ANNUAL REPORTS ON
NMR SPECTROSCOPY
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ANNUAL REPORTS ON
NMR SPECTROSCOPY Edited by G . A. WEBB Department of Chemistry, University of Surrey, Guildford, Surrey, England
VOLUME 30
ACADEMIC PRESS Harcourt Brace & Company, Publishers London
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LIST OF CONTRIBUTORS
J. D. Augspurger, Department of Chemistry, Cornell University, Ithaca, New York 14853, USA.
P. J. Barrie, Department of Chemistry, University College London, 20 Gordon Street, London W C l H OAJ, UK.
M. BudCSinsky , Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, 166 10 Prague 6, Czech Republic. C. E. Dykstra, Department of Chemistry, Indiana University - Purdue University Indianapolis, 402 North Blackford Street, Indianapolis, Indiana 46202, USA.
K. Kamienska-Trela, Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44, Warsaw 01-224, Poland. D. Saman, Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, 166 10 Prague 6, Czech Republic. K. Takegoshi, Department of Chemistry, Faculty of Science, Kyoto University, Kyoto 606, Japan.
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There are no lacunae in molecular science as far as the fecund applications of NMR spectroscopy are concerned. NMR is now generally accepted as an exoteric technique by scientists from a broad variety of backgrounds; this is a trend which shows little sign of abating. Volume 30 of Annual Reports on N M R Spectroscopy consists of reviews which serve to exemplify this viewpoint. It is a pleasure to be able to present in the present volume accounts on Calculation and Prediction of Structural N M R Shifts in Respiratory Proteins by Professors J. D . Augspurger and C. E . Dykstra, N M R Applications to Porous Solids by D r P. J. Barrie, Miscibility, Morphology and Molecular Motion in Polymer Blends by Professor K. Takegoshi, One-Bond 13C--13C Spin-Spin Coupling Constants by D r K. Kamienska-Trela and 13C N M R Spectra of Sesquiterpene Lactones by Drs M. Bud5Sinskq and D . Saman. The variety of science covered in these reviews helps to demonstrate the widespread importance of NMR spectroscopy. Finally, I am very happy to express my gratitude to the production staff at Academic Press (London) for their unstinting assistance in the production of this volume.
University of Surrey Guildford, Surrey England
G. A. WEBB
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Contents List of Contributors . . . . . . . . . . . . . Preface
.
. . . . . . . . . . . . . . . .
...
111
. v
Calculation and Prediction of Structural NMR Shifts in Respiratory Proteins J . D . AUGSPURGER and C . E . DYKSTRA 1. 2. 3. 4. 5.
Introduction . . . . . . . . . . . Theoretical Approach to NMR Parameters . Shielding Dependence on Protein Structure . Long-range Effects on NMR Parameters . . Property Correlations in Respiratory Proteins Acknowledgement . . . . . . . . . References . . . . . . . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
. . . . . . .
1 4 18 21 30 33 33
NMR Applications to Porous Solids P . J . BARRIE 1. 2. 3. 4. 5.
Introduction . . . . . . . . . . . . . NMR studies of microporous materials . . . . . NMR studies of mesoporous materials . . . . . '*'Xe NMR studies of porous materials . . . . . NMR studies of molecular transport in porous solids Acknowledgement . . . . . . . . . . . References . . . . . . . . . . . . . .
. . . . . 37 . . . . . 38
. . . . .
. . . . .
. . . . .
. . . . .
. . . . .
66 75 81 85 85
Miscibility. Morphology and Molecular Motion in Polymer Blends K . TAKEGOSHI 1. 2. 3. 4.
Introduction . Miscibility . . Polymer-polymer Morphology .
. . . . . . . . . . . . . . . . . 97 . . . . . . . . . . . . . . . . . 101 interaction . . . . . . . . . . . . . 110 . . . . . . . . . . . . . . . . . 115
5 . Molecular motion . Note added in proof Acknowledgement References . . .
1. 2. 3. 4.
5. 6. 7.
8. 9. 10. 11. 12. 13.
. . . . . . . . . . . . . . . . 122 . . . . . . . . . . . . . . . 126 . . . . . . . . . . . . . . . . 126 . . . . . . . . . . . . . . . . 126
One-bond 13C-13C Spin-Spin Coupling Constants K . KAMIENSKA-TRELA Introduction . . . . . . . . . . . . . . . . Theoretical considerations . . . . . . . . . . . . Unsubstituted hydrocarbons . . . . . . . . . . . Substituent effects on one-bond CC spin-spin couplings across single, double and triple bonds . . . . . . . . . One-bond CC spin-spin coupling constants in derivatives of benzene . . . . . . . . . . . . . . . . . . . One-bond CC coupling constants in heteroaromatic systems . One-bond CC couplings in substituted aliphatic cyclic and heterocyclic systems . . . . . . . . . . . . . The lone pair effect . . . . . . . . . . . . . One-bond CC couplings in structural studies of complexes . One-bond CC couplings in charged molecules and some related compounds . . . . . . . . . . . . . . One-bond CC couplings in biological studies . . . . . . Experimental methods . . . . . . . . . . . . . Application of the INADEQUATE method in structural . . . . . . . . . . . . . . . . elucidations Note added in proof . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . .
. . 131 . . 132 . . 140 .
. 144
. 153 . . 157
. . 161 . . 180 .
. 186
. . 196 . . 200 . . 212
. . 216 . . 219 . . 222
Carbon-13 NMR Spectra of Sesquiterpene Lactones M . BUDESINSKY and D . SAMAN 1. 2. 3. 4.
Introduction . . . . . . . . Structure classification . . . . . Methods of structure determination . Carbon-13 NMR spectra . . . . References . . . . . . . . .
. . . . . . . . . . . . . . . .
. . . .
232 232 235 242 456
Index . . . . . . . . . . . . . . . . . . . . . 477 Cumulative Indexes for Authors and Subjects. Volumes 21-30 . . . 485
Calculation and Prediction of Structural NMR Shifts in Respiratory Proteins J. D. AUGSPURGER* and C. E. DYKSTRAT *Department of Chemistry, Cornell University, Ithaca, New York 14853, USA ?Department of Chemistry, Indiana University-Purdue University Indianapolis, 402 North Blackford Street, Indianapolis, Indiana 46202, USA 1 4 4 7 9 10 18 18 19 19 21 21 26 29 30 33 33
1. Introduction 2. Theoretical approach to NMR parameters 2.1. Energy derivatives 2.2. Magnetic property operators 2.3. Choice of gauge 2.4. A b initio approaches and basis sets 3. Shielding dependence on protein structure 3.1. Variation with torsions 3.2. Variation with bond lengths 3.3. Dynamical variation 4. Long-range effects on NMR parameters 4.1. Chemical shielding 4.2. Nuclear quadrupole coupling 4.3. Spin-spin coupling 5. Property correlations in respiratory proteins Acknowledgement References
1. INTRODUCTION In the past decade, NMR has become a significant tool in the determination of three-dimensional protein structures, driven mainly by the advances in multi-dimensional NMR techniques.' These techniques exploit the nuclear Overhauser effect (NOE) to extract distances between particular nuclei.* These distances can then be used as constraints in conjunction with energy minimization to determine native protein structure in solution (e.g. refer-
ence 3). The ability to relate specific chemical shifts t o molecular structure was one focus of a recent NATO Advanced Research W o r k ~ h o p .This ~ capability ANNUAL REPORTS ON NMR SPECTROSCOPY VOLUME 30 ISBN 0-12-505330-4
Copyright 01995 Academic Press Limited AN rights of reproduction in any form reserved
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J. D . AUGSPURGER AND C. E. DYKSTRA
could provide information that would significantly expand the structural information which can be extracted from NMR data. This review surveys efforts toward that goal, and describes the current state of the art in calculating chemical shifts in macromolecules. Definition of terms is a proper place to begin. The chemical shielding, (T, is formally the second derivative of the molecular eigenenergy with respect to an applied, uniform magnetic field and the size of the nuclear magnetic moment. Its absolute value is not usually measured. Instead, the chemical shift, 6, is the measured shielding referenced to a particular shielding standard. For half a century, the sensitivity of the shielding and the shift to the type of chemical bonding at a given nucleus has been used extensively. There is also sensitivity to the entire molecular environment that comes about in other ways. For proteins, we shall refer to one of those ways as a “structural shift”, meaning the difference between the chemical shift of a particular nucleus in a folded (native) protein and the chemical shift of the same nucleus in the unfolded (denatured) protein. The latter is the random coil protein structure: (1) Random coil refers to a flexible, extended state of the protein where essentially all values of local conformational angles, $C and $, are sampled (i.e. averaged over). Thus, these properties are solely dependent on the primary structure of tne protein. For example, any amide proton of a leucine residue in a random coil protein would be expected to have nearly the same chemical shift. The random coil shifts of the protons of all 20 naturally occurring amino acids have been reported by Wuthrich and coworker^.^,^ Various approaches have been taken to calculate structural shifts in macromolecules. Early work in this area concerned predicting the contribution of ring currents to chemical shifts in nucleic acids.’ The theory of ring current contributions to chemical shifts and its application has been reviewed by Haigh and Mallion.8 Subsequent work included the contribution due to the magnetic anisotropy of the peptide carbonyl group.’ Buckingham first described the direct effect of electrical polarization on chemical shifts,” and this contribution was included in the description of structural shifts. The work on nucleic acids was reviewed extensively by Giessner-Prettre and Pullman in 1987.l2 Similar approaches have been less frequently applied to peptides and proteins: Sternlicht and Wilson13 included the effects of ring currents and electrical polarization in analysing the structural shifts in lyzosyme. Asakura er al. examined the changes in the chemical shifts of poly-L-alanine due to the helix to coil transition, concluding that changes from solvent effects are more significant than those due to conformation. l4 Perkins and Wuthrich compared the calculated ring current shifts to the sstruct
=
sobserved
- 6random
coil
STRUCTURAL NMR SHIFTS IN RESPIRATORY PROTEINS
3
experimentally observed structural shifts for bovine pancreatic trypsin inhibitor (BPTI)." They found that the ring currents were the dominant influence on the structural shifts for the peripheral side chain protons, but were not dominant for the backbone protons (amide and Ca>. Hoch et ~ 1 . ' ~ used molecular dynamics (MD) simulations to study dynamical influences on the ring current shifts in BPTI, and found that the fluctuations were sometimes large, up to +6ppm. However, the time averaged values were close to those of the averaged structure. Clayden and Williams17 attempted unsuccessfully to explain the experimentally observed geminal a-CH2 inequivalence via magnetic anisotropy and electrical polarization. More recently, work has been focused on finding empirical relations for experimentally observed chemical shifts in proteins of known structure. To date, the chemical shifts of about 120 proteins have been completely identified. '' There have been several reports concerned with cataloguing these data, and seeking empirical correlations. 19-*' Wagner et ~ 1 . ~reported " correlations between the structural shifts of the amide (NH) and C" protons and the inverse third power of the distance between the proton and the nearest carbonyl oxygen. Strong correlation has been reported between secondary structure and the structural shifts: upfield shifts of about 0.35 ppm in helices and downfield shifts of about 0.38 ppm for NH and C" proton^.^^-^^ Williamson and AsakuraZ5 empirically fit the C" proton chemical shifts of nine proteins with well-defined structures using a 10 parameter model based on astruct = aring current
+ arnagnetic anisotropy + aelectric
(2)
Osapay and Case26 catalogued the proton shifts of 17 proteins, whose structures had been identified via X-ray crystallography. They sought to fit the data empirically, adding a term to equation (2) to include solvent effects. They found that ring current effects alone do not represent the structural shifts accurately for C" protons, but that using the additional terms in equation (2) resulted in correlation coefficients of 0.85 or better for all except the NH protons. Wishart et a1.27have carried out the most extensive cataloguing of peptide and protein chemical shifts, collecting the shifts from 78 peptides and proteins, including 4888 NH, 5134 C", and 13 933 side chain proton resonances. In their analysis, besides the previously observed upfield/ downfield correlations with helix/sheet structures, they also observed that NH protons near the N-terminal end of the helix are shifted downfield relative to those near the C-terminal end. Spera and Bax" have observed similar types of correlations for 13C resonances from a database of 442 shifts. C" I3C nuclei are shifted upfield in helices and downfield in beta sheets, while Cp carbons exhibit the opposite
4
J. D. AUGSPURGER AND C. E. DYKSTRA
trend. The shifts of each group vary by about 6-8 ppm, compared to ranges of 1-2 ppm for protons. Oldfield et pioneered 170NMR in proteins, observing essentially linear correlations between 13C and 170 chemical shifts and vco IR frequencies in carbonmonoxyheme proteins. A molecular model based on intermolecular electrical polarization was shown by Augspurger et ~ 1 to . produce semiquantitative agreement with the observed correlations. Further, the range of structural shifts of various nuclei were shown to correlate with representative values of the shielding polarizabilities of the nuclei, indicating the contribution of polarization is likely to dominate for nuclei other than protons.32 19Fshifts, for instance, in "F-tryptophan labelled hen egg-white lysozyme were reproduced quite a c ~ u r a t e l y . ~ ~ As Oldfield has done,33 one of the simplest steps in analysing structural shifts is to regard them as arising from long- and short-range effects: ~
1
.
~
~
3
~
"
= @short + @long (3) then represents that part of the chemical shielding due to the local electron density at the nucleus as dictated by local structure (c$,I,!J). represents the long-range or interresidue interactions of the protein, as well as solvent interactions. Oldfield and coworkers have used ab initio calculations on representative molecular fragments to obtain @short and have incorporated long-range electrical effects by including corresponding point charges for the other atoms in the protein, including dynamical effects, through molecular dynamics (MD) sir nu la ti on^.^^-^^ @
@short
2. THEORETICAL APPROACH TO NMR PARAMETERS
Theoretical methods have been developed and have been available for over 20 years for the direct calculation of the chemical shielding tensor. For the most part, ab initio methods for such calculation have been limited to molecules that are quite small relative to proteins. However, this technology is advancing, and it is likely that many useful applications for protein structure will be developed in the years ahead. 2.1. Energy derivatives
From the standpoint of the quantum mechanical electronic structure of a molecule, the NMR chemical shielding is simply one of many intrinsic properties, each defined as a specific derivative of the molecular electronic energy. Energy derivatives may be calculated in several ways. One way is by taking finite differences. Since the energy is to be differentiated with respect to some parameter embedded in the Hamiltonian, then a set of calculations can be carried out to find the energy for various choices of the parameter's
~
~
STRUCTURAL NMR SHIFTS IN RESPIRATORY PROTEINS
5
value. If two such calculations are done, an approximate value of the first derivative is the difference in two energies divided by the difference in the parameter's values. The two possible difficulties in a finite difference procedure both have to do with the size of the parameter value increment. It may be so small that the energy difference in the numerator is of the size of the numerical accuracy of the energy values, and so the derivative value would not be reliable. Or, the parameter increment may be so large that the energy difference between two points is contaminated by higher derivatives. Both these potential difficulties are controllable and d o not have to interfere with the quality of the results, but considerable effort may have to be invested to be sure that the final results are, in fact, free of such numerical inaccuracies. A second way of obtaining first derivative properties is through computing an expectation value. A dipole moment, for instance, may be calculated by integrating the system's probability density function with the dipole moment operator. That result will be equivalent to the derivative of the energy if the wavefunction obeys the Hellmann-Feynman t h e ~ r e m ~ ' .or, ~ ' in general, if the wavefunction is completely variationally determined. Another means of obtaining properties is by analytical differentiation, the underlying idea being rigorous differentiation and subsequent solution of the Schrodinger equation. Differentiation is with respect to parameters embedded in the Hamiltonian. Within the Born-Oppenheimer approximation, for instance, the nuclear positions are parameters. Parameters may also correspond to some perturbation, and so field strength will be a parameter for any property that is defined as a derivative with respect to the field. Thus, the Hamiltonian will depend on the choice of parameters; that is, H = H ( a , b , c , . . .). At this point, we will take all Hamiltonian parameters to be independent. A specific choice of the parameters implies a specific Schrodinger equation. It is convenient to refer to some reference choice or zeroth order choice of the parameters and, in this discussion, that reference specification will be all parameters at zero. A zero subscript (e.g. a. or Ho) will refer to invoking this specification. Thus, from the general time-independent Schrodinger equation ( H - E)+ = 0, there comes a specific equation for solution (H" - E"M0 = 0
(4)
The task of differentiating the Schrodinger equation begins with formal differentiation of the Hamiltonian and then setting parameters to their reference value. Derivatives of the energy at the reference parameter choice are properties. The derivatives with respect to some parameter a of the Hamiltonian operator and of the wavefunction will be designated with superscripts:
6
J. D. AUGSPURGER AND C. E. DYKSTRA
First order differentiation of the Schrodinger equation yields a simple expression:
Ha$+ H$"
=
Ea++ E$"
(6)
With the reference choice of parameters, this becomes
H; *o+Ho
G = -% *o+Eo G
(7)
Solving this expression requires the zero order Schrodinger equation solutions, and this is analogous to perturbation theory. Indeed, the general procedure differs from perturbation theory in only one minor way. A perturbation expansion is in terms of the powers of the parameters, whereas the derivative expansion is a Taylor series expansion that has each nth power series term divided by n ! relative to the perturbation expansion. Equation (7) may be rearranged as
E: *o
=
(Ho - Eo)
+ H: *o
*?I
(8)
Integration with the zero order wavefunction yields an expression for the first derivative of the energy: E?l = ( *o I Ho - Eo I *o) + (*o I H : I *o)
(9)
If the zero order wavefunction is variational, then the first term in equation (9) is identically zero, and then the first derivative is simply an expectation value of the derivative Hamiltonian. This is one expression of the Hellmann-Feynman theorem. Rearrangement of equation (6) to collect terms involving the unknown derivative function yields the following: ( H - E)@
=
- ( H a - E")+
(10)
All higher derivative equations can be put into this same form, ( H -E)$" = X , where X is some function of wavefunctions and energies of derivative order less than a. Solving this type of equation is not significantly more complicated than solving the zero order Schrodinger equation, and the generality in form means that solutions can be found order-by-order to any level. Likewise, higher order derivatives of the energy are obtained, and this can be carried out for differentiation with respect to one or many parameters. As in perturbation theory, there is a "2n + 1 rule" applicable in electronic structure3w1, and it means that from the nth order wavefunctions, energy derivatives of order up to 2n + 1 may be evaluated. The derivative wavefunctions between n and 2n + 1 orders are not required explicitly. For example, with the first derivative wavefunctions known explicitly, the third energy derivatives may be evaluated immediately.
