NCS

CH2C12

PhF=CHEt Me

JACS (1973) 95 3420 Tetr Lett (1972) 649

73%

OLEFINS FROM KETONES

SECTION 207

207

NMe I1

c1 5"31

Fo

Me

1 PhSOCH2Li 2 AI-Hg

THF

c1 5H31 F=CH2

HOAC

90%

Me JACS (1973)

Ph I

Ph2CO

PhS02CLi2

Yh

Ph$=CS02Ph

Al-Hg

THF

H20

95 6462

<85%

Ph2C=CHPh

Chem Corn (1973) 351

<40% T e t r L e t t (1973) 447

48% Chem Comm (1973) 935

0

BF3'EtzO

PhCH2S

Ql

el:;::

boride

* JCS P e r k i n I (1973) 654

!2

67%

208

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

hv B u C H ~ C H ~ C H ~ C O P ~+

BuCH=CH2 JOC (1971)

Related methods:

Section 208

36

SECTION 209

74% 1838

O l e f i n s from Aldehydes (Section 199)

O l e f i n s from N i t r i l e s

000000000000000000000

No a d d i t i o n a l examples

Section 209

O l e f i n s from O l e f i n s 00000000000000000000

Homologation, a l k y l a t i o n and a r y l a t i o n of o l e f i n s .... .... Migration o f double bonds . . Cis-trans interconversion and e q u i l i b r a t i o n ..

.

1 B2Hg THF

2 HCZCCH2C1 3 MeLi Et20 HOAc

EtCH=CHEt trans

*

!Ie i-PrCBH2 I 1 Me

2 BuCXBr 3 MeONa MeOH 4 i-PrCOOH

.

.

. . . . . page ....... .......

208-209 209-210 210-211

f\r CH$H=CH2

U

69%

Synthesis (1973) 672

D

1 BH3 THF 2 BuCXH 3 BrCN CH2C12

EtCHCI42Et I

CH=CHBu

trans

78% Synthesis (19721 555 JACS ( i 9 7 1 j 93 6309 (1972) 94 4013

CH=CHBu trans

JACS (1972)

69%

94 6560

SECTION 209

EtCH=CH2

1 BH3

c

2 MeC,=/CH MeOH CH2

BuCH=CH2

209

OLEFINS FROM OLEFINS

E t (CH2 ) 3C=CH2 1 Me

91 %

T e t r Lett (1972) 4627

MeCo ( d r n g ) ~Pyr .

*

Li2PdC14 MeOH

BuCH=CHMe

32%

Chem Corn (1971) 849

-

FH3 1 PdC12 Na2C03 CH2C12 FH2CH2S02MeL j CH2Me EtCH=CPr L- EtCH=CPr EtCH=iPr 2 MeS02CHCOOMe EtNH2 Na 3 NaOH JACS (1973) 95 292 4 180"

NO2 @cH=cHph J O C (1972)

EtCH2CH=CH2

Ni-HCN

CH3

CgH6

t-BuOK Me2SO

2 2320

EtCH=CHMe

18-crown-6

Chem Ind (1971) 1465

t

T e t r L e t t (1972) 1797

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

21 0

PhCH2CH=CH2

R~C12(Ph3P)3 t-BuOOH

CH=CH2 P t C l 2 ( Ph3P)z

SECTION 209

PhCH=CHMe Chem Corn (1971) 562

SnCl2

0""'

HZ

*

or RuC12(Ph3P)3 or I r C l ( C O ) ( P h 3 P ) 2

JOC (1971)

36

2497

PtClH(PMe2Ph)2-MeS03F 'Chem Corn (1973) 766

S i l i c a gel

Ac 0

Me

T e t r Lett (1971) 2513

0

cis

'(::;;:)

I \

CHCH --+

((CH2)2

trans

1 PhpPLi

THF

+

2 Me1

q;;;;)

(1971) 93 4070 (1973) 822 T e t r Lett (1973) 1983

JACS

JOC (1973)

95

38 1247

< 75%

PrCH=CHPr cis

21 1

PROTECTION OF OLEFINS

SECTION 210A SnBuq h v

-*

PrCH=CHPr trans

Ber (1973)

106 505

The following catalysts may also be used f o r cis-trans equilibration: C~C12-hv PhzS-hV HSCH2COOH (i-Bu)~AlY-rays

Section 210

J O C (1972)

JACS (1972)

Chem Ind (1965) 507 Ber (1972)

105 88

Olefins from Miscellaneous Compounds 000000000000000000000000000000000000

JACS (1971)

Section 210A

37 3561 94 2124

93 4316

Protection of Olefins 000000000000000000000

The protection of isolated double bonds is considered in t h i s section

0

Ber (1955)

3 1654

21 2

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 210A

2 soc12 3 KOH

Ac 0

7

H

Zn

HOAc

( S t a b l e t o HBr, Na-Hg, Cr03-Pyr, CrC12 and H 2 / P t ) Chem Pharm Bull (1960)

CgH17CH'CH ( CH2) 7COOH

S 621

HO OH

1 H202 HCOOH

-- ------ -- --+

1

1

CgH17CHCH(CH2)7COOH

u 2 NaOH

( S t a b l e t o Br2)

1 HBr H2SO4 HOAc 2 Zn EtOH

&'Br2NaOAc

Ac 0

Acta Chem Scand (1952) JCS (1951) 1079 1087

HOAC

1127

Aco&

Et20

L NaI

5

Me2CO

Br Br ( S t a b l e t o NBS and H2/Pd)

JOC (1965) 30 1658 J Biol ChemTl958) 230 447 Org Synth (1963) C o l l Vol 4 195

Ac 0

&-@

S02C12 Pyr

Zn

HOAc

c1 ( S t a b l e t o HBr, Cr03, SOC12-Pyr and H Z / P t ) Rec Trav Chim (1971)

JCS (1961) 4547

90 549

21 3

PROTECTION OF OLEFINS

SECTION 210A

RCH=CH( CH2) nC,tfH(

0

MeOH

work-up

CH2) "C,H/CH (CH2),$OOMe

0

( S t a b l e t o H2/Pd)

Tetr Lett (1966) 379

00000000000000000000

Sections 211 t o 299 a r e reserved f o r f u t u r e a d d i t i o n s ( e . g . t h e p r e p a r a t i o n

o f n i t r o compounds)

Compendium of Organic Synthetic Methods, Volume2 Edited by Ian T. Harrison, Shuyen Harrison Copyright 0 1974 by John Wiley & Sons, Inc.

PR E PA RATI0 N OF DIFUNCTIONAL COMPOUNDS

Chapter 15

Section 300

Acetylene

- Acetylene

0000000000000000000000

Diacetylenes Review: The Coupling o f Acetylenic Compounds

Advances in

PhCXH

Cu(OAc)2 Pyr

MeOH

P

Org Chem (1963)

4

225

70-80%

PhCX-CECPh

Org Synth (1965) JCS (1959) 889

45

39

(1960) 3614 94 658

JACS (1972)

CECH

Et

1 EtMgBr

*

2 SOC12 THF

Et

Et JOC (1972)

21 4

37

3749

61 %

SECTION 300

1 EtMgBr

BuCECH

PhCECH

Et20

*

2 cuc12 3 I2

PhCzCH

- ACETYLENE

ACETYLENE

JCS (1954) 1704

- NaOH

THF

H20

CuC12

PhCfCBr

BuNH~

C6H6

1 BrCECCOOH

CuC12

NH20H.HCl

EtNH2

w

Me2CO

1 BrCECSiEtg EtNH2 2 WaOH

CuC12

DMF MeOH H20

1 EtMaBr

NH20H.HC1

Ber (1964)

*

5 318

PhCEC-CZCH

41 %

91 2586

-

PhCEC-CECH

Tetrahedron (1972)

g 4591

50%

5221

Et90

70%

3 BrCHzCECC5H11

BuBr

84%

PhCEC-ECPh

Advances in Org Chen (1963) JCS (1962) 3055

2 Copper tetrammine s u l f a t e

PhCECH

71 %

BuCX-CZCBU

Et20

Br2

21 5

C1 CH2CXCH2C1 NaNH2

t

JACS (1951) 2 4601 Org Synth (1970) 97

BuCX-CXBU

JCS (1951) 4 4

-

50%

SECTION 301

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

21 6

C5H11 C X - C X H

JCS (1955) 1007

L;i 1 LiCECCHSdi] PhCfCCH2Br

2 Zn

+

HOAc

&c0cH2c0cH3 Me

THF P hCXCH2CH2CECH T e t r L e t t (1972) 2117

1 Pc15

CgH6

,&C:C-CXH

2 NaNH2 NH3

Me

Me

Me

Tetrahedron (1972)

PhCOCH2CH2COPh

S e c t i o n 301

1 EtSH

HC1

dioxane

*

2 TsOH 3 Me2S04 4 NaOH

Acetylene

PhCEC-CZCPh

2 Chen (1969)

- Carboxylic

28 5221

2 229

Acid

0DD00000000000000D000000D000

Acetylenic acids Review: Recent Developments i n t h e S y n t h e s i s o f Fatty Acids Chen Rev (1957) 57 191

C11 H23CfCH

1 LiNH2

NH3

2 Br(CH2)4COOH

THF

C11 H23CZC( CH2)4COOH JCS (1965) 894

49%

SECTION 301

C12HpjCZCH

- CARBOXYLIC

ACETYLENE

1 EtMgBr

Et2O

*

2 c02

PhCHO

C (1971)

-

yr

KOH MeOH

C6H6

ocHo0

2013

PhCXCOOH

Org React (1965)

CH.CBi-2

Ph3Pt

154

PhCECCOOH

+

2 6-Naphthalene sulfonic anhydride 3 Acid 4 NaHC03

PhCH=CCOOMe

685

(1964) 2066 (Chem Abs 62 7629)

IZV

JCS

CBr4

Annalen (1965)

1 t-BuOK

--* PhCOCH (COOBU- t ) 2

Br Ph3P=kOOMe

76%

C12H25CZCCOOH

LiAlH4, C02

PhCOCl

21 7

ACID

14 270

- ocEc 1 B ~ L ~

2 c02

CH2C12

Tetr Lett (1972) 3769

0'

1 CuCXCOOEt

2 NaOH

PhCH=CHBr

1 BuLi

2 co2

Et20

Pyr

t

0

CECCOOH

JCS

(1969) 2173

PhCXCOOH

42% JACS (1940)

62 2327

-

COMPENDIUM OF ORGANIC SYNTHTIC METHODS VOL 2

218 HCXCH2CH20H

CrO3 H2SO4

SECTION 302

HCZCCH2COOH

Me2CO H20

28%

J C S (1949) 604

MeCOCH2COOEt

- 1 N2H4

EtOH

2 Brz

MeC-CBr2

NaOH H20

E; Lo NH

MeCECCOOH

29%

\ I

Also v i a :

Section 302

Acetylenic esters Acetylenic amides

Acetylene

J A C S (1958) 80 599 J O C (1966) z 2 8 6 7

Section 306 304

- Alcohol

00000000000000000000

Acetylenic a l c o h o l s , hydroxyacetylenes

b

PrCHCfCH

BUCH2CgCH

1 EtMgBr

THF

PrCHCECCH20H

80%

2 HCHO

Se02

EtOH

J C S Perkin I (1973) 720 JCS (1950) 2100

27%

BuYHCXH OH

C o m p t Rend (1933) 196 706

SECTION 3 0 2

B r CH2CZCH

CgH1 3CHO

- ALCOHOL

ACETYLENE

Mg

t

E t 2 0 o r Zn

THF

219

CgH13FHCH2CZCH OH

JCS (1955) 1740 1007

H C X M g B r THF

*

i-PrCHO

OH

0

86%

i- P r t H C X H

Bull SOC Chim Fr (1964) 3218

LiCSCH MeZSO G

O

HCZCH

Chem Corn (1969) 674

OCHZPh

Et2 CECC6H13 Et3N

to1 uene

bCH2Ph

Chem Corn (1968) 634 Tetr Lett (1970) 2695

HCECCH20H L i NH2

C”H23Br

NH3 THF

*

C11 H23CECCH20H

JCS .(1963) 5889

(1965) 4373

JCS C (1969) 2173

87%

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 2

H C X ( CH2)aOH LiNlip

THF

HCXH Na

SECTION 303

COOH I

(CH2)7CZC( CH2)80H

JCS

C

(1967) 1556 (1965) 894

CXH

NH3

LiCSCH*NH$H2CH2NH2

65-75%

Org Synth (1955) Coll Vol 3 416

JOC (1964)

29

1872

Ber (1962) 95 2557 JCS (1957) 573

C'CCooMe

i-Bu2Al H

*G

hexane

CXCH20H

T e t r Lett (1973) 1495

S e c t i o n 303

Ac&{;~n~o;o~~~e~Ide 0

A c e t y l e n i c aldehydes

JCS (1951) 2693 Org Synth (1963) Coll Vol 4 801

> 80%

SECTION 303

BuC-CH

ACETYLENE

1 NaNH2 NH3

- ALDEHYDE

BuCECCHO

>

2 HCOOEt EtzO 3 HOAc

BuCXH

1 EtMgBr

Et20

2 HCONMe2 3 H2SO4 H20

&

221

24%

JCS (1950) 3361

BuCECCHO

b

51 % JCS (1958) 1054

CXCHO

1 CuCXCH(OEt)2

Pyr

49%

*

2 H2S04 H20

JCS

C (1969)

2173

Nickel peroxide CECCH2OH

72%

CsH6

JCS C (1969) 2173 Mn02 JCS (1958) 1054 Ber (1973) 106 2755 Cr03-3,5-dimethylpyrazole Tetr Lett (1973) 4499

PhCH=CHCHO

1 Br2

HOAc

2 K2CO3 3 HC(OEt)3 EtOH 4 KOH

EtOH

b

PhCECCH(OEt)2

h2504

PhCZCCHO

H20

NH4C1 Org Synth (1955) Coll Vol 3 731

222

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

T s N H N H ~ HOAc

CH2C12

C5H11

w

lcHO Helv (1967) (1972)

Acetylene

27%

CZCC5H11

0

Section 304

SECTION 305

2101

55 1 2 7 6

- Amide

000000000000000000

Acetylenic amides

1 Na

BuCECH

NH3

BuCECCONMe2

2 Me2NCOC1

Section 305

Acetylene

60% Compt Rend (1955) 240 989

- Amine

000000000000000000

Acetylenic amines Review: Synthesis and Reactions o f t h e A1 kynylamines

Angew (1967) 2 744 (Internat Ed 2 767)

MeCXH

Et2NH Cd(OAc)2 Zn(0Ac)p 120"

*

MeCXCMe2 I NEt2 JACS (1961)

PhCECH

E t Z N H HCHO

dioxane

'

216

PhCECCH2NEt2

80%

Ber (1933)

66 418

'

SECTION 305

ACETYLENE

1 EtMgBr

PhCXH

Et20

*

2 CiNEt2

Me2NH 02

PhCXH

-M I N E Annalen (1960)

Cu(0Ac)p

Ye

Ye

t-BuCECC1

PhCH=CCl F

*

1 LiNEtp

BuCXNPh

Et20

*

2 110-120"

Et2O

LiNEt2

135"

Et20

*

75%

65%

BuCXNEt2

PhCECNMe2

Me3N

Bull SOC C h i m Fr (1965) 2787

Rec Trav C h i m (1964)

LiNMe2

> 40%

Tetr Lett (1968) 5357

L i C X N P h HMPA

PhCECCl

638 33

PhCXNMe2

) I

BuCECOEt

2%

PhCXNEt2

C6H6

BuBr

223

Angew (1964) (Internat Ed

16 537

1211

87%

3 506)

44%

t-BuCXNMe2 Angew (1964) 76 537 (Internat Ed 3 506 582) Ber (1970) 103 564

PhCfCNEt.2

86% Angew (1963) (Internat Ed

75 638 2 477)

224

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

Section 306

Acetylene

~

~

~

~

~

~

- Ester O

O

O

O

O

O

O

O

O

~

O

SECTION 306

~

Acetylenic esters C5H11 C X H

1BuLi THF

2 BF3

C5H11 CZCCHzCOOEt

3 N2CHCOOEt

C1 COOEt

MeCECH --+ MeCXLi

PhCXH

C(OEt)4

Can J Chem (1972)

71 %

JOC (1973) 38 3588 Annalen (1958) 614 37

* PhCECC(OEt)3

1 Ph3P=CHCOOEt CgH6

>

270"

2 1105

MeCSCCOOEt

ZnCl2

~ c o c l2

87%

--+

PhCXCOOEt

JACS (1958)

4607

()-

CXCOOEt

< 14%

70%

J Med Chem (1973) 16 72 Ber (1961)

94 3005-

Synth Corn (1972) 331

LiCHzCONMe2

COCHZCONMez Tetr Lett (1973) 1495

CECCOOMe

ACETYLENE

SECTION 307

CuCECCOOEt

- ETHER,

225

EPOXIDE

Pyr N

JCS

CgH17CfC(CH2)7COOH

C5H11 COCH2COOMe

COOH I (CH2)4COOMe

28%

JCS (1955) 2218

-

C5H11 CrCCOOMe

2 Tl(N03)3

Also via:

(1969) 2173

CgH17CEC(CH2)11COOMe

t

electrolysis

1 N2H4 MeOH

61%

Angew (1971) ( I n t e r n a t Ed

60 48)

-

90%

Acetylenic acids (Section 301)

Section 307

Acetylene

- Ether,

Epoxide

000000000000000000000000000

Acetylenic ethers and acetylenic epoxides Review: Ethynyl Ethers and Thioethers as Synthetic Intermediates

Advances i n Org Chem (1960) 2 117

CXH

1 BuLi

Et20

CXCH20Et

2 ClCH20Et Rec Trav Chim (1965) 84 31 Bull Soc C h i m Fr (196v4514

90%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

226

EtCHzCHO

1 PhCH20H

HC1

MgS04

t

CsH6 2 Br2 C6Hg

EtyH-yHOCH2Ph

Br Br

1 PhNEt2

SECTION 308

EtCECOCHZPh

C6H6 2 NaNH2 Rec Trav Chim (1964)

EtBr

HCECOBu-t

LiNH2 NH3

Acetylene

Rec Trav Chim (1961) 80 810 JCS (1954) 1860 Org Prep and Procedures (1972)

4 89

0

11

BuC~CC-CH~ I Me

2 BrCH2COMe 3 KOH Et20

Section 308

a 301

EtCECOBu-t

t

1 EtMgBr

BuCXH

60%

40% Zh Obshch Khim (1960) (Chem Abs 2 499)

30 1194

- Halide

~ ~ ~ ~ ~ O O O O O O O O O O O O O O

-

Acetylenic ha1 i d e s

BuCXH

C5H11 C X H

1 NaNH2 NH3

2 I(CH2)4C1

1 KNH2 NH3

2 Clp Et20

53%

BuCX(CH2)4Cl JACS (1948) 2 1699 JCS (1950) 2100 J O C (1951) 16 1405

C5H11 CXC1 JACS (1937)

TsCl

1307

Annales de Chimie (1931)

16 309

SECTION 308

ACETYLENE BuMgCl

PhCXH

THF

S02C12

hexane

- HALIDE

227

PhCECCl

t

48% JCS

C

(1968) 1265

638 33

C l N E t 2 or NBS Annalen (1960) JACS (1961)

Br2

PhCXH

NaOH

PhC3CBr

____t

THF

H20

@

CECH

89% JCS (1963) 2295 Org S y n t h (1965)

1 HgCI2

CH=CHBr

4663

KI

45 86

NaOH

79%

E t O H H20 2 B r 2 CgHg JCS (1963) 2295

C5H11 CECH

1 EtMgBr

Et20

*

2 Br2

C5H11CtCBr JACS (1937)

BrCN

PrCICH

1 MeMgBr

2 12

Et20

t

70%

2

1307

Annales de Chimie (1926)

25

Annales d e Chimie (1926)

5

PrCXI

JACS (1933)

55

2150

5

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

228

SECTION 309

40% -

S e c t i o n 309

-

Acetylene

Can J Chem (1971)

49 403

- Ketone

OOOOOODOOOOOOOOOOOO

Acetyl e n i c ketones

BuCZCH

1 BuLi

Et20 pet e t h e r

UJ

t-BuCECH

PhCXH

1 EtMgBr

2 EtCH-y=NOH I Me C1

Et2O C&

A c O

PhCXH

Ye

t-BuCZCCCHEt II NOH

b

93 7320

Ye

---L.

*

<69%

t-BuCXCOCHEt

T e t r Lett (1970) 2101

8%

PhC-CCOMe T e t r a h e d r o n (1962)

MeC(OEt)3 ZnC12

79%

CXBu JACS (1971)

1 EtMgBr

I \ ,COMe

w

2 Et2AlCl 3 &COMe

18 1381

C34%

PhCXC(OEt)2 --+ PhCrCFO I Me M e JACS (1958)

4607

SECTION 309

C6Hl3CX'H

- KETONE

ACETYLENE

1 AgN03-NH3 MeOH

H20

CgH13C:CCOMe

2 MeCOCl

BuCzCH

MeCOCl

--+ B u C X S i M e 3

PrCOOH

MeCOCl

BuECAg

1 ClCOOEt

A1C13

CC14

Na ( E t 3 B C X M e )

1 Ph+?P=CHCOPh #.

2 250-280"

2

JACS (1956) 1675 Tetr Lett (1970) 2659

*

2 PhCXLi

-

96 3280

BuCECCOEt

E t 3 N pet ether

75%

BuCXCOMe

Ber (1963)

PhCXCOPr

Ber (1964)

-

53%

57%

91 1649

MeCOCECMe Angew (1967) (Internat Ed

CH2C12

(PhCO ) 20

2 1675

JACS (1956)

cs2

EtCOCl

229

..

CHC12 J.

2 57 5 84)

60%

P hC X COP h JOC (1965)

2 1015

230

OF ORGANIC SYNTHETIC METHODS VOL 2

COMPENDIUM

@z:o

- FczCCoBu-

OH

- - ~~ c H f t ~ B u - BtF 3 a E t 2 0

c1

Et20

MeCN

Synth Corn (1972)

2 331

Quart Rev (1959) 13 61 Chem Pharm Bull (1973)

HCX:HOH Ph

PhCXCHOH I

Me

PrCECCH2Et

SECTION 309

CrOg

HzSO4

Me2CO H20

Na2Cr207.2H20 Et20

HCECTO Ph

HzSO4

H20

*

2 2051

80%

JCS (1946) 39

PhCXyO

70%

Me Tetrahedron (1962) 3 1381

Cr03'Pyr

CH2C12

PrCXCOEt

42%

Tetr Lett (1971) 4379

MeCECCHZCl

COMe 1 NaCHCOOEt 2 NaOH

H20

*

MeCXCH2CHZCOMe JCS (1951) 2445

37%

SECTION 311

ACETYLENE

0

- OLEFIN

231

0

58% Helv (1967) 50 2101 708 (1972) 55 1276

Section 310

Acetylene

-Nitrile

OOOOOOOOOooOoooOOOOO

Acetylenic n i t r i l e s

CXH

1 Mg

EtMgBr

2 ClCN

phCOC1

1 Ph3P=CHCN

Section 31 1

2 280'

CECCN

Annales de Chimie (1926) Bull SOC Chim Fr (1915)

PhCXCN

55

228

85% Proc Chem SOC (1961) 302 JCS Perkin I (1973) 2241

AC~~;',~C~~;~~~~~~;

A c e t y l e n i c o l e f i n s , enynes

CijH1T E C H

C U ~ O HOAC

60% Chem Ind (1962) 1684 Proc Chem SOC (1958) 303

COMPENDIUM O F ORGANIC SYNTHETIC METHODS VOL 2

232

EtpZn

PrCXH

Cr(OBu-t)4

+

SECTION 311

PrCXC=CH2 I Pr

Bull Chem SOC Jap (1961) 2 892

PhCECH

BrCHzCH=CH2

NaCN DMF

PhCH=CHBr

PhCECCu

*-+

DMF

Me 1 (i-Pr6H)zBH

BuC~-CXBU

2 HOAc

t

F

96%

Compt Rend (1970) 270 354

PhCXCH=CHPh

75%

Chem Corm (1967) 1259

NaNH2 NH 3

EtCH=CHC-CH

< 42%

Rec Trav Chim (1963) 82 1115

BuCH=CHCECBu

76%

JACS (1970) 92 4068

-

Ph3PCH2CXH B r NH3 MeCN

THF

C5H11 CZCCH2CH=CH2

-

HCHO EtOH ---------+ E t C H 2 C X C H 2 0 E t HC1

EtCH2CZCNa

PhCHO

-

--+ CrjH11 C X C u

C5H11 CZCH

c

59%

PhCH=CHCZCH Annalen (1965) 682 62 Tetr Lett (1973) 1495

PhBr

Mg --+

- CARBOXYLIC

CARBOXYLIC ACID

SECTION 312

@"

PhMgBr

THF +

233

ACID

35%

PhCH=CHCrCH

Chem Corn (1969) 710

CgH13Br

MeCHZCZCSEt NaNH2

NH3

MeCH=C=FSEt CgH13

KNH2

N68%

CgH13CH=CHCfCH

NH3

Rec Trav Chim (1964)

456

-4.

Me:=CHCH2CH2:0 Et

Ph3PCH2CH2CH2CXH

Et

EtONa

*

DMF

MeC=CHCH2CH2C=CHCH2CH2CXH I

Et

I

36%

Et

JCS Perkin I (1972) 361

PrC=CHCHzBr I

Me

S e c t i o n 312

HCXCH2MgBr

Carboxylic Acid

Pr!=CHCH2CH$XH Me

JOC (1973)

- Carboxylic

3 2733

Acid

ooooooooooooooooooooooooooooaooooo

. . . . . . . . . . . . . page 233-234 . . . . . . . . . . . . . . . 234-235 . . . . . . . . . . . . . . . . . . . 235-240

1,l-Dicarboxyl i c (malonic) acids 1,2-Dicarboxylic (succinic) acids Higher d i c a r b o x y l i c acids

Review: S y n t h e s i s o f A l k y l a t e d A1 k a n e d i o i c A c i d s Chem Rev (1959) BuCXH

1 (i-Bu)zAlH

2 kli 3 c02

THF

*

59

89

B U C H ~ CCOOH) H( 2 T e t r L e t t (1966) 6021

62%

234

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

1 LiN(Pr-i)2

SECTION 312

THF hexane

30%

T e t r L e t t (1971) 2339

C1 2H25CH2COOH

PBr3

C12H25CH2COBr

COBr 1 her C C I ~

*

2 H20

Ber (1958)

C7H15Br

CH2( COOEt ) 2

KOH H20

C7H15CH(COOEt)2

BuONa BuOH

C12H25CH(COOH)2

91 297

C7H15CH(COOH)2

Org Synth (1943) C o l l Vol 2 474 416 (1932) C o l l Vol 1 250 Org React (1957) 9 107

CN CHCH2COOEt I

1 CH2(COOEt)2

OHCJ&

piperidine HOAC CgHg 2 KCN EtOH H20

W

COOMe CH2Br OMe

>

3 160'

HC1 H20

COOH I CHCH2COOH

___t

HOAc

15%

J Med Chem (1972) 1297 Org Synth (1963) C o l l Vol 4 804

:I$'

1 bH2CH(COOMe)2 MeOH MeONa

2 NaOH

<42%

COOH CH2CHCH2COOH

OMe JACS (1965)

933

85%

SECTION 312

CARBOXYLIC A C I D

CN 1 iH2COOEt Ph2CO

PhEH

Electrolysis

2 KOH H 2 0

CN

toluene 2 KCN E t O H

PhCH

1 H2SO4 HOAc

Ph2kHCOOEt

HOAC

JOC (1950)

t -

C02

Bu4N

DMF

235

ACID

-

CN

*

NH40Ac

- CARBOXYLIC

I

COOH

30%

Ph2dCHzCOOH

381

PhCHCOOH PhbHCOOH

+

91 %

Synthesis (1971) 285

PhCH2C1

--+

1 CHpCHCN

PhCH2CH(COOEt)2

t-BUOH

2 HBr

KOH

*

P~CH~CHCH~CHZCOOH I

COOH

H20

JCS (1950) 1683

COOH

A i r CuO

C

NaOH

Ill

COOH I

H20

CH

H2

Pd-Bas04

*-

(FH2)2 ,CI

Me OH

COOH (iH218 COOH

N

80%

C C

111

C I

(y2)2

Annalen (1954) 589 222

COOH

COOH I Me2C(CH2)2COOH

E l ec t r o 1ys i s Na2C03

MeOH

*

COOH COOH Me 2 ( CH 2 ) 4 b M e 2

6

Bull SOC Chim Fr (1970) 183

30%

236

FooMe

(FH2)4 COCl

COMPENDIUM

1 Et3N

OF ORGANIC SYNTHETIC METHODS VOL 2

CgHg

2 KOH H 2 0

*

COOH I ( F H 2 14

co I

N2H4

FOOH (fH2)9

NaoH

COOH

---*

SECTION 312

<60%

(FH2)4 COOH

FOCl

($H2)4 COOEt

1 @CH24$ SnC14

CS2

2 NaOH E t O H 3 N2H4 KOH d i e t h y l ene g l y c o l 4 E t O H H2SO4

Org Synth (1963) Coll Vol 4 555

Q -

(CH2)cjCOOEt

@

CH2

(CH2)5COOEt

MeCOCl SnC14

6 CH2

CS2

NaOBr

COMe

G(CH2)cjCOOH

CH2

Ni-A1 H20

NaOH

COOH

(yH2)14 COOH

COOH

Bull SOC Chim Fr (1955) 1583

toNMe2 (FH2)8 COOMe

-

-

FoNMe2

MeONa

1 HBr H20

(FH2)7 FHCOOMe

Zn HgC12 HOAC H20

co I

(tH2)8 CONMe2 YOoE

(FH2)4 I

237

CARBOXYLIC ACID - CARBOXYLIC ACID

SECTION 312

EtCH ( COOEt ) 2

Eto''a

EtoH

*

COOH ({H2)17 COOH

JOC (1973)

FooEt

(?2)4 EtC(C0OEt)z

32%

2 1424

-

COOH (tH2)4 EtCH I COOH

1 NaOH H20

2 >140°

JACS (1928)

1967

JACS (1953)

75 3339

I

(fH2)3

Br(CH2)lzBr

Br(CH2112Br

NaCH ( COOEt ) 2

Na CH2COONa

decal in

FH(COOEt)2 (fH2112 CH( COOEt)2

1 Hydrolysis

2 A

JACS (1947)

COOH t

(FH2114 COOH

83%

69 2350

COOH (FH2)14 COOH

34% Annalen (1966)

691 61

S E C T I O N 312

COMPENDIUM O F ORGANIC S Y N T H E T I C METHODS VOL 2 03 C C 1 4 ___t

02 MeONa

_c__t

HMPA

COOH

25%

I

(yH2)13 COOH

Helv (1930) 13 142

COOH I

( y 2 110 COOH

40% JOC (1965) 30 3768

OAc C r O 3 HOAc ___t

Tetrahedron (1964)

20 1271

COOH COOH 2 H202

HC1

HOAc

H20

~ 6 7 %

JACS (1956) 7s 6331

COOEt ,

0

-

0

1 fI)X);t 2 Fe

A

E t O N a*

O E O O E t

NaOH C : O O H

47-54%

Org S p t h (1943) Coll Vol 2 531

CARBOXYLIC ACID - CARBOXYLIC ACID

SECTION 312

c1

HCONMe2

1 AgN03 2

239

NaOH C I : O H

NaOH H20 Ber (1960)

-57%

93 2743

0' 0' 5 1 ;;;;holine*

CO(CH2)7COOEt 2 N2H4 CIIl:CHZibCOoH KOH

2 (:H2)7COOEt

COCl

J A C S (1963) 8 j 207

YOOH

22%

< 70%

COOH

3 N2H4 KOH

Org Synth (1963) 43 34 Ber (1967) 4017

b 0

(CHz)3COOMe

1 BrCH2CH=CHCOOMe

MeOK MeOH

aMe. Go CH2'CHCN

EtONa EtOH

Ber (1953)

86

.

N2H4 NaOH

diethylene glycol Ber (1954)

87

COOH

* (yH2)8 COOH

38%

693

COOEt

CHCH2CH2CN

H20

NZH4 NaOH diethylene glycol

2 H2 Ni

n

0

1 Ba(OH)2

990

COOH

(FH2)4 CHMe ($42)~ COOH

60%

I

Newer Xeth Prep Org Chem (1963)

1. 5 1

6

240

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2 CH2-CHCOOEt

.

-

&(cH2)2c00Et

0 EtONa EtOH

“$4

NaOH

HOCH2CHzOH

0

SECTION 312 COOH ,

(FH2)7 COOH

Newer Meth Prep Org Chem (1963)

b0- 6

CH2C00Et

1 MaOH

2 N2H4 die thy1 ene glycol

0

NaMnOq

C02 H20

1. 51

COOH (iH2)6 COOH

Ber (1952) 6 1 290 Newer Meth Prep Org Chem (1963)

29%

I. 51

96

48%

95

~65%

i sooctane

COOH

JCS (1947) 818

0

KMn04 dicyclohexyl-18-crown-6 CsH6

c::::

JACS (1972)

J O C (1969)

A l s o via:

Diesters Dinitriles

Section 357 375

94 4024

34

116

100%

CARBOXYLIC ACID

SECTION 313 Section 313

Carkh5ylic Acid 000

a-Hydroxyacids . . . B-Hydroxyacids . . . Higher hydroxyacids PhCOCl

CH2N2 Et20

241

- Alcohol

00000000000000000000

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

PhCOCHN2

CH2CH2COOH

- ALCOHOL

EtSCl

KOH

PhCO!HSEt C1

1 LiN(Pr-i)2

H2°

Ber (1955)

PhfHCOOH OH 1988

OCH2~:c00

THF

2 Air

Page 24 1- 243 243-245 245-246

51 %

*

Synthesis (1971) 647

1 KI

1 Br2 P4

EtOH

2 KOH H20 Ber (1942)

PhCHO

1 (PhS)gCLi

2 1181

PhCHCOOH OH

+

2 HgC12 Me2CO H20

47%

Angew (1967)

(Internat Ed

@::

.

79 468

fi

442)

CHBq KOH LiCl

dioxane H20

c1

JOC (1968)

2 2565

242

COMPENDIUM OF ORGANIC SYNTHETIC KETHODS VOL 2

PhCOOEt

CH3SOMe

t-BuOK

1 HC1

PhCOCH2SOMe

Me2SO H20

*

2 C U ( O A C ) ~ EtOH

PhCHCOOH I

JACS (1966)

PhCO I

Me

- OH PhiCN

NaCN HC1

EtpO

H20

Me

1 HC1 H20

2 NaOH H20

SECTION 3 1 3

OH

88 5498

OH

PhiCOOH

29-30%

Me

Org Synth (1963) Coll Vol 4 58 JOC (1949) 2 1013

1 HCN

Ac CN

HOAc

1 LiCHC12

THF

+

COOH

Angew (1971) (Internat Ed

PYr

PhCO

OH PhhO

KMn04

A

NaCXH

-----+

03

cyclohexane

Ph C C X H

A

C12

PhCOCH3

TH

83 329

2 336)

OH PhkOOti

dioxane

*

JOC (1972)

PhCO

1 ~203

31. 1248

OH I PhCCOOH

A29

J O C (1964)

3419

Carbohydrate Res (1966)

HOAc

-

t43%

N

2

40%

315

NaOH H20

PhCOCHC12

PhCHCOOH I OH

76-87%

Org Synth (1955) C o l l Vol 3 538

SECTION 313

CARBOXYLIC A C I D

FH20H HOCH

- ALCOHOL

243

COOH

02 P t

kj&ao

NaHC03

OJ-

H20 O# Ber (1972)

105 1524 1648 2 600

(1956) Angew (1957)

Me I

~

c

o

c

o

o

88%

HE t 2 0 J Med Chem (1972)

Me2C H COOH

oo

1 LiN(Pr-i)*

6

THF

15 1029

Me2CCOOH

t

JACS (1972)

94 2000

15

(1951) 4221 J O C (1971) 36 1149 2403 S y n t h e s i s (1970) 615

Me2CHCOOH PhZCHCHO

?)OH

Li N ( P r - i ) 2

*

THF

Ph2CHFHCMe2 OH J O C (1971)

1 Me2C=COSiMe3 ?H PhCHO

2 Acid

*

50%

a 1149

FOOH P h FHCMe2

68%

OH T e t r L e t t (1972) 79

244

COMPENDIUM

PhCHO

1 BueBSBu 2 H202

OF ORGANIC SYNTHETIC METHODS VOL 2

CH2=CO

MeOH

*

H20

PhFHCH2COSBU OH

SECTION 3 1 3

PhFHCH2COOH

--+

OH B u l l Chem SOC Jap (1971)

44 3215

OH

0

1 BrCHpCOOBu-t

Zn

THF

76%

2 C6Hg ( r e f l u x ) Chem Corn (1969) 679 JCS C (1969) 2799

PhCO

it

1 BrCHpCOOSiMe3 Z n

CgH6

VH

Et20

*

80%

PhCCH2COOH I

2 H20

Et T e t r L e t t (1971) 3227

Me2CHCOOH

(i-Pr)eNH

THF

BuLi

P

?H FOOH

A

JOC (1971)

Me0

0e6

71%

(>C-CMez

36

1149 2403

ad; yh

2:b;ClOOH

-

Na nap h tha 1ene

Me0

38%

CHCooH

Bull SOC Chim Fr (1970) 1848 Chem Ind (1969) 1811 (1972)

80

Israel J Chem (1971)

S

731

- ALCOHOL

CARBOXYLIC A C I D

SECTION 313

0% 1

Q:

TtiF

Me

~HCH~COOH

2 HCECCOOE~ riaoH

H20

*

3 H202 H20

MeCH=CCOOH I

Me

2 NaBH4

Me BubHCH2CH2COOH

95 6837

OH I MeCHCHCOOH

MeOH H20

*

NaOH H20

-71%

trans

JACS (1973)

1 Hg(0Ac)z

245

56%

I

Me JCS Perkin I (1973) 109

KMn04

NaOH

Ye

70%

Bu$CH~CH~COOH

H20

OH

JCS (1953) 2129 3580

COOH

Me2 CH COOH

L i N( Pr-i ) 2

1

( -+lactone,

TH F JACS (1967)

bMe“0 HO CHzCH=CH2

Me

Sr, 2500

CH2=CHCHzMgB;

HO CHzCH2COOH

B2H6

2 CrO3

Chem Comm (1968) 1 2 2

81%)

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

1 NaBH4

Q

C7H15

1 Me2SO NaH

COCH2SOMe

2 Ac20 Pyr

(CH2)110Ac

___)

2 KOH 3 Ni

SECTION 314

COOH

(FH2)8 CHOH

29%

(iH2)4 C7H15

C (1961) 26 217 JCS (1960) 1502

1 BrCHZCOOMe NaH MeZSO 2 A1-Hg H20 THF 3 NaOH E t O H H20 4 Zn-Hg HC1 H20

463

Can J Chem (1968) 46 3767 Tetr Lett (1966) 5669

Also v i a :

S e c t i o n 314

Hydroxyesters Hydroxyarnides Carboxyesters

Carboxyl i c Acid

Section 327 325 31 7

- Aldehyde

000000000000000000000000000

Carboxyaldehydes, a l d e h y d i c a c i d s

!H2C\0 y 2p CH2CO

H2 CO 130"

c02(co)8 200 kg/cn2*

CH2COOH I yH2 CH2CHO

32% B u l l Chem SOC J a p (1971)

2 288

SECTION 314 yH2CO CH,C'Oo

BuFHCHO Et

- ALDEHYDE

CARBOXYLIC ACID Na~Fe(C0)4 THF

247

.CH2COOH I CHzCHO

+

81%

Tetr Lett (1973) 3535

CHz=CHCN H2°

-

CHO BuiCHpCH2CN Et

NaOH

H20

CHO Bu~CH~CH~COOH Et

J A G (1944)

CHz(COOMe)2

SOMe 1 CHz=CSMe

P

NaH THF 2 HClO4 H20 MeCN

CHO I CH2CH(COOMe)2

66

56

---t

CHO I CH2CH2COOH

Tetr Lett (1973) 4711 4715

&OH

HI04 H20

JACS (1948) 3470 Org React (1959) 179

lo

G

H

O

Ber (1950)

Also v i a :

Aldehydic esters (Section 336)

72%

83 390

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

248

Carboxylic Acid

Section 315

a

o

o

o

o

-hide ~

o

o

o

~

~

~

~

~

SECTION 316 ~

~

~

~

~

~

Carboxyamides cO)Zo

PhCHO PhCN

19% S y n t h e s i s (1973) 40

NHAc 1 tH(C0OEt)Z

Br

HAc CHCOOH

NaH DMF

2 Na2C03 EtOH H20

55%

JOC (1965) 30 1321 (1973) 38 457 Org React (1957) 9 107

Also via: Aminoacids (Section 316)

Section 316

Carboxylic Acid

- Amine

000000000000000000000000

a-Aminoacids, 6-aminoacids and higher aminoacids PhCH2COOH

1 LiN(Pr-i)2

2 NH20Me

i-PrCH2CH2COOH

HMPA THF

Br2 PCl3

*

PhtHCOOH NH2

55%

Chem Corn (1972) 623

i-PrCH2yHCOOH Br

NH3 EtOH

H2°

i-PrCH2FHCOOH NH2

28%

Org Synth (1955) Coll Vol 3 523 848

~

~

~

SECTION 316

P

EtCHCH(COOH)2

CARBOXYLIC ACID

1 Br2

P

Et20

EtCHCHCOOH I Br

____t

2 130"

- AMINE

NH3

H20

249

Ye

49%

EtCHCHCOOH NH2

Org Synth (1955) Coll Vol 3 495 705

PhCHO

PhCONHCH2COOH NaOAc

Ac20

t

PhCH=(

COO

I

N=CPh

HI P4

Ac~O

C a t a l y t i c reduction o f azlactones

CH2NMe I ;C=NH 2 Na-Hg

HO OMe

MeSCH2CH2CHO

-41 %

PhCH2CHCOOH NH2

Org Synth (1943) Coll Vol 2 489 Org React (1942) 1 2 1 0 JOC (1972)

37

2916

CH2:HCOOH NHMe

H20

3 Ba(OH)2

H20

NaCN

(NH4)2C03

Et3N

E t O H H20

*

~ 5 1 %

HO OMe Org Synth (1955) Coll V o l 3 586 Org React (1942) 1. 210

MeSCH2CH2CHCO I )NH NHCO

Ba(OH)2

EtOH H20

MeSCH2CH2:HCOOH

NH2 -83%

JCS (1952) 3403

83% JOC (1952) 17 1459 Org React (1942) 1 2 1 0

COMPENDIUM OF ORGANIC S Y N T H E T I C METHODS VOL 2

250

PhCHO

1

H

NaHS03

2 NaCN

H20 +

H20

1 H2SO4

PhiHCN

2 H2SO4

H20

26

J O C (1961)

i-PrCHO

C H C l 3 t-BuOK

1 KNH2

i-PrCHCC13 AH

t-BuOH

2 HC1 JOC

PhCH2CONHBu-t

t-BuOC1

t-BuOK

NH3

H20

1 t-BuOK

PhCH2COyBu-t c1

+

C1-

1 CH2=CHCOOMe 2

cu2+ HC1 HCOOH

PhCH2CHCOOH H20

76%

i-PrCHCOOH 1

NH2 1148

PhCHCOOH 1 NHBU - t

t-BuOH 2 HC1 H 2 0 JACS (1961)

P h N H 2 --+ P h N 2

PhiHCOOH

4741

29

(1964)

S E C T I O N 316

72%

83 4469

NH3

--t

PhCH2CHCOOH 1

NH2

kl Proc Chem SOC (1962) 117

P h C H 2 N H 2 --+ P h C H 2 N C

(Et0)zCO DMF

NaH

PhFHCOOEt NC J O C (1973)

1 HC1

2 NaOH

2 2094

PhCHCOOH

iH2

57%

CARBOXYLIC ACID

SECTION 316

1 Br2

PhCH2C1 --+ PhCH2CH(COOEt)2

2 NaN3

- AMINE PhCH2y(COOEt)2 N3

1 Ph3P

2 HBr

251 PhCHZCHCOOH

Annalen (1955) 117 Z iu'aturforsch (1960) l j b 811

NHAc NaOEt

NH238%

NHAc CH2CHCOOH 3 NaOH

Me

_---___---1

_/---

&---

COOEt CHZC1

1

aCQd C'o

Na (COOEt)2

2 HC1 HOAC H20

*

JOC (1973) 38 457 (1959) 2 1397 Org React (1957) 9 107 JACS (1948) 3918 (1946) 68 450 J Biol Chem (1934) 106 595

COOH ~H~CHCOOH

~ 4 1 %

NH2

Org Synth (1963) C o l l Vol 4 55

PrBr --+ Pt-LHCOOK

1 NzH4'H20 2 HN02

3 cCl4 (reflux)

HC1 H20

PrCHCOOH NH2 J P r a k t Chem (1930) JOC (1956) 21 1182

125 211

252

COMPENDIUM

MeOD

CH2Br

NC 1 MedHCOOR NaH THF

MeO.@,CH2~COOH

Me

Me 0

2 HC1 H20 3 NaOH H20

1 NaCN NH4Cl

H20

*

2 NH3 H20

SECTION 316

y 2

).

Me0

Et2CO

OF ORGANIC SYNTHETIC METHODS VOL 2

Chem Ind (1972) 687

HC1

Et2yCN NH2

H20

39-43%

Et2yCOOH NH2

Org Synth (1955) Coll Vol 3 66 84 88

,fiOC-YH

KOH

(NH4 $03 ___)

Na OH MeOH

S t e r o i d s (1965) 5 263 3 Med Chem (1973) 16 823

HO

BuCH2COMe

1 MeONO Et2O 2 Et2S04

Bu;COMe NaOH NOEt

1 NaOCl

dioxane

BuCHCOOH

t

H20

2 Zn

H20

,fiOOH

1

NH2

HOAc

JOC (1959)

24

1726

OH i-PrCN

1 Me2CCN d i i s o p i n o c a m p h e y l b o r a n e

2 MeOH 3 HC1 H20

*

i-Pr:HCOOH

NH2 T e t r L e t t (1972) 3145

45%

253

CAREOXYLIC ACID - AMINE

SECTION 316

H2 Pd-C

i-PrCOCOOH --+ i-PrCCOOH

I

H2°

hHPh

NH2

38

J O C (1973)

PhCH2COCOOH

NH2COOCH2Ph

:ooti

PhCH2C(NHCOOCH2Ph)2

PhCH2COCOOH

NH4Er LiBH3CN

Hp Pd EtOH

Me NH3 PhCHNHz-EH3

49%

JACS (1971)

66%

I

NH2

JOC (1972)

PhCHO

CHz (COOH)2 NH40Ac EtOH

t

93 2897

PhCH2CHCOOH

t

31 2347

PhCHCHZCOOH

48%

I

NH2

30%

5 878

I

NH2

NH4Br MeOH

PhCHZCHCOOH NH2

PhCHCOOH

+

MeOH

822

-

J O C (1941)

PhCOCOONa

87%

i-PrCHCOOH

JACS (1936) 299 J Prakt Chem (1965)

30

18

Tetrahedron (1962) 18 21 Zh Obshch Khim ( 1 9 6 3 33 2697 (Chem Abs

60 512)

254

OF ORGANIC SYNTHETIC METHODS VOL 2

COMPENDIUM

SECTION 316

NH20H EtOH

PhCH=CHCOOH

PhCHCH2COOH I

34%

NH2 Org Synth (1955) C o l l Vol 3 91

@fN i CH2OH

*

Ts (CH2)3CH=CC12

--*Ts( CH2)3CHCOOH

co

H2S04 Ber (1973)

CHzNH2

106 2513

Org Synth (1943) C o l l Vol 2 25

2 H2SO4 H20 Org Synth (1943) C o l l Vol 2 76

oo

1 PhS02C1 Pyr 2 3

A

w

@

4 HOAc

NH2 (CH2) 1 1COOK

Aminoesters Amidoesters

Section 351 344

KOH

H20

Ber (1967) Also v i a :

%1: 100 3039

48%

SECTION 317

CARBOXYLIC ACID

S e c t i o n 317

Carboxylic Acid

- ESTER

255

- Ester

000000000000000000000000

Car bo xyes t e rs

94% Tetr Lett (1971) 3001

Br Me2bCOOEt

FOOMe

Zn

C02

THF

COOH MepkOOEt

Ba(OHI2 MeOH

c

(CH2 )gCOOMe

50%

Chem Ind (1966) 1457

COOMe (tH2)gCOOH

60-648

Org Synth (1963) Coll Vol 4 635

MeCHCOO Et I (CH2)4COOEt

KOH

EtOH

MeCHCOOEt (CH2)4COOH JACS (1948) 70 3206 364

59%

69%

PhCHO Ac20

PhCH2COOH

Et3N

PhCHOAc PhiHCOOH

32% Synthesis (1972) 263

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

256

T1 ( O A C ) ~

BuCH2COOH

BuCHCOOH B ~ C H ~ C O ~

Also v i a :

Tetr Lett (1970) 5285

Section 357 31 3

Diesters Hydroxyac i ds

Section 318

SECTION 318

Carboxylic Acid

- Ether,

Epoxide

P

-

A1 koxyacids and epoxyacids PhCHO

CHC1-j

KOH

MeOH

PhCHCOOH

ooH

i-Pr

i-Pr

1 Na

Me

CH2=CHCN

Me MeCH=CCOOH

toluene,

~ 0 c H 2 c 0 0 H

2 ClCH2COONa

1 PrOH MeONa

78-841

Org Synth (1955) Coll Vol 3 544 (1943) CoII Vol 2 260

Me

50%

PrOCH2CHzCOOH

2 H2SO4 H20

JACS (1949)

1 Hg(OAc)2 MeOH 2 NaBH4

49%

JACS (1960) 82 4062 Chim Ther (1967) 2 9 (Chem Abs 67 99319) Synthesis (1971) 131

OMe

t

2 3480

Ye

MeCHCHCOOH I

OMe

JCS Perkin I (1973) 109

72%

PhCHCOOH OH

- HALIDE

CARBOXYLIC ACID

SECTION 319 Me2CO H2SO4

6

t-BUMgC1

PhCHCO

+

Et20

\ I

CMe2

PhCHCOOH I OCHMe2

JACS (1942)

Jr-

257

64 1567

CHCOOH

Me2SCHCOONa

-~60%

Me2SO JOC (1970)

MeCH=CHCOOH

Also v i a :

Section 319

*

A1 koxyesters Epoxyesters

Carboxylic Acid

35

1600

0 I \ MeCHCHCOOH

H202 Na2W04 NaOH H20

44%

50%

JOC (1959) 2 54 JCS (1962) 1116

Section 358 358

- Halide

'eoooooooooooooooooooooooo

Haloacids, Halogenoacids BuCH2COOH

i-PrCH2CH2COOH

C5H11 COCl

CuCl2 LiCl

sul phol ane

Br2

PCl3

*

Bu$HCOOH c1 Chem C o r n (1966) 544

i-PrCH2tHCOOti

< 54%

63-66%

Br Org Synth (1955) Coll Vol 3 523 8 4 8 (1943) Coll Vol 2 74

258

C1 CH2CH2COC1

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

NBS HBr

C1 CH2CHCOC1 I Br

HOAc

SECTION 319

< 70%

C1 CH2THCOOH Br

--+

T e t r Lett (1970) 3431

C10H21 CH2COC1

MeCH2(CH2)3COOH

i-PrCH(COOH)2

SOCl2 h v

C1 OH21 yHCOC1 c1

(i-Pr)*NCl

hr/

1 Br2 Et20 2 125-130"

t

---t

C1 OH21FHCOOH c1

JOC (1973)

38

nJ

90%

3919

Me:H(CH2)3COOH c1

JACS (1971) 2 438 Rec T r a v Chim (1964)

3 891

i-PrCHCOOH I Br

Org S y n t h (1943) C o l l Vol 2 9 3

chloroacids JCS (1950) 2900 PhCHO --+ PhFHCC13 OH

KOH oleic a c i d H20

* PhCHCOOH I c1

S y n t h e s i s (1971) 131

50%

SECTION 319

- HALIDE

CARBOXYLIC A C I D

259

82%

@@JNy?+

c1 1 C H 2 - C H C O Y ~ c H 2 t H c 0 0 H c1 ~ 5 1 % CU2+ 2 HC1 HCOOH

@@N2

H20 Bromoac id s NaOAc

Proc Chem SOC (1962) 117

Org Synth (1971)

NaI

O r g Synth (1966)

Me2CO

i -

*

Me2FCOOCH2CH2Cl c1

--* Me2FCOOH

Ber (1968)

1 NOCl

HC1

Et20 *.

2 HC1 H 2 0

HI

37

0

CH2-CH2

Me4N B r

MeCH=:COOH Me

46

/ \

CHCI 3

C5H11 CH=CH2

1

Ag

CHCl3

MefHFHCOOH I Me

c1

101 1299

C5H11 tHCOOH c1 Zh Obshch K h i m (1964) 2 1227 (Chem Abs 61 2967)

JACS (1929)

2528

<24%

260

COMPENDIUM

Also v i a :

- Ketone ........ ........ . ....... ........ ........

Carboxylic Acid

. . . .

0000000000000000000000000

.. .. .. ..

a-Ketoacids 8-Ketoacids Y-Ketoacids 6-Ketoacids Higher ketoacids

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

- CuCN

PhCOCN

HC1

H20

NHAc PhCHO

SECTION 320

H a l o e s t e r s ( S e c t i o n 359)

S e c t i o n 320

PhCOCl

OF ORGANIC SYNTHETIC METHODS VOL 2

CH2COOH Ac20

*

Na OAc

PhCH=F-FO

. . . . . . . . . page 260-262 . . . . . . . . . . . 262-263 . . . . . . . . . . . 263-265 . . . . . . . . . . . 265-267 . . . . . . . . . . . 267-268

PhCOCOOH

N45%

Org S y n t h (1955) Coll Vol 3 114 Can J Chem (1971) 49 919

1 H20 Me2CO

2 HC1

H20

PhCH2COCOOH

-65%

\\ /

CMe

(PhCH2)2CHCHO

--*(PhCH2)2CH!HCN OH

Org Synth (1943) C o l l Vol 2 519 1 Org React (1942) 1 2 1 0 1 H2SO4 2 CrO3

t-BuOH HOAc

*

(PhCH2)2CHCOCOOH

Synthesis (1971) 538

PrCHO

CH3COCOOH

Et2NH

PrCH=CHCOCOOH

EtOH

KBH4

KHC03

PrCH2CH2COCOOH

H20

Bull Soc Chim Fr (1966) 1435

C5H11CHO --+ C5Hi,CH=C(COOEt)2

1 H202

Na2W04 H20

2 KOH EtOH 3 180-200O

*

C5H11 CH2COCOOH

JOC (1964) 2 2080

77%

SECTION 320

PhCOOEt

1 Me2SO

2 HC1

t-BuOK H20

CARBOXYLIC A C I D

- KETONE

OH PhCObHSMe

Cu(OAc)2*H20

*

Me2SO

CHCl3

JACS (1966)

EtCHzCOOEt

EtyHBr

--.c

(C0OEt)p

EtONa

t

Et20

6OCOOE t

EtCHLi

he

Me

HZS04

EtCHCOOEt

NC I 1 t-BuCH2CMe2

*

2 COZ

CONEt2

555 4 1

JACS (1969)

NaOH

EtCOCONEt2

2 7778

92 6675

EtCOCOOH

Compt Rend (1927)

‘OCH3

KMn04

Me 0

MeRo@coCooH 0

H20

GIN

--+ Me2C=CCOOEt

184 825

NaOH

Monatsh (1952)

Me2CO

80%

I

Me

(c00H)2 H20

COOEt

--+ E t M g B r

1 H 2 0 2 NazW04 H20 2 KOH

EtOH EtOH

3 HC1

H20

64-73%

EtCHZCOCOOH

EtCHCOCOOH

(1970)

EtBr

PhCOCOOH

5498

H2° Annalen (1943)

Et20

261

*

Me2CHCOCOOH

JOC (1963) 28 3088

883

-55%

262

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

PhCHCOOH OMe

Br2 CHC13

1 (CF3CO)zO

i-PrCH2yHCOOH

2 NaOH H20

NH2

Me2CHCOOH

PhCOCOOH

1 LiN(Pr-i)2 THF

*

2 t -BuCOOMe 3 Me3SiCl 4 MeOH

Ber (1967) 100 3777

SECTION 320 90%

i-PrCHZCOCOOH Annalen (1962)

658 128

Me2yCOOH t-BuCO JACS (1971)

93 6321

89% Coll Czech (1961) 26 847

PhCOCH3

PhCOCH3

CO2 PhOK DM F

(MeOCOO)zMg

PhCOCHZCOOH

DMF

*

Chem Corn (1966) 618 JOC (1973) 2 4086

PhCOCH2COOH JACS (1959)

60%

68%

81 2598

CARBOXYLIC A C I D

SECTION 320

1 Li

0

NH3

2 C02

- KETONE

263

EtpO

0

EtzO

COOH

JACS (1965) 87 275 JOC (1968) 35-712 NaC ( COOCH2Ph 12 tH2COOCH2Ph CioH21COCl

-

1 H2 Pd-C C10H21COy(COOCH2Ph)2 CH2COOCH2Ph 2 170"

C~OH~~COCH~CH~COOH 66%

JCS (1950) 325

1 soc12 t

C5H11 COOH

tH2CH2CN NaOH C5H11C-N __t I

C5H11 COCHzCH2COOH

0 CPr-i

2 i-Pr:HCOOH

\ I

co

NH2

3 Ac20 4 CHzzCHCN

It

Angew (1971) (Internat Ed

Et3N

727

lo 655) 29%

co

FH2COC1

1 Et3A12C13

CH2CoC1

2 ~ 2 ~ 0H 4~ O

Annalen (1964)

678

113

90%

EtCOCH2CH2COOH Angew (1965) (Internat Ed

4

810

785)

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

264

SECTION 320

Org Synth (1955) C o l l Vol 3 6 (1943) C o l l Vol 2 81 (1932) C o l l Vol 1 517

CgH1 3CHO

CH2COOEt I CHpCOOE t t-BuOK

CgH13CH=CCOOEt dHpCOOEt

1 NaOH

H20

Br2 cc14 3 NaOH H20

C6Hl3COCH2CH2COOH

c 66%

JOC (1966) 31 616 Org Synth (1963) C o l l Vol 4 430

Ph I

HCECH Ni(CO)4

CO

t

HC1 H20 30 atmos

1

Pyrrolidine

2 MeOOCCZCCOOMe* 3 Hydrolysis

4 H2 Pt HOAc

PhCOCH3

1 BrCHzCOOLi

PhCOCH2CH2COOH Tetr Lett (1964) 2777

&~~~~~ > 6 C O O H

JOC (1971) (1963)

LiNH2 NH3

2 BrCH2COOH Et20

*

2 955

1459

PhCOCH2CH2COOH Chem I n d (1959) 255

61 %

SECTION 320

265

CARBOXYLIC A C I D -KETONE

CHO COCH=CHCOOH Br

Zn

B~

base

HOAc

COCH2CH2COOH H20

_____c Br

J O C (1973) (1958)

1 BrCHzCH=CH2

Me

NaH

*

MeOCH2CH20Me

2 RuO4

NaIO4

t-BuOH

H20

38 4044

2 1832

Meao MeCH2COOH

T e t r L e t t (1972) 1853

HCHO PhCOCH2 ih

MezNH.HC1

>

PhCOCHCH2NMe2

Ac20

I

Ph

1 Me1

2 KCN 3 HC1

H20

J O C (1973)

I COCH=CMe2

1 KCN

BuI

+ -

MeOH

t

2 KOH

PhCOCH2CH2tHCH2yH2

0 -co

EtOH H 2 0

1 NaOH H 2 0 2 CrO3

Pyr

68%

PhCOCHCH2COOH

bh

2 4044

8-1 2%

t-BuCOCHp:Me2 COOH Annalen (1971) 751168 JOC (1963) 28 1459

PhCOCH2CH2COCH2CH2COOH JACS (1963)

-

>45%

3 2937

BUCH2CO(CH2)$OOH

Ber (1952) 61 JCS (1957) 2202 Newer Meth Prep Org Chem (1963)

23%

2 51

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

266

1 CH20

SECTION 320

PhCl

81 %

2 Hydrolysis

Acta Chem Scand (1964) 18 2201

PhCOCH9Pr-i L

b

Ph

1 CH2=CHCN KOH

t

MeOH dioxane 2 KOH H20

1 CH2(COOCH2Ph)2

t-BuOK t-BUOH*

PhCOCHPr-i I CH2CH2COOH JCS (1948) 1741 Org React (1959) lo 179

( y bPh CH( COOCH2Ph)2

Pd-C 2 170180'

CH2COOH

Org React (1959) lo 179

H202 NaOH

Me

Me JOC (1970) 35 1275

H202 PhCN NaHC03 MeOH

H20

CO (CH2)3COOH

Bull Soc Chim F r (1969) 2871

30%

e7Ho

SECTION 320

267

CARBOXYLIC A C I D - K E T O N E

KMn04 K$O3 Nt-a Bu I O OH 4+

79-aax

0

Can J Chem (1961) 03 Can J Chem (1962)

R u O ~ ,NaIO4 J O C (1969) 34 1 1 2

39

599

40 2153

, JACS (1948)

81%

3352

46-55% Org Synth (1963) Coll Vol 4 19

Bull SOC Chim F r (1967) 3742

6

KMn04 dicycl ohexyl -1 8-crown-6

90%

C6H6 JACS (1972)

94 4024

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

268

SECTION 320

pJBu C:I";. 1 O3

HOAc

*

2 Zn Et20 H20 3 HCOOH H202 H20

BuBr

Can J Chem (1955)

1 Mg

63%

-

Et20

NaOH H20

33

1720

BuCO( CH2)4COOH

Bull SOC Chim Fr (1965) 3041

(PrC0)20

O0 prco6 NaOH H20

BF3

C10H21CH2COC1

JACS (1953)

1

(E; F;: k

2 Acid 3 NaOH

EtjN +

EtOH

2 KOH 3 Ni E t O H Also v i a :

PrCO(CH2)5COOH

Ketoesters Ketoami des

C10H21 CH$O(CH2)1iCOOH Ber (1967)

100 4010

JCS (1960) 1502

Section 360 34 7

5030

71 % 4017

CARBOXYLIC A C I D

SECTION 321 S e c t i o n 321 Cyanoaci ds

COOH I

(CH2)7COOH

oJ feM

Carboxylic A c i d

- NITRILE

269

-Nitrile

00000000000000000000000000

-

COOH

(NH2)2CO

(CH2)7CN

160-360'

<49%

73 343

JACS (1951)

-MepH KCN

280'

94%

CN

BuONO

HC1

Et20

EtOH

~

%,,

Bull SOC Chim Fr (1954) 88 Org S y n t h (1955) C o l l Vol 3 174

:;

QNoH

H20

JOC

NaOH,

5

(1941)

105

T e t r Lett (1968) 1127

r F CHOH o

w

(CH2)lo

HCONH2

acid

/7tm0> hv

(CH2)10

C-N

W

02

methylene blue

HO CHOH NH20H* HC1

0-t CH

H20

-1 MeONa MeOH

HO

Ber (1961)

COOH (iH2)10 CN

-80%

90 2440

JACS (1968)

EtOH

c

94 2897

~cooHrcN

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

270 Also via:

SECTION 322

Cyanoesters (Section 361)

Section 322

- Olefin ...... ...... ...... . . . ...