STRUCTURAL NMR SHIFTS IN RESPIRATORY PROTEINS
7
2.2. Magnetic property operators To carry out an ab initio calculation of an energy derivative (property), we require derivative operators, e.g. H". For NMR shieldings, the interaction term in the molecular Hamiltonian arises from the external field and the nuclear magnetic dipole. The strength of the field and the strength of the magnetic dipole are the parameters, and differentiation is carried out with respect to these. We may also be interested in the change in the shielding with respect to another influence, perhaps an electric field. Electric field strength is then also a parameter. The Hamiltonian for a molecule experiencing an external magnetic field depends on the vector potential, A, of that magnetic field: .
2rn
V is the usual potential energy operator in the molecular Hamiltonian and pi is the vector momentum operator for electron i, rn is the mass of an electron, e is the electron charge and c is the speed of light. Notice that whereas the Hamiltonian explicitly depends on the vector potential, A, not the magnetic field, B, the chemical shielding (T is a derivative with respect to B , not A. This problem can be surmounted in two ways. One way is for the Hamiltonian to be rewritten to depend explicitly on B, by writing A in terms of B. For a uniform magnetic field, this is accomplished by 1 A = -BXr 2
(12)
where r is the position vector. The other way is for the derivatives with respect to B to be written in terms of derivatives with respect to A.42 While this second approach is more general, the first is normally followed. The magnetic field of the nuclear magnetic dipole, for which the vector potential is
(where rN is the nuclear position vector), must be added to that of the external magnetic field, and the sum substituted into equation (11). The necessary derivative operators for calculating (T are
ifie 2rnc
- -(r x
V),
8
J . D. AUGSPURGER AND C. E. DYKSTRA
and
Note that these relationships hold for the Coulomb gauge, i.e. where V * A = 0. If a further perturbation by an external electric field or field gradient is included, the perturbing Hamiltonian will include field and field gradient terms, and these may be collected into a dot product: Helec =
M .V
Here, M is a vector composed of the electrical moment operators of the molecule, and V is a vector composed of derivatives of the external electrical potential (evaluated at the same centre as the molecule's electrical moments). The derivative of the Hamiltonian with respect to a particular electric field component is just the corresponding molecular moment operator. For instance, the derivative Hamiltonian operator with respect to the x-component of the gradient of the potential (the negative of the electric field in the x-direction) is the x-component of the dipole moment. To carry out a calculation of the molecular wavefunction, energy and properties where the wavefunction is represented by a linear combination of atomic orbitals, the matrix representation of the Hamiltonian and its
Table 1. Classification of (equation algorithm."
(18)) operators for general construction
Operator type or kind
Ikl
1'1
(1'4
Iml
Basis function overlap operator Kinetic energy operator Nuclear attraction Electric field, gradients Electrical potential interaction (multipole moments); magnetic field interaction (second order part) Magnetic field interaction (first order part)' Dipolar magnetic field interaction (first part)
0 0 0
0 0 0
0 2 0
0 20
>0 0
Without Without With With Without
0 0
0 0 0 0 30
20
0
Without
1
0
0
1
With
1
0
"/PI
In1
is the sum of the three integers in the set (px, p,., p z } ; (p represents k , I, rn or n). "This is for the coulomb gauge, where V . A = 0. Otherwise, another term is required where / k / = 0 and l n / 3 0 .
STRUCTURAL NMR SHIFTS IN RESPIRATORY PROTEINS
9
derivatives in the atomic orbital basis are required as input. A general approach for calculating all such one-electron integrals has been presented.43 This algorithm, implemented in the program MAGOPS,& calculates the matrix representation of the operator
where specification of any particular operator is made by specification of the superscript integers, represented in vector notation by (k,l,m,n). Table 1 presents several operators specified in this manner. A uniform approach for computing matrix representations of this operator, without limit as to types of Gaussian basis functions ( . ~ , p , d , f., . .) or the choice of the (k,l,m,n) integers has been implemented and is in use.43
2.3. Choice of gauge
Any vector Y for which V X Y = 0 may be added to the vector potential A without changing the magnetic field B. Of course, any such change in the vector potential must leave the magnetic field response properties unaffected. This arbitrariness in the vector potential is an arbitrariness in the choice of the gauge. Because of the basis set truncation in an ab initio calculation with conventional orbital functions, magnetic properties are not strictly invariant to the choice of this gauge. This is particularly problematic for small basis sets. D i t ~ h f i e l destablished ~~,~~ the use of orbitals that were dependent on A in such a way that the final results were independent of the choice of the gauge. These have been designated as gauge-invariant atomic orbitals (GIAO), though it is not the atomic orbitals that are invariant but the magnetic properties. Ditchfield has pointed out that “gauge-dependent’’ is a better way of describing these orbitals,47 and it has become customary to take GIAO to mean “gauge-including atomic orbital^".^^ GIAOs are constructed from conventional, atom-centred basis functions by choosing a coordinate system origin for the species under study and incorporating an origin-dependent function. Let %, be the position vector from that origin to the a-nucleus. For a uniform magnetic field, B, a G I A O basis function, $(r), at the centre a may be defined in terms of a conventional Gaussian function centred on the a nucleus, X(r):
4(r) = X(r) exp( - i B X R, r/2)
(19)
10
J. D. AUGSPURGER AND C. E. DYKSTRA
The GIAOs have a complex exponential dependence on the part of the vector potential arising from the external uniform magnetic field, and one may substitute A,,,
1 2
= -BX
R,
(20)
for the direct product in equation (20). The form of GIAOs leads to oneand two-electron integrals that are dependent on the external magnetic field. The one-electron current density associated with a wavefunction $ is defined49as j(r) =
1 L1
($*V$- $V$*) - A$*$/c
and should be gauge invariant and conserved. Epstein” has shown that use of GIAOs does not ensure current conservation because the GIAO wavefunction is not invariant to a gauge transformation. The gauge invariance is termed an “enforced” invariance because the gauge dependence of the GIAOs amounts to changing the basis to follow a gauge change, “or equivalently, by always returning to the original gauge to do the c a l c ~ l a t i o n ” .The ~ ~ GIAOs may be thought of as providing basis set flexibility that would be found only in larger conventional sets. The usefulness of GIAOs is something mainly demonstrated by calculational results.
2.4. Ab initio approaches and basis sets The primary distinction among ab initio approaches is whether they include or do not include correlation effects. The majority of calculational results available now are at the self-consistent field or SCF (uncorrelated) level. Fortunately, SCF appears to be well suited in many (not all) of the shielding problems of light elements in covalently bonded molecules. A second distinction among methods is whether the shieldings are obtained analytically or by finite fields. Mostly, this difference has implications on the cost of the computation more than on the results. A further distinction is the treatment of gauge dependence. Table 2 lists the identifiers now in use for ab initio approaches along with information on the type of calculation. The earliest work on methods for calculating derivatives of the SCF energy was based on perturbative approaches, which became known as “coupled-perturbed Hartree-Fock” (CPHF) .67-69 Gerratt and Mills7’ generalized the formulation of Stevens et ~ 1so that . ~ derivatives ~ with respect to basis-dependent parameters could be obtained with CPHF. This advance
STRUCTURAL NMR SHIFTS IN RESPIRATORY PROTEINS
11
Table 2. Designations for various ab initio methods/programs for calculating
chemical shifts and related properties. Designation
Wavefunction
DHF IGLO LORG DOGON TEXAS90 SOPPA SOLO GIAO-MP2
SCF SCFIMCSCF SCF RPA SCF MP2 MP2 MP2 MP2
-
Gauge treatment CommodGIAO Separate origin for each MO Local origin Local origin GIAO basis Common origin Same as LORG GIAO basis Common origin
Reference 41, 51 52-54 55, 56 57-59 60 61 62, 63 64,65 66
made possible Ditchfield’s use of G I A O to calculate chemical shieldings via CPHF.45“7 Kutzelnigg and ~ o - w o r k e r s ~have ~ - ~significantly ~ generalized the use of gauge-dependent orbitals for the calculation of NMR parameters. Instead of a common origin for & in equation (20), they use the centroid of charge of each different occupied, localized orbital, applying the same type of exponential involving the vector potential, but to the molecular orbitals. That is, the gauge is independent for each localized orbital (IGLO). Though additional terms must be computed, only conventional two-electron integrals involving the original basis functions are required. Applications of the IGLO method have already been reviewed.71 Hansen and B ~ u r n a n ’ ~have .~~ applied a conceptually similar local orbitalAoca1 origin (LORG) approach to the random phase approximation. Lazzeretti and ~ o - w o r k e r s ~have ~-~~ likewise introduced a multiple-origin gauge method, this one based on computing susceptibilities from nuclear electric shieldings which they term “distributed origin gauge with origin at the nuclei (DOGON)”.59Pulay and co-workers have recently reported a new, highly efficient implementation of the GIAO approach to calculate chemical shieldings, which takes advantage of certain recent advances in ab initio technology.@ The efficiency of this program, TEXAS90, makes possible calculations on larger systems, such as benzylideneaniline and retinylideneb~tylimime.~~ All of these approaches involve analytically solving the first order CPHF equations to calculate the chemical shielding. Via the CPHF equations,
where D is the one-electron density matrix and h is the matrix representation of the one-electron part of the Hamiltonian and its derivatives. Dykstra and J a ~ i e n , ~following ’ the derivative formalism of Section 2.1, devised a
12
J. D . AUGSPURGER AND C. E. DYKSTRA
procedure for solving derivative Hartree-Fock equations uniformly to all orders of differentiation. This approach is identified simply as derivative Hartree-Fock (DHF) theory. It was initially implemented to calculate non-magnetic properties, but has been extended to handle complex operators and thereby obtain magnetic proper tie^.^^ This method, by virtue of its generality, can yield not only electrical and magnetic properties, but mixed electro-magnetic properties. This capability has been exploited to calculate the direct influence on chemical shifts of external electrical perturbation^.^"^^'^^^^ These properties have been termed shielding polarizabilities because they measure the induced chemical shielding due to an external electrical influence:
DHF has also been used to explore how nuclear quadrupole coupling constants are influenced electr~statically.~~ Accurate calculation of molecular properties requires careful selection of the appropriate basis set. Chesnut’s 1989 review dealt with this topic e ~ t e n s i v e l y In . ~ ~his review of basis set tests carried out for the various methods described, he reports that the common gauge origin CPHF (or DHF), IGLO and GIAO methods require, respectively, [7s5pld/ 5slp],[5~4pld/3slp],and [4s3pld/2s] basis sets to calculate (T accurately for first row atoms and hydrogen. Second row atoms require even more extensive basis sets.79This assessment, of course, is subject to the limits one chooses for considering a value to be “accurate”. If basis sets were enlarged step-by-step beyond these three specific sizes toward a complete basis limit, gauge dependence in the non-GIAO treatments would necessarily diminish. Eventually, the basis requirements for the different treatments would be similar. So, the choice of gauge-including versus gauge-independent bases is a practical one: clearly, if a small basis is to be used, it is better that it be gauge-including. However, for limiting case studies (extended basis sets), there is a sizeable additional computational cost associated with the gauge-including bases that may shift the practical choice the other way. Apparent advantages of using gauge-including bases may be partly offset by computational costs. The IGLO method requires the calculation of a number of one-electron operators not required in a standard, fieldindependent basis calculation. Using a GIAO basis adds the further complication of additional derivative two-electron integrals. In effect, by incorporating the gauge into the basis set, differentiation generates derivative basis functions of higher angular momentum, creating a more flexible basis from a smaller one. A recent idea is that of Chesnut who demonstrated the use of “locally dense basis sets”.80The idea is based on (T being primarily dependent on the
STRUCTURAL NMR SHIFTS IN RESPIRATORY PROTEINS
13
local wavefunction, and so a larger, more flexible basis is used for the atom for which IT is to be calculated than for the other atoms in the molecule. It has shown promise in initial tests," and has been applied by Hinton et a1." to a system of 17 water molecules. We have recently carried out extensive basis set tests of not only u,but also the shielding polarizability, for carbon monoxide73 and The gauge sensitivity was also examined as a function of basis. For CO, we calculated these properties using DHF with a number of basis sets, ranging from double zeta to an extended set that was triple zeta, tripIy polarized with diffuse valence functions and a 4f function, while the common gauge origin was varied along the entire length of the molecular axis. These results are shown in Figs 1-3. Following the Kutzelnigg and Schindler result that extra flexibility in the p-functions is important, we compared the standard [5p/2p] and [6p/3p] Dunning c o n t r a c t i ~ nof~ ~the ~ ~Huzinaga ~ primitive basess4 to less contracted sets, [5p/4p] and [6p/5p]. In all cases, these less contracted bases yielded significantly less gauge dependence. We found little difference between [5p/4pJ and [6p/5p]. It is significant that for the 1 7 0 shielding, even unpolarized basis sets give shielding which are quite insensitive to the gauge origin, but which are 100 to 200 ppm lower than the larger basis results. In other words, gauge invariance does not go hand-inhand with basis quality and reliability. In our study of water,74 we examined the sensitivity of the proton isotropic and anisotropic chemical shielding. At the reference equilibrium geometry, the proton isotropic shielding and anisotropy were calculated, first with the gauge origin chosen to be the hydrogen centre and then with it chosen to be the oxygen nucleus. Comparison of the two largest basis results (Fig. 1) with the oxygen nucleus as the gauge centre shows a difference in isotropic shielding of 0.02ppm and a difference in the anisotropy of -0.05 ppm, demonstrating basis set convergence. Next, for the largest basis, we see that there is only 0.43 pprn difference between choosing the oxygen atom to be the gauge centre versus the hydrogen (30.86 with the gauge origin at the hydrogen versus 30.43 ppm for the gauge origin at the oxygen). A similar difference of 0.61 pprn is obtained for the anisotropy, and to this extent, gauge invariance has been achieved. Comparison of GI A O results shows the success of that approach, since a 6-311G basis gives very nearly the same result as our largest basis [10~7p5d3f/6~6p3d] result for the isotropic shielding. However, for the anisotropy, G I A O calculations show a lingering basis set dependence that matches our oxygen gauge origin calculations. In other words, the anisotropy is more demanding of basis set quality than the isotropic shielding, independent of gauge considerations. Likewise, the use of the less contracted oxygen p function set shows significant improvement in reducing the gauge dependence of the isotropic shielding, but not the anisotropy. It is interesting to see that choosing the gauge centre at the oxygen yields
14
J . D. AUGSPURGER AND C. E. DYKSTRA
the best agreement between small and large basis set results. This is not surprising in view of the successes of the IGLO In IGLO calculations, molecular orbitals are localized and a gauge origin for each orbital is placed at the orbital’s centroid of charge. In water, the centroid of the total electronic charge is very near the oxygen atom, and so the common origin calculations we have performed with oxygen as the gauge centre almost amount to invoking the ideas of IGLO. (For molecules with more than one heavy centre, this correspondence of approaches does not exist.) So, with the oxygen centre as the gauge origin, even the relatively small DZP basis gives an isotropic shielding and anisotropy which is within 1ppm of the Basis I11 result. It appears that a [7s7p4d/4s3p] basis is sufficiently flexible to achieve results within 0.5 pprn of the basis set limit with the gauge origin at the oxygen centre. While most calculations of chemical shielding have been at the SCF level, recently several methods have been reported for incorporating electron correlation. As the diamagnetic contribution is merely an expectation value, it can readily be calculated for any method of incorporating correlation. The complication arises from the paramagnetic term, which requires the first order response of the correlated wavefunction to the external magnetic field. Oddershede and Geertsen included correlation by using the polarization propagator approach to calculate chemical shieldings.61 They called this approach SOPPA (second order polarization propagator approximation). Bouman and H a n ~ e n ~utilized * > ~ ~ a similar approach to include correlation within their LORG algorithm, which was designated SOLO (second order LORG). They have used it to examine correlation effects in 31P shifts for a number of small molecules,62 and have looked at several six-member heteroatom ring systems, and benzene.63 They find that the isotropic shift is consistently greater with inclusion of correlation, up to 50 pprn for ”N and 10 ppm for I3C. Conversely, the anisotropy is consistently less. Gauss has developed a method for calculating chemical shieldings by analytical differentiation of the MP2 energy, using GIAO bases. The method is designated GIAO-MP2,64,65and it has been included in the ACES11 suite of a6 initio programs.*’ Cybulski and Bishop have also implemented analytical differentiation of the MP2 energy to calculate magnetic properties,66 using a relaxed density formalism.