Carboxylic Acid

0000000000000000000000000

aB-Olefinic a c i d s . . BY-Olefinic a c i d s . . Y6-Olefinic a c i d s . . Other o l e f i n i c a c i d s

. . . .

.. .. .. ..

.... .... .,.. , . . .

. . . . . . page 270-274 .,..... ........ ........ .

274-275 275 275-276

Review: Recent Developments i n t h e Synthesis of F a t t y Acids Chem Rev (1957)

CgH13CrCH

BuCXH

Ni(CO)4 HOAc cyclohexane

*

C6H13F=CH2 COOH

Chim Ind (Milan) (1964) 5 1063 Bull Chem SOC Jap (1968) 41 390 Annalen (1953) 582 1 JCS (1951) 48

1 (i-Bu)zAlH heptane 2 MeLi

51 191

b

Et20

BuCH=CHCOOH trans

78%

JACS (1967) 2754 J Organometallic Chem (1968)

3 c02

11 P7

58% J hled Chem (1970)

CgH1gCH2CH2COONa

1 (i-Pr)zNLi 2 DDQ

C6H6

HMPA THF

*

2

317

CgHl gCH=CHCOOH

Chem Comm (1973) 94

-30%

- OLEFIN

CARBOXYLIC ACID

SECTION 322

271

Chem Phys Lipids (1968)

C7H15CH2COOH

1 (i-Pr)2NLi 2 HCHO

HMPA THF +

213

90%

C7H15;COOH CHZ

J O C (1972)

PhCHO

2

(MeCH2CO) 20 EtCOONa

CHo

CH2(COOH)2

()Me

piperidine

31 1256

60-70%

PhCH=yCOOH

Me

Pyr*

Org React (1942)

L 210

@W~CHCOOH

OMe

OMe

87-98%

Org Synth (1963) Coll Vol 4 327 (1955) Coll Vol 3 425

Org React (1942) I 2 1 0 t-BuCHO

QCHO

NO2

1 CH2(COOEt)2

Z n C 1 2 ACpO

*

2 Hydrolysis 3 A

J O C (1965) 3 917 JACS (1938) 3 2901

N-CMe2 II I MeCH2C CH2 \ /

0

H20

6 J

CH=FCOOH

*

N a H S 0 3 toluene 2 HC1

t-BuCH=CHCOOH

90%

Me

NO2 J O C (1962)

27 4418

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

272

@CH2YHCOOH

1 ~~;~COOEt~

J ' @ ~ ~ ~ ~ ~

c1

NaOH

c1

2 Hydrolysis 3 Br9 4 168-170'

SECTION 322 CH=CHCOOH

+

c1

H20

Ber (1933) 66 1464

COCl 1 LOOEt AlC13* 2 NaOH

-vccooH

\-CoCooH

?2

1 MeMgI

76%

2 H2S04 di oxane

J Med Chem (1972) 15 1029

i -PrCHzCOCH3 --+ i-PrFHCOCH2Br Br

PhCO Me I

Pr2C0

CH2=CO BClg

KHC03 H20

H20 EtOH

i-PrCH=CHCOOH

Acta Chem Scand (1965)

(1963) Chem Corn (1968) 306

-

PhC=CHCOCl I Me

+

19 383 17 2766

47%

PhF=CHCOOH Me

Ber (1970)

CH2 (COOEt)2 Ti C14 CCl4 Pyr THF

-

Pr2C=C(COOEt)2

105 2003

--+ Pr2C=CHCOOH

< 42%

Tetrahedron (1973) 29 635

CHCOOH JOC (1973)

38

399

< 60%

CARBOXYLIC ACID

SECTION 322

EtOH MeCHR

- OLEFIN

273

2 KOH d i e t hy 1ene glycol

MeCHR

MeCHR

Tetrahedron (1968) JOC (1972) 37 2201

HOCH2CH2CH.CH2

-

1 EtOK HOCH2CH2yHCH2CC13 ____t HOCH2CH2CH=CHCOOH c1 2 Hy'drolysis

cc14

d i benzoyl peroxide

Coll Czech (1966)

PhCECCOOH

N2H4 02

Tetr Lett (1961) 353 Chem Rev (1957)

Me2CuLi

Et20

+

Ph

N2H4

---+

Me CCH P h I1 I

N, ,co

51 191

PhF=CHCOOH

Me

MeCOFHCOOEt

2 3765

PhCH=CHCOOH

C a t a l y t i c and chemical r e d u c t i o n o f a c e t y l e n i c a c i d s

Ph C X C O O H

24 3127

93%

JACS (1969)

1 Cl2 CH2C12

2 NaOH H20

*

NH

JACS-(1958) J O C (1969) (1966)

91 6186

MeCH=CJCOOH Ph

80 601

34 1717

31

2867

31 %

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

274

1 Li

CHBr

+

2 c02

KOCl

dioxane

HOAc d i - t - b u t y l

Org Synth (1955) Coll Vol 3 302

peroxide

HC(COOEt)3 d i - t b u t y l peroxide

2 610

49-53%

F

24%

BuCH=CHCH2COOH

Can J Chem (1966)

CgH13CZCH

60%

Me2C=CHCOOH

H20

BuCECH

CHC00rl

Angew (1965) 173 (Internat Ed 4 156) Acta Chem ScaKd (1959)

-

MezC=CHCOMe

] )=

MeOCH2CH20Me

SECTION 322

CgH13CH=CHC(COOEt)3

1 NaOH EtOH 2 160’

fi 2241

C6H1 3CH’CHCHzCOOH

Synthesis (1969) 76 !H2COONa PhCHO

1 CH2COONa

2

0

Ace0

n

PhCH=CHCH2COOH

Org React (1942) 1 2 1 0

t

C1- Ph3PCH2CH2COOH NaH Me2SO THF

CHCH2COOH

JACS (1964) 1884 JOC (1962) 2 3404

66%

hexane

hll

C7H15CH2CH=CHCOOH

JOC (1966)

CH2COOEt I 1 CH2COOEt t-BuOK 2 Ba(0H)Z

Cu ( OAC) 2 HOAC 2 Hydrolysis

Zn

toluene

6

HO

\

CH2CH2COOH

Chem C o r n (1973) 694 Synthesis (1970) 99

100%

Chem Corn (1973) 117

-

CHO

X

CH=CHfHC5H11 OH

70%

BuCH=CHCH~CH~COOH

t

Me2CCOOH I CH2CH=CH2

____t

(14%

JACS (1949) 1384 Org React (1951) 5 1

H20

1 CH2(COOEt)2 Mn(OAc)3

CHCH~~HCOOH Et

2 467

QMe

+

3 (COOH)2 HC1 Pyr

Br MeikO? CHz=CHCH2

1671

--*

CH2=CHPPh3 Br NaH Et20 DMF

BuCH2CH=CH2

33

0

EtCH(C0OEt)Z

Me

95%

C7H15CH=CHCH2COOH J O C (1968)

0

275

CARBOXYLIC ACID - OLEFIN

SECTION 322

t

P~~PCH~(CHZ)~COOH NaH Me2S0

HO

Tetr Lett (1970) 311 JACS (1971) 93 1490

OH

e

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

276

SECTION 323

0

Ac 0

0'' 0

Tetr Lett (1963) 1659 Angew (196,5) 229 (Internat Ed 4 216)

-

U

1 PrCHzSNa+

1 NaH CsHg

()s02cH2Pr

2 Brp 3 KOH HI20

2 Peracid

PrCH=CH( CH2)4COOH ~ 3 2 %

Bull SOC ChillT Fr (1964) 723

O l e f i n i c esters 01 e f i n i c ni t r i l e s O l e f i n i c amides Hydroxy a c i d s Acetylenic a c i d s

Also v i a :

Section 362 376 349 31 3 301

- Alcohol page 1,2-Diols . . . . . . . . . . . . . . . . . . . . . . . . . 1,3-Diols . . . . . . . . . . . . . . . . . . . . . . . . . . . 1,4- Di 01 s . . . . . . . . . . . . . . . . . . . . . . . . . . . Other d i o l s . . . . . . . . . . . . . . . . . . . . . . . . . . Section 323

C10Hpl COCl

Alcohol

000000000000000000

1 CH2N2 Et20 2 HOAc

C10H27 COC.H20Ac

A1 (OPr-i)3 i -PrOH

C10H21 FHCH20H OH

Org React (1954)

MeLi PhCOOH

Tic13

MeOCH2CH20Me .

276-281 281-282 283 283-284

8

218 228

ye ye PhC-FPh I OH OH Chem Corn (1970) 4 5 1

85%

SECTION 323 PhCHO

PhCOOEt

Mg Me3SiC1 HMPA

Me2SO

t-BuOK

ALCOHOL

- ALCOHOL

> 90%

PhCH-FHPh OH OH

PhCOCH2SOMe

277

T e t r Lett (1972) 75

lHCl Me2SO H20

* PhCHCH20H

2 NaBH4 NaOH

EtOH H20

JACS (1966)

COOMe 0 I I t CH=!(CH2)2CH=T(CH2)2CHCMe2 Me Me

75%

I

OH

5498

HC104 THF H20

COOMe I CH=f(CH2)2CH=C(CH2)2FH-fMe2 I Me Me OH OH JACS (1972)

94 5379 11 3938

HI04 JACS (1949) 2,4,6-Trinitrobenzenesulfonic acid, Me2SO T e t r Lett (1971)

411

T e t r Lett (1965) 3421 JACS (1973) 95 2361

T e t r L e t t (1970) 4271

Na Bull SOC Chim Fr (1967) Mg, MgI2 JACS (1942) 2 30 Bu3SnH hv JCS (1971) 1 2 4 1 Electrolysis S y n t h e s i s (1971) 285

c

2011

78%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

278

SECTION 323

=

JACS (1965) 654 Can J Chem (1967) 5 2921

Tetr Lett (1972) 2845

<6l%

trans

JACS (1969) 91 2632 Chem Ind (1960) 720

R

\

0@lONOb

t-BuOK

'ONQ[ 0

1 02 t-BuOK

L

27 MeCOCOOH NaBH4

2 NaBH4 Annalen (1972)

HO A

758 89

Review : Hydroxyl a ti on Methods Advances in Org Chem (1960) 1.103 Epoxidation and Hydroxylation o f Ethylenic Compounds with Organic Peracids Org React (1953) 378

EtCHZCHEt

1

2

03 Et20

i-PrMgBr

EtFH-YHEt OH OH

46% J O C (1963)

1159

SECTION 323

ALCOHOL

KMn04

- ALCOHOL

279

+

NaOH PhCH2NEt3 C1

CH2C12

50%

H20 ( 2 phases)

KMn04, MgS04 ( n e u t r a l c o n d i t i o n s )

Tetr Lett (1972) 4907

J Heterocyclic Chem (1972)

K2Mn04, NaOH JCS (1956) 2452

1 H202

HCOOH

9

979

H20

2 KOH MeOH Me

Me Tetrahedron (1968) 2 5701 Org React (1953) 1. 378

o - S u l f o p e r b e n z o i c a c i d Tetr Lett (1971) 691

Disuccinoyl peroxide, detergent

Synthesis (1973) 156

H202 Se02 t-BuOH

40%

trans

H20

36 268 (1957) 2 1682

Helv (1953)

H202, H2WO4 JOC H202, V2O5

1 OsO4 P y r

JACS (1937)

59

2342

THF

43%

2 H2S Tetrahedron (1971) 27 753 JOC (1960) 25 257 osO4 ( c a t a l y t i c q u a n t i t y ) , ~ ~ 1 0JACS 4 (1968) 90 5336

OsO4 (

'I

"

),

H$J2

JACS (1937)

2 2345

280

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 323

t67%

t-Bu

t-Bu

Can J Chem (1971) 49 2586 Tetrahedron (1964) 20 1017

JACS (1967)

1 12 ~ 1 0 3 HOAC

2 KOAc 3 KOH MeOH CgHg

+

4217

Heal

70%

HO

Tetr Lett (1973) 4485

1 I 2 AgOAc _____t

2 KOH MeOH 0

looH

JACS (1954)

OH

2 5014

Cis

JCS 4. (1966) 1327 Org React (1957) 2 332 JOC (1942) 7 227 12, s i l v e r trifluoroacetate Chem Corn (1966) 202 I(ocoCF3)3 Angew (1973) 175 (Internat Ed) 12 163

12, s i l v e r benzoate

67%

ooH

SECTION 323

1 $Z-.jCHO

ALCOHOL

- ALCOHOL

0::

Hg(OCOCF3)z

*

2 NaBH4 3 Zn HOAc

f iI 01 LiMe2Cu I

281

Chem Comm (1972) 1196

Et20

2 B2Hg THF

.-

f

I

3 H202 base

i

O

I

H

59%

Me T e t r L e t t (1972) 4031

1 82Hg

THF

2 H202

NaOH H20*

0:: trans

Me

Me

Tetrahedron (1968)

MeCOCH20H

Baker's yeast

2 5701

49-58%

MeFHCH20H OH

Org Synth (1943) C o l l Vol 2 545

Do

+-

CHCOOH

Me2SCHCOONa*

t-Bu

Me2SO

t-BU

49%

Et20 2 LiAlH4 J O C (1970)

35

1600

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

282 YOOH (CH2)4CH=CH2

-

HCHO HzSO4

HOAc

YOOH (CH2)4?HCHzfHz 0-CH20

1 CH2N2

2 H2SO4 MeOH

SECTION 323

COOH I

(CH2)4FHCH2CH20H OH

< 83%

JCS (1956) 3074

PhCH2CH=CH2

1 BuLi

PhFHCH2CH20H

2 B2Hg THF

3 H202

65%

OH

NaOH

JACS (1971)

PhCH=CHCHzOH

1 HS(OAC)2

2 NaBH4

93 6313

PhYHCH2CH20H

OH

T e t r L e t t (1968) 5105 Chem Corn (1968) 1073 (1967) 1283

CHPh

1 B2H6 THF

72%

2 H202 NaOH H20 JCS Perkin I (1973) 1707

79%

JCS Perkin I (1972)

1509

82% JACS (1968)

90

2927

283

ALCOHOL - ALCOHOL

SECTION 323

MeMgBr Et20

JACS (1940)

LiAlH4 Et20

CH20H OH

1 Bu3B CHZ=CHLi

62 1779

80%

JACS (1952)

3 5908

4336

noH

Et20

2 H202 NaOH H20

CH2fHO H Bu

77%

T e t r L e t t (1973) 4527

?Et 1 L i (CH2130CHMe Et20 2 HC1 H20 EtOH

*

86%

1 NaBH4 BF3 diglyme 2 160" 3 H202 NaOH H20

1

O3 MeOH

2 Hp

b

catalyst

*

yH20H MezCCH2:HCH20H Me JACS (1966)

8 1443

!H20H

(y2)10

CHzOH

Tetr Lett (1971) 3587

JACS (1957)

2 3165

85%

284

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

JACS (1972) (1962)

-

Me2!CH20H (?H2)2 COOH

Electrolysis

SECTION 324

3 3567 84 190

Me2CCH20H I (FH2)4 Me2CCH20H

Na2C03

52%

Bull SOC Chim Fr (1970) 183

Also via:

Section 327 357

Hydroxyesters Diesters

Section 324

Alcohol - Aldeh.yde 0000000000000000000

a-Hydroxyaldehydes . . . . . . . . . . . . . . . . . . . . . B-Hydroxyaldehydes . . . . . . . . . . . . . . . . . . . . . Other hydroxyaldehydes . . . . . . . . . . . . . . . . . . .

PhCOOH

i-PrCHO

--*PhCOCHN2

1 EtSCl Et20 2 MeSNa

1 MeSOCH2SMe

BuLi THF 2 Hydrolysis

PhCOCH(SEt)2 Ber (1958)

(1957)

.. ..

page 284-286 286 286-287

1 LiBH4 2 Br2 HC1 H20 HOAc

91 1043 90

1230

i-PrFHCHO OH Tetr Lett (1973) 4707

PhFHCHO OH

SECTION 324

CHO I

FHoH

CHOH

~HOH

ALCOHOL FH2N02

-

I

FHoH

MeONa

~HOH

1 NaOH

CHOH

CH20H

285 tHO

-

CHOH

CH3N02

- ALDEHYDE CHOH I

CHOH I CHOH

H20

H2S04 H2°

!HOH

CH20H

CH20H J O C (1964) 2 1790

FH=CH2

tH0

CHO 1

CHOH I

CHz=CHMgCl

1 03

CH20 FHoX 2 H2

EtOAc

CHOH 1

____t

CH20

PhCOOEt

Me2SO Na H

Pt02

Can J Chem (1967)

1 SOC12

PhCOCH2SOMe

CH2C12

2 MeSH CH2C12 3 NaBH4 H20 4 I2NaHC03 H 2 0

*

g 2921

PhFHCHO OH

JOC (1969) 2 3618 JACS (1966) S 5498

Ye

1 Mg

BuBr

BuCCHO

2 MeCOCH=NOH

3 (COOH)2

15%

I

OH

H20

Annales de Chimie (1939)

11 453

(- i ) C H L i

Me

0

'{ 0

2 BF3

HgO

62% OH

Ber (1972) 105 1978 Angew (1965) 1134 (Internat Ed 5 1075) Annalen (1972) 758 89

286

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

yhco

CHC12Li THF

K2CO3 i-PrOH

_____t

JOC (1972) Ber (1973)

i-PrCH2CHO

I0\ (Et0)2CHCHCH2

HCHO K2CO3 Et20 H20

1 Lids] S'

i-PrCHCHO I CH20H

TH F

2 HgO BF3eEt20

?-

OH

Mg Et20

37

1248

106 2620 52%

JACS (1948) 70 1694 Org React (1968) 2 1

(Et0)2CHyHCH2CHO OH JOC (1971)

MeCHCH=CH2

SECTION 324

MeCHCH=CH2

36 366

-,/fl 1 OsO4 EtpO

2 Na2S03 3 Pb(0Ac)a dioxane

Ber (1959)

92

1564

JOC (1969) 34 1122

MeCHCHO

66%

SECTION 325

0"

ALCOHOL

51 %

2 A1-Hg E t 2 0 H20 3 HgC12 MeCN

CsHg

CUCl

LiAlH4

Tetr Lett (1972) 3929 JOC (1973) 38 36

(oi

*

OCOPh

THL

fiH: Me OH (i-Bu)pAlH

S e c t i o n 325

--+

C C H O

Angew (1961) 73 65 Acta Chem Scand (1961) 15 249 Tetrahedron (1961) 13 241

0;

Also v i a :

287,

NCH2 1 LiCH2qSbH2 THF

PhC002Bu-t

Me

- AMIDE

(lactol)

JACS (1953)

64%

2413

Helv (1963) 5 2799

Acetoxyaldehydes ( S e c t i o n 336)

Alcohol

- Amide

0000000000000000

a-Hydroxyamides . . 6-Hydroxyamides O t h e r hydroxyamides

. . . . . . . . . . . . . . . . . . . . page ........................ ......................

287-289 289 289-290

98 %

HC1, HCOOH

Compt Rend C (1971) 272 1157 Annalen (1971) 749 198

288

OF ORGANIC SYNTHETIC METHODS VOL 2

COMPENDIUM

1 NaCN

K2CO3

MeOH

2 H202 H 2 0

YONH2 CHOH

H20

*

JACS (1971)

Me2CO

MnO2

--+ Me2FCN

OH

CH2C12

SECTION 325

48%

93 3812

< 53%

MezCCONH2

Ati Chem Corn (1966) 121

Me

Ber (1965) 98 936 Tetrahedron (1968) 2 3795 Annalen (1968) 715 47

PhCO I

Me

Ph$O

P h y HCOOH OH

(Et2NCO)zHg TH F

BuLi

*

?H

PhFCONEt2 Me

LirMe2NCONi (CO)3] THF

*

Angew (1967) ( I n t e r n a t Ed

2 NH3

*

79 819 6 805)

Ph$CONMe2 OH

1 Me2CO H2SO4

66%

<30%

JOC (1971)

2 2721

62%

PhfHCONH2 OH

Org Synth (1955) Coll Vol 3 536

S E C T I O N 325

ALCOHOL

@ coco'N jMe2

- AMIDE

289

E t 2 0 t 2 e MN O $ @

Me2N

79%

Me2N JOC (1959) 2 265

PhCHO

---t

-

OH PhCHCXOEt

PhNH2 EtOH

PhCHCHzCONHPh

<41%

CIH Rec Trav Chim (1956)

Ph2CO

LiCHzCONMe2 THF

Ph2FCH2CONMe2

b

;Ie

BrCHCONEt2

15 1377

OH

90%

Ber (1968) JOC (1968)

Zn-Cu

101 3113 33

4275

CHCONEt2 30%

toluene

r\

EtCHCH2

CH3CONMe2

NaNH2

NH3

JACS (1948) 70 677 I 57 Organometallics in Chem Synth (1970) ,

EtyHCH2CH2CONMe2 OH

Ber (1972) 105 1621

PhNHZ EtMgBr

c1 OH21

c1 OH21

Rec Trav Chim (1965) 5 1177 Can J Chem (1969) 47 3671 Pharm Acta tfelv (1945) 20 79

44%

290

COMPENDIUM

OF ORGAYIC SYNTHETIC METHODS VDL 2

SECTION 326

NaBH4 MeOH

0

JOC (1968) 2 206

H

S e c t i o n 326

- Amine ...... ...... ...... ......

Alcohol

0000000000000000

1,2-Aminoalcohols 1,3-Aminoalcohols 1,4-Arninoal coho1 s 1,5-Arninoalcohols

PhCHO

.

. . .

. . . .

Ph2NCHzSnBu3 B u L i

*

hexane

.. .. .. ..

.. ... .. ... I

I

. . . . . . . . page 290-293 . . . . . . . . . . 293 . . . . . . . . . . 294 . . . . . . . . . . 294

Ph2NCH2THPh

83%

OH JACS (1971)

1 NaHS03 E t y HCHO

PhCOCl

40%

CH20H CONH2

2 NaCN

CuCN

---+

TH

H20

*

PhCOCN

EtTHCHCN

Me

L i A1 H4 Et20

LiAlH4 Et2O

2 4027

OH EtTHbHCH2NH2

46%

Me Ber (1973) 106 1365

86%

PhTHCH2NH2 OH JACS (1952)

74 5514

SECTION 3 2 6

-WINE

ALCOHOL

291

94%

0 PhCHCH2 I\

T e t r a h e d r o n (1972) 28 3475 Helv (1961) 44 1164Synth Comm (1973) 3 177 JACS (1965) 87 1353 Chem I n d (1973) 1111

si

Me3 1 HCONMe 2 A 3 HC1

Me3SiONa

PhCHCH2NHMe

t

AH

H20

4 NaOH

Ber (1969)

1

;;

NH4C1

102 14

EtOH

47% Me

H2

PhBr

1 BuLi

THF

____t

Pt02

PhCOCONMe2

2 (CONMe212

EtoH

J Med Chem (1973) 16 2 3 Ber (1963) 96 1411-

L i A l H 4 THF

77%

PhFHCH2NMe2 OH

S y n t h Comm (1973)

2 325

NC

1 Ni

CH2COOEt NaH THF

EtOH

*

YH COOEt

CHO

T e t r Lett (1972) 5 3 5 3

NH2CHCH2OH

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

292

Ph2CO

1 PhzC=NCHzLi

THF

Et20

*

2 H20 3 HC1 H20

SECTION 326

Ph2YCH2NHz OH Angew (1970)

( I n t e r n a t Ed

- - ~O

@ ~ ' ~ ~ ~ ~ 2 ~ ~ Me

i C H z M e

82 138 9 163)

@i H

PhMgBr

Me

Me

Ph

- CHMe AH2

J O C (1943) 8 99

CH2N02

H2 N i HOAc

JACS (1951) 2 2359 (1952) 2 2924 Org Synth (1963) C o l l Vol 4 221

1 HCN

CH2NH2

piperidine

2 Ac20 3 LiAlH4

MeCOCl Et20

D

O

H

J O C (1964)

29 2914 Helv (1950) 2 1093 JACS (1952) 2 1861

C a t a l y t i c r e d u c t i o n o f c y a n o h y d r i n s Helv (1943) 288 R e d u c t i o n o f c y a n o h y d r i n e t h e r s Compt Rend (1953) 237 1006 236 387 Tetr Lett (1971) 9 2 3 Chem Corn (1973) 55

1 Pyrrolidine

Tic14

2 B2H6 3 H202 NaOH H20

C6H6

aoH

Bull SOC Chim Fr (1971) 1649 3978

SECTION 326

ALCOHOL

- AMINE

293

2 190" 3 KOH

JOC (1967)

OH CHCH2COOEt 1 N H

3 2 NaN02

PhCHzO

A v iH

CH-CH2 1 Me2SOq MeOFla 2 HC1 H20

co

J O C (1951)

LiAlH4 Et20

--+ PhCHSCCN

49%

16 8 4

tH20H PhCHzCHCH2NH2

Ber (1950)

- -

yf;CH2NHMe

v

\ /

HOAc

PhCHO

2 540

445

A

Me2CHCHO

o-NH.HC1 HCHO

H2

MepH0

PtOp

HOAc

FH2

Me2tCH20H

r:> y 2

JACS (1951)

0 I \ Me CHCHMe

1 PhCHZNC

pentane 2 HC1 H20

BuLi

THF

t

2 685

?H MeCHCHMe

<66%

I

PhCHNH2 Angew (1973) (Internat Ed

355

12 323)

294

Me0

PrBr

CCIMPENDIUil

OF ORGANIC SYNTHETIC METHODS VOL 2

oCHo ,:Y(tI2)3NEt2

1 Mg

Et20

MgF

SECTION 327

FH( CH2) 3NEt2

Me 0 @OH

JACS (1945)

67 1472

JACS (1952)

14 1064

HO( CH2)4CHNHPr

20%

I

Pr

QNHP r

B u l l SOC Chim F r (1963) 2468 (1954) 575

- Ester a-Hydroxyesters . . . . . . . . . . . . . . . . . . . . . . page 6-Hydroxyesters . . . . . . . . . . . . . . . . . . . . . . . . Other h y d r o x y e s t e r s . . . . . . . . . . . . . . . . . . . . . . Monoesters o f d i o l s . . . . . . . . . . . . . . . . . . . . . . S e c t i o n 327

CgHlgCOOEt

Alcohol

D000000000000000

1 Me2SO

-------base

.t

CgH1gCOCH(OMe)2

SnC14

dioxane

+

CgH1 gFtICOOMe

H2*

2 12 a c i d

OH

J O C (1967)

2

0

3947

OH

CoPh Me

1 Na

NH3

2 (Et0)zCO

Et20* Me

JOC (1965)

294-295 295-297 297 298

k0OEt

30 3804

SECTION 327

Pry0 Me

ALCOHOL

- ESTER

- NaCN NaHS03

?H PrFCN

H2°

HC1

EtOH

Me

295

OH

PriCOOEt

74%

Me

JCS (1957) 3262

O C O C O O E t

PhMgBr

0

Et20

e:OOEt

Ph JACS (1951) 73 2216 Tetr Lett (1972) 3011

FooMe CH2iCOOMe CH2

CFQCOO~H Na2HP04

*

CHCl3

-

FooMe CH2C;COOMe

"0

LiCu(Bu-i)*

FOOMe

Et20

CH2CCOOMe I\ OH CHZBu-i

CH2

Tetr Lett (1973) 4561

Et I

Me M 0e o ~ c H o 21 H2SO4 EC t H=!,%

FHCHCOOEt EtOH B u L*i

Me Meo@JOH 0

JACS (1970)

F?

BufHCHO Et

BrCHCOOEt

Zn

CgHg

?H Bu$HCHCHCOOEt

Et

92 6644

87%

Me

Org Synth (1963) Coll Vol 4 444 (1955) Coll Vol 3 408 JOC (1970) 35 3966 Org React (1942) 1 1 JCS 2 (1969) 2799Organometallics in Chem Synth (1970) 1.57 Continuous f l o w system JOC (1974) S 269

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

296 PhCHO

LiCH2COOEt

THF

PhFHCH2COOEt

w

HCHO

EtONa

1 Ph3CNa

Me2CHCOOEt

Pr I

2 PhCHO

co

c02(co)8

MeCHCH2COOMe OH

MeOH

FH20H CH2COOMe THF

55% Ber (1966)

99 2407

JACS (1939)

61 793

FOOEt Me2CCHPh I OH

-

MeC/HkH2

J A C S (1970)

PhtHCOOEt CH20H

DMSO

80%

92 3222 (1973) 95 3050 JOC (1972) 31 2468

OH

PhCH2COOEt

SECTION 327

L i N( Pr-i ) 2

--

40% J O C (1961)

26

2102

Bull Chem SOC J a p (1964)

37

672

FH20H PrCHCOOMe

90%

Tetr Lett (1973) 2429

F 1 BrMgCXOEt

E t 2 0*

,J$CH~COOE~ OH

C6H6

2 H2SO4 T H F JACS (1954) 76 1715 Advances i n Org Chem (1960)

2 117

SECTION 327

ALCOHOL

Ye

Ph2C0

81 %

Ph2CCHCOOBu-t OH

Et20

JOC (1966)

oo Et20

-975%

*

E t z N M g B r , CH3COOBu-t

T i ( O P r - i )4 CH2=CO

+

EtpO

31 983

oH2co

i -PrMgCl

CH3COOBu- t

(i-Pr)$O

297

Me

B r CHCOOBu- t

Mg

- ESTER

Bull SOC Chim Fr (1966) 3243 1 3 1 125 JACS (1952) 14 6254 Tetrahedron (1967) 2 4271

52%

(i-Pr)2$CH2COOPr-i OH Synthesis (1972) 608

t-Buao H2

COOEt

EtOH

PtO2

EtOH* t - B u a o H

(or NaBH4)

H2SO4

87-95%

COOEt Tetrahedron (1972) 8 3475 KBH4 JCS (1963) 2743

COOEt nd

JOC (1966)

53%

31 485

H2SO5 MeOH

70%

P

Tetrahedron (1973)

29 1447

298

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2 HOCHzCH20H

C7H15CN

BuCOOH

C7H1 gCOOCH2CH20H

( r e f 1u x )

NaOH

Tetr Lett (1972) 4643

Hydroxyacids

S e c t i o n 328

Alcohol

58-6346

BuCOOCH~CH~OH

H20

Also v i a :

58%

JCS (1963) 2417

CHz-CHz

SECTION 328

JACS (1944) 66 1420 JOC (1961) 5 4 5 6 3

( S e c t i o n 313)

- Ether,

Epoxide

00000000000000000D0000000

1 ,2-Hydroxyethers, epoxides

1 ,3-hydroxyethers,

o t h e r h y d r o x y e t h e r s and hydroxy-

trans

82%

OMe

JACS (1943)

EtZCO

LiCH20Me

CH2 ( OMe 12

65 2196

75%

Et2yCH20Me

OH

EtOCH2MgCl

Tetr Lett (1964) 1503

Compt Rend

C

JOC (1967)

2 1417

(1966) (1967)

0

262 848 264 399

SECTION 328

ALCOHOL

0' --+

0 : J

- ETHER, EPOXIDE

*o

LiAlH4 AlCl3 Et20

OCH2CH20H

JACS (1962)

1 Hg(0Ac)z i-PrOH

88%

84 2371

Bull Chem SOC Jap (1965)

Me

299

38 958

52%

OPr-i

2 NaBH4 base JOC

(1970)

35

1041

<45% Can J Chem (1967) 45 2547 J O C (1965) 30 2441-

HO(CH2) 1 oOH

Resin-COC1

Resin-COO(CH2)1 DOH

1 Ph3CC1 Pyr

Can J Chem (1973) (1972)

OH

HO( CH2)100CPh3

2 NH3 H20 dioxane

t-BuOOH vanadyl acetyl acetonate

84%

C6H6 JACS (1973)

2452

50 2892

95 6136

300

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

Section 329

Alcohol

- Halide

SECTION 329

00000000000000000

Fluorohydrins, chlorohydrins, bromohydrins and iodohydrins

e7 0

0;

Et3N*HF,

40%

Bull SOC Chim Fr (1969) 3647

HF Can J Chem (1960) 2 1495 KHF2 J Med Chem (1972) 15 1092

HC1

CHC13

____3

@ OH

JCS (1958) 1657 JOC (1961) 2403

HBr H20

Ph

CHCl3

Ph

Ph

&C8H17

O?’

Ph

J O C (1968) 33 3385 JCS (1951) 2598

qp I

JCS

C

(1971) 1466

HI JCS (1951) 2598

70-73%

Org Synth (1932) Coll Vol 1 158

NH2CONHCl Org Synth (1963) Coll Vol 4 157 Cr02C12 JACS (1956) 78 3749 (1950)

11.4353

&

ALCOHOL

SECTION 329

- HALIDE

*-*OH

NBA HC104 dioxane

0

301

-

1'

H20

-

> 90%

JACS (1953) 75 2273 (1957)

1130

NBS, Me2SO JACS (1968) 90 5498 KBr, H202, enzyme Tetr Lett (1968) 4057

BrNj Tetr Lett

ncHz v

OH

flCHzBr

1 Hg(OAc)2 Me2CO

v

2 NaBr 3 Br2 CCl4

PrCHeCH2

1 I2 H20

(1968) 3 9 2 1

J O C (1968)

F

2 H202 Me2CO H20

2 3953

85%

PrYHCH21 OH

Can J Chem (1964) KI03, HzS04 JCS (1970) 846

CH=CH2

1 12

CF3COOAg MeCN

42 2710

ICHCH20H

2 MeOH Can J Chem (1972) 507 Org React (1957) 9 332

PhCOCH2Cl

PhLi

Et20

78%

Ph2:CtizCl OH

JACS (1951)

73 4030

phaoH

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

302

PPh h a Br o

LiAlH4 Et20b

Br

Ph

SECTION 330

93%

trans

JOC (1968) 2 3385

NaBH4 JCS (1958) 1657

Bull Chem SOC Jap (1962)

LiBH4 Helv (1953) 36 1241 Fluorohydrins JCS Perkin I (1973) 1462 1 NaOCl

t

2 h u CHCl=CHCl

MeyH( CH2)30H c1

J O C (1972)

2 2044

-234%

31 3514

(i-Pr)zNCl, hv J A C S (1971) 93 438

45-502 Org Synth (1955) Coll Vol 3 446

Section 330

Alcohol

a-Hydroxyketones . . 6-Hydroxyketones . . Y-Hydroxyketones . . Other hydroxyketones

EtCXEt

- Ketone

00000000000000000

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

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

TI (NO3) 3 HClO4

glyme H20

h

EtCOtHEt OH

page 302-307 307-309 31 0 310-311

70-90% JACS (1973)

95

1296

SECTION 330

ALCOHOL

- KETONE

303

JACS (1948) (1950)

OH

Ag2C03-Cel it e

OH

C6H6

2

142

11 5161

45% ( A l s o a p p l i c a b l e t o 1,3 a n d 1 , 4 - d i o l s ) Chem Comm (1969) 1102 T e t r a h e d r o n (1973) 2 2867

NCS, Me2S T e t r Lett (1974) 287

+-

HO

PhsC BF4

HO

CH2C12

HO

JCS P e r k i n I (1972) 542

:::

@JcH0

EtOH, Me0

Me0

+

Bu4N C N

PhCH2CHO

KC N

PhCHZCHCN AH

-

PhCHZMgCl

OMe Org React (1962) 4 269 Org Synth (1941) C o l l Vol 1 94

T e t r Lett (1971) 287

PhCH2:HCOCH2Ph OH Helv (1945) 28 741 Bull SOC Chim F r (1955) 784

52%

304

PhCHO

OF ORGANIC

COMPENDIUM

1 CH2=CHOEt t - B u L i

SYNTHETIC METHODS VOL 2

*

CH2'CHSEt

HoiH I

H20

HCOH I

CH20H

Me2SO

t-BuOK

PhCOCHzSOMe

1 HC1

Me2SO

2 NaOSOCH20H Cu(0Ac)z

F

C11H23COOMe

Na

xylene

2 3325

PhCOCH20H

88 5498

C11 H23COf.HC11 H23

OH

80-90%

Org React (1962) 4 256 ' Org Synth (1963) Coll Vol 4 840

The A c y l o i n Condensation as a C y c l i z a t i o n Method

Chem Rev (1964)

($H2)8 COOMe

60-65%

EtOH JACS (1966)

FooMe

2694

23%

JACS (1950)

Review:

763 208

H~OH

CH20H

PhCOOE t

95

HOCH

1 HOCH2CHzN02 base

2 H2S04

Annalen (1972)

JACS (1973)

HCOH

CHO

HCOH

57%

PhFHCOMe OH

MezNCH2CH2NMe2 pentane 2 HC1

H$OH

SECTION 330

1 Na ClSiMeg 2 HC1

H20

xylene

THF

b

64 573

-co (CH2)8 L~HOH

53%

Ber (1964) 97 1383 Can J Chem (1969) 47 3266 Synthesis (1971) 236 JACS (1953)

2 6231

SECTION 330

ALCOHOL

oo

*

Li[BuCONi (CO)3]

1 Mg

2 MeCOC=NOH

b

I

Me

3 (COOH)2

76%

JOC (1961) 1681 Compt Rend (1965) 261 1990

Et2O

b

OH PhCH2FCOBu Bu

JOC (1970)

BuBr

305

Crf

BF3-Et20 Me2SO

PhCH2Br

- KETONE

58%

35 4183

OH

BukOMe Me

Annales de Chimie (1939) 11 453

H20

Ph2CO

Me

JOC (1965)

0

2

3804

CH20H

co I

1 LiC-COEt

2 EtSH h v RO

di-t-butyl peroxide

3 HC1 H20 4 LiAlH4 5 HgCl2 HC1

Rec Trav Chim (1960)

79 1293

0 oo

306

ooMe

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

CrCH

------+ NaCXH

SECTION 330

65-67%

HgO H2SO4 H20

Org S y n t h (1963) C o l l Vol 4 1 3 T e t r a h e d r o n (1964) 20 1119

62% 2 HgO B F 3 . E t 2 0

THF

H20

OH

T e t r Lett (1972) 3945 Annalen (1972) 758 89 JOC (1971) 2035

a

1 Br2 2 N2H4

H20

3 H2SO4

+

EtOH

MeOH H20

HO

J O C (1967)

PhCOCH2Me --+ PhCOCHMe I Br

HCOOK MeOH

Ib,.OH 2 3723

PhCOyHMe OH

Annalen (1936) 526 143 Org Synth (1943) C o l l Vol 2 5

NaOH JCS (1954) 3257

02

t-BUOK

t-BuOH

CONHz

HO

A \ COMe JACS (1968) 90 2448 J O C ( 1 9 6 8 ) s 3294

SECTION 330

ALCOHOL

- KETONE

307

- 1fi OAc I

Ac20

1 Monoperphthal i c

TsOH

acid

2 KOH HO

t-BUCOCOBU-t

Zn

DMF H20

CHC13 MeOH

JCS (1954) 747 Helv (1959) 42 2043

t-BuCOCHBu-t

87%

bH Annalen (1971)

(Et0)3P

745 164

Can J Chem (1969) ftl 3266

6' ~po

OH OH I

1

Phzc-CPh~

0

73%

decalin

Tetr Lett (1971) 3403

COMe N-Methylmorphol i n e N-oxide.H202 Pyr

1

MeoQcHo

OMe

Me

30%

OsO4

t-BuOH JCS C (1968) 2647 JOC (1960) 25 1968

t-BuOK

41 %

t-BuOH THF 2 NaOH E t O H MeZCO 3 h v H20

OMe JACS (1971)

93 281

308

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2 Me C5H11 CH=COBBu2

PhCHO

y5H11 PhFHCHCOMe OH

t

Ye

BuCH=COLi

PhCHO

ZnCl2

MeOCH2 CH20Me

SECTION 330

91 % JACS (1973)

95 967

Bu

*

PhCH 6HCOMe

E t 20

OH JACS (1973)

95 3310

* 2 CdC03 HgC12 Me2CO H20 Chem Corn (1970) 741

BuBr

1 Li

*

2 Me2CCH2Bu-t

Me2CCH2Bu-t I Bu!=N Li

CF;

Review:

0 I\ 1 MeCHCH2 :

2 (C0OH)p

BuCOCH27HMe OH

JAGS (1970) 92 6675

Org React (1968) 16 1

The Aldol Condensation

Ph COCH2Me

H20

1 PhNH2-EtMgBr

C6H6 EtpO 2 i-PrCHD

*

PhCOCHMe I

i-PrCHOH

Org React (1968) 5 1

90%

SECTION 330

ALCOHOL

- KETONE

309

CH20H

NaH PhCH20CH2C1 h

dioxane

0

EtOH J C S (1963) 4634

(1964) 4521

JOC (1971)

Ph2CO

1 PhSOCHZCOMe

NaH BuLi

THF

*

3070

Ph 2 YCH 2COMe

85%

*91%

OH

2 A1-Hg

0J (

36

T e t r Lett (1974) 107

~

1 THF ~ 3

___t

a:H

JACS (1968)

- I Bu3SnH h V

82%

90 2927

..,OH 27%

C6H6

AcO

Cr(0Ac)p A1-Hg

Helv (1967)

2259

Coll Czech (1961) 5 1207 J O C (1973) 38 3187

310

COMPENDIUM O F ORGANIC S Y N T H E T I C METHODS VOL 2

SECTION 330

Me

yH2CHOSiMe3 / 0\

CH2-CH2

1 Me2CN=C=CMe2

2 (COOH)2

PhMgBr

THF >

PhCOyMe2

H20

30%

CH2CH20H

JOC (1973)

38

2129

Tetrahedron (1969)

BuCH=CH2

1 B2Hg

THF

2 Me3SiCZCH 0

BuLi

*

25 3157

BUCH~CH~COCH~CH~YHM~

21 %

OH

/ \

3 CH2-CHMe

4 H202

NaOH

H20

Tetr Lett (1973) 2741

MeCH20H

h r,

AcO

I

b

O ...,$HHMe

JCS (1967) 2032

YEt 1 L i [ (CH2)30CHMe]2Cu 2 CHC12COOH

H20

-6

Et20

(CH2)30H

JOC (1972)

31 1947

40%

SECTION 331

CH2=CHCOMe

ALCOHOL

1H 6 c

- NITRILE

i-PrOH THF

F

2 H202 base

31 1

HO( CH2)6COMe Chem Corn (1969) 1009

JACS (1969) (1973)

91 3083

95 3251

Also via: Acyloxyketones (Section 360)

Section 331

Alcohol

- Nitrile

000000000000000000

a-Hydroxynitriles (cyanohydrins) and B-hydroxynitriles

KCN HOAc

P

CHC13 EtOH

Ms 0 NaCN, NaHS03 HCN, Et3N Et2AlCN Me2FCN OH

JCS

C

(1968) 2283

Org Synth (1941) C o l l Vol 1 336

JACS (1956)

2 4100

T e t r Lett (1966) 1913

JACS (1953)

2 650

31 2

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

ft

PrCHO

BrCHCN

Zn THF

*

SECTION 332

EI t PrCHCHCN OH

-

66%

Compt Rend C (1969) 269 861 Organometallics in Chem Synth (1970) 1 5 7

CH3CN BuLi

PhCHO

PhTHCH2CN

f

THF

OH

83% Ber (1968)

101 3113

OH

HCN

Et3A1

THF

JCS

Ph2CO

CH3CN NaNH2 NH3

b

Section 332

C

93% JOC (1968) 33 3402 Ber (1968) 101 3113

Cyanohydrin trimethylsilyl ethers Cyanohydrin e s t e r s

Alcohol

(1970) 2365

Ph2TCH2CN OH

Also via:

56%

HO"

Section 366 361

- Olefin

0000000000000000d

..................... page ..................... ...................

Allylic alcohols Homoallylic alcohols Other o l e f i n i c alcohols

-

C=C-C-OH, Allylic and benzylic hydroxylation (C=C-CH i n section 41 (Alcohols and Phenols from Hydrides)

313-316 316 317

etc.) is listed

SECTION 332

ALCOHOL

1 (i-Bu)eAlH

BuCXH

2 MeLi

heptane

*

EtpO

- OLEFIN

31 3

73% (R=H) 68% (R=Me)

BuCH=CH$HOH

R

3 RCHO

trans JACS (1967) 89 2754 5085 T e t r L e t t (1971) 4571

1 Ph3P=CHMe

CgH13CHO

THF

3 HCHO

H\ /

Me

/

c=c

73%

\

CgH13 CH20H Me

\

/

Me

c=c

H'

67%

'FHOH

C6H13

h

C

H

( COOEt)2

U

-

JACS (1970) 92 226 6636 (1972) 94 4013 T e t r L e t t (1970) 447

NaH L i A l H 4

62%

MeOCH2CH20Me

J O C (1967) Ber (1970)

0

I \

EtCH2CHCHPr

1 PhzSez-NaBHq 2 H202

H20

EtOH

*

2 113 103 3771 98%

EtCH=CHCHPr OH

J A C S (1973) 95 2697 T e t r Lett (1973) 1979

0

OH

LiNPr2 BuLi (i-Bu)pAlH Li3PO4 (180') o r t-BuOK

JOC (1971) (1969)

34 3583

1365

J O C (1971)

a 3266

JOC (1972) 31 2060 Ber (1960)

93 2712

S y n t h e s i s (1972) 194

314

COMPENDIUM

-.

1 PhSOCHzCH=CMe2 ( i - P r ) z N L i

C6H13I

i-BuBr

OF ORGANIC SYNTHETIC METHODS VOL 2

2 (Me0)3P

THF

MeOH

--+ i-BuCuaMgBt-2

SECTION 332

CgH13CH=CH$Me2

OH Tetr Lett (1973) 1385 1389 JOC (1973) 38 2245 Chem Corn (1972) 702

1 EtCFCH

Et\

/

/

c=c

H 66%

\

BrCH20CH2CH2C1 i-Bu CH20H 3 BuLi Tetr Lett (1973) 2407

o:e

NaCZCH NH3,

C'CH

H2

Pd-SrCOg

Me

JCS (1952) 1610 642 Org Synth (1955) Coll Vol 3 416 JACS (1954) 3 4482

MezC=CH( CH2)2COMe

CH2=CHMgBr

THF +

VH

Me2C=CH( CH2)2yCH=CH2

83%

Me

Advances in Org Chem (1960)

1 Ph3P=CH2 THF

0

CHCH20H

2 EtCHLi I Me

3 HCHO

Me 2 CO

BuCH=CHAl (Bu-i ) 2 Et20

1. 1

37%

Synthesis (1972) 575

>

Me2fCH=CHBu OH Tetr Lett (1971) 4571

42%

ALCOHOL

SECTION 332

- OLEFIN

31 5

i-Pr

3 H202 4 A Bull SOC Chim Fr (1971) 3978

2 MeONa

OH

3 Ag(NH3)2N03 4 HOAc H20

EtCH=CH2 --+

(EtCH$H2)3B

H20

JACS (1972) 94 4013

0 I\ CH2-CHCHCH2

air

t

C6H6

Et(CH2)3CH=CHCH20H

JACS (1971)

93 2792 OH

1 :CBr2

2 BuLi

1 HgS04 HCOOH

CH=C=CH Et20

2 Ba(OH)2 H2:

((CH2)6’

CH=CHhH ((CH216

Bull SOC Chim Fr (1964) 3273

1 LiAlH4

/2 CECCH20H

12

3 MeeCuLi 12 LI 2i A l H 4

MeONa

* A l C l 3*

&cH20H

&\ /

3 Me2CuLi

JACS (1967) 89 4245 (1968) 90 5618

H20H

(73%

31 6

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 332

Zn Et20

CH212

t

93%

JOC (1971) 2 3515

0

N2H4

HOAc

EtOH

*

O

O

66%

H

JOC (1961) 26 3615 (1968) 33 3347

83% A1H3 Et2SiH, (Ph3P)3RhC1

C5H11 C X H

1 BuLi

THF

4 HOAc

5 I2

0

Chem Corn (1970) 213 JOC (1969) 2 2206

T e t r Lett (1972) 5035

BIJ

\

/

C5Hll

75%

c=c

34 % CHZFHEt OH T e t r Lett (1973) 2741

C ;;HCHZBr

(One-step procedure) JOC (1973) (1963)

38 326 28 3269

(CH2=CHCH2)2Cd Bull SOC Chim F r (1969) 4038 8-Methal l y l n i c k e l bromide JACS (1967) 89 2755

95%

SECTION 333

ALDEHYDE

- ALDEHYDE

31 7

52% JCS

BuBr

1 Mg

2

C

Na EtpO

EtzO

c1y)

Bu

CIAO)

(1968) 2448

BuCH=CH(CH2)30H trans

J Med Chem (1967) lo 533 (1971) 14 236

?Et 1 Li(CH2)30CHMe

-73%

2 SOC12 Pyr

3 HC1 H20 EtOH

Pr$=CH(CH2)2CHO

71 %

J O C (1972) 37 1947

1 Ph3P=CH(CH2)40Li

THF

*

Pr2C=CH(CH2)2CH=CH( CH2)40H

-72%

Tetrahedron (1971) 2 5979

A l s o via: Acetylenic alcohols (Section 302)

Section 333

Aldehyde

- Aldehyde

00000000000000000000

Dialdehydes PhCH2CH2CHO --+ PhCH2CH2CH(OEt)Z

1 2‘

COC12 HCONMe2 NaOH H7O -

* PhCHZCH(CH0)2

Coll Czech (1958) 23 452 Synthesis (1973) 604 T e t r Lett (1973) 3979

31 8

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 333

JCS (1959) 2441 Advances in Carbohydrate Chem (1961)

2 105

HI04 Ber (1956)

2224 Org React (1944) 1. 341

Pb(OAc)4 JACS (1949)

oo

m

2 3310

82% T e t r L e t t (1973) 4599

1 03 E t O H 2 Zn

HOAc

H20

EtOH

'

E

C

H

JACS (1957)

97%

O

2 3165

~ a 1 0 4 ,os04 JOC (1956) 2 4 7 8 Ru04 JACS (1958) 6682

0 Annalen (1962)

659 20

Electrol v s i s

30% Bull SOC Chim F r (1970) 183

ALDEHYDE

SECTION 335 Section 334

Aldehyde

-hide

Aldehyde

- Amine

- AMINE

31 9

0 0 0 0 0 0 0 0 0 0 0 0 0 ~ 0 0 0

No examples

Section 335

00000000000000000

Aminoaldehydes

n

OuNH*HC1

Me2CHCHO

PhCHO --+

A

HCHO

e! NCH2CCHO L-/ tie

0

t

1 3

iCH=N

85%

JACS (1951) 13 685 (1948) 2 2592 Ber (1932) 65 378 Org React (1942) 1 3 0 3

LiCii’I)

‘s

t

2 Chloramine-T

c1

(46%

PhCHCHO I

v

Tetr Lett (1972) 2991

Me2C=CH2 --+ Me2CCH2NO t1

Me2CCHO I

Br

Me2NH H20

1 EtNH2

EtOH

2 NaN02 HC1

t

H20

Me2:CHO EtNH

Zh Obshch Khim (1960) 30 805 (Chem Abs 55 556)

32%

Me2tCHO NMe2 JACS (1948)

2 2592

320 Section 336

COMPENDIUM OF ORGANIC SYNThETIC METHODS VOL 2

SECTION 336

Altebdwi0; 5 s t e r 00

0

0

0000

Esters of hydroxyaldehydes and e s t e r s o f carboxyaldehydes C5H11 CH2CHO

Pb(OAc)4 BF3

+

C5H11 FHCHO

C6H6

OAc

T1 (OAc)3

-

MeZFCHO c1

MeONa

EtzO

DMF

AgOAc

RCH2CtiO --+ RFHCHO I

Bull SOC Chim Fr (1968) 4083 Synthesis (1973) 567

2 3359

J O C (1968)

RCHCHO OAc

Bull SOC Chim F r (1968) 4083

-

0 Me$-CHOMe

1 HOAc E t Z O

I \

2 Et3N

JACS (1957)

Ph CHCOC 1 I

OAc

L i A1 H4

t-BuOH

diglyme

MezCHCHO --+ MeZC=CHN

t

10%

2 3448

55%

Ph:HCHO

OAc

3

DAc I Me2CCHO

B u l l SOC Chim F r (1968) 4083

1 N2CHCOOEt CuCl

t

2 HC1

E t O H H20

MeZFCHO CH2COOEt

Synth Corn (1973)

2

255

SECTION 336

1 BuBr

ALDEHYDE

9 3 N'

CH2COOEt

2 HC1 H20 3 NaBH4 E t O H THF

t-BuOK

- ESTER

THF

*

Ye

CO

COOEt

pH 5-6

JOC (1973)

H2 (600 atmos)

67%

BuTHCHO

4 (COOH)2

CH?=CCOOMe

321

38

36

Ye

MeCCOOMe

b

94%

Brennst-Chem (1967) (Chem Abs 66 85430)

3 46

SOMe 1 CH2=CSMe L i N ( P r - i ) p

EtCH2COOMe

THF

t

2 HC104 MeCN H20

90%

E t FHCOOMe CH2CHO

Tetr Lett (1973) 4711 4715

MeCH=CHCOOMe

1 EtSCH2SOEt BuLi

THF

t

2 ~ ~ 1 0 4

MeFHCH2COOMe

CHO Tetr Lett (1973) 3271

r t o

1 HC(OEt)3 H2SO4 E t O H 2 TsOH

t

flCoEt 1 03 E t O H

(CH2)10

EH

w

2 H2 Pd-BaCO3

Annalen (1962)

JACS (1952)

Also v i a :

Carboxyaldehydes ( S e c t i o n 314)

656 97

If_ 5324

CI O O E t

(FH2)10 CHO

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

322 S e c t i o n 337

- Ether,

Aldehyde

SECTION 338

Epoxide

OOOOoOOOOOOOOOoOuOOoooooo

Aryloxyaldehydes, a1 koxyaldehydes and epoxyaldehydes

PhOH

1 EtONa

*

PhOCH2CHO

2 BrCHzCH(OEt)2 3 H2SO4

MeCH=CHCHO

H20

PrOH

NaOH

JCS (1937) 1057

45%

MeCHCH2CHO I

OPr

JCS (1952) 4083

350'

50%

( v a p o r phase)

PhCH=CHCHO

t-BuOOH

MeOH

CHO JACS (1960)

73%

PhCHCHCHO \ I

0

J O C (1960)

H202 JACS (1956)

S e c t i o n 338

Aldehyde

82 6419

25 275 78 3087

- Halide

000000000000000000

Hal o a l dehydes

t-BUCECH

Et2NC1

hv

H2SO4 H20

60%

t-BU$HCHO c1 J O C (1967)

32

3263

SECTION 338

O C H o

ALDEHYDE

- HALIDE

323

O H 0

B r 2 CHCl3+

80%

JCS (1949) 737

Br2, CaC03

2 456

JACS (1957)

IBr

Chem Corn (1968) 849

30 587

CuBr2 J O C (1965)

EtCH2CHO

CuC12 DMF

3448

EtCHCHO

tl

30 587 32 4008

J O C (1965) (1967)

S02c12

2 3448

JACS (1957) (1954)

76 2695

-1 6 Ye

Me

1 Br2

2 H20

R

JACS (1957)

C5H11CH2CHO

Ace0 KOAc

C5H11 CH=CHOAc

1 Br2

CCl4

2 MeOH 3 HC1

7s 1115

C5H11 FHCHO

h

Br

H20

Org S y n t h (1955) C o l l Vol 3 127

Iodoaldehydes

EtCH2CHO

--+ EtCH=CHOEt

JACS(1953)

N-Bromophthalirnide MeOH

t

?Me

2 3493

EtCHCHOEt I

Acid

---*EtCHCHO

Br

Tetr Lett (1972) 4055 Brz;, NaHC03, H20 JACS (1955) 6365

1

Br

35%

324

Ph2CO

COMPENDIUM 1 LiCHC12

OF ORGANIC SYNTHETIC METHODS VOL 2

THF

+

2 LiCl

I

r.7

1 B2Hg THF

2 CH2=FCHO

Aldehyde

Tetr Lett (1969) 2181 (1972) 4661 Annalen (1966) 691 33

MeCH2CHCH2FHCHO I

81 %

Br

Me

Br

S e c t i o n 339

74%

Ph2CCHO LI

-

MeCH=CHMe

SECTION 339

JACS (1968) 9 0 4 1 6 5

- Ketone

000000000000000000

K e t o a l dehydes

1 HC1

CoCHN2

COCHO

2 Piperidine 3 Hg(OAc)2 HOAc H20 Ber (1971) 104 2475 Helv ( 1 9 4 3 ) z 2050 Rec Trav Chim (1971) 90 429 PhCH2COCl

--+

PhCH2COCHN2

1 EtSCl

Et20

*

2 EtSNa 3 B r 2 HC1

H20

PhCH2CH2COC1

--+

PhCH2CH2COCHN2

PhCH2COCHO

HOAc Ber (1957) 90 1230

1 Ph3P

2 NaN02 HC1 H20 THF

PhCH2CH2COCHO

Ber (1963) 2259 (1959) 2 1345

SECTION 339

PhCOOEt

PrCOOEt

ALDEHYDE

-

Me2SO t BuOK

*

t-BuOH

MeSOCH2SMe BuLi

THF

- KETONE

325

1 HC1

PhCOCH2SOMe

H20

PhCOCHO 2 Cu(OAc)2 CHCl3 Org Synth (1968) 48 109

64-73%

J O C (1967) 32 2 7 8 6 J A C S (1966) 88 5498

PrCOTHSOMe SMe

Hydro1y s i s

PrCOCHO

Tetr L e t t (1973) 4707

@-

CHCl2COC1

Me

c;o;3+

JQJCOC'"