Fig. 1. The proton (a) isotropic shielding (5= 1/3[c, + ayy+ a,,) and (b) shielding where a33> azz> a l l ) of water plotted as a anisotropy (Au = 1/2[2u33 - azz- all], function of basis set, comparing the choice of gauge origins to be at the proton (0)or at the oxygen nucleus (m). GIAO results are indicated by s. Solid lines indicate the valence basis was a standard D Z or TZ set, whereas broken lines indicate the less contracted sets, e.g. DZ’ and TZ’. The 4-31G basis result is from ref. 85, and the other GIAO results are unpublished results of deDios and Oldfield.86
I
STRUCTURAL NMR SHIFTS IN RESPIRATORY PROTEINS
90 80 70
60
50 40 30
45
15
16
J . D. AUGSPURGER A N D C. E. DYKSTRA
-150 ?
I
cd
-200
W
6 a
a+,
A -250
h
b -300
t
-3501. -0.5 0.0 1
-275
-325 h
I
-
cd
W
.
1
,
0.5
1
.
8
1
.
1.5
1.0
.
I
2.5
2.0
4 7 :
(b)
TZ+3Pi DZP
-375-
2 -4251 TZ
-475
DZ' TZ'
t
DZ
-5251' -0.5 0.0 1
.
8
0.5
.
1
1.0
.
8
1.5
.
8
.
2.0
8
2.5
Gauge Origin (a.u.) Fig. 2. cr\,,,.(ppm) for (a) I3C and (b) "0 as a function of gauge origin along the molecular axis (x-axis) for different basis sets. On the scale of the graph for I3C, the results for the TZP and TZ+3P bases are essentially coincident, as are those of TZ'P, TZ'2P, and TZ'+3P with TZ'+3Pf. For I7O, the DZP basis result is essentially coincident with TZ+3P, as are TZ'2P and TZ'+3P with TZ'+3Pf. The nearly coincident curves are not displayed. Broken lines are used for clarity only. The carbon atom lies at the origin, the centre of mass is at x = 1.218, and the oxygen atom is at x = 2.132.
STRUCTURAL NMR SHIFTS IN RESPIRATORY PROTEINS
17
-
-200 h
I
cd -400 -
v
E a a
-600 -
h
2-800 -1000
t
-12001 -0.5
"
0.0
.
1
'
'
.
I
.
I
.
I
0.5
1.0
1.5
2.0
2.5
0.0
0.5
1.0
1.5
2.0
3600.
c
=I
TZ
3200
r5
-
DZ TZ: DZ
.
DZP
v
E a a h h X
2800
26-
2400
TZP
TZ+3P TZ P DZ'P TZ+3Pf
-
TZ'2P
2000 I
1
-0.5
.
2.5
Gauge Origin (a.u.) Fig. 3. A,,,, (pp,m/a.u.) for (a) 13C and (b) " 0 as a function of gauge origin along the molecular axis (x-axis). For 13C,the DZ' basis result is essentially coincident with TZ', DZ'P results are essentially coincident with TZ'P results, and TZ'2P and TZ'+3P results with TZ'+3Pf results. For "0, the TZ'+3P and TZ'+3Pf bases are essentially coincident. The nearly coincident curves are not displayed. The carbon atom lies at the origin, the centre of mass is at x = 1.218, and the oxygen atom is at x = 2.132.
18
J. D. AUGSPURGER AND C. E. DYKSTRA
The accuracy of calculated chemical shieldings values is such that they are being used as independent checks of three dimensional structure in small to medium sized molecules.88 This level of accuracy was largely based on a study of 21 boranes and carboranes," where IGLO was employed to calculate the chemical shifts using MP2/6-31G* optimized molecular geometries. The standard deviation of the calculated "B chemical shifts versus experimental results was 3.1 ppm for all 21 compounds. However, for two compounds, 1,5-C2B3H5 and 1,2-C2B3H7, the differences were 10 and 8ppm respectively. The chemical shifts of these two compounds have subsequently been studied with the inclusion of electron c o r r e l a t i ~ nThe .~~ boron shifts in these compounds were calculated via the GIAO-MP2 method,64,6sand the differences with experiment were less than 1ppm. 3. SHIELDING DEPENDENCE ON PROTEIN STRUCTURE
Chemical shielding is most strongly dependent on the local electron density, due to the r-3 dependence of the perturbing Hamiltonian operators (see equations (16) and (17)). Small changes in electronic structure are readily manifested in the chemical shielding. These small changes which result from non-covalent interactions, such as electrical perturbation, ring currents and magnetic anisotropy , can be described via classical approaches. These long-range influences will be discussed in the next section. However, variation in the covalent bonding, such as changes in bond lengths and bond angles, must be described quantum mechanically.
3.1. Variation with torsions As it is clearly not possible to carry out rigorous, fully a b initio calculations on proteins, the approach taken must be to carry out calculations on model . recently ~ ~ carried out peptide or peptide-like fragments. deDios et ~ 1 have such a study of the dependence of 13C and "N chemical shifts in model peptides. To model the 13C chemical shifts of C" and C p , they chose terminally blocked alanine. By varying the 4 and CC, backbone angles, they find similar ranges of variation in the 13C shift as seen experimentally.28 They then calculated the C" and C p shifts of this model amino acid for the 12 alanines in staphylococcal nuclease (Snase), using the local structures as determined by X-ray crystallography, obtaining reasonably good agreement with experiment. In further tests, they find that these intra-molecular influences are dominant for C" and C p shifts. They then examined 15N shifts, using an alanine-valine dipeptide as the model fragment. When o-(N) was plotted as a function of the sidechain angle, ,yl, it exhibited a maximum for the
STRUCTURAL NMR SHIFTS IN RESPIRATORY PROTEINS
19
staggered conformationand a minimum for the eclipsed conformation. The shift varied by about 20 ppm over the entire range of xl. Again, reasonably good agreement was found when the amide 15N shifts of valine in Snase were calculated using this model dipeptide. Bartield and co-workers have also looked at the torsion angle dependence of u.91They studied the terminally blocked Gly-Gly dipeptide, mapping out u as a function of the 4 and +b angles. Their results reproduced the experimental trends of C" and C p chemical shifts in helices and sheets. While there are many factors influencing chemical shifts, calculations such as these may be useful in understanding conformationally strained, small peptides.
3.2. Variation with bond lengths Chesnut has carefully reviewed calculations that show the variation in the shielding with bond length.78 The first derivative of the shielding with respect to a geometrical parameter, u',can be readily c a l c ~ l a t e d and ,~~~~~ there have been examinations of basis set effects for small molecules. Using 6-311G* basis for first row and [66 211(s)/6211(p)/ll(d)] for second row atoms, Chesnut has presented the following c o n c l ~ s i o n s : ~ ~ (1) ur is less than zero for stretching a heavy atom-heavy atom bond;
(2)
ur varies
for hydrogen-heavy atom stretches;
(3) u' is mostly due to paramagnetic contributions; (4) for hydrides, u' decreases, then increases going across the periodic table.
An indirect indication of the significance of the dependence of u on bond length is the finding that chemical shieldings calculated from theoretically optimized geometries show better agreement with experiment, than when experimental geometries are used.94 Chesnut and Wright9' carried out calculations of ur and w'' (d2u/dR2)for a large number of small molecules, and found that both are typically less than zero. For multiply bonded atoms, d correlates with u,but not for singly bonded atoms.
3.3. Dynamical variation
Dynamical effects on chemical shieldings become an important theoretical concern once a meaningful level of accuracy has been achieved for the shieldings of static structures. That seems to be the situation of contemporary ab initio methodology, and so there are some exciting attempts to
20
J . D . AUGSPURGER AND C. E. DYKSTRA
incorporate dynamical effects. In spite of the newness of some developments, the problem is an old one. Buckingham outlined the effects of diatomic vibration on NMR shieldings three decades ago.96 Dynamical treatments are mostly of two types, quantum mechanical and classical. The classical treatment is that of molecular dynamics (MD) simulation wherein the forces acting on each atom according to some chosen force field are integrated through small time steps to yield instantaneous velocities and displacements. For sufficiently small time steps, this exactly follows Newtonian laws that give the spatial positions of the atomic particles as a function of time. A time-average of any property can be obtained provided that the property of interest is known for the structure of the system at each of the numerous time steps. Quantum mechanical treatments tend to be limited to smaller systems than MD simulation because of the computational cost. A variety of techniques may be used, but there is a requirement that is in common with that of MD simulations: to obtain an on-average property, a property surface (the dependence of the property value on the structure) must be explicitly or implicitly available. In protein NMR, the important dynamical questions concern protein molecule dynamics and solvent dynamics. The chemical shielding surface information necessary for obtaining average shieldings, quantum mechanically or classically, is mostly the variation due to long-range effects. As discussed in the next section, techniques have been devised to model these effects in a manner that makes possible rapid computation for different structures (i.e. an implicit property surface). Franken97 has carried out a preliminary quantum mechanical study that hints at the nature of dynamical effects in a solvent, water. Using diffusion quantum Monte Carlo (QMC)98-100 implemented for the intermolecular vibrations among rigid molecules, 101,102 a rigorous average of proton shielding in the water dimer has been obtained. The water-water interaction averaged over the ground vibrational state of the isolated water dimer was found to change the proton shielding anisotropy by 3.3 ppm. Oldfield, Warshel and c o - w o r k e r ~have ~ ~ , ~used ~ classical MD simulations to calculate averaged 19Fchemical shifts of the five "F-labelled tryptophan (Trp) residues in galactose binding protein (GBP) from E. c01i.'03 Since fluorine is singly bonded, the short-range (quantum mechanical) changes in the chemical shift will likely be small, and thus, the structural shifts should be closely represented by the average electrical perturbation:
AAVJ +
+A y y V y y ) +
(24) Several simulations were carried out over 20 ps trajectories, using a modified version of the program ENZYMIX.lo4 This program uses a local reaction field approach to calculate the long-range electrostatic force^,"^ and explicitly incorporates electrical polarizability for some atoms. The results b " C t
=
~ X X ( V X J
~22(V22)
STRUCTURAL NMR SHIFTS IN RESPIRATORY PROTEINS
21
showed good agreement for the structural shifts, or relative differences for the five 19Fresonances in GBP. The 19F in TrpZs4,which is the most solvent exposed Trp residue, exhibited the largest fluctuations in Sstruct,indication that solvent interaction may be a dominant influence on chemical shifts. Gregory and Gerig1O6 have also examined the I9F chemical shifts in a "F-labelled fragment of the S-peptide. They used a semi-empirical approach to calculate S from ring current and van der Waals contributions. Their results showed that 6 calculated for static, energy-minimized structures were significantly different from the averaged values of the MD simulations.
4. LONG-RANGE EFFECTS ON NMR PARAMETERS
Long-range effects are those that arise in the absence of real chemical bonding interaction between the perturbing species and the given magnetic centre. They develop because of a change in the local electronic structure at the magnetic centre as a result of the perturbation. This change should be regarded as a very small change, but of course, one of the wonderful aspects of NMR is its unique sensitivity to small electronic structure differences. To understand the long-range effects, let us consider each type of NMR parameter.
4.1. Chemical shielding
There have been a number of recent attempts to rationalize the chemical shifts observed in proteins in structural terms, with most emphasis being placed on analysing 'H shift^.^^-^^ For 'H NMR, moderately good agreement between experimental and predicted chemical shifts based on known structures can be obtained by using random coil shifts, computed ring current effects, magnetic anisotropy, and electrical polarization.26 However, there has been much less progress in interpreting I3C, I5N and "F shifts, which are very much larger. Since ring current and magnetic anisotropy effects will be of the same magnitude, it seems unlikely that they will be as important for heavy nuclei as they are important in 'H NMR. Thus, it appears that the long-range contributions to these large variations in structural shifts for heavy nuclei must originate from electrical perturbation. To quantify the direct influence of electrical polarization on chemical shielding we may begin by formally expanding the chemical shielding as a power series in the electric field, as Buckingham has done:" 1 2
uaP= c & + A E , + - B E ~ + .
..
(25)
Table 3. Representative System
H-H IJ-C84C
8-CF3 H-CN H-CCH H3-CCN H(styrenes) H2S H~CCHZ HhCh H20
HOCH3 H3N
HF IJCl HBr
HI H-N(Uraci1) CH4
CO HzCO HzCCHz H-CCH
A,(ppmla.u. field)" 50.3,' 38.9,' 24.8,'77,' 70,' 50.5,d 49.4' 30,' 48,' 50,' 65' 45.1,'46.3' 50' 54.1' 67.2' 51,' 58' 53' 450," 69.9 64.4g 87.5' 47.3,' 47.3' 430" 27.7,' 26.6 81.5,' 45,' 71.5,' 79.4,d 79.1,'83.9 570,' 680,' 117.9 1100,' 110.71 1571
90" 0.0 374.5,' 376.9,d 393.6' 697.4,' 769.0k 1144.5k 733.9,' 750.7h
A,,A,,,and A,
h) h)
shielding polarizabilities.
Ax,x(ppmla. u. field2)"
A,(pprn/a.
189.7,' 185.89,d 191.26'
5.8'
114.4,b 43.4 234.9' 173.2' 13.6'
2.1' 89.5' 109.5'
190.8,' 39.q 80.4,' 62.9 278.3,' 277.4 329.9,' 325.0,d 269.2,e 314.g
3.5' 18.1' 61.8'
100,' 344.d 469.7' -359.7,' 535.5,' 3874.9,' -434.2k 1106.9,'
-269.6k 448.2,d -286.4' 3955.0k
532.7' 746.0'
1166.2k
351.8'
u.
efg)"
645.0h 422.6,h 428.6k 215.9fi 631.2k -30.0k 222.Ok 2093.7' 50.8' 1051.7,d 777.0' 1910.1,h 1927.0' 902.8* 401.1,' 381.6' 1526.7,' 1561.5,d 1242.4' 7018.9,' 6555.3' 3 195.7g 636.5,' 704,' 605.2," 597.1,d 490.2," 585.5' 551.4: 792," 505.2' 18843 1955.5* 1984.9 -181.5' 534.1' 1149.8'
1502.9,' 1489.6k -41 1.6k -238.4k - 1383.6k 12 991.8' 1613.4' 2761.2,d 1593.6' 11 336.1,h 11 334.0' 4339.3,' 4094.0' 5906.1,' 5937.6,d 1080" 70 843.0.' 47 862.0' 8486.1,h 1930,' 1621," 7760,d 6122,' 7674.8' 10 686.6'
512.1'
333.3h 603.6' 190.8' 1044.0' 1377.8' 741.7' 4319.3'
15 659.6' -5355.6' -11 364.6'
"Units are in ppm/a.u. field, (field)2 or field gradient. The xx-component of the field gradient corresponds to the xx-element of the Cartesian quadrupole moment (Mxx= 112 C,q,xT). The x-axis was generally chosen to be the axis of highest symmetry. The convention for this table is that implicit in equations (25)-(28). 'Reference 41. Tabulated in reference 110. "Reference 111. 'Reference 112. These values include electron correlation at the MP2 level. 'Reference 114. KReference 32. "Reference 113. 'Reference 107. 'Reference 109. 'Reference 115. 'Reference 116. "'Reference 108. N
w
24
J . D . AUGSPURGER AND C. E. DYKSTRA
The coefficient A in equation (25) can be identified as the x component of the dipole shielding polarizability, A,,,,, from equation (23). Likewise, B is the dipole shielding hyperpolarizability , B,,x,,, . Similarly, one can define the effect of a field gradient as the quadrupole shielding polarizability, e.g. A,,,, , analogous to the electrical quadrupole polarizability. These properties are derivatives, and can be obtained by the methods outlined earlier. As these properties are tensors, a somewhat more simplified representation can be found by defining isotropic shielding polarizabilities:
Table 3 shows calculated values of the shielding polarizabilities in the literature. Bishop and Cybulski have recently reported the first shielding polarizability values to include electron correlation. '12 Their results indicate that correlation effects at the MP2 level are larger for heavy atoms than for hydrogen. If the direct influence of electrical fieldsheld gradients is the main long-range contribution to structural shifts, it seems likely that there should be a correlation between the magnitude of the shielding polarizabilities of these heavy atoms, and the range of variation in their structural shifts. That is, as there is likely to be a maximum electric field attainable at any particular nucleus in a protein, the maximum variation in structural shifts should be proportional to this field value times the shielding polarizability of the particular nucleus. In Fig. 4, representative A, values are plotted versus the observed shift ranges for 'H, 13C (aromatic), 13C0, C170 and 1YF 30,103,117-120 These results can be fit to a linear equation, assuming the dominance of the dipole shielding polarizability: A8(ppm) = 0.00578 A,
+ 1.13
(29)
The slope in this equation, AVx = 0.006 a.u. (or -3 x lo7Vcm-'), represents the range of effective fields experienced by the nuclei in question, and it appears to be reasonable value, based upon previous electrostatic calculations of electric fields in proteins. Recently, we used a charge field perturbation approach to explore the effects of electrostatic influence on chemical shielding of 19F in different chemical environment^.^^ A conventional ab initio calculation was carried out to obtain the absolute shielding, and then included in the molecular
STRUCTURAL NMR SHIFTS IN RESPIRATORY PROTEINS
5
10
15
25
20
Shift Ranges (ppm) Fig. 4. Graph showing relationship between the isotropic dipole shielding polarizabilities, A, computed for prototype small molecules using derivative Hartree-Fock theory, and the observed chemical shift ranges, for (left to right) 'H, 13C (C-0), 13C (aromatic), "O (C-0) and "F nuclei in proteins.