QOCHO

Me

85%

Me T e t r L e t t (1971) 199

SeO2

dioxane*

@JcoCHo

-71%

PhO

PhO@ J C O C H 3 COCHC12

f

1 MeONa

PhCOCH3 --+ PhCOCH2Br

Me2SO

2 HC1 HOAc H20 J Med Chem (1964) 1 2 5 5 Org Synth (1943) C o l l Vol 2 509 Org React (1949) 2 331

PhCOCHO

a-picoline-1-oxide

J A C S (1957)

(71%

2 6562

Yakugaku Zasshi (1964) sd, 287 (Chem A b s 61 638)

COMPElUDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

326

yH20H

1 6

94 %

BuCOCH~CHO

(47%

CHO I

Air

CU(OAC)~

MeOH

HO.,'

BuCHO

SECTION 339

JOC (1963) 2 2001 Annalen (1973) 2078

-

1 HS(CH2)$H

HC1

2 ClCH$H(OEt)2 3 HOAC THF

H20

Bu,C,CH~CHO --+

ss U T e t r L e t t (1972) 3735

Me2CHCHO

--+

u -

n 0

Me2C=CHN

PhCOCl

dioxane

Me2yCHO

<86%

COPh

JOC (1967)

32 404

< 59% Angew (1965) ( I n t e r n a t Ed

'7 380 5 358)

SECTION 340

ALDEHYDE - NITRILE

t-Bu

MeOCH2CH20Me

t-BuD

I

327

H

90%

O

J O C (1971)

2 3070

J O C (1965)

30

HCOOEt, MeONa JCS P e r k i n I (1972) 1721

A1 C13 hexane

2502

C17H35COCH2CHO

60%

T e t r Lett (1969) 5205

0’

SOMe I

1 CH2=CSMe MeCN

t

2 HClO4 MeCN H20

CH2CHO

87%

T e t r Lett (1973) 4711

i-PrCH2CHO

- 3 P i peridi ne

7-PrCH=CHN

1 CH2=CHCOMe

(‘OoH)2

* i-PrCHCHO

H2°

Chern Corn (1965) 340

Section 340

bH2CH2COMe 60%

Aldehyde - Nitrile 0000000000000000000

Cyanoal dehydes 77% JACS (1944) 66 56 JCS (1958) 3986 Org React (1949) 2 79

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

328

A

c

SECTION 341

1 NH2OH.HCl ~ NaOAc MeOH 2 SOC12 KOH

O

49-56%

__l__t

0

T e t r L e t t (1972) 261

0

2 PCl5

Et20

JACS (1966) JOC (1962)

S e c t i o n 341

Aldehyde

88 3168 29

-Olefin

00OOOOOOOOOOOOO000

. . . . . . . . . . . . . . . . . . .page ...................

a B - O l e f i n i c aldehydes Other o l e f i n i c aldehydes

328-333 334-335

F o r t h e o x i d a t i o n o f a l l y l i c a l c o h o l s t o o l e f i n i c aldehydes see s e c t i o n 48 Vol 1 (Aldehydes f r o m A l c o h o l s )

FH2CXH CH2CH=CHPr

EtCEEt

1 EtMgBr

Et20

CH2CZCCH(OEt)2

1 H2

H i 2CH=CHPr

2 H2S04 H20

EtOAc

*

FH2CH=CHCHO CHzCH=CHPr

JCS (1955) 4244 1007

1 ClS02CNO CH2C12 2 LiAlH4

Pd

*

Et

\

H

/

c-c

Et

/

\

CHO

T e t r L e t t (1970) 27

29%

SECTION 341

ALDEHYDE

- OLEFIN

0

HCC_H

~ c ~ [ ~ ) 6 c o o M e A1 C13

-6 1 NaOH

~

329

(CH2)&OOMe

COCH=CHCl 2 NaBH4 3 H2SO4 H20

CH=CHCHO

Tetr Lett (1966) 465

*@

CH=CHCHO

1 Me3Si CZCSiMe3 CH2Cl2

Ph @Jcocl

Ph

2 MeONa MeOH 3 NaBHq 4 HC1

84%

J O C (1973)

H20

2

2254

(43%

Me Chem Corn (1967) 947 JCS C (1970) 220 JCS Perkin I (1973) 2741

Org React (1968)

Review: The Aldol Condensation

EtCH2CHO

NaOH H20

EtCCHO EtCH&H C HO I

Org React (1968)

16 1

16 1

-1 6 CHO

HCHO

KOH

MeOH H20

RO

86%

Steroids (1969)

14 637

77%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

330

PhCHO

1 ClMgCrCSiMeg

2 H2 Pd-C

Pyr

Et20 EtOAc

*

H2S04 Ph$HCHCHSiMe3 MeOH OH

3 m-Chloroperbenzoic a c i d

,

-

~

-

0

I \

JACS (1971)

QCH(OEt)2

SECTION 341

PhCHECHCHO

2 2080

1 CHz=CHOEt

@cH=cHcHo

BF3 * E t e O 2 HOAc NaOAc

OMe

41%

OMe

t41%

"20 Ber (1961) 94 838 Bull Chem S z J a p (1970) 43 1586 Helv (1956) 2 249

Ye

CgH1 ~ C H O

Ph3P=CCHO CgHg

*

Ye

72%

CgH13CH=CCHO Chem Ind (1960) 202

Ph3P=CHCHO JCS (1961) 1266 (Et0)2POCH2CH(OEt)2, NaNH2 Bull Chem SOC J a p (1962) 35 1498 Ph3P=CHCioI] 0

ocHo 0: % 3

CHo

JCS Perkin I (1974) 37

PhNEtz

ocHo 60%

JCS 119491 737 Bull 'SOC Chin F r (1971) 4012

(1968) 283

Ac20 __+. CSH~~CH~CH~CH O KOAc

1 Br2 C C l 4 C~H~~CH~CH=CHOAC 2 MeOH 3 KOH MeOH

*

CsH17CH=CHCHO 9%

t-BuOH

4 C i t r i c a c i d HpO

V i a enamine

JACS (1957) 79 889 Tetr L e t t (1969) 3139 JACS (1957)

79 1115

SECTION 341

ALDEHYDE

HC1. EtDAc

1 PhSeCl

CgH1 gCH2CH2CHO

2 H202

- OLEFIN b

H20 THF

CgH1 gCH=CHCHO JACS (1973)

OMe 1 MeSCH26HCH2SMe C5H11Br

2 HgC12

MeCN H20

(i-Pr)zNLi r

331

95 6137

C5H11 CH-CHCHO JACS (1971)

52%

93 1724

Me 1 CH2=CHCHzSCH=CH2 C8H17Br

PhBr

2 A CaC03

1 Mg

EtCHLi

MeOCH2CH20Me

Et20

H20

CgH17CH=CHCHO JACS (1973)

t

57%

95 2693

53%

PhCH=CHCHO

t

2 MezNCH=CHCH=NMez C1O4 3 HCl

*

-

103 222

6 01 0 Ber (1970)

CECOEt

LiCrCOEt

___t

:-I,,'"

CHCHO

EtpO

R

R

R

Helv (1967)

&

G C H

1606

1 H3PO4 Ac20 * !?!?I 2 Ag2C03 Na2C03

&Ho

HOAC H20

Helv (1959)

42 1945

-61%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

332

SECTION 341

86%

NaH THF 2 (COOH)2 H20

Tetr Lett (1968) 4359 JCS C (1969) 460 (Et0)2POCH2CH=CHOEt Bull SOC Chim Fr (1970) 1369

1 LiCH$H=No

Ph2CO

Pr2CO

2 (COOH)2

1

Et20

Org Synth (1970) 50 66 Angew (1968) 80 8(Internat Ed 7 7) JOC (1969) 34 1122

& N

CH2Li THF

2 NaBH4 EtOH THF pH 5-7 3 (COOH)2 H20

Qo-

2 TsCl Pyr

3 BUSH

Ph2CzCHCHO

t.

H20

t

Q

Tetrahedron (1971) JACS (1969) 91 764 JOC (1973) 38 36

27

CHSBu 1 NaBH4 NaOH H20 2 HC1 H20 Et20

0

1

ClCH2COOEt

t-BuOK 2 NaOH

5979

QCHO

JCS Perkin I (1972) 1721 Helv (1951) 34 728

/b

1

-

70%

-65%

Pr2C=CHCHO

,CHCOONa

_____t

-

Pyr-HBrj

2 NHzNHCONH2 3 MeCOCOOH

JACS (1956) 78 3087

16

30%

SECTION 341

ALDEHYDE

C5H11 CH2COMe

1 HCONMe2 POCl3 2 Zn

EtOH

*

- OLEFIN

333

C5H11 y=CHMe

CHO Chem Pharm Bull (1972)

1 LiCHC12 THF CgH11CH2'? Me

*

2 A 3 LiC104

CaC03

20

309

C5H11CHzyCHO

74%

Me

HMPA

Tetr Lett (1973) 2465

54%

2 (Me0)3P

0

P

c

O

o

M

e

JOC (1960) 25 1031

-

P

C

O

O

M

55%

e

J A C S (1969)

0

I \

CH2-CHCHO

1 Sodium ( c y c l o p e n t a d i e n y l ) - d i c a r b o n y l f e r r a t e

*

THF 2 HBF4 3 NaI

Me2CO

J A C S (1972)

1 BuLi C5Hll CECCH20

91 4933

THF

*

2 K2CO3 MeOH H20

HoAc THF

CHz=CHCHO

94 7170

C5H11CH=CHCHO

Tetr Lett (1972) 1815 (1971)

591

334

COMPENDIUM

OF

ORGANIC SYNTHETIC METHODS VOL 2

ocHo

oCH CH=CH2

- - + t - B u ~ c H o E t 1 N2CHCOOEt

cucl

t-Bu

SECTION 341

(Et0)3P t - B u

2 LiA1H4

3 HC1

H20

Tetr Lett (1972) 5121

Oo

1 PhSCH2Li CHSBu

THF

2 H g C 1 2 HC1 EtOH H20 3 L i NH3 4 Me1

JACS (1972)

EtCH2CHO

C 5 H l l CHzCH=CHz Cu(OAc)2*HzO

Mn(OAc)3*2H20 HOAc

*

0::: <41%

Me

94 4758

EtCHCHO 1

25%

C5H11 CH=CHCH2 Synthesis (1972) 376

1 (Et0)2POCH2SCH2CH=CH2 cycl o h e x a n e 2 HgO 190'

EttHLi

82%

THF JACS (1970)

92 5522

SECTION 343

AMIDE

0' --.f

Me EtCHkH2

- AMINE Me 1 CH2=bCH20H Na

o-co 0 C H 2 - h N O

*

2 A J O C (1969)

Et

1 EtOCH=CH2 Hg(OAc)2

\

f

2 110-1 20"

OH

335

H

'

c= c

/

\

34

0

CH2t=CH2 Me

1220

Me 35% CH2CH2CHO

J A C S (1973) 95 553 J C S Perkin I (1973) 1791

A1 so v i a : 6-Hydroxyaldehydes ( S e c t i o n 324)

Section 342

Amide

Diamides

AcNH(CH2)5COOH

Also v i a :

Electrolysis

Diamines Dicarboxylic acids

Section 343

Amide

Arni noamides PhCHO

- Amide

00000000000000

1 Me2NH

AcNH(CH2)10NHAc 2 Naturforsch (1947)

&

182

Section 350 312

- Arnine

00000000000000

-

NaHS03 H20 H2S04 + PhCHCN PhCHCOHH2 I p&e2 J O C (1961) 4741 2 NaCN H20 NMe 2 Annalen (1971) 749 198 JCS (1949) 2323-

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

336

SECTION 345

CgHl gCOCH2CN

Can J Chem (1968)

PhCHzNH2

CHZ=CHCONHP h

FN

(!H2)4 CN

EtOH

(basic)

93%

PhCH2NHCHzCH2CONHPh

___t_

30C (1960)

Ion exch r e s i n H20

*

,

‘ONH2 (FH2)4 CN

H2

Nj

hide

S 1822

CONH2 50%

NH3

CHzNH2

Ber (1959)

S e c t i o n 344

5 3617

92

2616

- Ester

00000000000000

Acylaminoesters NHAc BUCH=CH2

CHZCOOEt

hV

10-1 2%

_____cBuCH~CH~FHCOOE~

Me$O

S e c t i o n 345

t-BuOH

hide

NHAc

Chem Corn (1965) 471

- Epoxide

0000000000000000

Epoxyamides CDNH2 95% PhCON

JACS (1956)

79 3087

SECTION 347

AMIDE

Section 346

Amide

- KETONE

337

- Halide

Hal oamides EtzNH CCl4

PhCHCOCl Br

MeCONHCl

PhCHCONEt2 i Br

49% JACS (1949) 71 3479

(1955)

4840

hv Tetr Lett (1971) 4425

Section 347

Amide

- Ketone

OOOOOOOOOOOOOOO

h i d e s of a , 6 , Y and 6-ketoacids, acylaminoketones

PhCOCl

BuNC

(PhCH2)zCHCHO

---w

Can J Chem (1971)

PhCOCONHBu

Ber (1961)

49 919

94 1116

1 H2SO4 t-BuOH (PhCH2)2CHFHCN * OH 2 CrO3 HOAc

OMe

48%

46%

(PhCH2)2CHCOCONHBu-t

Synthesis (1971) 538

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

338

1 BuLi

PhBr

Me2N

THF

2 (CONMe2)z

@

PhCOCONMe2

Synth Corn (1973) 3 325 Compt Rend (1927) 184 825

1 (COC1)2 Et20 2 Me2NH

.*

SECTION 347

81 %

EDcocoNMe2 68%

Me2N

J O C (1959)

E t O H H20 2 KOH E t O H JOC (1963)

24 265

3088

58% BuCH~CO

PhNH2

MeCOCH2COF

MeCOCH2CONHPh

Et20

PhNH2

D i ketene

CsH6

Ber (1959) 92 1456

74% J O C (1961)

2 225

MeCOCH2CONHPh

74 % Org Synth (1955) Coll Vol 3 10 Ber (1959) 92 1456 5654 JACS (1964)

a

AMIDE

SECTION 347

- KETONE

339

LiCH2CONMe2

Tetr Lett (1973) 1495 JOC (1959) 24 1551

0-o

1 Morpholine

2 PhNCO

3 HzSO4 H20

oo CONHPh

Via s i l y l enol e t h e r

PhNHz

PhCOCH2COOEt

PhBr

xyl ene

__+

1 Mg

Et20

2 CH2CQ

bH2C6 NH

Annalen (1964) 673 132 Ber (1962) 95 9 2 6 JOC (1961) 2 3043

Tetr Lett (1973) 4271

74-76%

PhCOCHZCONHPh

Org S p t h (1955) Coll Vol 3 108 (1963) Coll Vol 4 80

65%

PhCOCH2CH2CONH2

Chem Pharm Bull (1971)

19 391

340

COMPENDIUM

OF ORGANC SYNTHETIC METHODS VOL 2

SECTION 349

1 Morpholine 2

~

Ac20

MeFHCOOH NH2

Also v i a :

Pyr

64%

o( r CH2=CHCOOH l

a:H2CH2CONA

U0 18 2201

Acta Chem Scand (1964) T e t r Lett (1965) 2869

81-88%

MeyHCOMe NHAc

Org Synth (1963) Coll Vol 4 5

Ketoacids ( S e c t i o n 320)

S e c t i o n 348

-

hide

3

-Nitrile

Cyanoamides

JOC (1950) Ber (1959)

Also v i a :

31 %

92

800 2616

Cyanoacids ( S e c t i o n 321)

S e c t i o n 349

hide

-Olefin

000000000000000

O l e f i n i c amides

PhCHO

FOOH CHzCONHz

piperidine

PhCH=CHCONH2 JACS (1948) 70 2596 (1949) 2 3562

AMINE

SECTION 350

PhCHO

MeCH2CONHCOCH3

*

NaOAc

- AMINE

PhCH=CHCONH2 46%

f

341

PhCH=yCONH2 Me 37%

Rec Trav Chim (1951)

PhCOMe

Ph C X NMe2

BF3 ' E t 2 0

Ph I

84

PhF=CCONMe2 Me

Ber (1970)

*

2 MeCH=CHCONEt2

ye2 CH$(OMe)2

80%

CH2=CHtHCHCH2CONEt2

a

Me T e t r Lett (1971) 3251

O N M ;2e;

P

Me

xylene

Helv (1964) 41 2425 Ber (1971) 104 3689 JCS C (1971) 2950

OH

Also v i a :

A c e t y l e n i c amides O l e f i n i c acids

1,l-Diamines,

Et2NH

103 564

COOMe

COOMe

Me

1,2-diamines,

HCHO

x

Et

1 Mg

EtCH=CHCH2Br

70 146

Section 304 322

1,3-diamines

and h i g h e r d i a m i n e s

(Et2N)zCHz JACS (1932)

54

4172

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

34 2

68 1905

JACS (1946)

NH / \ CH2-CH2 Al C13

Bu~NH

SECTION 350

Bu~NCH~CH~NH~

C6H6

JACS (1946) (1948)

2006 184

C8H17

0:' s&Mscl

LiAlH4

1 NaN3 Pyr

*

NaN3 Me2So

__t

Et20

105 2654

Ber (1972)

99 1502 2 511

(1966) J O C (1967)

67 1 5 8 1

JACS (1945)

PrCO

,&

- 1 NaHS03 H20

2 NH3 H20 3 NaCN

yH2 PrCCN ' Me

H2 Pt02 HC1

H20

yH2 PrCCH2NH2

28%

,&

JACS (1960) (1949)

JOC (1967)

696

2 2530

32

511

Tetrahedron (1973)

29

3137

AMINE

SECTION 351

BuNH~

CHz=CHCN

BUNH(CH2)2CN

- ESTER

Ni

Hp

NH3

EtOH

34 3

BuNH(CH~)~CH~NH~

JACS (1946)

68

< 66%

1217

0rg S p t h (1955) C o l l Vol 3 256 254

CgH1 gCOCH2CN

1 NH20H.HCl

NaOAc

2 H2 P t E t O H

*

CgH1 gCHCH2CONH2 I

NH2

B2H6

THF

CgH1 gFHCH2CH2NHZ

Can J Chem (1968)

1 03

ROH

2 Hz P t 3 MeNH2

H2

NH2

46

3617

NHMe

t

73%

NHMe

Rh T e t r L e t t (1971) 3591 3587

Also v i a :

S e c t i o n 351

Diamides ( S e c t i o n 342)

hine

- Ester

00000000000000

D i r e c t e s t e r i f i c a t i o n o f aminoacids and amino,,ld h a l i d e s . Other p r e p a r a t i o n s of e s t e r s o f aminoacids. E s t e r s o f arninoalcohols.

Me!HCOOH NH2

1 COC12 THF’

2 PhCH20H HC1 E t 2 0

76%

MeCHCOOCH2Ph I

NH2

Coll Czech (1958)

25 1947

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2'

344

PhCHZCHCOOH I NH2

PhCH20H PhS03H

*

I

NH2

0

COOH

H

PhCHZCHCOOH NH2

MeOH SOC12

JACS (1952) zfl 1092 Chem Ind (1955) 16 Annalen (1961) 640 139 JOC (1965) 2 3575 JACS (1954) 76 5781

i-PrCHZCHCOOMe

83-86%

t

NH2

Helv (1953) 36 1109 JACS (1956) 78 381

Me2S03 TsOH

Me$=CH2

H

H2SO4

*

dioxane

-

COOMe

91 %

JCS (1963) 1927

PhCH2CHCOOBu-t I NH2

N

70%

Chem Ind (1959) 1121

t-BuOAc HClO4 Annalen

HC1.NHzCH2COCl

75%

PhCH2CHCOOCH2Ph NH2

TsOH SO2C12 SOCl2 Polyphosphoric acid

i-PrCH2CHCOOH

SECTION 351

PhCH20H

NH$H$OOCHZPh

(1961)

Helv (1929)

646 134

12 332

i-PrCH2$HCOOMe

93-96%

NH2

Helv (1953)

36

1109

345

AMINE - ESTER

SECTION 351

PhCHpBr Angew (1968) 80 797 ( I n t e r n a t Ed 1 8 0 9 )

MeCH2CN

---.. MeOH

MeCH,C=NH.HCl L l OMe

HC 1

1 NaOCl H20 2 t-BUOK 3 HC1 H20 -

MeCHCOOMe I

NHZ

JACS (1960)

MeZCCOC1

--.c

I

Br

MeFHCOOEt Br

Me2CCONHPr I Br

-

t-BuOK EtzO

82 4 4 2 2

41%

MepCCOOBu-t NHPr I

JACS (1964)

1356

JACS (1934)

697

H

MedHCOOEt

1 CHz'CHCN

2 EtOH H2SO4

H

(71% CH2CHzCOOEt JACS (1945)

PhNHz

CH2=CHCOOMe

HOAc

67

1071

69%

PhNHCHZCHzCOOMe JACS (1949)

2

1901 2124 2532

-

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

346

MeCH2NEt2

Me 2 C= CH COOMe

SECTION 352

Me2 yCH2 COOMe

hu

MeCHNEt2 Chem C o r n (1968) 180

0f-J

;

:;OHA90CN

3 KOH MeOH 4 HOAc

Section 352

Amine

03::c

Et20

J Med Chem (1973)

16 23

- Ether

00000000000000

Ami naethers

C7H150H

PhCHO

PhCH20H

Et2NH HCHO

Et2NH BuOH

NH / \ CH2-CH2 HBF4

1 NaNHz

JACS (1932)

PhCHOBu Et2h

HgC12 CaS04

PhCHZtHOH Ph

C7H150CH2NEt2

CgH6

OKH2CH2Cl

JACS (1955)

54 4172

11 1098

PhCHzOCH2CH2NH2

51 %

Ber (1964)

*

47%

97

510

3

PhCH2yHOCH2CH2N Ph

JACS (1948)

2 3098

73%

SECTION 353

AMINE

S e c t i o n 353

Amine

- HALIDE

347

- Halide

000000000000000

Aminohal i d e s

1 NOCl

Me2C=CMe2

MeOH

2 SnC12

a

HC1

*

H20

Me2CI

:Me2

NH2 C1

JACS (1960)

6068

Me 1 12 AgOCN E t 2 0

0

Also v i a :

H20 J Med Chem (1973)

16 2 3

1 N-Bromophthal i m i d e

2 HC.1 H20 Bull SOC Chim F r (1966) 1910

Me2NCHzCH20H

Et2NH

2 HC1

SOCl2

Br ( CH2)3C1

67-80%

Me2NCH2CH2Cl

Org Synth (1963) C o l l Vol 4 333

Et2N(CH2)3C1

Haloamides ( S e c t i o n 346)

JACS (1945)

67 1 4 7 2

70%

OF ORGANIC

COMPENDIUM

348 Section 354

Amine

SYNTHETIC METHODS VOL 2

SECTION 354

- Ketone

000000000000000

a , B , Y and 6-arninoketones

1 CH2COOEt

PrCOCl

2 HC1

I

-

NH7

PhH

1 SnC12 HC1

---+ PhCOCN

PhCHCH3

1 t-hOC1 2 MeONa

2 HC1

b

H20

CgHg MeOH

Et20

*

HC1*NH2CH2COC1 ~ 1 ~ 1cs2 3

37

318

PhCOCH2NH2

55-72%

Org Synth (1961)

41 82

60%

PhCOCH2NH2 J P r a k t Chem (1957)

1 NH20H.HC1

K2CO3

MeOH H20 2 TsCl Pyr

*

3 EtOK

1 Me2NNH2

2 Me1 E t O H

2 91

aNH <43%

PhCON

JACS (1956)

4 HC1 H20

3 Na

67%

PhCOCH2NH2

JOC (1972)

3 HC1 H20

PhCH2COMe

61 %

JOC (1973) 2 3571 Synth Corn (1972) 2 237

CuCN

PhCOCl

PrCOCH2NH2

b

1,8-diazabicyclo[5.4.O]undecene

78 3087

PhCHCOMe

17%

I

NH2

JOC (1957)

22 358

a

SECTION 354

0

PhCN

AMINE

- KETONE

349

*'\YOH - -;"x..' 0

i-PrCH2CH20N0

U

EtONa

2 NH3 3 t-BuOC1

PhCCH2Ph

kl

1 MeONa

66%

PhCOCHPh I

HC1

NH2 4422 459

/fi

dPBr i6NH & NHPr-i

i-PrNH2

___+I

J O C (1967) 32 549 J A C S (1950) 4059

11

1 m-Chloroperbenzoic acid

CHC13

*

2 i-PrNH2

HO

41 %

J C S (1934) 1568

J A C S (1960)

HO

__

2 3104

JOC (1961)

1 PhCH2MgBr

H C l Pt02 H2 MeOH H20

J O C (1967)

32

549

350

COMPENDIUM

CH2N2

----+ PrCOCHN2

PrCOCl

OF ORGANIC SYNTHETIC METHODS VOL 2 1 Et3B THF b

2 Me2N=CH2 I Me2SO t

Reviews:

-

PrCOFHCH2NMe2 Et

J A C S (1973) 95 602

The Mannich R e a c t i o n

Org React (1942) 1 3 0 3

Advances i n t h e Chemistry o f Mannich Bases

S y n t h e s i s (1973) 703

3

H C ~ . H N HCHO ~

PhCOCH3

HC1

SECTION 354

PhCOCH2CH2N

EtOH H20

85%

Org React (1942) 1.303 329 Org Synth (1955) C o l l Vol 3 305

fl ’ CH2=NMe2 CF3COO

0

-t

a C H 20 N N e 2

JACS (1968)

oph C0CH3

1 Mesi tylrnagnesiurn bromide EtOCH2N3

EtCOCH=CH2

Et2NH Et20 v

94%

90 5622

3

75%

Bull SOC Chim F r (1962) 273

EtCOCH2CH2NEt2 J A C S (1950) 72 4059 Org Synth (1941) Coll V o l 1 196 J O C (1964) 29 2346

37%

SECTION 354

AMINE

- KETONE

2 I2 KI NaHC03 THF H20 3 Na NH3 DMF

1

+- /

PrCOCH2CH2Cl

Me

PhCH2NHMe

PhCHzNMe3 + OH -

H20

t

JACS

351

(1972) 94 9128

PrCOCHzCH2NH2

85%

PrCOCH2CHzNCH2Ph 1 Me JACS (1971) 93 2492

82%

-

NCH2CHCN I Me

PhMgBr Et20

J A C S (1955)

cNCH$:COPh

71 2815

OH

CHMe NEt2

Chem Corn (1968) 180

Et2N(CHz)3Cl

1 MeCOCH2COOEt Na xylene

2 HC1

H20

*

EtzN(CH2)3CHzCOMe

J A C S (1947)

69 1 2 5 8

26%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

352

S e c t i o n 355

Amine

SECTION 355

-Nitrile

OOOOOOOOOOOOOOOO

Cyanoami nes , ami n o n i tri 1 es

@JC ' Ho

NaCN Me2NH

c1

c1

NaHS03

JOC (1961) 2 4741 JACS (1960) 696

NHMe

- 0 KCN HCHO

NaHS03

NCHzCN he

H20

JACS (1946) 68 1905 Org Synth (1955) Coll Vol 3 275

33% JOC (1954) 19 285

PhNHEt

FN

CHz=CHCN

~1c13

1

PhNCHzCH2CN I Et

@zNK

EtOH

70% Annalen (1972) 760 151 Org React (1949) S 79 Org Synth (1963) Coll Vol 4 146

CN

JCS (1947) 1369

SECTION 356

AMINE

Section 356

Atnine

- OLEFIN

353

- Olefin

000000000000000

Olefinic amines, enamines For a l l y l i c amination see section 101 v o l 1 (Amines from Hydrides) Reviews :

Enami nes

Advances i n Org Chem (1963)

Enami nes

Chem I n d (1970) 1188

51

- 3 HNC)K$03

EtCHZCHO

EtCHsCHN

Ber (1936) 69 2106 JACS (1963) 85 207

80-90% JACS (1963)

85

207

TsOH xylene Org Synth (1968) 48 56 Molecular sieves J O C (1971) 2 1570 Rec Trav Chim (1972)

Tic14 J O C (1967) 32 213 Trisdial kylaminoboranes JCS (1965) 5142

91 605

@-)-l$t--) Hg(OAc12

I

I

Me

PrCH2Br

1 Mg

Me

Et20 THF

2 HCONBU~

+-

J O C (1961)

26 1104

PrCH=CHNBuZ J O C (1973)

80%

38 3074

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

354

EtCHO

1 NaH

Et2NH

+

2 CH2=CHPPh3 Br DFlF

+

EtCH=CHCHzNEt2

-

THF

17%

J O C (1966)

cNH Me CH2=CHC=CH2

SECTION 357

2 467

Sodi urn-naphthalene

'

Chem Ind (1973) 231

80-90%

LiAlH4 Et20

PhCH=$CONMeZ Ph

70%

PhCH=:CH2NMez PI1

Ber (1970)

Also via:

103 564

Acetylenic amines (Section 305)

Section 357

-

Ester

a

- Ester

Esters o f malonic acids . . . . . . Esters of succinic acids . . . . . Esters o f higher dicarboxylic acids Esters o f hydroxyesters . . . . . . Esters of dials . . . . . . . . . .

. . . . .

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

.

. . . .

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

.. .. .. . . . .

. page , . . ... ... ...

355 356 356 357 357-358

SECTION 357 PrCH2COOEt

ESTER

CO( OEt) 2

- ESTER

45%

PrCH(COOEt)2

I:tONa

J A C S (1941)

(COOEt)2, EtONa Org ClCOOEt, Ph3CNa

CH2(COOEt)2

BuBr

EtONa

*

EtOH

355

63 2056

Synth (1963) C o l l Vol 4 141 (1943) C o l l Vol 2 288

J A C S (1941)

63 3156

BuCH(COOEt)2

80-90%

Org Synth (1932) C o l l Vol 1 250

36 3944 Org React (1957) 9 107

J O C (1971)

EtOMgCH(COOEt),? CH2(COOEt)2, NaH CH2(COOEt)2, basic ion exch resin Aromatic halides

OMe

C5H11CH=CH2

MeCHCOOMe Br I

J A C S (1950)

2 351

J O C (1961) 26 644 Synth C o r m (1973) J O C (1963) JACS (1959)

2 359

28 504 1627

OMe

JOC (1971) 36 3260 Org Synth (1970)

CH2(COOEt)2

*

Mn( OAc)3 *2H20

NaCo(C0)a CO MeOH

38

C~H~TCH~CH~CH(COOE~)~

50%

Chem C o r n (1973) 693

d i cyclohexylami ne

+

MeCH ( COOMe)2

J A C S (1963)

& 2779

18%

356

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 2 THF

BUCH2COOEt 2 CuBr2

b

BuCHCOOEt

63%

BukHCOOEt

JACS (1971)

-

MeZCCOOEt I

Br

Zn CuC12

Me2CCOOEt

TH F

Me2bCOOEt

Synthesis (1971) 306

j

I

( y 2 ) 10 Br

1"

Electrolysis DMF

CH3COOBu-t NH3

43%

coo~OOMe

J bled Chem (1969)

PhCH20

Br

93 4605

38%

12 0 2 MeONa

Me2C=CHCOOEt

SECTION 357

2 192

+ -

Et4N TsO

Me2FCH2COOEt

b

Me2CCH2COOEt Compt Rend (1967) 265 751 JOC (1964) 2 1670-

LiNH2

EtpO

*

FH2CooBu-t (?2)10

N

98%

CH~COOBU-t

JACS (1959) 1 5 8 1 7

FOOMe (CH~)&OOH

Electrolysis KOH H20

+

FOOMe (CH2) 16COOMe

40-55%

Org Synth (1955) C o l l Vol 3 401 JCS (1950) 3326

Advances in Org Chem (1960) 1 1

SECTION 357

ESTER

FOOH OAc

PrCOOH

CH2- LHCOOEt

OAc PrCH2bHCOOEt

electrolysis

b

MeONa MeOH

357

- ESTER

JCS (1954) 1460

oCHo OAc CH2=6OEt

@~HcH2c00Et OAc

NO2

BuCHCOOEt

6OOH

NO2

1 Pb(OAc)a, C6Hg

Chem Corn (1969) 1216

60%

BuCHCOOEt

L

2 200"

70%

Ac

Compt Rend (1960)

251 2544

62% Coll Czech (1969)

Ye

CH~=COAC PhCOCH2Me

PhCH2CH=CH2

1 ( ~ - B u ) ~ A ~ H MeYHOAc

-------+ PhF=CHMe

Acid

OAc

I2

C6H6

-

2 340

PhCOOAg

PhCHCHMe

Ac20

I

65%

OAc

Annalen (1972) 763 75 Synthesis (1972) 694

PhCH2FHCH20COPh PhCOO Org React (1957) 9 332 JOC (1972) 37 789-

85%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

Se02 HOAc

C6H13FHCH20Ac

H2S04

Electrolysis

Dicarboxylic acids Hydroxyes t e r s Diols

Ester

Section 358

- Ether,

32%

Tetr Lett (1969) 4439 B u l l Chem SOC Jap (1969)

OAc

Also via:

SECTION 358

AcO(CH2)100Ac Chem Ing Tech (1970) Synthesis (1971) 285

42 2056

83%

42 170

Sect i on 31 2 327 323

Epoxide

00000000000000000000000

A1 koxyesters and epoxyesters (glycidic e s t e r s )

PrOH PrONa

CH2=CHCOOPr

BuCOONa

ClCH20Me H20

*

PrOCH2CH2COOPr JACS (1946) (1947)

59%

68 544 69 2966

BuCOOCH20Me Suom Kemist (1969) 42 6 (Chem Abs 70 77263)Synth Corn (1972) 2 361 JCS (1965) 2127

f&

PhCO

C1 CH2COOEt C6H6

NaNH2

+

0 I , Pht-CHCOOEt Me

62-64% Org Synth (1955) C o l l Vol 3 727 (1963) C o l l Vol 4 649 Org React (1949) 5 413

continued

SECTION 359

ESTER

- HALIDE

359

JACS (1953) 2 4995 Rec Trav Chim (1970)

C ~ C H ~ C O O B U - t~- B, u O K

89 18

BrCHzCOOEt, LiN(SiMe3)z T e t r Lett (1972) 3761 Br$HCOOEt, BuLi Tetrahedron (1972) 3 3009

CH2=CHCOOMe

m-Chloroperbenzoic acid

0

/ \

*

CH2-CHCOOPle

radical inhibitor C l C H 2 C H z C J

Chem Corn (1972) 64 J O C (1966) 2 2509 JACS (1959) 81 680

CF3C002H T e t r L e t t (1973) 4561

Also via:

Section 359

Section 31 8 31 8

A1 koxyacids Epoxyacids

Ester -Halide

000000000000000

Esters o f haloacids and e s t e r s o f halohydrins

PhCECH

--+ P h C X B r

T I (N03)3

MeOH

PhCHCOOMe I

Br JACS (1973)

g N -H - 2~' $f 2

CH2=CHCOOMe ~

95 1296

, @ CH2FHCOOMe c1

cuZ+ CF3

CF3

CF3 Proc Chem SOC (1962) 117 Org React (1960) 11 189

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

360

SECTION 359 95% (X.1)

92% (X=Br) Tetr Lett (1971) 3995

Ye C10H21 CHCOOMe

CH2CQ I ,NX CH2C0

Me CioH216COOMe

benzoyl peroxide

b

CCl4

i

J O C (1953)

BuBr --+ BuCH(COOEt)2

KOH

EtoH

Br2 Ber

(1960)

-

Br2 BuCHCOOEt BuFHCOOEt LOOH cc14 Br J A C S (1949)

Bu I

MeCOCH2COOBu-t NaH THF

X=C1 or Br

18 842 649 2 2222 2549

1 NaH

BuYHCOOBu-t COMe

2 Br2 CH2C12

3 Ba(OH)2

k

EtOH

<67%

2 3107

BuCHCOOBu-t 1 Br

87%

Tetr Lett (1972) 4067

1 B2Hg THF 2 Br2CHCOOEt t-BuOK

OH

47%

k

J A C S (1968) 90 1911 Can J Chem (1972)

c1 (Ph0)3P.MeI (iodoesters)

N=O

or 5

Tetrahedron (1967)

J C S (1953) 2224

2387

2 359

SECTION 359

CH2=CHCOOMe

CsHl3CH=CHz

HBr

Et20

ESTER

- HALIDE

361

80-8~

BrCH2CH2COOMe

Org Synth (1955) C o l l Vol 3 576

BrCHLOOEt L -

*

C6Hl3fHCH2CH2COOEt

diacetyl peroxide

Br JACS (1948)

HBr

EtOH (COO

Br

EtCHZCOOMe

70 1055

1 LiN(Pr-i)p

THF

2 Br(CH2)gBr

*

77-844

Et Org Synth (1965) 5 42 S y n t h e s i s (1973) 538

90%

EtCHCOOMe (LH2 )3Br T e t r L e t t (1973) 2425

MefHOH MeCHOH

MeC(OMe)3

MefHO MeCHOxMe

OMe

Me3SiC1 c

MeCHCl ' MeCHOAc

JOC (1973) 38 4203 1173 JACS (1973) 95 278

90% Ber (1973) 106 606 1,2-Acyloxyhal i d e s (acyl=HCO, MeCO, EtCO, e t c . , halide=Br, C1) JACS (1959) 81 2195 Chem Pharm Bull (1972) '& 2707

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

362

0 = ax

SECTION 360

X=Br o r I R=Me or Ph

OCOR

Org React (1957) 9 332 Tetrahedron (1972) 2 3475

12, KIO3, HOAc Tetr Lett (1973) 4485

Also v i a :

Section 319 329

Haloacids Halohydrins

Section 360

Ester - Ketone 000000000000000

. . . . . . . . . . . . . . . . . . . page 362-364 . . . . . . . . . . . . . . . . . . . 364-366 . . . . . . . . . . . . . . . . . . . 366-368 . . . . . . . . . . . . . . . . . . . . 368-369 . . . . . . . . . . . . . . . . . . . 369-370 . . . . . . . . . . . . . . . . . . . . . . 370-372

Esters ofa-ketoacids E s t e r s of B-ketoacids . . E s t e r s o f V-ketoacids . . E s t e r s o f 6-ketoacids . E s t e r s o f o t h e r ketoacids . . Acyloxyketones

BuCXH

PhCHO

PhCHO

--+ B u C X B r

03 MeOH

1 Me2NCH2COOEt NaH

Et20 EtOH 2 HC1 H20

PhSH ZnC12

HOAc

+

PhCH(SPh)2

40%

BuCOCOOMe JOC (1973)

38

3653

72%

PhCH2COCOOEt Annalen (1967)

1 NaH DMF

2 ClCOOEt 3 Hydrolysis

703 37

PhCOCOOEt

JOC (1963) 28 961

SECTION 360

ESTER

Me2SO

t-BuOK

0

363

!OH

~ c H Z c o o E tO:l::

PhCOOEt

- KETONE

CCooEt

EtOF

H2S04

PhCOCH2SOMe

EtOH

HCHO

HC1

Et20

H20

Ber (1960)

1

(:iCHCOOEt

NaH

DMF

C6Hg

55%

PhCOCOOEt

88 5498

56%

BuCOCOOEt

t

2 NBS

74%

93 1387

JACS (1966)

BuBr

O c o c o o E t

JOC (1972)

31 505

FOC’ BuBr

--+

Bu2Cd

COOEt

LiBr

THF

*

70%

BuCOCOOEt JCS

A

(1966) 456

JACS (1954) 76 1914

COOEt

PhCOCH3

--+

PhCOCH2Br

A1 C 1 3

99%

Se02

EtOH

J bled Chem (1972)

PhCOCOOEt

1029

(70%

JOC (1959) 2 1825

Ye

BuCECCOOMe

1 (i-PrCH12BH 2 H202

>

H20 p H 8

BuCH2COCOOMe

61%

Organometallics in Chem Synth (1971) 1 2 4 9

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

364 0

Ph6tkHCOOEt

BF3 C6H6

PhCH2COCOOEt

1 ClS02NCO CH2C12

EtCXEt

*

2 MeOH

SECTION 360 80%

JACS (1958)

2 6386

58%

EtCOFHCOOMe Et

T e t r Lett (1970) 27

1 NZCHCOOEt

PhCOCl

2 Ph3P i-Pr20 3 MeOH H20 4 ZnC12 EtpO 5 Pyr

?Si (Me2)Bu-t Et3N THF

t-BuOH

b

2 HC1 H20

2 TsOH CgH6

1

Di ketene

-

EtCH2COCH2COOEt

EtCOCHZCOOEt

>

85%

60%

JACS (1944) 1286 (1959) 2907 JCS C (1971) 2821

MeCOCHZCOOEt Na CgH6

2 NH3 NH4C1 H20

96 1948

T e t r L e t t (1973) 1297

COOBU- t 1 EtOMg-iHCOOEt Et20

EtCOCl

45%

Ber (1963)

1 CH24OEt

EtCH2COCl

PhCOCl

PhCOCH2COOEt

b

PhCOCH2COOEt

50%

Org Synth (1943) Coll Vol 2 266 (1963) Coll Vol 4 415

MeCOCH2COOBu-t

Org Synth (1962) 42 28 g 225

MeCOCH2COF JOC (1961)

7540%

SECTION 360 Review:

ESTER

- KETONE

365

The Acetoacetic E s t e r Condensation Org React (1942) 1 2 6 6

CH3COOEt

Na 3

MeCOCHZCOOEt

Org Synth (1932) C o l l Vol 1 235 NaH B u l l SOC Chim F r (1954) 504

NaN(SiMe3)z

Me2CHCOOEt

1 PhgCNa

Et20

2 PhCOCl

Ba3N4

Angew (1963) (Internat Ed

793

2 617)

2 Naturforsch (1969)

2 937

Me

50-55%

PhCOLCOOEt

Me

L i t h i u m N-isopropylcyclohexylamide

Org Synth (1943) Coll Vol 2 268 Tetr Lett (1971) 2953

77% J O C (1956)

11 245

RX, K2CO3 Synthesis (1973) 316

Y - A l k y l a t i o n o f B-ketoesters

JACS (1970)

JOC (1972)

EtCOEt

N2CHCOOEt CHzC12

92 6702

31 3687

+-

Et3O BF4

*

EtCOFHEt COOEt JACS (1970)

86%

92 5767

366

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 2

A

Morpholine

S E C T I O N 360

- 0' C1 COOEt

<62%

C6H6

JACS (1963)

COOEt

85

207

91 -94%

Org Synth (1967) 47 20 J O C (1973) 38 3 2 4 r (1972) 37 2202

EtONa; A Org Synth (1943) C o l l Vol 2 531

(COOEt)2,

( E t 0 ) 2 P O C O O E t , NaH T e t r L e t t (1966) 2201

'OCH3 Me 0

PhgCNa; C02; CH2N2

Helv (1945)

(COBr)2;

Ber (1960)

1 cs2

2 TsOH

Me1

EtOH

NaH

EtOH

C&

28 1677 93 551

* @

COCH2 COOE t

Me0

72%

T e t r L e t t (1973) 4207

Br Me2kOOEt

EtCN

l;1e

Zn

EtCOCCOOEt

1 BuLi

Me

B u l l SOC Chim F r (1966) 1819 Org Synth (1963) C o l l Vol 4 120

hexane

3 BrCH2COOEt H202

4 NaOAc

80%

I

C6H6

78%

H20

T e t r L e t t (1973) 4491

ESTER - KETONE

SECTION 360 PhCHO

MeCH=CHCOOEt NaCN DMF

PhCOyHCH2COOEt Me

367 33%

Angew (1973) ( I n t e r n a t Ed

85 89

12 81)

-

Me2SO 1 NaH THF PhCOOEt -----+ PhCOCH2SOMe t-BuOK 2 BrCH2COOEt 3 Zn HOAc

PhCOCH2CH2COOEt

J O C (1969)

SOMe

EtCH2COOEt

1 CH2=CSMe LiN(Pr-i)2

2 Me1 3 HClO4 MeCN H20

i-Pr(CH2)2Br

PhI

1 Mg

Et20

2 CdC12 3 (!H2)2COOMe COCl

H C X H Ni (CO)4

ROH HC1

w

THF

t

2 3624

< 52%

3618

EtyHCOOEt CH2COMe

T e t r L e t t (1973) 4715

*

i -Pr( CH2)2CO(CH2)2COOMe

Cstis

59%

JACS (1944) 66 46 Org Synth (1955) C o l l Vol 3 601

PhCOCHzCH2COOR T e t r Lett (1964) 2777

BrCHCOOEt

MeOH

(44% tie

JACS (1963) 85 207 Coll Czech (1966) 2 602

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

368

cro

OEt 1 N2CHCOOEt copper bronze cycl ohexane 2 HC1 EtOH H20

PhCH=CHCOOMe

BuLi

EtpO

C5H1-jCXCH2COOEt

PhCOCH2Br

PhCH2COOEt

Ni(CO)4

EtOH

3 255 59%

PhYHCH2COOMe BuCO

2 4926

JACS (1969)

HgS04 H2SO4

CH2COOEt

*

Synth Corn (1973)

-

SECTION 360

85%

C5H11 COCH2CS2COOEt

Can J Chem (1972)

1105

- 3+ 1 Pyr

2 K2CO3 H20

PhCOCHN -

CH2=CHCOMe L i NH2

1 BrCH2COOEt NaH DMF

PhCOCH2CH2COOEt

2 Zn HOAc

Aust J Chem (1967)

2 2441

PhFHCOOEt CH2CH2COMe J O C (1964)

56%

29%

2 2346

MeCH=CHCOOEt

JACS (1963) 85 207 Tetrahedron n 9 6 4 )

Me

2 1737

<56%

SECTION 360

PhCH=CHCOOEt

t-BuCOCH3

NaNH2

ESTER

64%

Me2CHCH2CO( CH2)3COOEt

84%

2 CH2=CHCH$OOEt 3 co

+

1 NazFe(C014

2 EtI

14 261

J O C (1949)

i-PrFBH2 1 Me

Br(CH2)4COOEt

369

~-BuCOCH~$HCH~COOE~ Ph

Ye

Me2C=CH2

- KETONE

J A C S (1967)

74%

EtCO(CH2)4COOEt

N 03

5285

JACS (1972)

94 1788

1 BrCH2CH=CHCOOMe

<52%

2 H2 Pd-C

Tetr Lett (1965) 959

Rec Trav C h i m (1953)

Nippon Kagaku Z (1968) (Chem A b s

69 76716)

84

89 516

Org Synth (1955) C o l l Vol 3 6 0 1

370 YOOMe (CH2)4COOH

C1OH21COOH

COMPENDIUM

MeCOCHzCH2COOH e l e c t r o l y s i s

1 SOC12

2 CH2N2 EtpO

I

CI H ~ O A C --t

CHO, A c O ~ H CHPh

CHOH

CHO'

CH20Ac

CH~OAC

I

Nippon Kagaku 2 (1956) (Chem Abs 52 268)

-

20%

77 163

HOAc C10H21COCHN2 + C1OH21C O C H ~ O A C Org React (1954)

-

8

> 90%

228

:H~OAC

co

CrO3

AcO~H

HOAc

LHOCOPh CH20Ac Aust J Chem (1971)

0"

SECTION 360

YOoMe (CH2 )4CHzCH2COMe

*

MeONa MeOH

?H20Ac CHOH I AcOCH

OF ORGANIC SYNTHETIC METHODS VOL 2

24

1219

Morphol i n e ____t

T1 (OAc)3 JOC (1968) Dibenzoyl peroxide JOC (1963)

OAc

1 m-Chl oroperbenzoic acid 2 HC1

CHC13

*

Et20 JOC (1967)

(1962)

33 3359 g 581

aAc 2 3934

2 2131

Chem Pharm Bull (1972)

JCS (1955) Synthesis JCS (1961) Chem Corn

4426 (1973) 567 4472 (1970) 406

2 2156 61 %

SECTION 360

ESTER

1 NH20H.HCl 2 Ac20

+

- KETONE

NaHC03 MeOH

Et2O

371

6 1

40-51 %

Ac

-

3 Me30 BF4 CH2C12 Et3N Acid H2°

JOC (1969)

@-

34 1430

C8Hl7

+-

EK,

Me4N OAc Me2C0

0

A

c

O

a

j

0 JOC (1961) 26 4563 JCS (1961) 2725 Tetrahedron (1963)

CgH13CH=CH2

Mn(0Ac)g Me2CO HOAc

*

CgH13FHCH2CH2COMe

KMnO4 Ac20

24 %

OAc JACS (1971)

CgH17CH=CH2

19 8 6 1

93 524

38%

C~H~~COCH~OAC JACS (1971)

Acta

93 3303

Chem Scand (1960)

14 1445

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

372

SECTION 361

Tetrahedron (1967) 2 2453 Bull SOC Chim Fr (1960) 1079

Also via:

Section 320 330

Ketoacids Hydroxyketones

Section 361

- Nitrile

Ester

aooooo0oo000~0~0

a , ,6 and higher cyanoesters.

PrCHO

Review:

CN tH2COOEt

He

Pd-C

HOAc

Esters o f cyanohydrins

FN

*

PrCH2CHCOOEt

94-96%

Org synth (195s) c o i l v o i 3 385

The Alkylation o f Esters and Nitriles Org React (1957) 9 107

FN

i-PrBr

QcHZBr

BuCHCOOEt

F"

EtONa

*

EtOH

BuCCOOEt I i-Pr

.

1 Mg

87% Org React (1957) 9 161 Tetr Lett (1972) 1279

Ye

QCH2i;,~COOEt

2 Me2C=yCOOEt

OMe

CN

OMe

JOC (1972) 37 825

SECTION 361

C

C

ESTER

e

- NITRILE

373

1 HCN MeOH

Me

2 Br2 NaHC03 CH2C12 H20 3 (Me0)zCO MeOLi MeOCH2CHzOMe JACS (1971)

PhCH2CN

CO(0Et)p to1 uene

PhCH=C(COOEt)2

NH2.HCl

-

EtONa

KCN H20

PhCHCN iOOEt

< 25%

93 4318

70-78% Org Synth (1963) C o l l Vol 4 461 JACS (1971) 2 4237

PhcHCH2COOEt

Pb(0Ac)q. CH2C12

EtOH

a:: COOEt

"HCOOMe

cN

Org Synth (1963) Coll Vol 4 804 (1955) C o l l Vol 3 377 J Med Chem (1972) 15 1297

COOEt

25%

C C N J O C (1971)

5 3668

OAc

J O C (1959) (1949)

24

1650

14 1013

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

374

O0Also v i a :

OCOPh 80% Compt Rend (1971)

Ester

272 1554

Section 331 321

Hydroxyni tri l e s Cyanoacids

Section 362

SECTION 362

- Olefin

000000000000000

. . . . . . . . . . . . . . . . . . . . . page 374-379 ....................... 379 ....................... 380 ..................... 380 .......................... 380-381

aB-Olefinic esters BY-Olefinic e s t e r s YG-Olefinic e s t e r s Other o l e f i n i c e s t e r s Enol Esters

For a l l y l i c a c e t o x y l a t i o n see s e c t i o n 116 vol 1 and 2 (Esters from Hydrides)

C5H11 CH2CECH

CgH1gCH2;HCOOH Me

NBS

NaOAc

HOAC

H20

C5H11CH2COCHBr2

1 Br2

PBr3

2 MeOH

Et3N

MeOH

C5H11CH=CHCOOMe cis

46%

Proc Chem SOC (1964) 148

-

Br Quinoline CgH1gCH2iCOOMe

Me

CgH1gCH=FCOOMe Me

Org Synth (1963) C o l l Vol 4 608 616

PhCHO

CH3COOEt EtOH

EtONa +

PhCH=CHCOOEt

68-74%

Org Synth (1932) Coll Vol 1 2 5 2

SECTION 362 8uCHO

PhCHO

ESTER

COOH CH2COOEt Pyr

*

p i peridi ne

1

375

Bu CH=CHCOOEt

78%

JACS (1948)

SCN bH2COOEt KF Et2O

*

2 NaOH EtOH

70 2601

PhCH=CHCOOEt Bull Chem SOCJap (1971)

-

CHO (iH2)3CHO

- OLEFIN

Ph-jP=CHCOOMe

44 1357

CHO (kH2)3CH=CHCOOMe

Me Ph3P=bCOOEt (Et0)2POCH2COOEt, NaH 8rCH2COOEt, (Me2N)3P, MeONa CH2=CHCOOEt, Ph3P

Annalen (1962) 658 91 Ore React (1965) 14 270

JACS (1972)

94 4298

2 1040 682 58 (1968) 90 1647

JOC (1971)

Annalen (1965)

JACS T e t r L e t t (1964) 1653

OiLi Pr-i

PrCHCH2COOMe it

1

THF

2 Me2S2

PrF=CHCOOMe

t

3 NaIO4 MeOH H20 4 120"

CgH1 gCH2CH2COOEt

1

R2NLi THF

2 PhSeCl

72%

Et

JACS (1973)

f

3 MeC002H EtOAc

2 6840

CgH1 gCH=CHCODEt JACS (1973)

95 6137

ocH2

376

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

SECTION 362

B u ~ P ~ H C O O E ~(JCH=CHCOOEt ~

89 5850 93 1693

JACS (1967) (1971)

CgH13I

PrCH2Br

CH2 ( COOMe) 2

NaH THF

CijH13CH(COOMe)2

--+ P r C H = P P h 3

-

CijH13iCDOMe Me2NH. HC1 CH2 2 Me1 3 75" Synth C o r n (1973) 3 359

I MebHCOOEt

1 HCHO Me2NH

I

Me

Ber (1970)

PhI

CH2=CHCOOMe

Pr3N

N-methylpyrrol i d o n e

CH2Br

1 MeCOCH2COOMe

CH=CMe2

NaH BuLi TH; 2 CH2=COAc TsOH I Me

Review:

P d ( OAc ) 2

T h e Wittig R e a c t i o n

*

103 685

81 %

PhCH=CHCODMe JOC (1972)

OAc YH$H&=CHCOOMe CH=CMe2

55%

PrCH=CCOOEt

C6H6

37

MepCuLi

-

1

Et20

<47%

2320

Ye

CH2CH2C=CHCOOMe CH=CMeZ

Synth Corn (1973)

Org React (1965)

3

321

14 270

SECTION 362

ESTER

oo

- OLEFIN

{Et0)2POCH2COOBu-t

NaH MeOCH2CH20Me

377

J O C (1971) 36 1024 Org Synth (1965) 45 44

Ph3P=CHCOOMe 150" Proc Chern SOC (1961) Ph3P=CHCOOEt, PhCOOH Angew (1963) 2 858 ( I n t e r n a t Ed

Review: The Reformatsky Reaction

83%

CHCOOBU-t

454

2 619)

Org React (1942) 1 1

J Med Chem (1972)

1297

BrCHzCOOBu- t , Mg JOC (1966) 31 983 Dehydration o f 8-hydroxyesters with: DCC, CuC12 JCS Perkin I (1973) 2738 AcC1, PhNMe2; EtONa T e t r L e t t (1969) SO17

0

1 LiCXOEt Et20

2 HC1

CHCOOEt

N

H20 Et2O

50%

Advances i n Org Chem (1960) 2 117 203 204 Rec Trav Chirn (1956) L5_ 1377-

JOC (1973)

2 399

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

378 Br2 EtFHCOCH3 -+ Me

MeCXCOOEt

?r

EtFCOCH2Br Me

MeONa

Et$=CHCOOMe Me

29%

JACS (1950) 12 974 J O C (1971) 2 3266 Org React (1960) 11 261

Pr2CuLi

SECTION 362

THF

Pr\

/

c=c, /

Me

49%

COOEt T e t r L e t t (1973) 1277 Org React (1972) 2 1 JACS (1969) 91 1851 1853 6186

BuCECCOOMe

Me I \ 1 (i-PrCHl2BH

THF

*

2 HOAc

BuCH=CHCOOMe cis O r g a n o m e t a l l i c s i n Chem Synth (1971) 1 2 4 9

MeONa

PhCH2CHCOOMe --+ PhCH2CCOOMe I NH2 ;;2

~

cis trans

PhCH=CHCOOMe

BF3.Et20 DCC

T e t r Lett (1973) 4267

0

I \

MeCHCHCOOEt

1 Sodium (cycl opentadienyl )dicarbonyl f e r r a t e

*

THF

2 HBF4 3 NaI Me2CO

MeCH=CHCOOEt 96%

JACS (1972)

Ph2PLi; Me1 JACS (1973)

94 7170 95 822

SECTION 362

Ph3P=CMe2

PhCOCOOMe

THF

Cook

ESTER PhCCOOMe II CMe2

EtCHICH2

72% Can J Chem (1971)

2 2143

85% JOC (1968)

1 BuLi hexane

*

2 (CgH13)3B diglyme 3 BrCHzCOOEt 4 HOAc 1 B2Hg THF

>

2 BrCH2CH=CHCOOEt potassiurn 2,6-di-tbutylphenoxide

MeCH=CHCOOEt

379

Fe ( CO)5 octane

C6H13CECH

- OLEFIN

1 LiN(Pr-i)2 2 EtI

THF

*

C6H13,

H

33

1550

,CgH1 3

c=c, /

69%

CH2COOEt

T e t r L e t t (1973) 4491

EtCH2CH2CH=CHCH2COOEt JACS (1970)

92

1761

CH2=CHyHCOOEt Et

T e t r L e t t (1973) 2433

MeCH=CHCOOEt

hv MeCN

72%

CH2=CHCH2COOEt T e t r Lett (1968) 4987 Chem Corn (1965) 137

96%

380

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 2

Ye

Me

1 MeCSSCH2C=CH2 EtbHLi

CgH17Br

2 Me1 3 CuC12 CuO

ye

CH2=CCH2CH2:HC=CH2 Me

OH

THF

b

EtOH

Ye

C$l7CH=CCH2CH2COOEt

JACS (1973)

MeC(OEt)3 EtCOOH

SECTION 362

95 5803

Ye

CH2=CCH2CH2CH=CCH2CH2COOEt

92%

I

Me

JACS (1970) 92 741 Synthesis (1971) 175

CsH17CH=CH( CH2)7COOH

fOOH (CH2)eCOOMe e l e c t r o l y s i s

C8H17CH=CH(CH2)13COOMe

t

MeOH

,. 37%

JCS (1954) 448

3 Wolff-Kishner

4 MeOH a c i d 5 Nickel boride

RCHO

PhjP=CH( CH2) NCOOR '

F

Synth Corn (1972)

RCH=CH( CH~)NCOOR'

Acta Chem Scand (1966)

N=2 N=4 N9. N-10

CgH13CZCH

1 Hg(OAc)2

BF3.Et20

2 KOH E t 2 0 H20

2 415

20 992

Bull SOC Chim Fr (1965) 2988

Ber (1972)

105 3591

Ivz (1960) 1900

2

(Chem Abs

Ac~O b

14294)

CgH13:=CH2

N

OAc

JOC (1973)

38

4254

70%

SECTION 362

C5H11CH2CHO

ESTER

Ac20

KOAc

- OLEFIN

381

C5H11 CH=CHOAc

45-50%

Org Synth (1955) Coll Vol 3 127

JOC (1967)

32 489

JCS (1953) 3864

F

EtCHCOCHMe2

1 i-PrMgC1

Me EttHC=CMe2

HMPA

>

2 Ac20

OAc Tetrahedron (1973)

2 479

OR Ac20

HC104

96%

____t

0

EtOAc

AcO

Ac20, HC104, CCl4 (PhC0)20, HClO4 ( e n o l benzoate)