Hamiltonian was a particular electrostatic perturbation. Since dipoles are the longest range contributor to the electrostatic potential of a neighbouring neutral molecule or molecule fragment, our charge field perturbation calculations were carried out with an ideal dipole in a chosen position in the vicinity of the molecule. Comparison with the calculated value in the absence of a dipole provides the relative chemical shielding, a shift, due to the dipole. We used a dipole of l.Oa.u. (2.54 D) as representative of local bond dipoles that may exist in bio-organic molecules. The dipoles were placed at a number of distances from the fluorine atom of the molecule being studied and were aligned with the axis of fluorine's chemical bond. The molecules that were studied are a sampling of different bonding environments for fluorine in hydrocarbons. Of course, since fluorine forms only single bonds, the dif€erences in the environments are secondary, at the connected centre. An analysis of the shifts due to electrostatic interaction comes about from partitioning the shielding values into the diamagnetic and paramagnetic contributions. The shift range due to electrostatic interaction shows very good correlation with the paramagnetic shielding, whereas the shift range and diamagnetic shieldings turn out to be uncorrelated. From these results, it is clear that the greater the paramagnetic shielding, the proportionately greater is the response to an external dipole. Since the paramagnetic shielding diminishes the overall shielding ( a = vdiag uPara, gars < 0), then
.
+
26
J. D. AUGSPURGER AND C. E. DYKSTRA
there is an anti-correlation between the total shielding and the shift range to the extent to which the diagmagnetic contribution is either unchanging or changing in parallel.
4.2. Nuclear quadrupole coupling Interaction of an electric quadrupole moment of a nucleus with an electric field gradient of the electron cloud is a small perturbation of the molecular energy, but it is measurable via nuclear quadrupole resonance, nuclear magnetic resonance, and also microwave spectroscopy. 12’ The existence of an electric field gradient requires a non-spherical charge distribution such as that arising when chemical bonding distorts the spherical symmetry of the electron distribution around a nucleus. There may be small field gradient changes that result from external or long-range perturbations. The original picture of variations in nuclear quadrupole coupling goes back to a series of paper^'^^-'^^ wherein Sternheimer presented an analysis of the effect of an external point charge on the electron distribution’s field gradient at a nucleus. This gave, as well, the extent to which a nuclear quadrupole polarizes an isolated atom’s electron distribution since, as shown,’23 it was equivalent to take the perturbation as an external charge or as a nuclear quadrupole. The phenomenological outcome of this analysis was the idea that the field gradient at a nucleus, V,,, can be taken to be a “shielded” external field gradient:
v,, = V,=X‘(1 - y )
(30)
where y is the Sternheimer shielding factor. Sternheimer shielding is sometimes introduced with a factor (1 + y ) instead of (1 - y), making for an opposite sign of y. Unlike chemical shieldings, IM does not generally turn out to be much less than 1.0. Sternheimer analysis has been extended to ionic diatomic molecules125to include the added effect of the induced dipole moment, and Buckingham’26 devised an expression to include explicitly the effects of uniform fields on ions, in effect, adding a term onto equation (31):
v,, = V;Tt
(1 - y ) + &(V,ext)2 (31) where E is a parameter. Engstrom er a1.I2’ applied these ideas to covalent molecules, using a perturbation approach. A different truncation of effects, V,, = V::‘
(1- 7)
+F Vyt
(32) was employed by Legon and Millen’2s~’29for microwave data on a series of HCI complexes. The most general analytical approach to nuclear quadrupole coupling constants, or electric field gradients at a nucleus, is to employ a power series expansion in terms of all the elements of the external electrical potential,
STRUCTURAL NMR SHIFTS IN RESPIRATORY PROTEINS
27
which has already been pointed out and considered by Baker et al. 130 Taking V F as the electric field gradient at a particular nucleus, an expansion in terms of external field components V,, V,, V , (suppressing the "ext" superscript used above), external field gradient components, V,,, Vxy,and so on, and higher tensor components is
v,",""= v2; + vg: v, + vp;v, + v::; v, + 21 vg;,v',, + . . . (33) The parameters in equation (33) (e.g. V,",::) are response properties of second and higher order. When the interaction with the nuclear quadrupole moment is included in the molecular Hamiltonian, these parameters are simply derivatives of the molecular eigenenergy to second and higher order. Bacskay et al. 131,132 and F o ~ l e r ' ~ ha ~ ve , ' ~used ~ finite field approaches to calculate certain of the terms in equation (33), and we have developed a fully analytical ab initio approach77 for all the response properties in equation (33). A difficulty in using these field derivatives of V z u c is the question of convergence in the multipole expansion. The contributions due to field gradients, hypergradients, second hypergradients, etc., do not necessarily decrease uniformly, as has been found by Baker et ~ 1 . ; ' ~they " calculated the terms in equation (33) through Vr",lt,,, (the first order response of V,","' to the second electrical hypergradient) for the 35Cl nucleus in HCI. Another question which arises is the origin dependence of these field derivatives. For a molecule with multiple heavy atoms, like HCN, the properties, and their relative contributions to V z " " , will be quite different if the centre of the expansion of the external field gradients is taken to be the centre of mass of HCN, as opposed to the 14N nucleus. Baker et ~ 1 . ' ~found " that inclusion of the first order terms in equation (33) through the second hypergradient was necessary to agree with finite perturbation calculations, where the partner molecule was represented by its low order multipole moments. These difficulties may be examined by reformulating the problem. Instead of asking how the field, field gradient, and so on, of a partner molecule influence the field gradient at the nucleus, we may ask: how does an ideal dipole, quadrupole, octupole, etc. at a given location directly influence the field gradient at the nucleus? This eliminates the question of origin dependence, as there is no Taylor series expansion of the external electrical potential to carry out. This leads to a new form of equation (33), where
28
J. D. AUGSPURGER AND C. E. DYKSTRA
Table 4. Generalized linear and non-linear Sternheimer shieldings for 14N in HCN and 35Clin HCI (a.u.).
Property"
HCN, origin
92 922
9xx 9221
9zxx 9z.z 92.22
92 ,xx 9z.rzz 92,ZXX
922.22 9ZZJX
9zz.zzz 9zz,zxx
9 x x Jix 9xx.y.v 9xx.zzz
9xx.zxx 9XX.ZYY
9zzz.zzz 9zzz.zxx 9zxx.zxx 9zxX.zYy
HCl, origin
centre of mass
I4N
7.126 4.229 -1.966 6.206 2.868 10.25 46.50 4.984 77.20 -2.924 63.99 5.173 145.4 24.23 -29.44 18.93 13.23 17.43 8.036 327.3 19.97 -10.95 -4.807
7.126 -3.785 -1.966 5.957 3.605 10.25 34.97 4.990 31.39 -4.792 -27.62 -0.432 67.57 27.68 -29.43 -18.93 10.57 28.47 15.13 116.7 -13.08 -28.16 -13.49
3 5 ~ 1
17.40 25.05 -16.67 33.38 -0.367 67.35 98.35 -3.718 290.3 -23.96 242.3 -46.54 413.3 -6.845 -222.7 -94.90 -0.139 - 10.28 2.560 1038 33.40 -54.45 - 16.98
O q Z = VY:; and so on (see equation 33).
Table 5. Moment shieldings of I4N in HCN (a.u.). R(A)b
Property"
3.0 qM,i
qM. qMz. qM:::
qM2;,:
qMrrr, qMU,,,,
3.5
4.0
4.5
5.0
6.0
7.0
0.277 23 0.093 31 0.063 32 0.045 74 0.200 53 0.150 58 0.116 91 -0.10020 -0.064 74 -0.042 83 -0.029 49 -0.021 09 -0.011 83 -0.007 27 0.007 10 0.003 30 0.001 73 0.049 58 0.030 19 0.017 96 0.011 05 -0.022 39 -0.016 79 -0.009 62 -0.005 43 -0.003 17 -0.001 22 -0.000 55 -0.004 42 0.009 01 0.005 89 0.003 21 0.001 74 0.000 56 0.000 22 0.010 37 0.005 44 0.002 57 0.001 27 0.000 66 0.000 21 0.000 08 -0.012 58 -0.000 93 0.000 37 0,000 34 O.OO0 21 0.000 07 0.000 03
''qMU,,= VY:; and so on (see equation 34). Only symmetry-unique, non-zero properties listed.
Due to Laplace's condition, several elements are related by the traceless properties of the and qM,,,, = - %4MzZz:. electric field (hyper)gradient tensors: qMx = - % q M M , , q M X M , ;=, - '/2qMz2, 'The moment properties given are calculated with respect to moments located at a distance R along the positive z-axis where the HCN centre of mass is at the origin and the I4N nucleus is on the positive z-axis.
29
STRUCTURAL NMR SHIFTS IN RESPIRATORY PROTEINS
Table 6. Moment shieldings of 3sCl in HCI (a.u.).
R(AIb
Property” 3.0
3.5
4.0
4.5
5.0
6.0
7.0
1.260 98 0.820 17 0.571 88 0.420 28 0.321 43 0.20498 0.141 80 -0.628 35 -0.340 52 -0.200 80 -0.127 36 -0.085 55 -0.043 81 -0.025 30 0.452 15 0.207 64 0.104 27 0.057 25 0.033 84 0.013 94 0.00673 -0,38951 -0.161 78 -0.070 85 -0.033 93 -0.017 70 -0.005 88 -0.002 38 0.363 53 0.147 73 0.058 67 0.024 81 0.011 48 0.003 09 0.001 04 0.212 71 0.064 96 0.023 20 0.009 49 0.004 34 0.001 16 0.OOO 39 0.006 14 0.002 92 0.001 40 0.000 39 0.000 13 -0.030 95 0.008 90
= VyJC, and so on (see equation 34). Only symmetry-unique, non-zero properties listed. Due to Laplace’s condition, several elements are related by the traceless properties of the electric field (hyper)gradient tensors: qicl, = - ~ q M z ,qMxu,,,= -%qw,,, and qMM,,,= -%qMzZz,. bThe moment properties given are calculated with respect to moments located at a distance R along the positive z-axis where the HCI centre of mass is at the origin and the 35Clnucleus is on the negative z-axis. uqM,
( M o , M , , M,,, represent components of the charge, first moment, and second moment, etc.) All the response properties in both equations (33) and (34) have been calculated for the heavy nuclei of HCN and HCl via DHF. These results77 are reproduced in Tables 4-6.
4.3. Spin-spin coupling Spin-spin coupling tensors have proven to be the most challenging NMR parameters to obtain from ab initio calculations. The coupling arises through the interaction of two nuclear magnetic moments with the electronic environment. There are interaction terms in the Hamiltonian for each nuclear magnetic source, and the spin-spin couplings are second derivatives with respect to the magnetic moments of two different nuclei. Calculations by Lazzeretti and ~ o - w o r k e r shave ~ ~ ~shown , ~ ~ the ~ major importance of the Fermi contact portion of the interaction in isotropic spin-spin couplings. Sekino and Bartlett137 carried out extensive correlated calculations on the very simple molecule H D . Their results suggest that somewhat unlike chemical shieldings, electron correlation effects tend to be much more important than inclusion of polarization functions in the basis set. In fact, it is often presumed that correlation effects are essential for meaningful evaluation of spin-spin coupling; of course, such rules-of-thumb tend to be broken somewhere. A study of several organic molecules by Laaksonen et al. 13’ indicates that correlation effects on spin-spin coupling are primarily those associated with dynamical versus non-dynamical correlation. Also important, is that agreement between correlated evaluations and
30
J. D. AUGSPURGER AND C. E. DYKSTRA
experimental values for H H and 13CH coupling in several small organic molecules was mostly better than 10 Hz. Spin-spin coupling may be regarded as arising both through space and through the electronic structure of the molecular framework. The Contributions from Localized Orbitals within the Polarization Propagator Approach (CLOPPA) method139 has been employed to distinguish contributions. For instance, in calculations on methylenedioxyben~ene,~~~ CH coupling was found to increase by several hertz because of the proximity of an aromatic CH bond cis to the oxygen lone pair. CH coupling appears to be a sensitive probe of intramolecular hydrogen bonding.'417142In proteins, the influence of intramolecular hydrogen bonding and solvent effects on spin-spin coupling are becoming fertile ground for ab initio calculations, given that it is likely that prototype or fragment molecular species calculations will provide suitable information.
5. PROPERTY CORRELATIONS IN RESPIRATORY PROTEINS
Almost any correlation of chemical shieldings with other molecular properties is of potential value in molecular structure elucidation, in analysing electronic structure reorganization, and in establishing certain structure/ function relationships. We have found that the long-range influences on chemical shielding in respiratory proteins can be correlated with a number of other proper tie^.^' The first correlation involves the C O in carbonmonoxyheme proteins. This correlation was based on the ideas of long-range effects in the last section, and so the first step was determining response properties of the C O group. A vibrational potential for unperturbed or isolated C O was obtained'43 from large basis set calculations using well-correlated, coupled cluster wavefunctions. 144-146Electrical and magnetic properties of C O were analytically calculated as a function of the bond distance, r, via DHF.41,51The basis set for these calculations was a large, 96-function set of contracted Gaussians. The chemical shielding tensors at the oxygen and carbon centres were evaluated along with shielding polarizabilities and nuclear quadrupole couplings. Vibrational wavefunctions for CO were calculated by the NumerovCooley rnethodl4' which provides an exact numerical determination of the vibrational energies and wavefunctions. This was done for C O experiencing various types of external electrical environments. The first and simplest type was a uniform electric field. The second type was a field gradient (only). The third type was the potential due to a positive ( + e ) and a negative ( - e ) charge arranged as a dipole, oriented either along or perpendicular to the C O axis. The charges were separated by 0.1 a.u. and their centre was at least 4 A from the CO multipole centre. These are four hypothetical
STRUCTURAL NMR SHIFTS I N RESPIRATORY PROTEINS
31
electrical perturbations of the CO molecule that correspond in a rough way to the types of electrical perturbations that proximate molecules or ligand groups might generate. For these same electrical environments, the effects on the chemical shieldings of carbon and oxygen were obtained via the shielding polarizabilities. The results showed a nearly linear relation between the isotropic chemical shifts and the vibrational frequencies that are in good, semi-quantitative accord with the trends found for C O in variously perturbed heme proteins .30 In particular, the opposite trends in 13C and 170chemical shifts and "0 nuclear quadrupole coupling constants with changes in C O vibrational frequency, usually described in terms of "backbonding", appear to be well predicted solely on the basis of electrical polarization. Figure 5 shows the net relation between the vibrational frequency and the chemical shifts for three different types of electrical environments that we examined, that of a uniform field, a field gradient and an axial point-charge dipole together with experimental I3C and I7O isotropic chemical shieldings and vibrational frequencies for a range of carbonmonoxyheme proteins .30 This shows the opposite pattern for 13C and 170,and this is mainly because of the shielding polarizability properties of CO. Since the electrical perturbation arising from almost any molecular charge distribution will have a uniform field component, and since this seems to be the important and dominant long-range influence on the chemical shieldings and vibrational frequencies, then this correlation should hold for many other systems. Finally, an additional set of ab initio calculations was done to find the nuclear quadrupole coupling constant of 170,and its correlation with the vibrational frequency. Electronic structure calculations determined the electric field gradient at the nucleus as a function of the bond length, r , and of the strength of the external axial electric field. Using a value of -2.64 fm2 for the nuclear quadrupole mornent,l4' we obtained the quadrupole coupling constant, e2qQlh. Then, the vibrationally averaged value, (e2qQ/h), for the ground vibrational state was found as a function of the external field. (The behaviour of the electric field gradient at the nucleus as a function of the vibrational coordinate has already been considered in detail in ab initio studies of Cummins et a[.148 and Amos.149) From this, we obtain the correlation of (e2qQlh)with vibrational frequency shift, which agrees nicely with the experimental data for h e~ n e - C O . ~ ' In addition to the correlation of properties among various carbon monoxyheme proteins brought about through common electrical perturbation, Oldfield et al. have identifiedI5' a correlation of the relative conformational substate energies with the electrical perturbation source. For a wide variety of heme proteins, including the haemoglobins, myoglobins and several peroxidases, the vibrational frequency shifts can be related to electric field differences arising from 180" ring flips of the Ha and Ha tautomers of distal histidine residues.