JOC (1966)

2 324

Org Synth (1972) 51 39 JOC (1969) 34 1962

Ac20, BF3 JOC (1969) 34 1425 CH2=COAc, a c i d Tetrahedron (1971) I JCS (1962) 1323 Me

JCS (1953) 3869

Also v i a :

Acetylenic esters 0-Hydroxyes t e r s O l e f i n i c acids

Section 306 327 322

21 5987

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

382 Section 363

Ether

SECTION 363

- Ether

00000000000000

1,l-Diethers (acetals and ketals)

CgH13CHO

MeOH TsOH

C6H13CH(OMe)z

HC ( OMe ) 3

JCS Perkin I (1973) 2738

The following reagents may also be used f o r the preparation of acetals from aldehydes and alcohols: NH4C1, HC(OEt)3 Bull SOC Chin Fr (1965) 1007 NH4N03, HC(OEt)3 Org Synth (1963) Coll Vol 4 21 TsOH, molecular sieves Synthesis (1972) 419 HC1 JCS (1953) 3864 CaC12 JOC (1966) 31 3406 PhS02NHOH JOC (1970) 35 1962 Me&, NaOH Ber (1958) 91 410

OBr 1 Mg

Me

EtpO

2 HC(0Et)j

i-PrOH

@

~

TsOH

Me

~

~

~

(

~

~

~

)

2

> 74%

JOC (1941) 2 489 Org Synth (1955) Coll Vol 3 701

OPr-i OPr-i

82%

molecular sieves Synthesis (1972) 419

The following reagents may also be used f o r the preparation of ketals from ketones and alcohols: Ion exch resin (acid) JOC (1959) 24 1731 BF3mEt20 JACS (1954) 76 1728 TsOH, HC(OFle)3 JACS (1968) 2448 Annalen (1962)

656 97

TsOH, MezC(OMe)2 JOC (1960) 2 521 525 continued

ETHER

SECTION 364

- HALIDE

353

76 6113 101 1154

Se02 JACS (1954) (Ph3P)3RhCl

S e c t i o n 364

Ether

Ber (1968)

- Halide

000000000000000

a - H a l o e t h e r s , B - h a l o e t h e r s , Y - h a l o e t h e r s and h i g h e r h a l o e t h e r s Review:

The a - H a l o a l kyl E t h e r s

HO(CH2)100H

HCHO

HC1

Chem Rev (1955)

C1 (CH2)100CH2Cl

C6H6

J O C (1949)

a-Bromoethers

PhCH2CHO

EtOCH2Me

EtOH

HC1

Nap04

PhIC12

hv

55 301

2 754

2 258

JACS (1949)

696

94%

PhCHZyHOEt

"

JACS (1949)

2 4007

79%

EtOCHMe I

c1

Annalen (1969)

728

12

56% Synthesis (1972) 693

75%

J O C (1952) JACS (1955)

11 68

1738

384

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

0

C1 CH20Me

MezC=CH2

Section 365

c1

Ether, Epoxide

1;

JACS

- Ketone

koxyketones a n d epoxyketones

*

EtCOFHEt OMe

MeCOCl

(1971) p3 438

0000000000000000OO000000

T1 ( O A C ) ~ MeOH

--+

69 2706

MeCH(CH2)40Me

t

H2SD4 H20

60% Ber (1936)

(i-Pr)pNCl hv

a-Al koxyketones, B-a1

PhCOCl

2360

Me2FCH2CH20Me

ZnC12

MeCH2( CH2 )4OMe

EtCICEt

2196 JACS (1943) t-BuOBr Bull SOC Chim F r (1961) BrN3 T e t r Lett (1968) 3921

SECTION 365

PhCOCHN2

Et20 hu

JACS

(1973)

95 1296

i-PrOH BF3.Et20 * PhCOCHZOPr-i JACS (1950) 12. 5161

MeCHOEt LOMe

Angew (1965) ( I n t e r n a t Ed

85%

2 216 5

239)

c-r

69%

ETHER, EPOXIDE

SECTION 365

PhBr

1 Mg

Et20

71 -78% Org Synth (1955) Coll Vol 3 562

THF

1 (i-PrCH)zBH

2 H202 NaOH H20

*

1 Mg

Et20

*

1 Pyrrolidine

96 316

82%

PhCOCH2CH20Et

2 CdC12 CgHg 3 EtOCH2CH2COCl

0

61 %

BuCH2COCH20Et JACS (1974)

PhBr

385

PhCOCH20Me

2 MeOCH2CN

BuCXCH( O E t 12

- KETONE

JACS (1949)

cro

11.3480

~ 6 ~ 6

*

2 MeOCH2C1

33%

CH20Me

JACS (1963)

207

aMe d:20cH2ph PhCH20CH2C1

0

NaH dioxane

JCS (1963) 4634 (1964) 4521

?Et PhCOCH3

CHzZCPh. BF3mEt20

*

?Et PhCOCH2FMe Ph Synthesis (1972) 378

37%

386

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

Me2C=CHCOMe

MeOH

ion exch r e s i n (acid)

*

SECTION 365

Me+CH2COMe

57%

OMe JOC (1958)

DOMe Review:

2 937

E t O H hJ

62%

The a-Epoxyketones

JACS (1967) 89 3949 Tetr Lett (1968) 2025 Bull Chem Soc Jap (1967)

40 945

Annales de Chimie (1966)

11 159

-0 0

BrCH2COP h

MeONa

EtOH

NO2

02 hv

HO

88%

GCHCOPh

JACS (1955) 71 590 JCS C (1970) 1154

Pyr

75%

0

hematoporphyrin

JACS (1963)

1894

H202 NaOH

70-72%

MeOH H20

t-BuOOH,

t

-

Org Synth (1963) Coll Vol 4 552 , JCS Perkin I (1972) 2051

PhCH2NMe3 OH JACS (1958) (1968)

continued

5845

90 6495

ETHER, EPOXIDE

SECTION 366

- NITRILE

387

H202, DMF (neutral) Chem Pharm Bull (1969) NaOCl, Pyr J O C (1963) g 250 Tetrahedron (1968)

PhC002H J A C S (1950)

Section 366

72 367

24

1206

6583

- Nitrile

Ether, Epoxide

00000O0000000000000000000

a-Cyanoethers, B-cyanoethers a n d epoxynitriles

C6Hl3e0

Me

BuOH

$JSiMe3 Me2CCN KCN 18-crown-6

CH2=CHCN

F)SiMe3 C6H13Ycb1

*

Me

+

95%

T e t r L e t t (1973) 4929 Ber (1973) 106 587

-

PhCH2NMe3 OH

*

86%

BuOCH~CH~CN Org React (1949) 2 79 110 JCS (1945) 535

I \

MezC-CHz

Me3SiCN AlCl3

t

CN

ClCH2CN PhCH2NEt3 + C1 NaOH H20

93%

Me2FCH20SiMe3 Tetr L e t t (1973) 1449

OH o\CN Tetr L e t t (1972) 2395 J Indian Chem SOC (1963)

79%

40 114

388

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

EtTHCHO

c1

NaCN H20

0 I \ EtCHCHCN

SECTION 367

Bull SOC Chim Fr (1967) 1587

30%

~~ty;o;o~~~~~~

S e c t i o n 367

V i n y l e t h e r s ( e n o l e t h e r s ) and a l l y 1 e t h e r s

CgH13CXH

1 Hg(OAc)2 MeOH 2 NaBH4 NaOH

h

59%

CgH13$=CH2 OMe JOC (1973)

2 4254

Et 77%

CH2=CdHOH Me

J A C S (1973) 2 553 J C S Perkin I (1973) 1 7 9 1

JACS (1953)

CH24HOAc

a. CH20H

1 NaH CH2=CHCH2Br

O%

CsH6 2 t-BuOK

CH20CH=CH#e

*

Me2SO

75 2678

t /

J C S (1965) 2205

JCS Perkin I (19721 1535 J O C (1973) 2 ' 3 2 2 4

1 BrCH2CH2Br NaOH H20 * 2 t-BuOK CgH6

a o c H = c H 2 NO2 Synthesis (1972) 693

ETHER

SECTION 367 HC(OEt)3

Me2CHCHO

NH4C1

EtOH

EtOH HC1

C11H23CH2Br

389

H3P04

Me2CtiCH(OEt)2

MezC=CHOEt

55%

Bull Soc Chim Fr (1965) 1007

-

PrCH2CHO

t.

- OLEFIN

NaOAc

PrCH2:HOEt c1

1 Ph3P

2 MeONa THF

37 %

PrCH=CHOEt J O C (1958) Ber (1956)

23 670

1468

HCOOEt

C11H23CH=PPh3

C11 Hz$H=CHOEt

Zh Org Khim (1966) 2 2181 (Chem Abs 66 85406)

6%

<85% J O C (1969)

0

0

FJJ;;CHzOMe +

C1

34 1220

a

PhLi

CHOMe

71%

Org React (1965)

2 270

399

(Me2N)2POCH20R Compt Rend (1971) 272 100

Annalen (1962)

656 97

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

390

Me2SO

1 t-BuOK

PhCOCH3

OMe

t

PhCHO

Phf,=CHZ

t

2 MepSO4

SECTION 368 68%

Chem C o r n (1966) 51

-

CH2=CHPPh3 Br EtONa

PhCH=CHCH?OEt

*

EtOH

54%

L

J O C (1966)

2 467

J O C (1974)

39

1 PliSeBr

BuCZCCH(OEt)2

Me I 1 (i-PrCH]zBH THF

b

2 HOAc

H202 NaoH H20

Section 368

Halide

429

BuCH=CHCH20Et

65%

cis

J A C S (1974)

316

- Halide

0000000000000000

1,l-Dihalides and 1,2-dihalides BuCECH

-

HF Pyr THF

BuCFz I Me

70% S y n t h e s i s (1973) 779

75% Synthesis (1973) 787

MoF6 T e t r a h e d r o n

(1971)

3965

SECTION 3 6 8

PhCHO

HALIDE

Ph3PeC12

- HALIDE

PhCHC12

59%

626 26 Org Synth (1943) Coll Vol 2 549 Annalen (1959)

PC15

Ber (1959) NH20H; C12 JOC (1971) MeOCHC12

i-PrCHO

@J

NO2

BuCHMe2

1 N2H4 2 I2

NH2

391

+

Et3N

NaOAc

-

62%

Aust J Chem (1970) JCS (1962) 470

HBr

2 CH2=CHBr

PhHgCC12Br

i-PrCHI2

Et20

1 NaN02

92 83 36 2146

H20* CuBr2

H20

2 989

@H2cHBr2

< 77%

NO2

JACS (1954) 76 3005 Org React (1960) 2 189

20%

BueMe2 CHCl2

JOC (1970) 35 1989 Annalen (1969) 2 33

23%

R2NSF3

Synthesis (1973) 787

JACS (1962) 4 4275 MoF6 Tetrahedron (1971) 21 3965 COF2

86% Ber (1963)

1387

SECTION 368

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

392 i-PrCOMe

1 NZH4 * 2 12 Et3N Et2O

i-PrCI2 I Me

50%

Aust J Chem (1970)

CJ-

CHMe2

Br2 hl/

CHMe2

2 989

-50%

Rec Trav Chim (1964)

oo

Ph3P.x~

67

X=C1 or Br

___t

Tetrahedron (1971) 21 2617 Tetr L e t t (1972) 3869

COC12 Ber (1962) 2 2976 S02c12 Can J Chem (1966) 44 2339 MeZN=CHCl C1 Chem C o r n (1967) 1152

+

MeCH2yMe2 Br

MezC=CMe2

C5H11CH=CH2

NBS CCl4

MetH-CMe2 I Br Br

1 HF NBS Pyr Et2O

2 AgF

-

t

20% J O C (1953)

18 649

Me2C-CMe2 I

1

F F Synthesis (1973) 780

Pb(OAC)a, HF

JACS (1962)

C12

C5H11 $HCH2C1 Synth Corn c1 C12, Pyr or C12, SbC13 JOC (1959) Continued

84 1050

(1972) 2 129 2 1621

86%

HALIDE

SECTION 368

- HALIDE

393

C1zY SbClg Chem Corn (1971) 1064 PhIClZ NCS, HC1

3 3329 4 1621

JACS (1951)

J O C (1959)

(1971)

a 1024

J O C (1959) 24 1621 JACS (1959)-% 2191

S02c12, Pyr Rec Trav Chim (1971) 90 549 J O C (1971) 2 3566

NC13 Synthesis (1969) 135 J O C (1971)

36 3566

Pc15 J O C (1971) 2 3566 CuC12 Bull Chem SOC J a p (1971) 44 1973 (1970)

43

1439

TIC13 Bull Chem SOCJ a p (1972) 45 1482 Pb(OAc)4, MeCOCl Tetrahedron (1969) 25 1545

50% Rec Trav Chim (1964) 67 Org Synth (1943) Coll Vol 2 171

Pyr.HBr3 Org Synth (1966) 46 46 CuBr2

PrCH=CH2

BuCHzCH2

12

+

J O C (1971)

94 7118

a 3324

PrFHCHzI

I

NCS HF Pyr sulfolane

JACS (1972)

Can J Chem (1964)

fll 2710

BUFHCHZCl F

40% Synthesis (1973) 780

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

394

0NBA

SECTION 369

HF

JACS (1959) 4107 2191 Org Synth (1966) 5 10

Synthesis (1973) 780 Can J Chem (1969) 9 3 6 1 Br2, AgF Chem Ind (1967) 1787

NBS, HF

BuCHZCH~

HF

I2 AgN03 Pyr

*

sul folane

80%

BuFHCH~I

F

Synthesis (1973) 780 12, AgF or NIS, HF Can J Chem (1969) 47 3 6 1 JACS (1960) 4007-

PhCH=CH2

NBA HC1

PhyHCHpBr c1

H20

t-BuCH=CHz

Section 369

I 2 cuc12

MeCN

Halide

JACS (1951)

(1959) (1952)

73

74

998 2191 4891

73%

t-BuFHCH21 c1

JOC (1971) 36 3324 2088 12, HgC12 JACS (1948) 70 828

- Ketone

000000000000000

a-Haloketones . . . B-Haloketones . . . Higher haloketones PrCECMe

36-44%

. . . . . . . . . . . . . . . . . . . . page ...................... ......................

Et2NC1 H2SO4 HOAc

*

PrFHCOMe c1

394-399 399 400 33%

JOC (1967)

32 3263

SECTION 369

C5H11 C-CH

HALIDE

1 EtMgBr

Et2O

2 Br2

- KETONE

CgH11C:CBr

1 HgO B F 3

2 HC1

2 PhIC12 3 Na2C03

cocl

C6H6 H20

C5H11 COCH2Br

H20

JACS (1937)

1 Ph3P=CHPr

395

59

1307

[>CO,HPr

*

c1

2 1871

Tetrahedron (1969)

OR

RO@CH2CH2COOH

CH2CH2COCHN2

Me

EtpO

HC1

\TCH~CH~COCH~C~

H20 E t 2 0

14

J Med Chem (1971) 641 Org Synth (1955) C o l l Vol 3 119

B r o m o k e t o n e s J O C (1970) 5 1381 I o d o k e t o n e s v i a b r o m o k e t o n e s JACS (1943) 65 1516

Ye

?Me Me tH2C=CHCOOMe Ph3P=CEt CH2L=CHCOOMe NCS c ' CH2CH=F(CH2)2CHO THF CH2CH=C (CH2)2CH=TEt Me Me OMe

*

Me

p o l y p h o s p h o r i c acid

1

2 5374

1 Mg

Et2O

2 EtCHCOOEt

;

5379

40%

Me

Synth Corn (1972)

PhBr

60%

ococH2

JACS (1972)

C1 CH2COOH

Me CH2C=CHCOOMe t H 2 C H = y ( CH2)zFHCOEt Me C1

1.97

ClCH2COC1, A l C l 3 Org Synth (1955) C o l l Vol 3 183

PhC0F;HEt F

50% Bull SOC Chim Fr (1970) 991

396

BuBr

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

1 Mg Et20

2 ClCH2COC1

BuCOCH2Cl

1 Mg THF

PhBr

$OSiMe3 * N=C=CMe2

3 Br2

4 (COOH)2

Ye

$H2C=CHCOOMe CH2CH=F(CH2)2Br Et

SECTION 369

Org React (1954) 8 28 J A C S (1945) 67 19T4

PhCOFMe 2 Br

51 %

40%

H20

2 2129

J O C (1973)

Ye

Li 1 EtCOiHCOEt cuc12 Licl DMF* 3 Ba(0H)p EtOH

VH$=CHCOOMe CH2CH=C(CH2)2:HCOEt Et C1

90 6225 66 1132

J A C S (1968) (1944)

@-* ctl F"'a C8H17

(CF3 h C 0 F

or SF5OF or CF3OF

AcO

0

0

C h e m C o r n (1972) 122

FC103 Via ethoxalyl derivative Via enamine

A

1 2

LiCHC12

+ Lithium piperidide THF

40-62%

J C S Perkin I (1973) 2365 JACS (1960)

JOC

A

(1958)

2 2312

23 1406

PhCHCO

T e t r Lett (1972) 4117 4661 Ber (1973) 106 2626

< 70%

SECTION 369

HALIDE

- KETONE

cJo- Cr:1

397

61-66% Org Synth (1955) Coll Vol 3 188

Clz, HOAC Pyr-HC13 JACS (1953) 2 3500 630 CuCl2 JOC (1963) s02c12 Org Synth (1963) Coll Vol 4 162

SeOCl2 PCl5 t-BuOC1 Pb(OAc)4, MeCOCl Chlorination o f inines

JCS (1953) 3869

J O C (1972) J O C (1963)

2 2436 2

1128

Compt Rend (1963) 256 1996

JACS (1953) 75 3500

25 1545 (1970) 26 5191

Tetrahedron (1969) Tetrahedron

/fi2 ?Ac

--+

NCS

dioxane

JACS (1959)

AcO

81 2383

C12 JOC (1961) 3 4569 Br2 CCl4

COCH3

= o

7

COCHZBr

Tetrahedron (1970)

2 5611

Br2, HBr, HOAc or dioxaneVBr2 JCS (1954) 3257 PyrrolidonemHBr3 Can J Chem (1969) 2 706 CuBr2 J O C (1964) 29 3459 JACS (1968)

90 6218

NBS, benzoyl peroxide JCS Perkin I (1972) 50 Angew (1959)

continued

2 349

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

398

+

-

PhNMe3 Brg Bromination o f Ketals Bromination o f en01 acetates Bromination o f lithium enolates Bromination o f enol ethers

&

0

J O C (1971) 2 4 1 2 4 Bull Soc Chim Fr (1962) 90

Tetrahedron (1963) 19 861 Bull SOC C h i m Fr (1962) 90 JACS (1965) 87 817 Chem Pharm Bull (1969)

(1972)

g 1585

2 2576 (1959) 24 1564

J O C (1973)

2156

aCHo mB

Bromination o f imines

HCOOEt+

JOC T e t r L e t t (1972) 4055

Tetrahedron (1970)

26

5191

1 Brp KBr+

MeONa

0

NaOH

?Ac CH2=CMe H2SO4

?Ac BuCH=CMe

BuCH2COMe

0 29%

2 NaOH

J O C (1970)

+ - ,

SECTION 369

35

753

NIS or ICI

7

BueHCOMe

Bu:HCOMe Br

NBA CCl4

12, CaO

1,3-Diiodo-5,5-dimethylhydantoin

Via oxalyl derivative

2

1

NaI Me2CO

JACS (1953)

75 3493

2 1966 30 1101 (1952) 2 4974

J O C (1960) JOC (1965) JACS

OAc

F & o c AAcO -&

dioxane H20

NOF

0 JCS Perkin I (1973) 1462 Chem Ind (1965) 1929

13%

HALIDE

SECTION 369

- KETONE

No c1

399

MeCOCH2CH2COOH

93%

HC1 H20 J O C (1967)

32 4136

79% JOC (1973)

BuCH=CH2

1 B2H6 THF

38

185

BuCHpCH2CHCOPr-i I Br

*

2 i-PrCOCHN2

3 NBS 4 NaOH H20

Can J Chem (1972)

2387

Br ?H

OAc

NBA HClO4

t

~

CHzbH-CHPh O

dioxane H20

A

Ccr03

~2~04.

Br CH2tHCOPh ~

O

A

C

Me2CO H20 JACS (1972) (1956) Helv (1944)

94 5386 78 3749 821

JCS (1952) 3945

PhH

BrCH2CH2COCl ~

1 cs2 ~

*

1

~

BrCH2CH2COPh

< 93% JACS (1940)

62

1435

400

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

I (CH2)1oCOCl

Bu2CuLi

SECTION 371

I (CH2)1 oCOBU

Et2O

93%

JACS (1972)

94 5106

Halide - Nitrile

Section 370

00000000000000000

Halonitriles PhNH2

--+

+ -

PhN2 C1

CHzsCHCN Cu2+

PhCH2fHCN c1

L

N

60%

Proc Chem Soc (1962) 117 Org React (1960) 11 189

bH

38%

Cl

JACS (1945)

61 690

POC13, lutidine JACS (1950) 2 1753

EtCH=CH2

1 9-BBN

t-butylphenoxide THF

Section 371

*

2 C12CHCN potassium 2,6-di-

EtCH2CH2yHCN c1

JACS (1970)

92

5790

Halide - Olefin 0000000000000000

Vinylic halides, allylic halides, homoallylic halides and other olefinic ha1 ides.

For the conversion of allylic alcohols to allylic halides see section 138 vol 1 and vol 2 (Halides from Alcohols) For allylic halogenation with NBS etc. see section 146 vol 1 and vol 2 (Halides from Hydrides)

75%

SECTION 371

C5H11CHO

HALIDE

Ph3PICHF

F

F

h

*

2 Me3SiC1

~1203

44%

2 818

95%

PhC-CHCH2Ph

CH2C12

Et20

-

JOC (1971)

PhCH2C1 ZnCl2

1 EtMgBr

35%

Synthesis (1969) 75

CH2C12

BuCZCH

401

CgH11CH=CHF

THF

ooPhCXH

- OLEFIN

JCS Perkin I (1973) 2491

BuCXSiMe3

1 Dicyclohexyl borane + BuCH=CHX 2 HOAc trans 3 H202 base

X=C1 or Br

4 x2 5 MeONa Tetr Lett (1974) 543 t

Ph3PCH2C1 C1 piperidine

BuLi Et20

b

A -

81 %

DC=CHCl

Ber (19721 105 1683 Org React (1965) 2 270

PhHgCHClBr, Ph3P J Organometallic Chem (1965)

MeOCH2CH20Li

J A C S (1970)

3 337

OCHX X=C1 o r I

92 4309

COMPENDIUM OF ORGANIC S Y N T H E T I C METHODS VOL 2

402

S E C T I O N 371

32% JACS (1952) 2 3643 P h 3 P C 1 2 Annalen (1959) 626 26 C l z C H O M e , Z n C 1 2 Ber (1959) 92 83 P h 3 P , C C l 4 Chem Corn (1972) 443

@::PC13

PrCXH

Me 1 (EtbH)2BH

2 By2

THF

CCl4

3 NaOH

b

3a

*

Ber (1963)

96

1387

JOC (1971)

36

1024

cis

PrCH=CHBr

trans JACS (1967)

oczcH

(1973)

4531

95 6456

H B r DMF,

Me0

Me0

Helv (1964)

BuCECH

HBr

oBr

peroxides

*

1 Mg E t z O 2 BrCHzC'CH2 I

Br

BuCH=CHBr

78%

47

194

Org React (1963)

0

2

150 234

CH2FzCH2 Br Org Synth (1932) C o l l Vol 1 186

74%

SECTION 371

oo

HALIDE

t

;::gH2Br

Br

- OLEFIN

403

OCHBr

PhLi

*

89%

JOC (1965) 30 2208 Org React (1965)

CH=CH2

- YCH=CHBr 1 Br2 CCl4 2 KOH

Me

3 270

EtOH

J Med Chem (1972)

15 1262

t-BuOK J O C (1965) 30 2208 NaNH2, t - B u O K Chem Corn (1972) 1289 Bu4N Br, CH2CH2 Ber (1973) 106 1648

+ -

\ I

0

85% JOC (1965) 30 2208 JCS C (1971) 2352

BuCECX

1 Dicycl ohexyl borane THF *L

2 HOAc

BuCH=CHX cis JACS (1967)

BuCZCH

CgH13CXH

1 (i-Bu)zAlH

heptane

+

2 X2 THF 3 H2SO4 H20

JACS (1967)

1 Catechol borane 2 H20 3 NaOH H20 4 I2

BuCH=CHX trans

Et20

~95% (X=Br) (85% (X=I)

3 5086

72% (X=Br) 74% (X=I)

89 2753

CgH13CH=CHI JACS (1973) 95 5786 T e t r L e t t (1974) 543

71%

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2 SECTION 371 NCOOK 1 BuLi Et20 NCOOK CgH11CHCZCH C5H11CHCZCI C5H11YHCH=CHI ~ 6 5 % HOAc MeOH 2 I2 OTHP ~THP 404

bTHP

_____.+I

J A C S (1972)

PhCOCH2Me

1 N2H4*H20 EtOH

+

2 I2 Et3N Et2O

94 9256

cis

60-65%

PhC=CHMe

;

A u s t J Chem (1971)

(1970) J C S (1962) 470 J O C (1969) 34 3502

24 1425 3 989

27% J O C (1971)

2 1024

50% Tetr L e t t (1972) 2743

CHz=CHCHzBr

1

Me

COCH2COOEt

NaH THF 2 Ba(OH)2

CH2=CH(CH2)2yH OH

3 LiAlH4

I(CH2)3C1

Ye

EtC=CHCu

CH2=CH(CH2)2.

H J A C S (1968)

F;1'

EtC=CH(CH2)3Cl

,c=c,

,Me (CH2)zBr

90 2882

6225

46% T e t r L e t t (1973) 2407

Also via: Acetylenic halides (Section 308)

SECTION 372

KETONE

- KETONE

405

- Ketone 1,2-Diketones . . . . . . . . . . . . . . . . . . . . . . . page 405-407 408-410 1,3-0iketones . . . . . . . . . . . . . . . . . . . . . . . . . 1,4-Diketones . . . . . . . . . . . . . . . . . . . . . . . . . 410-412 412-413 1,5-Diketones . . . . . . . . . . . . . . . . . . . . . . . . . 1,6-Di ketones . . . . . . . . . . . . . . . . . . . . . . . . . 413

Section 372

Ketone

a

o

o

o

o

o

Ru02 NaIO4

BuCXBu

CCl4 H20

o

~

~

o

~

BuCOCOBu

+

-

~

~

~

~

T e t r L e t t (1971) 2941

NBS HNO3 KMn04 T1 (N03)3

1 PrCH2PPh3 Br

O C O C l

~

C a n J Chem (1971) J A C S (1956)

2522

1063

JACS (1973)

PhLi Et20

2 1099

78 2518

J O C (1952)

70%

5 1296

COCOPr

2 KMnO4 MgS04 CgHg H20

Tetrahedron (1968) 24 2419 Ber (1969) 102 2259-

OH OH CgH13bH-iHC7H15

PhCHO

PhCHO

PhSH

ZnCl2

--+

NBS EtOAc H20

(Ph3P)3RuC12, PhCH=CHCOMe

PhCH(SPh)2

PhCHSNPh

JCS

2 Hydrolysis

2 HC1 H20

C

(1968) 2617

J O C (1972)

1 NaH PhCOCl DMF

1 NaCN DMF

35%

CgH13COCoC7H15

*

37

1832

PhCOCOPh

J O C (1963)

961

PhCOCOPh J O C (1972)

71%

2 135

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

406

BuBr

(COC1)2

--+ BuZCd

Se02

THF

dioxane

vo 02

MeONO HC1

EtpO

H20

37%

BuCOCOBu JCS

A

(1966) 456

Org Synth (1963) Coll Vol 4 229, Annalen (1962) 659 64 Synthesis (1971) 215

Ql

~

t-BuOH

-

2 3266

H20

t-BuOK

HMPA

BuCH2COMe

LiBr

Can J Chem (1969)

SECTION 372

BuCCOMe

{OH

Bull SOC Chim F r (1967) 3742 Tetr Lett (1961) 554 H2SO4 H20

---------* BuCOCOMe

V i a hydroxymethylene d e r i v a t i v e

JOC (1959) 2 1726 Org Synth (1955) Coll Vol 3 20

JACS (1964) & 3068 Chem Comm (1968) 1055

SECTION 372

KETONE

- KETONE

407

2 p-Nitrosodimethyl a n i 1 i ne

0

3 HC1

H20

4 KOH

H20

0

Helv (1944) 27 524 J O C (1964) E l 6 7 7

48% JACS (1971)

OH

CObH qcHz)2

93 3303

Cu ( OAc) 2 HOAc

88-89%

MeOH H20

Org Synth (1963) C o l l Vol 4 838 J O C (1964) 29 1677

A i r , CuSo4, Pyr Org Synth (1932) C o l l Vol 1 87

CrO3, HzSO4, Me2CO Chem Ind (1972) 807

Ac20, Me2SO J O C (1967) 32 3204

Mn02 J O C (1966) 2 615 B i z 0 3 JACS (1956) 78 2518 JCS (1951) 793 TlOEt

JCS (1952) 2771

HgC12 JCS

(1966) 366

Na[Sb(OAc),j] Ph3P.Br2

Ber (1964)

(Ph3P)3RuC12, PhCH=CHCOMe

J O C (1972)

91 124

S y n t h e s i s (1972) 697

NBS JCS

C

Qo- Q:

37

1832

(1968) 2617

J O C (1959) 24 719 Helv (1962) 45 2575

65%

408

BuCECH

COMPENDIUM

OF ORGANIC SYNTHETIC METHODS VOL 2

1 MeCOOH (CF$O)20 2 MeOH

t

SECTION 372

20%

BuCOCH2COMe +

-

JCS (1953) 3628

RCO BF4 T e t r Lett (1972) 4935

(EtCH*C0)20

1 BF3

2 (BuC0)20

(1971) 3101

EtCH2COFHEt

80%

COBu Annalen (1963)

668

15

JCS P e r k i n I (1972) 1509 Review:

The A c y l a t i o n o f Ketones t o Form +Diketones

or B-Keto Aldehydes

Org React (1954)

8 59

Ber (1972)

105 2216

JACS (1963)

& 207

SECTION 372

Ac20

BuCH2COMe

KETONE

TsOH

BuCH=CMe ()Ac

- KETONE

AcOH *BF3

Ac20

Acylation o f ketals

409

BuCHCOMe I

JACS (1963)

3901

ocooMe

COCH3

NaH

Me2SO

64-77%

COMe Org Synth (1971) 90 JACS (1953) 75 5030 T e t r a h e d r o n (1966) 2 2039 J O C (1969) 2 1425

ococH2co 83%

J O C (1962) 21 2742 Org Synth (1955) C o l l Vol 3 251 291

CHzN2

KOH

90%

E t 2 0 H20 Annalen (1962)

MeCOCH2COMe peroxides

659 64

C6H13CH2CH2CHCOMe I COMe Proc Chem SOC (1964) 142

65-70% CH3

EtCOCHZBr

PrCOSH Et3N

Et20

EtCOCH2SCOPr

T e t r Lett (1969) 2553 J O C (1971) 2 1447

-

B i s [ 3 - d i met h y l amino-

+ EtCOCH2COPr p r o p y l l - p h e n y l phosphine -86% L i B r MeCN H e l v (1971)

54

710

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

41 0 RX

RCOCH2COR

RCOFHCOR R

__.c

base

Base:

K2CO3 Org Synth (1973) C o l l Vol 5 785 T l O E t JACS (1968) 90 2421 NaH J O C (1961) NaNH2 Org Synth

1 BuLi

CgH13CECH

SECTION 372

hexane

2 (Cgtt13)3B

75%

CgH13COFHCH2COMe

f

diglyme

C6H13

3 BrCH2COMe

4 H202 NaOAc

26 4112 (1967) 47 92

H20

T e t r Lett (1973) 4491

Ye

EtCOCl

--+ EtCOCHN2

1 CHz=COAc

+

cuprous a c e t y l acetonate 2 Base

PhCHO

PhCH=CHCOMe

KCN

DMF

Cgti13CHO

---t.