32
J. D. AUGSPURGER AND C. E. DYKSTRA
60 20
40
t
0 4,
0 20
-20
0
** t
-40
-20
-60
t
40
-100
0
1
-60
-40
-20
0
-40
-20
20
40
60
10
0
-10
-20
-60
O
20
A vo1 Fig. 5. Plots of the isotropic chemical shifts for 1 7 0 and for 13C versus the change in the fundamental vibrational transition frequency, calculated for (a) various uniform electric fields, (b) various field gradients and (c) various positions of an axial dipole consisting of two point charges, and (d) measured experimentally for a range of carbonmonoxyheme protein^.^' For the experimental values, the carbonmonoxyheme proteins (from ref. 30) were: Glyceru dibrunchiatu haemoglobin, picket fence porphyrin, haemoglobin Zurich, Physete cutudon myoglobin (pH = 7.0, 7.2 and “low”), rabbit haemoglobin (a-chain), rabbit haemoglobin (/.?-chain), human adult haemoglobin (a-chain), human adult haemoglobin (/.?-chain), lactoperoxidase, horseradish peroxidase isoenzyme A (pH = 9.5, 6.8 and 4.5) and horseradish
STRUCTURAL NMR SHIFTS IN RESPIRATORY PROTEINS
33
The correlation of chemical shieldings, other properties and relative energetics via electrical influence suggests that important structural information can be extracted from NMR shieldings of proteins provided there is available information on shielding polarizabilities. The ultimate role of ab initio calculations in protein NMR is in the evaluation of these properties and, more broadly, in the attempt to determine a local or relative effect on a shift. Valuable information can be obtained short of an ab initio calculation on an entire protein. This conclusion opens the door to further connections between ab initio studies and NMR experiments.
ACKNOWLEDGEMENT
This work was supported, in part, by a grant from the United States National Institutes of Health (Grant No. 19481).
REFERENCES 1 . G. Wagner, Prog. NMR Spectrosc., 1990, 22, 101. 2. D. Neuhaus and M. P. Williamson, The Nuclear Overhauser Effect in Structural and Conformational Analysis, VCH, New York, 1989. 3. P. Giintert, W. Braun and K. Wiithrich, J. Mol. Biol., 1991, 217, 517. 4. J. A. Tossell, ed., Nuclear Magnetic Shielding and Molecular Structure, NATO AS1 Ser., Ser. C , 1993, 386. 5. A . Bundi and K. Wiithrich, Biopolymers, 1979, 18, 285. 6. K. Wiithrich, NMR of Proteins and Nucleic Acids, Wiley, New York, 1986. 7. C. Giessner-Prettre and B. Pullman, J. Theor. Biol., 1970, 27, 87; 1971, 31, 287. 8. C. W. Haigh and R. B. Mallion, Prog. NMR Spectrosc., 1980, 13, 303. 9. C. Giessner-Prettre and B. Pullman, Biochem. Biophys. Res. Commun., 1976, 70, 578. 10. A. D. Buckingham, Can. J. Chem., 1960, 38, 300. 11. C. Giessner-Prettre and B. Pullman, J. Theor. Biol., 1977, 65, 171. 12. C. Giessner-Prettre and B. Pullman, Quart. Rev. Biophys., 1987, 20, 113. 13. H. Sternlicht and D. Wilson, Biochemistry, 1967, 6, 2881. 14. T. Asakura, I. Ando and A. Nishioka, Makromol. Chern., 1977, 177, 1111; 1521. 15. S. J. Perkins and K. Wiithrich, Biochim. Biophys. Acta, 1979, 576, 409. 16. J. C . Hoch, C . M. Dobson and M. Karplus, Biochemistry, 1982, 21, 1118. 17. N. J. Clayden and R. J. P. Williams, J. Magn. Reson., 1982, 49, 383. 18. M. P. Williamson, Nut. Prod. Rep., 1993, 10, 207. 19. K.-H. Gross and H. R . Kalbitzer, J. Magn. Reson., 1988, 76, 87. 20. G . Wagner, A. Pardi and K. Wiithrich, J. Am. Chem. SOC., 1983, 105, 5948.
peroxidase isoenzyme B (pH = 10.5, 7 and 6.4); these are referenced to adult haemoglobin. The solid lines represent the straight line, least squares fit of the data. The slope of the line for 13C is -0.07ppm cm-' and the corresponding slope from the calculations in (a) is -0.23 ppm cm-'. The slope of the line for "0 is 0.26 ppm cm-' and the corresponding slope from the calculations in (a) is 0.47 ppm cm-'.
34 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. SI. 52. 53. 54. 55. 56. 57. 58. 59. 60. 61. 62. 63. 64. 65.
J . D. AUGSPURGER AND C. E . DYKSTRA A. Pardi, G . Wagner and K. Wiithrich, Eur. J . Biochem., 1983, 137, 445. L. Szilagyi and 0. Jardetzky, J . Magn. Reson., 1989, 83, 441. A. Pastore and V. Saudek, J . Magn. Reson., 1990, 90,165. M. P. Williamson, Biopolymers, 1990, 29, 1423. M. P. Williamson and T. Asakura, J . Magn. Reson., 1991, 94, 557. K. Osapay and D . A. Case, J . Am. Chem. Soc., 1991, 113, 9436. D. S . Wishart, B. D. Sykes and F. M. Richards, J . Mol. Biol., 1991, 222, 311. S. Spera and A. Bax, J . Am. Chem. Soc., 1991, 113, 5490. H. C. Lee and E. Oldfield, J . Am. Chem. Soc., 1989, 111, 1584. K. D. Park, K. Guo, F. Adeboun, M. L. Chiu, S. G . Sligar and E. Oldfield, Biochemistry, 1991, 30, 2333. J. D . Augspurger. C. E. Dykstra and E . Oldfield, J . Am. Chem. Soc., 1991, 113, 2447. J. Augspurger, J . G . Pearson, E. Oldfield, C. E. Dykstra, K. D. Park and D. Schwarz, J . M a p . Reson., 1992, 100, 342. A . C. deDios and E . Oldfield, Chem. Phys. Left., 1993, 205. 108. A. C. deDios, J . G . Pearson and E. Oldfield, Science, 1993, 260, 1491. J . G . Pearson, E. Oldfield, F. S . Lee and A. Warshel, J . Am. Chem. Soc., 1993, 115, 6851. D. D. Laws. A. C. deDios and E. Oldfield. J. B i d . Nucl. Magn. Reson., 1993, 3, 607. R. P. Feynman, Phys. Rev., 1939, 56, 340. A . C. Hurley, Introduction to the Electron Theory of Small Molecules, Academic Press, New York, 1976. T . 3 . Nee, R. G . Parr and T. J. Bartlett. J . Chem. Phys.. 1976, 64, 2216. N. C. Handy and H. F. Schaefer, 1. Chem. Phys., 1984, 81, 5031. J . D. Augspurger and C. E. Dykstra, J . Phys. Chem., 1991. 95, 9230. C. E. Dykstra. A b Initio Calculation of the Structures and Properties of Molecules, Elsevier, Holland, 1988. J. D. Augspurger and C . E. Dykstra, J . Comput. Chem., 1990, 11, 105. J. D. Augspurger and C. E. Dykstra, MAGOPS, available from the Quantum Chemistry Program Exchange, Bloomington, Indiana. R. Ditchfield, Chem. Phys. Lett., 1972, 15, 203. R. Ditchfield, J . Chem. Phys., 1972, 56, 5688. R. Ditchfield, Mol. Phys.. 1974, 27, 789. J . F. Hinton, P. L. Guthrie, P. Pulay and K. Wolinski, J . Magn. Reson., Ser. A , 1993, 103. 188. C. P. Slichter, Principles of Magnetic Resonance, Springer-Verlag, New York, 1980. S. T. Epstein, J . Chem. Phys., 1973, 58, 1592. C. E. Dykstra and P. G. Jasien, Chem. Phys. Lett., 1984, 108, 388. W. Kutzelnigg, Israel J . Chem., 1980, 19, 193. M. Schindler and W. Kutzelnigg, J . Chem. Phys., 1982, 76, 1919. C. van Wuellen and W. Kutzelnigg, Chem. Phys. Lett., 1993, 205, 563. Aa. E. Hansen and T. D. Bouman, J . Chern. Phys., 1985, 82, 5035. Aa. E. Hansen and T. D. Bouman, J . Chem. Phys., 1989, 91, 3552. P. J . Stephens, K. J. Jalkanen, P. Lazzeretti and R. Zanasi, Chem. Phys. Lett., 1989, 156, 509. P. J. Stephens and K. J. Jalkanen, J . Chem. Phys., 1989, 91. 1379. P. Lazzeretti, M. Malagoli and R. Zanasi, Chem. Phys., 1991, 150, 173. K. Wolinksi, J. F. Hinton and P. Pulay, J. Am. Chem. Soc., 1990, 112, 8251. J. Oddershede and J. Geertsen, J . Chem. Phys., 1990, 92, 6036. T. D. Bouman and Aa. E. Hansen, Chem. Phys. Lett., 1992, 175, 292. T. D . Bouman and Aa. E. Hansen, Chem. Phys. Left., 1992, 197, 59. J. Gauss, Chem. Phys. Lett., 1992, 191, 614. J . Gauss, J . Chem. Phys., 1993, 99, 3629.
STRUCTURAL NMR SHIlTS IN RESPIRATORY PROTEINS 66. 67. 68. 69. 70. 71. 72. 73. 74. 75. 76. 77. 78. 79. 80. 81. 82. 83. 84. 85. 86. 87. 88. 89. 90. 91. 92. 93. 94. 95. 96. 97. 98. 99. 100. 101. 102. 103. 104. 105. 106. 107. 108. 109.
35
S. M. Cybulski and D. M. Bishop, J . Chem. Phys., 1993, 98, 8057. R . McWeeny, Phys. Rev.. 1961, 126, 1028. R. M. Stevens, R . M. Pitzer and W. N. Lipscomb, J . Chem. Phys., 1963, 38, 550. P. W. Langhoff, M. Karplus and R. P. Hurst, J . Chem. Phys., 1966, 44,505. J. Gerratt and I. M. Mills, J . Chem. Phys., 1968, 49, 1719. W. Kutzelnigg, U. Fleischer and M. Schindler, in NMR, Basic Principles and Progress, Vol. 23, p. 165. Springer-Verlag, New York, 1990. J . F. Hinton, P. L. Guthrie, P. Pulay, K. Wolinksi and G. Fogarasi, J . Magn. Reson., 1992, 96, 154. J. D. Augspurger and C. E . Dykstra, Chem. Phys. Lett., 1991, 183, 410. J. D . Augspurger and C. E . Dykstra, Mol. Phys., 1992, 80, 117. J. D. Augspurger, A. C. deDios, E . Oldfield and C. E . Dykstra, Chem. Phys. Lett., 1993, 213, 211. J. D . Augspurger and C. E . Dykstra, J . Am. Chem. Soc., 1993, 115, 12016. J. D . Augspurger and C. E . Dykstra, J . Chem. Phys., 1993, 99, 1828. D . B. Chesnut, in Annual Reports on N M R Spectroscopy (ed. G. W. Webb), Vol. 21. p. 51. Academic Press, London, 1989. D . B. Chesnut and C. K. Foley, J . Chem. Phys., 1986, 85, 2814. D . B. Chesnut and K. D . Moore, J . Comput. Chem., 1989, 10, 648. J . F. Hinton, P. Guthrie, P. Pulay and K. Wolinski, J . Am. Chem. SOC., 1992, 114. 1604. T. H. Dunning, J . Chem. Phys., 1970, 53, 2823. T. H. Dunning, J . Chem. Phys., 1971, 55, 716. S. Huzinaga, J . Chem. Phys., 1965, 42. 1293. R. Ditchfield, J . Chem. Phys., 1976, 65, 3123. A. C. deDios and E. Oldfield, unpublished results. J . F. Stanton, J. Gauss, J. D . Watts, W. J . Lauderdale and R. J . Bartlett, ACES 11, an ab inirio program system, Quantum Theory Project, University of Florida, 1991. T. Onak, J . Tseng. M. Diaz, D. Tran, J. Arias, S. Herrera and D . Brown, Znorg. Chem., 1993. 32, 487. M. Buhl and P. v. R. Schleyer, J . Am. Chem. SOC., 1992, 114, 477. P. v. R. Schleyer, J. Gauss, M. Buhl, R . Greatrex and M. A . Fox, J . Chem. Soc., Chem. Commun., 1993, 1766. D. Jiao, M. Barfield and V. J. Hurley, J . Am. Chem. Soc., 1993. 115, 10883. D. B. Chesnut and C. K. Foley, J . Chem. Phys., 1986, 84, 852. D. B. Chesnut, Chem. Phys., 1986, 110, 415. D . B. Chesnut and C. G . Phung, J . Chem. Phys., 1989, 91, 6238. D. B. Chesnut and D . W. Wright, J . Comput. Chem., 1991, 12, 546. A. D . Buckingham, J . Chem. Phys., 1962, 36. 3096. K. A. Franken and C. E. Dykstra, unpublished. J. B. Anderson, J . Chem. Phys., 1975, 63, 1499; 1976, 65, 4121. D . Ceperly and B. Alder, Science, 1986, 231, 555. W. A. Lester and B. L. Hammond, Ann. Rev. Phys. Chem., 1990, 41, 283. V. Buch, J . Chem. Phys., 1992, 97, 726. K. A. Franken and C. E. Dykstra, J . Chem. Phys., 1994, 100, 2865. L. A. Luck and J. J. Falke, Biochemistry, 1991, 30, 4248. A. Warshel and S. Creighton, Computer Simulation of Biomoleculur Systems (eds W. F. van Gunsteren and P. K. Weiner). ESCOM, Leiden, 1989. F. S. Lee and A. Warshel, J . Chem. Phys., 1992, 97, 3100. D . H. Gregory and J. T. Gerig, Biopolymers, 1991, 31, 845. M. Zaucer and A. Azman, Z. Nuturforsch. A , , 1979, 34, 1279. M. J. Packer and W. T. Raynes, Mol. Phys., 1990, 69, 391. M. Volodicheva and T. Rebane, Teor. Eksp. Khim.,1984, 19, 387 (p. 357 in English translation); 1987, 21. 391 (p. 373 in English translation).
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110. W. T. Raynes, in Specialist Periodical Reports (ed. R. K. Harris), Vol. 1, 36. Chemical Society, London, 1972. 111. D. M. Bishop and S. M. Cybulski, Mol. Phys., 1993, 80, 199. 112. D. M. Bishop and S. M. Cybulski, Mol. Phys., 1993, 80, 209. 113. J. D. Augspurger and C. E. Dykstra, Mol. Phys., 1992, 76, 229. 114. M. Grayson and W. T. Raynes, Chem. Phys. Lett., 1994, 218, 270. 115. M. Grayson and W. T. Raynes, Chem. Phys. Lett., 1993, 214, 473. 116. M. Grayson and W. T. Raynes, Mol. Phys., 1994, 81, 533. 117. A. Allerhand, R. F. Childers and E. Oldfield, Biochemistry, 1973, 12, 1335. 118. E. Oldfield and A. Allerhand, J . Biol. Chem., 1975, 250, 6403. 119. W. E. Hull and B. D. Sykes, J . Mof. Biol., 1975, 98, 121. 120. M. P. Gamcsik, J . T. Gerig and R. B. Swensen, Biochim. Biophys. Acta, 1986, 874, 372. 121. W. H. Flygare, Molecular Structure and Dynamics, Prentice-Hall, Englewood Cliffs, NJ, 1978. 122. R. Sternheimer, Phys. Rev., 1950, 80, 102; 1951, 84, 244; 1952, 86, 316; 1954, 95, 736; 1956, 102, 731. 123. R. Sternheimer, Phys. Rev., 1966, 146, 140. 124. R. M. Sternheimer and H. M. Foley, Phys. Rev., 1953, 92, 1460. 125. H. M. Foley, R. M. Sternheimer and D. Tycko, Phys. Rev., 1954, 93, 734. 126. A. D. Buckingham, Trans. Farad. Soc., 1962, 58, 1277. 127. S. Engstrom, H. Wennerstrom, B. Jonsson and G. Karlstrom, Mol. Phys., 1977, 34, 813. 128. A. C. Legon and J. D. Millen, Chem. Phys. Lett., 1988, 144, 136. 129. A. C. Legon and J. D. Millen, Proc. Roy. SOC.A , 1988, 417, 21. 130. J. Baker, A. D. Buckingham, P. W. Fowler, E. Steiner, P. Lazzeretti and R . Zanasi, J . Chem. SOC.,Farad. Trans. 2, 1989, 85, 901. 131. G. Bacskay and J. E. Gready, J . Chem. Phys., 1988, 88, 2526. 132. G. Bacskay, D. 1. Kerdraon and N. S. Hush, Chem. Phys., 1990, 144, 53. 133. P. W. Fowler, Chem. Phys. Lett., 1989, 156, 494. 134. P. W. Fowler, Chem. Phys., 1990, 143, 447. 135. P. Lazzeretti, E. Rossi, F. Taddei and R. Zanasi, J . Chem. Phys., 1982, 77, 2023. 136. P. Lazzeretti and R. Zanasi, J . Chem. Phys., 1982, 77, 2448. 137. H. Sekino and R. J. Bartlett, J . Chem. Phys., 1986, 85, 3845. 138. A. Laaksonen, J. Kowalewski and V. R. Saunders, Chem. Phys., 1983, 80, 221. 139. A. C. Diz, C. G . Giribet, M. C. Ruiz de Azua and R. H. Contreras, Int. J . Quant. Chem., 1990, 37, 663. 140. R. R. Biekofsky, A. B. Pomilio and R. H. Contreras, J . Molec. Struct. (Theochem.), 1990,210,211. 141. A. V. Afonin, M. V. Sigalov, S. E. Korustova, I. A. Aliev, A. V. Vaschenko and B. A. Tromifov, Magn. Reson. Chem., 1990, 28, 580. 142. H. Satonaka, K . Abe and M. Hirota, Bull. Chem. SOC. Japan, 1987, 60, 953; 1988, 61, 2031. 143. C. A. Parish, J. D. Augspurger and C. E. Dykstra, J . Phys. Chem., 1992, 96, 2069. 144. J. Cizek, J . Chem. Phys., 1966, 45, 4256; Adv. Chem. Phys., 1969, 14, 35. 145. R. J. Bartlett, Ann. Rev. Phys. Chem., 1981, 32, 359. 146. R. J. Bartlett, J. Paldus and C. E. Dykstra, in Advanced Theories and Computational Approaches to the Electronic Structure of Molecules (ed. C. E. Dykstra), p. 127. Reidel, Holland, 1984. 147. J. W. Cooley, Math. Comput., 1961, 15, 363. 148. P. L. Cummins, G . B. Bacskay and N. S. Hush, J . Chem. Phys., 1987, 87, 416. 149. R. D. Amos, Chem. Phys. Lett., 1979, 68, 536. 150. E. Oldfield, K. Guo, J. D. Augspurger and C. E. Dykstra, J . A m . Chem. SOC.,1991, 113, 7537.
NMR Applications to Porous Solids P. J. BARRIE Department of Chemistry, University College London, 20 Gordon Street, London WClH OAJ. UK
1. Introduction 2. NMR studies of microporous materials 2.1. Zeolite molecular sieves 2.2. Aluminophosphate-based molecular sieves 2.3. Other microporous materials 3. NMR studies of mesoporous materials 3.1. Silicas, aluminas etc. 3.2. Novel mesoporous materials 3.3. Catalysts 4. 129XeNMR studies of porous materials 4.1. 129XeNMR of zeolites 4.2. 129XeNMR of other porous solids 5. NMR studies of molecular transport in porous solids 5.1. Pulsed field gradient measurements 5.2. Applications of NMR imaging Acknowledgement References
37 38 38 55 62 66 66 72 73 75 75 79 81 82 84
85 85
1. INTRODUCTION
NMR techniques have become increasingly important methods for characterizing materials. In particular, high-resolution solid-state NMR spectroscopy has become a routine tool in the study of many materials as it provides detailed structural information on the local environment and dynamic behaviour of the nucleus under investigation. Porous solids have been extensively studied by this technique due to their great commercial applications, particularly in the area of heterogeneous catalysis. One major NMR application to porous solids is the investigation of the structure of the solid, and to gain information about the solid surface where possible. Another area is investigating the behaviour of adsorbed species. These may be probe molecules which reveal something about the structure of the solid. Alternatively, it may be the dynamics and transformations of the adsorbed ANNUAL REPORTS O N NMR SPECTROSCOPY VOLUME 30 ISBN 0-12-505330-4
Copyright 0 1995 Academic Press Limited AN rights of reproduction in any form reserved
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molecules themselves that is the major topic of interest. As well as conventional solid-state NMR techniques on porous solids, there has been increasing use of field gradients in order to make diffusion measurements and in the area of nuclear magnetic resonance imaging. Porous materials may conveniently be divided into the classification of microporous ( ore diameters <20 A), mesoporous (pore diameters in the range 20-500 ), and macroporous systems (pore diameters >500 A).’ In this review, first microporous systems and then macroporous systems are discussed, even though the division between the categories is to some extent arbitrary. Those materials containing both micropores and mesopores are discussed in the mesoporous section. There are two further sections which are on the application of I2’Xe NMR and on NMR studies of molecular transport within porous solids. Any review on a topic as wide as NMR applications to porous solids is necessarily selective. While this chapter is a long way from being comprehensive, I have tried to give a flavour of the information available from different NMR techniques on a variety of types of porous solids, concentrating mainly on recent methods and discoveries.
w
2. NMR STUDIES OF MICROPOROUS MATERIALS
2.1. Zeolite molecular sieves
Zeolites are crystalline aluminosilicates which consist of S O 4 and A104 tetrahedra linked by the sharing of oxygen atoms to form a framework of high internal surface area with regular channels and cavities which permeate the entire volume of the solid. These pores are of molecular dimensions, enabling zeolites to be used as molecular sieves, as they can only adsorb molecules of certain dimensions. Each aluminium atom present in the framework induces a negative charge, requiring a charge-balancing cation to be present in a non-framework position. These cations are relatively mobile and can readily be exchanged by other cations, leading to a number of ion-exchange applications. When the charge-balancing cations become hydrogen ions, zeolites become highly acidic shape-selective heterogeneous catalysts. As such, they have become key catalysts in the oil industry, being used for cracking, alkylation, isomerization and other hydrocarbon transformation reactions. Because of their great commercial applications, zeolites have been extensively studied by NMR spectroscopy, and there have been a number of excellent reviews.2-6 It is appropriate here, however, to consider some of the pertinent points and recent advances in the study of these materials as the various information obtainable by NMR spectroscopy on zeolites is also relevant to the study of other porous solids.
NMR APPLICATIONS TO POROUS SOLIDS
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2.1.1. "Si N M R of zeolites
The 2'Si environment in zeolites is always tetrahedrally coordinated and so only has a small chemical shift anisotropy. Thus spinning sidebands are normally negligible in magic-angle spinning (MAS) experiments, even at spinning speeds as low as 2 kHz. Following the pioneering work of Lippmaa and c o - ~ o r k e r s 'there ~ ~ was an explosion of interest in performing 29Si MAS NMR experiments on these materials. In general, for a zeolite there may be up to five different 29Si environments present, depending on the number of aluminium atoms connected to them via bridging oxygens. These may be denoted as Si(nA1) where 0 6 n 6 4 , and these give rise to peaks separated from each other by about 5 p p m (depending slightly on the structure, the Si/Al ratio and cations present). The Loewenstein rule,' which states that Al-0-A1 linkages are unfavourable, is believed to apply to all natural and hydrothermally synthesized zeolites and this means that the framework composition (%/A1 ratio) can readily be calculated from the relative intensities of the different Si(nAl) peaks.2,1",11Provided that sufficient time has been left between scans for the spectrum to be quantitative, it may be possible from the relative intensities of the different Si(nA1) peaks to distinguish between possible ordering schemes for the aluminium positions in the framework.12 The determination of the framework Si/AI ratio is a particularly important measurement as it enables various dealumination processes to be monitored. Heating an ammonium-exchanged zeolite in a water vapour atmosphere can result in the removal of some aluminium from the framework which is then replaced by silicon migrating from other parts of the c r y ~ t a 1 . This I ~ process is known as ultrastabilization in the case of zeolite Y (a synthetic version of the mineral faujasite), and gives an increase in the framework Si/AI ratio which results in improved thermal stability and higher acid strength. Most commercial catalysts are in this form. The bulk composition of the zeolite remains unchanged by this process (unless the sample is further treated to remove non-framework aluminium species), and so it is only through the 2ySi MAS NMR spectrum that the framework structural changes can be monitored in detail. 29Si MAS NMR spectroscopy has also revealed that it is possible to reinsert the aluminium species back into the framework by mild hydrothermal treatment with a strong base; this can restore the original Si/Al ratio for the The realuminated sample has, however, a different distribution of Si(nA1) peak intensities, implying a different ordering of aluminium within the framework to the starting material. Other ways of dealuminating the framework without losing significant crystallinity have also been developed including treatment with chelating agents such as EDTA,I7 treatment with SiC14 vapour at high temperatures18 and treatment with aqueous ammonium hexafluorosilicate solution. l9 These other methods have also been studied by 29Si MAS NMR spectroscopy to a greater or lesser extent .20,21
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It is worth noting that the 29Si MAS NMR spectrum provides indirect information about the Si-OH-AI Bronsted acid sites in the hydrogenexchanged form of the zeolite. The different Si(nAl) units for n = 1-4are likely to have bridging hydroxyl units of different acidic strengths. A recent study found four infrared stretches for hydroxyl groups hydrogen bonded to benzene or chlorobenzene in zeolites X and Y, and an attempt was made to correlate the intensities of these with the four types of bridging hydroxyl units anticipated from the 29SiNMR spectrum.22 The situation is more complicated for zeolites with more than one crystallographic site, such as mordenite, offretite and zeolite omega.23In the case of zeolite omega, for example, there are two distinct crystallographic sites in the relative population ratio of 2:l corresponding to sites in the 12-membered rings, and sites that are only in the eight-membered rings. The difference in chemical shift between these sites is such that there is overlap between the Si(nAI)* peaks from site A with the Si(n+l A1)B peaks from the other site. This means that a simple interpretation of the spectrum to obtain the framework SUAI ratio is not possible. Allowance for the existence of the two sites during deconvolution of the spectrum does lead to a satisfactory analy~is.’~In those cases where there is more than one crystallographic site, it may be necessary to dealuminate the sample so that the 29Si NMR spectrum shows only the Si(OA1) peaks. Such a spectrum immediately shows the number of distinct crystallographic sites in the zeolite, and allows their position to be determined which can be an important aid in the analysis of the spectrum of the sample before d e a l ~ m i n a t i o nThe . ~ ~positions of the peaks are, however, shifted slightly by the change in SUAI ratio of the framework. Another method of determining the true position of distinct Si(0AI) peaks without dealuminating the sample was recently demonstrated by Anderson who measured spin-echo Fourier transform (SEFT) spectra of zeolites using different echo times.25 This can give T2-selective spectra in which only those environments which have comparatively long T2 relaxation times appear. In the case of zeolites it is found that, due to the influence of aluminium in the first coordination sphere, Si(nA1) with n>O have significantly shorter T2 relaxation times than Si(0AI) sites. Thus in the case of modernite the spectrum recorded after the spin-echo shows only Si(OA1) environments (see Fig. 1). This method also successfully identifies the Si(0AI) peak positions of the two distinct crystallographic sites in zeolite omega.25 A number of correlations between 29Si chemical shift and structural parameters such as mean Si-0-T bond angle (where T denotes either Si or Al) for both Si(OA1) and Si(nAl) peaks have been suggested.2c30 Perhaps the most reliable of these are the semi-empirical correlations of Engelhardt and Radeglia which show a linear dependence of chemical shift on cosO/(cosO - 1) where 8 is the mean Si-0-T bond angle.26,27 The sensitivity of the 29Si chemical shift to even small changes in local
NMR APPLICATIONS TO POROUS SOLIDS
-80
- 100
41
-120
6 /PPm Fig. 1. T2-selective "Si MAS NMR spectra of mordenite recorded using a SEFT pulse sequence with increasing echo delays from top to bottom. The delay between each spectrum is 51.2 ms. Note that resolution of the distinct crystallographic sites of the mordenite structure is not possible at this Si/AI ratio. (Reproduced with permission from M. W. Anderson, Magn. Reson. Chem., 1992, 30, 898.).25
geometry means that even the charge-balancing cations present have an influence on the spectrum. This may be useful as, for example, it enables NMR to demonstrate that cation exchange can take place between crystallites even in the solid state.31 Another recent utilization of the influence of cations affecting 29Si chemical shifts is in distinguishing between faujasite (cubic symmetry, denoted FAU) and its hexagonal symmetry analogue (sometimes referred to as Breck's structure six, denoted EMT) which coexist in zeolites ZSM-2 and ZSM-3 for example.32 Figure 2 shows that in the 29Si spectrum of the Na-exchanged forms of zeolite ZSM-2 the Si(nA1) peaks from the two polymorphs completely overlap. However, in the Li-exchanged forms the chemical shifts from the faujasite phase occur at higher frequency by about 3 ppm, while the chemical shifts in the hexagonal analogue are unaltered. This allows the relative amounts of the two phases to be determined, as well as their framework composition^.^^ Another way that cations can influence the 29Si spectrum will take place if the cation is paramagnetic. It has been recently demonstrated that partial ion exchange with Cu2+ in zeolite Y can cause selective broadening of the Si(4Al) peak, thus indicating the site preference for Cu2+ cations.33 The resolution of 29SiMAS NMR spectra of zeolites is mainly impaired by
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I
( I AllF + (2AllE
/
(4AIIF
4
(I AllE $
I
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I
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Fig. 2. "Si MAS NMR spectra of (a) Na-ZSM-2 and (b) Li-ZSM-2. The peak labels give the number of surrounding aluminium atoms for the faujasite (denoted F) and EMT (denoted E) components. (Reproduced with permission from J. A. Martens et al., J . Phys. Chem., 1993, 97, 5132. 01993, American Chemical S~ciety.)~'
the dispersion of chemical shifts within the sample, which is caused predominantly by the influence of aluminium slightly distorting the structure in its environment. Hence it is found that in highly crystalline dealuminated zeolites extremely narrow 29Sipeaks may be obtained, down to linewidths of 6 Hz in the case of silicalite (the completely siliceous form of zeolite ZSM-5) in which 21 of the 24 crystallographic sites can be resolved.34 Resolution at this level allows subtle changes in structure with temperature and phase changes in the presence of adsorbates to be e ~ a m i n e d .29Si ~ ~ ?spectra ~ ~ of dealuminated zeolites of complicated or unknown structure are particularly useful as they may be correlated with structural parameters and complement crystallographic The ability to observe narrow peaks in the 29Si spectrum of siliceous zeolites also offers the possibility of observing two-dimensional spectra of these materials in order to establish connectivities. The first such studies were performed by Fyfe and co-workers on a 29Si-enriched sample of ZSM-39 which still contained the organic template used in the synthesis.38339 This allowed cross-polarization to be used in order to shorten the delay time between scans which, together with the 29Si enrichment, meant that the applicability of different two-dimensional techniques could be explored in a reasonable time period. Figure 3 shows the two-dimensional COSY spectrum of ZSM-39 at 373 K, which clearly reveals cross-peaks between the Sil and Si2 sites, and between the Si2 and Si3 sites in agreement with the known
NMR APPLICATIONS TO POROUS SOLIDS
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3 1-124
I
Si2Si3
-112
t4 -108
@ sil si2
-104
-108
-112
-116
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-124
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6 /PPm Fig. 3. *'Si COSY experiment on ZSM-39 at 373 K. (Reproduced with permission from C. A. Fyfe et a!., J . Am. Chem. SOC., 1989, 111, 7702. 0 1989, American
Chemical S~ciety.)~'