+

T e t r Lett (1971) 2575

PhCOFHCH2COMe Ph

C6H13CH(SPh)2

EtCOCH2CH2COMe

1 BuLi 2

67%

Angew (1973) 89 ( I n t e r n a t Ed 12 81) T e t r Lett (1973) 1461

THF

CUI

hexane

b

CgH13COCH2CH2COMe

72%

3 CH2=CHCOMe 4

CUCl

CUO

Me2CO H20

C6Hl30~s

1 EtSOCH2SMe BuLi 2 BuLi 3 CHz=CHCOMe 4 HgC12

HC1

HMPA

*

JACS (1972)

94 8641

CgH13COCH2CH2COMe

T e t r Lett (1973) 3275 3271

76%

SECTION 372

KETONE

- KETONE

41 1

FONMez PhBr

---P

(CH2)NCONMe2

PhLi

Et2O

t

J O C (1973)

Li BuBr

N=2 or 3

PhCO (CH2) NCOPh

38

901

Me BuCOCH2CH2COMe

t

2 HgC12 CdC03 Me2CO H20

Chem C o r n (1972) 529

1 Li-Q-Me EtCH=CHCH2CH2Br

THF 4

2 H2SO4

HOAc

H20

EtCH=CHCH2CH2COCH2CH$OMe J O C (1966)

31 977

Nickel peroxide

< 80% JCS P e r k i n I (1974) 280

JACS (1963)

207

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

4 12

PhCOCHO

Ph3P=CHCOPh

PhCOCH4HCOPh

SnC12

HOAc

HC1

PhCOCH2CH2COPh

H20

Aust J Chem (1971)

JACS (1964)

Me 2 C=CHCOMe

Ni(CO)4

BuLi

*

pentane

SECTION 372

< 85%

24 2137

86 935

Ye

89%

BuCOFCH2COMe Me

Synthesis (1971) 55

EtCHzN02

CHz=CHCOMe (i-Pr)pNH

EtfHCH2CH2COMe NO, L

Ph

0'

1 E t 2 N C X M e MeCN + 2 HC1 H 2 0 HOAc

Tic13 glyme

H20

EtCOCH2CH2COMe

64%

JACS (1971) 93 5309 Tetr Lett (1972) 1331 JOC (1974) 39 259

PhCOCHzCH2COCH2Me

Tetr Lett (1971) 1565 1569

Bull Soc Chim Fr (1970) 4429

56%

KETONE - KETONE

SECTION 372 PhBr

1 Mg Et20

0

413

PhCO(CH2)3COPh Zh Org Khim (1969) 2 83 (Chem A b s 3 87453)

Pyrrol idine

1 CHz=CHCOEt dioxane 2 HOAc NaOAc H20

J A C S (1963)

BuCOOH

CHz=CHMgCl CuCl

*

THF

65%

S 207 53%

BuCO( CH2)4COBu

Can J Chem (1972)

2786

92% (R=Me) 90% (R=Bu) J A C S (1972)

COCl I (CH2)4 COCl

PhH AlCl3

MeCO( CH2)2COOH

COPh I ($H2)4 COPh

Electrolysis

MeONa

MeOH

94 5106

75-81% Org Synth (1943) Coll Vol 2 169

MeCO(CH2)4COMe '

,nalen (1953)

21 -26%

580 125

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

414 Section 373

Ketone

- Nitrile

00000000000000000

a , B, Y, 6 a n d

e-ketonitriles

BuCECH --+ (BuCX)2Hg

CUCN

PhCOCl

NOCl

BuCOCN

Proc Chem SOC (1963) 1 3

PhCOCN

60-65% Org Synth (1955) C o l l Vol 3 112 Can J Chem (1971) 2 919

@;;;c0cH2cN

40%

JOC (1960)

CH3CN Ph3CNa

PrCOOEt

Et20

PrCOCH2CN

oo

JACS (1942)

1 ClS02NCO 2 DMF

25

736

64 2720

-

Pyrrolidine

Me

SECTION 373

d i oxane

JACS (1959)

CH2C12

a : N

c 93%

81 5400

Me

S y n t h e s i s (1973) 682

69%

SECTION 373 MeCOOEt EtONa

PhCH2CN

PhCN

KETONE

41 5

66-73%

PhCHCN I

EtOH

COMe

1 CH3CN NaNH2 Et20

2 HC1 E t O H H20

EEfi

- NITRILE

CN

*

Org Synth (1943) C o l l Vol 2 487 (1963) C o l l Vol 4 174

PhCOCH2CN Ber (1949)

21 NaH HC1 dH2SO4 i o x a n e H20*

E

i

b

g

254

C

N

46%

t o 1 uene Can J Chem (1965)

PhCOCH2Br

LiCN DMF

PhCOCH2CN J O C (1964) 29 1970 JACS (1947) 69 990

Tetrahedron (1968)

3 ACZO

92512

Angew (1971) ( I n t e r n a t Ed

83

24

727

lo 655)

5959

41 6

O

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

C

H

D

CH2=CHCN NaCN DMF

SECTION 373

oCO(CH2)$N

32%

T e t r L e t t (1973) 1461 Angew (1973) 85 89 ( I n t e r n a t Ed 12 81)

COCH3 Me2NH.HCl

*Q -

HC1 H20 EtOH

OMe

6

KCN NH4C1

KCN

CO(CH2)2NMe2

HCHO

OMe

Qco~cH2)zcN

H20

+LN

DMF

JCS (1947) 1190

J O C (19721

37

J O C (1959)

2 879

OMe

44%

268

Org Synth (1943) C o l l Vol 2 498

JCS P e r k i n I (1972) 2765

HCN, Et3A1 Org Synth

(1972) 52 100 3 4 6 z 4654

JACS (1972)

Me2fCN JCS CH (COOTHP) 2 Me0 @‘OC1

0

1 h;tI2CN

Pyrrolidinf

43

CO(CH2)jCN

80%

Na Me0

2 HOAc

0

OH

(1958) 4193

B u l l SOC Chim F r (1963) 2471 T e t r Lett (1973) 1 4 1

B u l l Soc Chim F r (1969) 4437

O

N

?

0

1 CHz=CHCN dioxane

(CHz)$N

2 H20

JACS (1963)

207

80%

SECTION 374

KETONE

- OLEFIN

41 7

CHpCHCN Me

Triton B MeOH JACS (1964) 465 Org React (1949) 2 79

2 Na2CO-j H20

A \v

Section 374

JACS (1952)

2 5.597

P h I (OAc)2-Me3SiN3 CH2C12

Ketone

65% Synthesis (1972) 285

- Olefin . . . . . . . . . . . . . . . . . . . . page ...................... ......................

0000000000000000

aB-Olefinic ketones BY-Olefinic ketones YG-Olefinic ketones

417-425 426 426-428

For the oxidation of a l l y l i c alcohols t o o l e f i n i c ketones see section 168 v o l 1 (Ketones from Alcohols and Phenols)

For the oxidation o f a l l y l i c methylene groups (C=C-CHz

-+ C=C-CO) see section 170 vol 1 and 2 (Ketones from Alkyls and Methylenes)

For the alkylation o f o l e f i n i c ketones see also section 177 vol 1 and 2 (Ketones from Ketones)

Annelation reactions a r e n o t 1 isted

PrCH2ECBu

MeC002H

PrCH=CHCOBu Ber (1954)

1478

COMPENDIUM OF ORGANIC S Y N T H E T I C METHODS VOL 2

41 8

Y?

S E C T I O N 374

i-PrCBH2

1 BuCXC1

PrCXH

Me

2 MeONa 3 H202

C5H11C X H

NaOAc

1 RLi

48%

Chem Corn (1973) 606

THF

42% -

._

3 MeCOCl 4 C r O 3 H2SO4

MezC=CHLi

PhCOOLi

PrCH=CHCOCH2Bu

t

Me2CO

Et20

b

T e t r Lett (1973) 795

40%

PhCOCH=CMeZ JCS (1950) 2012 Advances i n Org Chem (1960)

EtCHCOCl I Me

1 CH2=CH2

AlCl3

PhN02

b

2 PhNEt2

21

EtyHCOCH=CH2 Me Gazz (1967) 91 610 (Chem Abs 68 12401)

PhCOOH

HOCH2CZCH --------+ P h C O O C H 2 C X H

660'

( v a p o r phase)

PhCOCH=CHz

JACS (1972)

PhCH20H

1 MeMgI

2 Me2CO

<80%

94 5086

PhCH=CHCOMe T e t r Lett (1964) 3481

PhCHO

CH3COMe NaOH

H20

+

PhCH=CHCOMe

65-78%

Org Synth (1932) C o l l Vol 1 7 7 78 8 1 283 Org React (1968) 16 1

SECTION 374

KETONE

- OLEFIN

41 9

COMe

1 CH2COOBu-t

PrCHO

piperidine

EtOH

*

2 TsOH

PrCH=CHCOMe

73%

Acta Chem Scand (1963)

Me CHO

ClbHCOMe Mg _____t

Et20

y

Ye

CH-CCOMe

Rec Trav Chim (1950)

(Et0)2POCH2COMe

Me2CH2CHO

NaH MeOCH2CH20Me

acid

*

76%

Bull SOC Chim F r (1967) 2477 JACS (1969) 91 5675 Org R e a c t (1965) 2 270 Ber (1962)

95 1513

ocoMe 25%

T e t r a h e d r o n (1968)

0

I \

PhCHCH2

1

BuLi

2 Hydrolysis

l:idt-BuOH

24 553

< 70%

PhCH=CHCOMe

EtSCH=CH2, RLi

@OM'

69 307

Me2CH2CH=CHCOMe

Ph3P:CHCOR

Polyphosphoric

17 2216

RNH2

*,

Angew (1965) ( I n t e r n a t Ed JACS (1973)

1134

4 1075) 95 2694

oo

S y n t h e s i s (1972) 391 Advances i n Org Chem (1972)

5

1

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

420 MeCHBr

@

t

-

A

2Li - (MeO)2POCHCOCH2

MeCHCH2COCH2PO(0Me)z NaH Me2CO

f

PrBr

J O C (1973)

1 Mg

MeCHCH2COCH=CMez

A

I _

MeOCH2CH20Me

Me

SECTION 374

2 2909

PrCH=CHCOMe

t

2 EtzNCH=CHCOMe

B u l l SOC Chim Fr (1960) 515 (1966) 287

ArOC=CHCOR' Compt Rend (1964) 258 5234 I R MeCOCl AlCl3 Me

CHCl3 Tetr L e t t (1968) 5455

PhCOCH2 I Me

1 LiN(Pr-i)2

*

2 PhCH2SCH2Br

3 ~a104 4 Toluene (reflux)

4 50"

PhCOC=CH2 I Me

52%

Chem Comm (1974) 135

JACS (1973)

95 6840

PhSeCl, H202 JACS (1973) 95 6137 PhSeBr, NaIO4 JACS (1973) 95 5813

-trcH=cH Chem Corn (1973) 695

CH2CHzCOMe

HI04 dioxane H20

Chem Comm (1973) 746

02, palladium acetylacetonate JOC (1971)

a 752

SECTION 374

Review:

KETONE

- OLEFIN

The Aldol Condensation 1 MeCHO KOH

i-PrCHzCOCH3

Org React (1968)

i-PrOH

w

2 (COOH)2

Me Ph2CO

c>

2 Acid

*

16 1

i-PrCH$OCH=CHMe JCS

1 Li CH&=N

421

4 (1970)

1469

50%

Ph$=CHCOMe Angew (1968) 8 ( I n t e r n a t Ed I 7 )

aNuo -

0'

n

Morpholine*

i-PrCH2CHO

Ber (1962)

-86% CHCH2Pr-i

95 1493

1 Zn Me2SO C& Br

2 MeCHO

*

57%

0 ; H M e

JACS (1967)

0

1 CS2 4-methyl-2,6di-t-butylphenol

BuLi

2 Me1

5727

LiCuMe2

* C( SMe 12

T e t r L e t t (1973) 3817

Org Synth (1955) C o l l Vol 3 22 JACS (1953) 2 4740

422

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2 NHBu Ph2POCH=CPh

Ph2CO

______+.

NaH THF

Ph2C.CHCOPh

SECTION 374 62%

T e t r L e t t (1971) 14 1 1419 J O C (1971) 36 2892

3 NaOH JACS (1973)

95 289

Ye

BrCHCOOEt

--------+

J O C (1971)

0

36

3232

0

0

DMF Dehydrohalogenation with:

CaC03, DMA L i B r , Li2CO3, Me2SO LiBr, Li2C03, DMF LiC1, DMF HMPA Coll idine PhNEt2

J O C (1972)

37

268

JCS (1961) 2532

JCS Perkin I (1972) 50 Tetrahedron (1973) J O C (1972) 2 2436

29 2575

T e t r Lett (1968) 2105 JCS (1961) 1583

I z v (1953) 889 (Chem Abs 49 1082)

Pyr Helv (1942) 5 821 NH2NHCONH2 JACS (1952) 483 JCS (1961) 2532

NH2NHCOOEt JCS (1959) 1691 continued

SECTION 374

KETONE

- OLEFIN

423

2 3951

2,4-Dinitrophenylhydrazine JACS (1952)

- +

(1950)

2290

(Fle0)ZPOz NMe4 B u l l SOC Chim F r (1971) 2962 2551 JACS (1960)

,Ac20

aoAc . a:e

HC104,

1 MeLi

Me

\I

LiN(Pr-i)Z 2 MegSiCl

130

*

2 61-2 3 LiBr Li2CO3

,3::iMe3

;;;i

0

~

M 0e

3 LiBr Li2CO3

EtCH=CH2

MeCH=CH2

1 B2H6

THF

2 HCXCOMe 3 Air

1 MeCOCl

J O C (1973)

72%

EtCH2CHzCH=CHCOMe JACS (1970)

AlCl3 CHzC12

2 Quinol ine

38 2576

*

9 3503

I>leCH=CHCOMe

Org Synth (1971) MeCOOH, (CF3CO)zO JCS (1953) 3628

51 115

*Q

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

424

1 EtONO

EtOH

2 HC1 3 NH20HaHCl 4 (COOH)2

C5H11CXCH20Me

SECTION 374

-

60%

Pyr

H20

1 BuLi

JACS (1951) 73 5856 NOF JOC (1968) 2 3699

Me2NCH2Cti2NMe2

*

2 Me2S04 3 BuLi

C5H11:=CHCOMe Me

4 Me1

5 Acid

T e t r L e t t (1973) 2585

C0CH2CH2C00H

Pb(OAc)4 Pyr

CU(OAC)~

*

C6H6

COCH=CH2 i-pr@JMe

31%

Synthesis (1973) 541 J O C (1968) 2 2008

1 HCHO Me2NH HC1

+

dioxane

C6H13COF=CH2

2 Me1

3 DMF 75'

Me T e t r L e t t (1973) 5037

T e t r L e t t (1973) 2071

Via en01 e t h e r

Chem Corn (1973) 907

52%

SECTION 374

KETONE

0

- OLEFIN

425

0 1 LiA1H4

Et20

62-75%

2 H2SO4

OEt

Org Synth (1973) Coll Vol 5 294

1 TsNHNH2

0

H2SO4 MeOH

52%

2 K2CO3 H20 JOC (1973)

38 3637

75%

JOC (1973) 38 3658

CH2CH2COOEt Piperidine 0 TSOH CgH6

0

CH2CH2COOEt 1 Hp P t MeOH 0 2 KOH E t O H

Ber (1964)

1 NBS

C1

2 PhS-

,

91 1723

Cyclohexene,

0

3 m-Chl oroperbenzoi c

acid

0

Chem Corn (1974) 21

COMPENDIUM OF ORGANIC SYNTHETIC METHOOS VOL 2

426

1 BuLi

hexane

C6H13,

*

CgH13CECH

2 (C6H13)$ diglyme 3 BrCH2COMe 4 HOAc

Ph Ph3P=C=COLi

EtCH2COPr

H

/

SECTION 374

/C6H13

c=c

\

75%

CH2COMe

T e t r L e t t (1973) 4491

52%

EtCH=CCHzCOPh I

Pr T e t r L e t t (1972) 933

1 t-BuOK

t-BUOH

2 HOAc

0

T e t r L e t t (1962) 669 S t e r o i d s (1964) 3 183

Via enol t r i c h l o r o a c e t a t e Tetrahedron (1969)

Me$HCH=CHCOMe

hv Et2O

25 1717

Me2C=CHCH$OMe

75%

T e t r L e t t (1964) 1203 JCS C (1966) 571

70% T e t r L e t t (1971) 3101

PhCOOH

C1 MgCH=CH2

THF

PhCOCH2CH2CH=CH2

84% Synthesis (1970) 189

SECTION 374

- OLEFIN

KETONE

427

PhOCti2CH=CH2

0J-(

a

Ph3P

--+

Pd ( O A C ) 2

70%

CH 2 CHzCH2

C6Hg

T e t r L e t t (1973) 121

Br

--+

@c0cH3

Br

0

COCH2Br ?r-Methallylnickel bromide

@JOCH2CHH 2[;i2

*

DMF

JACS (1967)

Br 2755

- OPh 1 HCOOEt

0 CHOCH$=CH2 he

MeONa 2 CH24CH20H Me

62%

2 K2CO3 CH2C=CH2 Me

35 570

J O C (1970)

Me

OH MezbCH=CHZ

I

CH2=COMe H3PO4

*

Me2C=CHCH2CHZCOMe

94%

Helv (1967) 2091 2095 T e t r L e t t (1969) 3243 JACS (1973) 95 553

TH

EtCCH=CH2 1

Me

Diketene MeONa

MeCOCH2CO? EtCCH=CH2 i

Me

A1 ( O P r - i ) 3

Etv=CHCH$H2COMe Me

Tetrahedron (1969)

CH2=CCH2C1 tie

MeCOCH2COMe K2CO3

EtOH

5 1667

CH2=yCH2CH2COMe Ne Org Synth (1973) C o l l Vol 5 767

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

428

Hp Pd-CaC03

MeCECCHzCH2COMe

SECTION 375

MeCH=CHCH2CHpCOMe

EtOAc

78%

JCS (1951) 2445 JACS (1972) 94 507

0

0

THF EtpO

JACS (1972) 94 7823 Can J Chem (1970) 48 1626 Helv (1971) 54 1 9 3 r Org React (1972) 19 1

(i-Bu)pAlCH=CHR Tetr Lett (1972) 4083 Me

M

-

t

O?, Oto I Ph3PCHz(CH2)2CMe I I

e

w

Also v i a :

Section 375

NaH MeZSO

Acetylenic ketones 6-Hydroxyketones

Nitrile

LI

Ye

/\IC=CH(CH2)2COMe Me

I

I

JCS P e r k i n I (1972) 2653

Section 309 330

- Nitrile

oOOODOOoOoODOOOOo

D i n i triles

75%

SECTION 375

NITRILE

CH2'C(CN)2

C12CHCHC12

A l C13

PhCH2CN NaCN

MeOH H2O

0

429

CHzCH(CN)2 Me

-

PhCHO

- NITRILE

JACS (1954)

76 1076

JACS (1958)

1752

Ph$H-$HPh CN CN

CN CN

NaCN

-40% Org Synth (1963) C o l l Vol 4 273 274 66 JACS (1965) 4403

PhCH2CN

CHz=CHCN EtONa

Ph$HCN CH2CHzCN

+

20-30% JACS (1943) 65 437 Org React (1949) 79

+-

MeCH=CHCN

Me$(CH2)zCOOH CN

Electrolysis Et4N OTs

f

DMF

MeCHCH2CN

Compt Rend

Electrolysis Na2CO3

MeOH

Me2F(CH2)4yMe2 CN CN

C

(1967)

265

751

Bull SOC Chim F r (1970) 183 Z Naturforsch (1947) & 185

60%

430

COMPENDIUM

S e c t i o n 376

OF

ORGANIC SYNTHETIC METHODS VOL 2

SECTION 376

-Olefin

Nitrile

00000000000000000

a#, By, and h i g h e r o l e f i n i c n i t r i l e s

1 (i-Bu)zAlH

BuCZCH

hexane ~

2 MeLi

Et20

BuCH=CHCN

87%

J A C S (1968)

3

COOH ~ .

3 7139

.

CH2CN

NH40Ac 74-78% Org Synth (1973) Coll Vol 5 585 JCS P e r k i n I (1973) 2241 J A C S (1949) 2 3562

+

Ph3PCH2CN C1

42%

MeCN Ber (1970) + (Ph3P)zCHCN 2Br, NaOH J O C (1971)

NH2 NCS

NaN02 HC1 Me2 3 2 CH2=CHCN CuC12

H20

3 Et3N

PhH

CHz=CHCN HOAc

103 2077

a 2026

NCSo c H = C H C N

JCS Perkin I (1973) 2241 Org React (1960) 11. 189

Pd( O A C ) ~ w

PhCH=CHCN Tetrahedron (1969)

2 4819

60%

SECTION 376

NITRILE

- OLEFIN

431

J O C (1972) 2 2201 T e t r a h e d r o n (1968) 24 3127 Can J Chem (1969) 41 3266

(Et0)2POCH2CN

NaH

v

b

MeOCH2CH2014e

J O C (1971) (1965)

Ph2CO

1 CH3CN B u L i

THF

hexane

36

30

1024 505

PhZC=CHCN

+

2 H3PO4 H20

75%

58%

J O C (1968) 33 3402 Angew (1972) 767 ( I n t e r n a t Ed 722)

11

i

PhCHZCN

-

HCHO PhCH2NMe3 OH

t

EtOH

I

CN JACS (1950)

EtCHO

CHpCHCN

Ph3P

t-BUOH

86%

PhCzCH2

2 5645

EtCH=CHCH2CN

44%

T e t r L e t t (1967) 2401 (1964) 1653

tOOH

1 CH2CN NH40Ac

76-91 %

2 165-175"

Org Synth (1963) Coll Vol 4 234 (1973) C o l l Vol 5 585

V i a enamine

Chem Pharm B u l l (1973)

21

1601

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

432

+

-

H C X H PhCHzNEt3 C1

EtCHCN I Ph

NaOH Me2SO

SECTION 377

CH=CHz Et!CN Ph

80%

Tetr Lett (1966) 5489

1

0

NHZOH-HCl Pyr

64%

2 TsCl JOC (1970) Coll

s 186

21 1961 1965 Czech (1962) 21 377

(1962)

Also via: Acetylenic nitriles (Section 310)

- Olefin 1,3-Dienes . . . . . . . . . . . . . . . . . . . . . . . . 1,4-Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . 1,5-Dienes . . . . . . . . . . . . . . . . . . . . . . . . . . Other dienes . . . . . . . . . . . . . . . . . . . . . . . . . Section 377

EtCXEt

Olefin

0000000000000000

1 B2Hg THF

2‘ I2 NaOH

page 432-435 435-436 436-437 437

Et EtCH=C-b=CHEt cisEt trans

68% JACS (1968) 90 6243 JOC (1973) c 1 6 1 7

Me

BuCgCH

--+

BuCSCC1

1

i -PriBH2

Me

2 PrCZCH 3 MeONa 4 i-PrCOOH

BuCH=CHCH=CHPr trans trans Chem Corn (1973) 606

45%

SECTION 377

- OLEFIN

1 D i cyclohexyl borane THF

BuCXCXBU

BuCECH

OLEFIN

2 HOAc 3 H202 NaOH H20

1 (i-Bu)zAlH hexane

*

CuCl THF 3 H2SO4 H20 2

t

433

BuCH=CHCH=CHBu c i s cis

JACS (1970)

79%

92 4068 73%

BuCH=CHCH=CHBu trans trans

JACS (1970) 92 6678 Annalen (1960) 629 222

42% JACS (1953)

S;H3 MeTOH MeCOH I

CH3

HBr H20

Org Synth (1955) Coll Vol 3 312 123

MeZSO 160' JOC (1964)

+

PhCHO

MeC=CH2 MeC=CH2

75 384

-

PhCH=CHCH2PPh3 C1 EtOLi EtOH

NH2

1 NaN02

*

PhCH=CHCH=CHPh

40%

Org Synth (1973) Coll Vol 5 499

HC1 H20

2 CH2=CHCH=CH2 CuCl NaOAc Me2CO H20 3 KOH MeOH

CH=CHCH=CH2

57-62%

Org Synth (1963) Col.1 Vol 4 727 Org React (1960) 11 189

434

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

1 Mg

PrBr

THF

+

SECTION 377

PrCH2CH=CHCH=CH2

2 CH2=CHCH=CHCH2Br

Bull SOC Chim Fr (1964) 2485

Me

J

CH~=CHCH~PO:~ N I Me BuLi

THF

CHCH=CH2 t

2 H20

JOC (1969)

3 110-120"

2 3053

1 B r 2 CH2C12 2 LiCl HMPA

Li2CO3 JACS (1972) 2 2155

Org Synth (1973) Coll Vol 5 285

1 NBS b e n r o y l p e r o x i d e

+

CC14 2 t-BuOK

CECCH20THP

THF

59%

LiA,H4 THF

CHCH=CH2 52%

Acta

Mee , b e H

>

Me

Me

94 7118

JACS (1972)

Chem Scand (1972) 26 2540

Na2N203 HC1

H20

H JACS (1966)

MeCH=CHCH=CHMe

cis

88 1335

trans 2858

OLEFIN

SECTION 377

0 c H 2 N E l e 2 1 Me1 hexane+

- OLEFIN t

435

-

-

O - [ P Z N M e 3 OH

180'

2 Ag20 H20 J O C (1972)

*

1 TsNHNH2

2 MeLi

Et20 C&

-3

2 2201

90 4762

OAc I

Bu20 Ac 0

PhCH=CHBr

<40%

T e t r Lett (1973) 447

1 Mg THF

2

57%

80%

JACS (1968)

FH3

(JCH*

PhCH=CHCH=CHPh

soc12

Mg; CuCl

J O C (1972)

2 3749

Angew (1967) ( I n t e r n a t Ed

2 101 5 85)

K4[Niz(CN)6] T e t r Lett (1970) 4567

82%

Reviews: Reductions by Metal-Ammonia Solutions and Related Reagents Advances in Org Chem (1972) S 1

A Comparison of Methods Using Lithium/Amine and Birch Reduction Systems

S y n t h e s i s (1972) 391

436

COMPENDIUM OF ORGANIC SYNTHETIC METHODS VOL 2

aC
P

p"

Na NH3 EtOH

i -Pr

i -Pr

Aust J Chem (1955)

Electrolytic reduction

CH2=CHCH2Br

1 Mg

SECTION 377

Et2O

2 BrCH2THOEt

J O C (1969)

34 3970

S

512

CH2=CHCHzCH=CH2

< 59%

Br

3 Zn ZnC12 BuOH

Org Synth (1963) Coll Vol 4 748

CH~=CHOBU

80-90% Tetr Lett (1971) 2127

CHz=CHCHzBr

1 PhSCHzCH'CH2

BuLi

THF

* CH2=CHCH2CH$H=CH2 1,4-diazabicyclo[2,2,2]octane 2 Li EtNH2 Tetr Lett (1968) 5629

Ye (MeO)jCHCH$H2C=CHCH2Cl

Me I CH2=CCH2MgCl

THF HMPA

(1969) 3707

Ye

Me

(Me0)2CHCH2CH2C=CHCH2CH$=CH2 Tetr Lett (1969) Org Synth (1955) Bull SOC Chim Fr Tetr Lett (1972)

Me0 ( CH2)40Me

1393

Coll Vol 3 121 (1964) 2485 1471

CH2=CH(CH2)2CH=CH2

JOC (1971)

36

1838

<53%

SECTION 377

OLEFIN

- OLEFIN

437

fie

JACS (1968)

Et

1

B2Hg THF

2

NaOH H20

90 209

Et Synthesis (1971) 229

PrCX( CH2)4CZCCONHBu-i

I( CH2)4Br --+

Hp Pd-CaC03 EtOAc

CH2=CH( CH2)4MgBr

PrCH=CH( CH2)4CH=CHCONHBu-i JCS (1950) 115

CHz=CHBr

FeC13 THF

CHz=CH( CH2)4CH=CH2

Synthesis (1971) 303

-31%

CHz=CH(CH2)8COONa

Electrolysis

MeOH

Synthesis (1972) 134

CHz=CH( CH2) 16CH=CH2 JCS (1953) 2393