structure. The additional structure in the Si3 cross-peak is real and reflects the absence of a three-fold symmetry axis in the sample studied. However, it is known that COSY experiments depend critically on T; relaxation and the experimental parameters need to be carefully chosen to optimize crosspeaks. Indeed, a COSY experiment at room temperature on ZSM-39 failed to detect the cross-peak between the Sil and Si2 sites as the TZ value of the Sil site at room temperature is relatively short.39 The possible use of double-quantum filtered COSY and spin-diffusion measurements was also explored.39 Fyfe and co-workers then extended their study to more complicated zeolite structures with natural *'Si abundance, investigating siliceous ZSM-12, ZSM-22, ZSM-5, ZSM-11 and zeolite DD3R.4w4 In the case of ZSM-12, an optimized COSY experiment revealed splittings in the cross-peaks in the F2 dimension indicating two-bond J(29Si-29Si) couplings between 9 and 1 6 H ~ . ~ This ' observation is particularly important as it
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enables two-dimensional INADEQUATE experiments to be performed. These have the great advantage that they remove the strong diagonal peaks from the spectrum and so weak cross-peaks close to the diagonal can be readily identified, but suffer the disadvantage that the technique is rather insensitive and extremely long experiment times are required. Notwithstanding this difficulty, successful INADEQUATE experiments have been performed and these have enabled the complete assignment of the 29Si peaks in the zeolites investigated, including the extremely complicated siliceous ZSM-5 structure in the presence of different adsorbate^.^^ Use of the J-scaled COSY technique has also been suggested as a useful assignment tool and demonstrated for siliceous m ~ r d e n i t e It . ~ can ~ be concluded that two-dimensional 2ySiNMR techniques can be extremely powerful characterization tools, but they depend critically on the sample giving narrow NMR lines. 2.1.2. 27AlNMR of zeolites
27Al MAS NMR spectra of hydrated zeolites normally only show a single peak in the range 50-65 ppm indicating tetrahedral environments, other coordinations being forbidden by the Loewenstein rule. The exact position of the peak depends on the structure and on the magnetic field as 27Al is affected by the second-order quadrupole interaction. In some cases it is possible to resolve more than one tetrahedral peak due to different crystallographic site^,^^,^^ but this is the exception rather than the rule even at very high magnetic fields. 27Al spectra of dehydrated zeolites may give far broader peaks; this is principally due to the fact that the aluminium sites experience higher electric field gradients and hence larger quadrupole coupling parameters. It has recently been shown by using a spin-echo method on a static sample that 27Al sites balanced by sodium cations in dehydrated zeolites Y and ZSM-5 have quadrupole coupling constants of 4.7 and 5.5 MHz respectively, while 27Al sites balanced by acidic hydroxyl groups have quadrupole coupling constants of 12.7 and 16 MHz .~ ' These latter values are so high that MAS techniques at accessible spinning speeds are inappropriate for the study of such environments. They also mean that caution is needed in the interpretation of 27Al spectra of dehydrated zeolites as some broad aluminium components may not be detected (depending on the method used). Hence, unless it is the structure of the dehydrated zeolite itself that is of interest, it is common to ensure that the zeolite is fully hydrated before acquiring the 27Al spectrum in order to avoid this difficulty. As well as tetrahedral aluminium environments in the zeolite framework, 27Al NMR will also detect any non-framework aluminium species. These are often, but not always, in octahedral coordination and so give rise to a well-separated resonance near 0 ppm. The investigation of non-framework aluminium has been a major topic of interest as such species can enhance
NMR APPLICATIONS TO POROUS SOLIDS
45
catalytic activity, probably by providing Lewis acid sites, and such species are present in steam-treated zeolite Y which is used on a large scale commercially. In early solid-state 27Al NMR work on these materials, the relative ratios of the 27Al peaks for tetrahedral and octahedral aluminium were often different from that expected on the basis of elemental analysis and the 29Si results. This difference was caused in part by the experimental conditions used, and in part by Si-OH defect environments complicating the 29Sispectrum. For quantitative work on half-integral quadrupolar nuclei in solids it is necessary to use very short pulses ( < d l 2 flip-angle for a spin I = 5/2 nucleus) and strong r.f. pulse^.^^'^ It is also advantageous to use as high a magnetic field as possible due to the second-order quadrupole interaction, and very fast magic-angle spinning to avoid overlap with spinning sidebands. 27Al spectra of steamed zeolite Y samples have been the topic of considerable debate, as in a number of spectra a peak at about 30ppm has been detected, as well as peaks at about 60ppm (framework tetrahedral) and 0 pprn (non-framework octahedral). This additional peak has been variously assigned to a tetrahedral environment with a high quadrupole coupling constant ,’* or to a five-fold coordinated en~ironment.’~The situation has been extensively studied by a variety of methods including two-dimensional quadrupole nutation” and ‘H-27Al cross-p~larization.’~~~’ The latter technique clearly showed that the peaks at 30 and Oppm were enhanced relative to that at 60ppm7 suggesting that the 30ppm species originates from a distinct five-coordinate environment. However, it is dangerous to draw firm conclusions from 27Al CP/MAS spectra of this nature as the different crystallite orientations present giving rise to the quadrupolar powder pattern may cross-polarize at differing efficiencies and so give rise to unexpected line shape^.'^ Much of the argument has finally been resolved in a recent double-rotation (DOR) study by Ray and S a m o ~ o n . ’They ~ investigated three samples of zeolite Y thermally treated in the presence of water vapour, two of which had been subjected to a single thermal dealumination removing about 25% of framework aluminium (samples LZ-Y72 and LZ-Y82), and one of which had been subjected to a second thermal treatment to remove about 65% of the framework aluminium (sample LZ-Y20). The 27Al MAS NMR spectra of these samples in both 14.1 T and 9.4 T magnetic fields were fairly similar, though the peak at about 30ppm was stronger in the sample that had experienced two heat treatments. The 27Al DOR spectra, however, gave different results for the samples, as shown in Fig. 4. The two samples which had a single thermal treatment gave tetrahedral peaks at 59 pprn and 47 ppm, which indicates in this case the peak at 30ppm in the MAS spectrum results primarily from distorted tetrahedrally coordinated aluminium (with a quadrupole coupling constant of the order of 6 MHz). The peak at 20-25 ppm is believed to be due principally to a spinning sideband. On the other hand, the sample which
46
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I.
I
I
00
1
I
I
I
I
0
40
I
I
1
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6 /PPm Fig. 4. ”A1 DOR NMR spectra of steam-treated zeolites: (a) LZ-Y20 (after two heat treatments), (b) LZ-Y82 and ( c ) LZ-Y72 (both after a single heat treatment). (Reproduced with permission from G . J . Ray and A. Samoson, Zeolites, 1993, 13, 410.)”
had been given two thermal treatments did not give narrower peaks on DOR, indicating that the linewidths were caused mainly by chemical shift dispersion rather than second-order quadrupole effects. Thus in this sample, the peak at 30 ppm arises principally from five-coordinate aluminium. The fact that this peak occurs at this position independent of magnetic field together with the results of the DOR experiment imply that this site has a fairly low quadrupole coupling constant. It is now known that this is indeed possible for certain five-coordinate aluminium g e ~ m e t r i e s .Hence ~~ it appears that the nature of the peak at 30 ppm depends on the sample’s exact thermal history, and it may have contributions from both four-coordinate and five-coordinate aluminium species. There has been another recent DOR
NMR APPLICATIONS TO POROUS SOLIDS
47
study on ultrastable zeolite Y, but the details of the sample preparation were not given.s9 This latter study found that most of the central peak was due to distorted tetrahedral aluminium, and pointed out that aluminium sites in zeolites can experience a broad distribution of electric field gradients and quadrupole interactions. It should be mentioned that while D O R removes broadening due to the second-order quadrupole interaction, much of the 27Al linewidth in the spectra of hydrated zeolites recorded at high magnetic fields arises from the effects of chemical shift dispersion, and so D O R has only limited applicability to the study of these materials.
2.1.3. N M R of Brgnsted acid sites One particularly useful experiment when studying zeolites is to look at the Bronsted acid sites directly using 'H NMR spectroscopy.6@62 This is, however, not quite as straightforward as it may first appear, as it is necessary to perform the experiment on dehydrated samples otherwise water would mask the signals of interest. For high-resolution work the dehydrated sample may be sealed in a glass ampoule designed to fit snugly inside the rotor for MAS studies, or alternatively packed into a specially designed air-tight rotor inside a glove-box. Fortunately for most zeolites the distance between 'H environments is sufficiently large that MAS alone is sufficient to give high-resolution spectra without using multiple-pulse line narrowing methods which can be difficult to implement successfully. The Si-OH-A1 B r ~ n s t e d acid sites in zeolites may give resonances between about 3.8 and 5.2ppm depending on acidic strength (affected by the Si/AI ratio) and the detailed structure. In zeolite Y, for example, two Brmsted sites are observed: one at about 4 p p m (peak B) due to bridging OH groups pointing towards the large supercage, and the second at about Sppm (peak C) arising from bridging OH groups pointing towards the smaller sodalite cages.63 However, 'H spectra of zeolites are rarely that simple as there will also be peaks due to non-acidic silanol hydroxyl groups at the surface and at crystal defects (1.3-2.3 ppm), from any Al-OH groups attached to non-framework aluminium species (2.5-3.5 ppm) and from any residual NH4+ cations (6.5-7.0 ppm). Attempts have been made to correlate the chemical shift of the hydroxyl groups with their infrared stretching frequencies.a The question of the inherent resolution of 'H MAS studies of zeolites has been addressed by B r u n r ~ e rwho ~ ~ showed that in aluminiumrich zeolites very fast spinning and high magnetic fields are advantageous as they remove the effects of residual 'H dipolar broadening. In medium strength magnetic fields at moderate spinning speeds partial deuteration of the sample can significantly enhance resolution (see Fig. 5).65 It is not always the case that high-resolution 'H spectra are desired as
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20
0
1 0
-10
6 /PPm Fig. 5. 'H MAS NMR spectra recorded at 300 MHz with 3 kHz MAS: (a) zeolite H-Y (Si/Al = 2.6), and (b) partially deuterated sample. (Reproduced with permission from E. Brunner, J . Chem. Soc., Faraday Trans., 1993, 89, 165.)65
static 'H spectra can give information about distances between nuclei. Thus the second moment of the static 'H spectrum has been used to calculate that the mean distance between a framework aluminium atom and the acidic bridging hydroxyl hydrogen atom is 2.38 ? 0.04 A in zeolite H-Y and 2.48 ? 0.04 &. in zeolite H-ZSM-5.66 Spinning sideband intensities in the 'H MAS experiment have also been analysed giving an Al-H distance of 2.5 A in zeolite H-ZSM-5.67 More recently, the spin-echo double resonance (SEDOR) technique has been applied to measure 27Al-iH dipolar coupling directly, and this gives an A1-H distance of 2.43 f 0.03 Thus it is clear that NMR can be used to obtain detailed information about the geometry of the Brmsted acid sites, which may be compared with the results of ab initia quantum chemical calculation^.^^ Wideline 'H NMR has also been used as the basis of a proposed acidity
NMR APPLICATIONS TO POROUS SOLIDS
49
scale by measuring spectra at very low temperatures (4K) on samples containing the same number of water molecules as Bronsted acid sites.70 The resulting dipolar-coupled spectra may be fitted to include contributions from H 3 0 + ions, H 2 0 - H O hydrogen-bonded groups, O H groups of the solid and unbonded H 2 0 molecules. In zeolite H-Y, for example, it is found that with increasing water content the number of H 3 0 + ions and H 2 0 - H O groups increases at the expense of acidic OH groups in the solid not bonded to water. Above a concentration of one water molecule per Brmsted acid site there is no change in the concentrations except that a contribution from non-bonded H 2 0 is now ~ b s e r v e d . ~These ' results provide a basis for measuring acidities of Brmsted sites in solids as high proportions of H30+ groups will be detected in highly acidic solids, predominantly H 2 0 - H O groups will be detected for mildly acidic solids, while non-acidic solids will not give rise to either group. 'H MAS has also been used profitably to look at deuterated Brmsted acid sites in zeolites,48 and the quadrupole coupling constant of the Si-OD-A1 sites increases with framework aluminium content of the zeolite from 208 kHz (zeolite H-ZSM-5) to 236 kHz (zeolites H-X and H-Y). Probe molecules that are basic may also be used to study acid sites in zeolites. Bases such as ammonia, trimethylamine, pyridine, acetonitrile and trimethylphosphine may bond to Bransted or Lewis acid sites, and these may be studied by 'H, 13C, "N or 31P NMR as appropriate. 'H NMR chemical shifts of ammonia, water and methanol molecules interacting with Bronsted acid sites have been calculated using ab initio calculations.71 Experimental 'H MAS NMR spectra of methanol adsorbed inside zeolites show that the O H resonance position is highly influenced by the formation of methoxonium ions and by the extent of hydrogen bonding within the pore system.72 For instance, the methanol O H resonance comes at 9.4ppm in H-ZSM-5, 5.1 ppm in H-Y, 4.7 ppm in Na-Y and 3.6 pprn in Na-ZSM-5. 'H MAS NMR has also been used to observe hydrogen bonding as a function of temperature for acetylene, ethylene, carbon monoxide and benzene in zeolite H-ZSM-5.73 I5N NMR spectroscopy of "N-enriched ammonia adsorbed in zeolite H-Y (recorded with or without cross-polarization) can give peaks due to NHZ cation^.^^,^' The number of "N resonances observed depends on sample loading as there can also be peaks from NH3 hydrogen-bonded to NH: cation^.^' 'H MAS NMR has also recently been used to study ammonia adsorbed inside zeolite Y with different loadings and different cations.76 There are at least two ammonium species which show fast hydrogen exchange with B r ~ n s t e dhydrogen atoms; these probably arise from the difference between the acid sites in the supercages and in the sodalite cages. A peak due to NHZ without exchange may also be detected at 8.1 ppm in some cases. The results of 15N studies of trimethylamine adsorbed within zeolite H-Y clearly show the formation of [(CH3)3N-H]+.75 The spectra
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only show a single peak, presumably because hydrogen-bonding effects are negligible with this base. The larger size of this base should preclude entry into the smaller sodalite cages. The 15N linewidth observed depended on sample history.75 Studies of pyridine inside zeolites using I5N NMR can in principle clearly distinguish between physisorbed species, Lewis acid sites and pyridinium ions (bonded to B r ~ n s t e dacid sites).77 'H NMR spectra of pyridine have also been used to distinguish between accessible and non-accessible Bransted acid sites in zeolites.63 The use of trimethylphosphine as a sensitive probe that can be studied by 31PNMR has been similarly explored, and in the absence of proton decoupling, J-coupling between 31Pand 'H can sometimes be observed for [(CH3)3P-H]+ cations (Fig. 6).78,79Species due to trimethylphosphine bonded to different Lewis acid sites arising from non-framework aluminium in dealuminated zeolites can also readily be detected.797s0In the event that oxygen is not rigorously excluded from the sample, then there may also be 31P peaks from phosphine oxide environments.80 While acid sites in zeolites have received much attention, some reactions may occur through basic sites, and there has been a recent suggestion that nitromethane may be a suitable probe molecule for investigating these." 2.1.4. N M R studies of other nuclei in zeolites The other framework element in zeolites is oxygen, and this too can be studied by solid-state NMR if a degree of I7O isotopic enrichment is used. The lineshapes are dominated by the second-order quadrupole interaction. Due to their difference in quadrupole coupling constants, Si-0- A1 environments may be distinguished from Si-0-Si environment^.^^,^^ Values of the quadrupole coupling constant may either be obtained from static spectra (which has the disadvantage that there are additional contributions to the lineshape from chemical shift anisotropy), or from MAS spectra (which has the disadvantage that the quadrupolar features are less distinct). Si-O- Al environments typically have NMR parameters of e2qQ/h = 3.1-4.3 MHz, 17 = 0.2 and ais0 of 31-45ppm, while Si-0-Si environments have 2qQl h = 4.6-5.8MHz7 17 = 0.1 and ais0of 4 4 - 5 7 ~ p m . ~ ~ , * ~ A number of other elements can be isomorphously substituted into zeolite frameworks to a greater or lesser extent. Gallium can be incorporated into the framework of a number of zeolite structures, and it affects 29Sispectra in a similar fashion to aluminium.84 The @Ga and 71Ga isotopes can also be studied directly by NMR. Due to the differences in Larmor frequencies and quadrupole moment of these isotopes (both of which are spin Z = 3/2), they experience different second-order quadrupole interactions, and so measurement of both the 69Ga and 71Ga isotopes enables an estimate of the quadrupole coupling magnitude to be ~ b t a i n e d . ' ~In the case of Gasubstituted H-ZSM-5 it is found that the quadrupole coupling constant at
NMR APPLICATIONS TO POROUS SOLIDS
240
160
00
0
-80
-160
51
-240
6 /PPm Fig. 6. 3'P MAS NMR spectra of PMe3 adsorbed on zeolite H-Y: (a) with 'H decoupling showing peaks at -67 and -2 ppm due to physisorbed and chemisorbed PMe3 respectively, and (b) without 'H decoupling, showing 3'P-1H J-coupling for the
chemisorbed species, and spinning sidebands resulting from dipolar coupling to protons. (Reproduced with permission from W. P. Rothwell et al., J . Am. Chem. SOC.,1984, 106, 2452. 01984, American Chemical Society.)78 the G a sites is rather larger than for analogous aluminium environments (69Ga 3.0MHz7 7'Ga 1.9MHz, 27Al O . ~ M H Z ) . 'The ~ loss of tetrahedral gallium upon thermal treatment in a process akin to dealumination has also been explored in Another element that can have a profound effect on catalytic behaviour when in the framework is titanium. The 29Si spectrum of TS-1 (the titanium-containing analogue of ZSM-5) shows broad peaks due to Si(4Si) and Si(3Si,lTi) environments, and changes with temperature." Modification of zeolite H-ZSM-5 by impregnation with phosphoric acid is one way of altering catalytic activity and selectivity, and this reaction has also been studied by NMR.89-91 It appears that the acid initially causes partial dealumination resulting in a reduction of Brmsted acid sites and the formation of amorphous aluminium phosphate within the pores. However, subsequent thermal treatment of the modified zeolite can give a lower degree of dealumination than would have been the case for the unmodified zeolite. Hence the treatment can affect catalytic activity, selectivity and diffusivity. There is no evidence for phosphorus incorporation into the framework. There have been comparatively few studies of cation environments in
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zeolites directly by NMR. This is because most of the cations of interest are quadrupolar. In the case of sodium cations, 23Na NMR spectra show a fairly narrow average peak for hydrated zeolites, while in the dehydrated form only a broad peak is observed due to a large increase in quadrupole coupling constant. There have recently been several 23Na studies of dehydrated zeolite Na-Y using D O R which gives a significant improvement in resolution. The first of these observed three peaks, which were assigned to Na in sites I , I' and II.92-94 However, another study only detected two 23Na e n ~ i r o n m e n t s while , ~ ~ a more recent study concluded that there were four distinct 23Na sites on the basis of simulation of the spinning sideband^.'^ These differences in assignment may be due in part to the magnetic field dependence of the second-order quadrupole interaction; it is also possible that traces of residual water affect the results. 23Na D OR spectra were also obtained on loading dehydrated zeolite Na-Y with water and t r i m e t h y l p h ~ s p h i n eThese . ~ ~ cause significant changes in sodium environment due to coordination to the cation. The interaction of the sodium cations with Mo(CO)~has also been explored.93 This is of interest as M o ( C O ) ~can be converted to M o o 3 inside the zeolite. In slight contrast to the 23Na D O R results,95 Mo TI measurements on M o ( C O ) ~inside zeolite Na-Y indicate that Mo(CO)~experiences significant rotational freedom within the supercages, with a correlation time at room temperature three orders of magnitude higher than in solution.97 The motion of adsorbates within zeolites has been the subject of a large number of studies. lZ9Xe NMR and pulsed field gradient (PFG) NMR studies to measure diffusion coefficients of adsorbates are discussed in later sections of this review. Static *H NMR spectra as a function of temperature have proved to be particularly useful in characterizing molecular reorientations of deuterated organic molecules inside zeolite^.^^^^ For instance, *H NMR shows the existence of a binding site for C6D6 in zeolite Na-Y, presumed to be sodium cations on site SII, while isotropic reorientation of benzene occurs even at temperatures as low as 155 K within a siliceous form of zeolite Y containing no cations."" A recent advance in the study of organic molecules within zeolite molecular sieves is the use of multiplequantum NMR to measure the apparent spin network size as a function of excitation time. This has been applied to 'H spins in hexamethylbenzene and benzene inside zeolite Na-Y. In principle the results correspond to the number of 'H spins present inside a zeolite cavity, thus giving the average number of molecules within each cavity. 1023103
2.1.5. In-situ NMR studies of catalysis by zeolites There has recently been an upsurge in using NMR to study catalytic reactions taking place inside the zeolite. The general approach is to use I3C-enriched reactants, and to seal the sample inside an air-tight container
NMR APPLICATIONS TO POROUS SOLIDS
53
such as a glass ampoule.lm Spectra may then easily be measured at room temperature after heating the sample at a particular temperature for a known time ,105,106 or alternatively acquired truly in situ by heating the sample in the probe. lo' A whole range of hydrocarbon transformations inside zeolites have now been observed by these methods, and the 13C NMR spectra have shed new light on reaction intermediates, reaction mechanisms and aspects of shape selectivity. There has been an elegant series of papers by Haw and co-workers who have developed designs for preparing catalyst-adsorbate samples suitable for in situ MAS work while still allowing subsequent adsorption of additional reagents to be made. 108~109The same group have also successfully adapted a probe to allow temperatures as high as 673 K to be reached so that zeolite catalysts can be studied at the same temperature at which they are employed commercially. 'lo The conversion of methanol to gasoline in a single step (MTG reaction) using zeolite H-ZSM-5 has been studied over many years, but the mechanism, particularly with regard to the formation of the first C-C bond, remains a subject of debate. This reaction is one of the most successful routes to synthetic fuels, and now produces one third of New Zealand's gasoline supply. 13C relaxation time measurements of methanol adsorbed within H-ZSM-5 have shown that there may be up to three different species present at room temperature depending on SUA1 ratio. The variable temperature 13C NMR studies have shown that methanol is first dehydrated to dimethyl ether at relatively low temperatures. After heating to temperatures of 573 K and higher a whole range of aliphatic and eventually aromatic products form within the zeolite (see Fig. 7). The distribution of products inside the zeolite is different from that expected on thermodynamic grounds, indicating shape selectivity at the active site, and differs from the distribution of products that can escape from the zeolite due to product selectivity. 105~106High-temperature in situ studies have shown that ethylene is the first olefin produced in the reaction and that water from the dehydration reactions can substantially modify the observed acidity. '12 The mobility of the adsorbed species means that conventional two-dimensional methods may be used to help with peak assignment^.'^^^'^^ In some cases carbon monoxide may be observed before the transformation to higher hydrocarbons. This was initially suggested to be a reaction intermediate of potential ~ i g n i f i c a n c e , ~but ~ ~ ~this ' ~ ~has subsequently been questioned following results showing that addition of 13C-enriched carbon monoxide and natural abundance methanol to zeolite H-ZSM-5 did not result in the formation of any hydrocarbons containing significant amounts of 13C.'15 The most popular proposed mechanism for C-C bond formation involves the formation of a trimethyloxonium ion. This proposal suffers the drawback that this ion has not been detected in 13C NMR results on methanol conversion. It has, however, been detected at room temperature in the expected position of 80 ppm for H-ZSM-5 samples loaded with dimethyl
"'
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z 5 min at 523 K
45min at 5 2 3 K
I
6 0 min at 523 K
I
I 75 min at 523 K
250
200
150
100 8 /PPm
50
0
-50
Fig. 7. In situ I3C MAS NMR spectra showing the conversion of "C-methanol to hydrocarbons on ZSM-5 recorded at the temperatures indicated. Expansions of the aromatic region are also shown. (Reproduced with permission from E. J. Munson ef al., J. Phys. Chem., 1992, 96, 7740. @ 1992, America1 Chemical Society.)"'
ether (a known intermediate in the MTG process).'16 Thus the exact mechanistic role for trimethyloxonium ions in this reaction is still uncertain. There have recently been further studies of trimethyloxonium, trimethylsulphonium and trimethylselenonium ions in zeolites using in situ I3C NMR."' The conversion of olefins inside zeolites has also been studied, and reaction intermediates have been detected at low temperatures (down to 143K)."s121 It is beyond the scope of this review to discuss all the other acid-catalysed reactions which have been studied by in situ I3C
NMR APPLICATIONS TO POROUS SOLIDS
55
~~~,107,110,122-125 though the power of the technique has hopefully been demonstrated. One other catalytic reaction studied by NMR is worthy of mention as it proceeds essentially via a basic reaction mechanism, unlike most transformations in zeolites. It is also of interest because this reaction was discovered by NMR. 13C NMR shows that methyl iodide forms framework-bound methoxy species within alkali-metal exchanged zeolites such as Cs-X,126,127and these react to form ethylene and other hydrocarbons at temperatures as low as 500 K.'26
2.2. Aluminophosphate-based molecular sieves Since 1982, several new families of molecular sieve based on aluminophosphate framework structures have been synthesized, and these exhibit many properties similar to those of aluminosilicate zeolites. The first such family, known as the AlP04 molecular sieves, is composed of alternating A104 and PO4 tetrahedra. As they have neutral frameworks, the A l P 0 4 family possess no exchangeable cations, but are of potential application as molecular sieves and hosts for guest materials. 128,129 Some of these materials have the framework topologies of known zeolites, but many have novel crystal structures. 13" Incorporation of a reactive source of silicon into an aluminophosphatebased synthesis mixture can result in the formation of framework silicoaluminophosphates (denoted SAPO), while addition of metals can give metalloaluminophosphates (MeAPOs). The metals most commonly used are magnesium, manganese, iron, cobalt and zinc, though others such as vanadium, chromium, nickel and tin have also been claimed to be incorporated into the framework structures. Some of these new materials have the framework topologies of known zeolites or AlP04 structures, while many have novel structures. 1 3 1 ~ 1 3 2The SAPO and MeAPO molecular sieves resemble zeolites in that, as well as being molecular sieves, they have negatively charged frameworks balanced by cations located within the channels. Thus they have potential uses as ion-exchangers and catalysts. A number of other elements have also been claimed to substitute into the framework of aluminophosphate-based molecular sieves, including lithium, beryllium, boron, titanium, gallium, germanium and arsenic, giving ElAPO materials. It is also possible to accommodate more than one different heteroatom into the framework, and to have both metals and silicon simultaneously in the framework, giving rise to MeAPSO and EIAPSO species. 132 Once again, this leads to several new structural types being formed. This wide variety of novel molecular sieves (over 50 structure types) and their compositional variants offer a large number of parameters to tailor to specific adsorption or catalytic requirements. One particular feature of the
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structure of many of these materials, in contrast to zeolites, is the capability of framework aluminium to bind to one or two extra-framework oxygen species such as -OH or -OH2, and thus have a higher coordination number than four. 133 Prompted by the considerable information gleaned from solid-state NMR studies of zeolites, there have been a large number of NMR investigations into the structure and the ordering of the framework elements in these materials and these have been reviewed.134
2.2.1. Studies of A1PO4 molecular sieves Both 27Al and 31P are sensitive nuclei, so NMR spectra can easily be obtained. 31P chemical shifts for P(OAl)4 environments in AlP04 materials are normally between -23 and - 3 5 ~ p m . lA~ ~correlation between mean P-0-A1 bond angle and 31P chemical shift has been suggested for dense AIP04 phases,135and seems to work respectably in those cases where the 31P is bonded via oxygens to four tetrahedrally coordinated aluminiums. However, there may be significant deviations to higher frequency in those AIP04 materials containing higher coordinated aluminium, and 31P peaks as high frequency as -5.7ppm have been r e ~ 0 r t e d . lGenerally ~~ the 31P spectrum is capable of revealing the number of crystallographic sites, though there may be considerable overlap between the different sites. For example in hydrated AlPO4-ll four of the five sites give rise to a composite peak at -29.6 ppm, while the fifth gives a resolved peak at -23.4 The use of 31P MAS NMR to reveal structural information is well illustrated by the example of VPI-5. This aluminophosphate has attracted great interest since its discovery, as its structure consists of channels circumscribed by 18-membered rings, which are larger than those found in any known aluminosilicate zeolite. 137 Early structural refinements suggested that there were two crystallographic sites for both phosphorus and aluminium in the population ratio of 2:1,138,139and two 31P NMR peaks are indeed observed in this intensity ratio for dehydrated VPI-5.l4' However, for hydrated VPI-5, the 31P MAS NMR spectrum clearly shows three peaks of equal intensity, indicating that in this form there are three distinct sites.14' Following this NMR study and others, there was an improved crystallographic refinement of hydrated VPI-5 which successfully took into account the structure of the water within the channels in order to remove the di~crepancy.'~~ It is interesting to observe that it is possible to transform hydrated VPI-5 to the high-temperature phase even in the presence of water, and this has been elegantly demonstrated by variable temperature NMR. Heating the sample in a sealed rotor so that water vapour cannot escape shows that the water motion within the channels at temperatures above 80°C is such that the high-temperature phase is adopted, and that this transition is completely reversible upon cooling (Fig. 8).142,143
NMR APPLICATIONS TO POROUS SOLIDS
57
A
fl70"C
0,
.-0C
(L 0
V
120°C
80°C
(c)
Q,
c .+
60°C
(b)
0
-20
0
b)
I
-40
6 /PPm Fig. 8. Variable temperature 31PMAS NMR spectra of hydrated VPI-5 in a closed rotor system. (Reproduced with permission from L. Maistriau et al., A p p l . Catal. A : General, 1992, 81, 67.)'43
The fact that framework aluminium in A1P04-based materials can exist in four-, five- and six-fold coordination means that 27AlMAS NMR becomes a particularly useful characterization tool, particularly at high magnetic fields when the complications arising from the second-order quadrupole interaction are reduced. Thus in the case of hydrated VPI-5, 27Al MAS NMR shows that one-third of the aluminium is in octahedral coordination due to additional bonding to two water molecules. The two distinct tetrahedral sites have very similar isotropic chemical shifts, but may be resolved by DOR at magnetic field strengths of 9.4 T or lower as they have different quadrupole coupling parameters. 144~145
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The assignment of the three 27Al and 31P NMR peaks in VPI-5 to specific crystallographic sites is an important question. However, there are conflicting assignments in the literature based on considerations such as the spectral changes that occur with temperature and mean P - 0 - A1 bond angles. More direct information on spectral assignment may be obtained by more sophisticated NMR techniques, and these have been demonstrated on VPI-5 as a model system. Coherence transfer between spin Z = 1/2 and quadrupolar nuclei is possible and both 27Al+31P and 31P+27A1 crosspolarization (CP) spectra have been achieved on VPI-5.'46 Recently it has been demonstrated that improved coherence transfer between these nuclei in VPI-5 occurs if the CP process takes place while the sample is spinning parallel to the magnetic field (and then switched to the magic-angle during d e t e ~ t i o n ) . 'This ~ ~ is due to the significant reduction in TI, relaxation time of quadrupolar nuclei under MAS condition^.'^^ Experiments using pulse sequences based on rotational-echo double-resonance (REDOR) and transferred-echo double-resonance (TEDOR) methods have also been demonstrated on VPI-5; these pulse sequences restore the heteronuclear dipolar coupling between the nuclei under MAS conditions. 14s151 Thus two-dimensional heteronuclear correlation experiments can be performed as an aid to spectral assignment. A two-dimensional 27Al-31P correlation spectrum on VPI-5 is shown in Fig. 9. All three P sites give correlation peaks indicating proximity to both tetrahedral and octahedral aluminium, but the 31P site at -33.6ppm gives a noticeably stronger correlation to the octahedral aluminium site indicating unambiguously that it arises from the P1 site sharing four-membered rings (which is linked via oxygens to two octahedral aluminiums rather than just one). Despite the use of these methods, a full assignment of the 27Al and 31P NMR peaks in VPI-5 to specific peaks still relies on correlations involving bond angles, 27Al quadrupole coupling parameters or cluster model calculations of the interaction of water within VPI-5, and there is still disagreement in the literature.145*152,153 NMR studies have also been performed on molecules within the channels of VPI-5. The small amount of organic material retained during synthesis gives a high-resolution 'H MAS NMR spectrum when acquired using a spin-locking pulse sequence (which has the effect of suppressing the 'H signal from water).'54 13C NMR spectroscopy has been used to show that buckminsterfullerene, C60, may be accommodated intact within the The dynamics of adsorbed molecules such as D 2 0 and ND3 within the channels of VPI-5 have been studied by variable temperature static 2H NMR spectroscopy. 157~158 As the A l P 0 4 molecular sieves are highly crystalline and can have a range of different sites, they have proved ideal candidates to demonstrate the power of the D O R technique to remove second-order quadrupolar linebroadening. As well as the studies on VPI-5,144,145there have been D O R
NMR APPLICATIONS TO POROUS SOLIDS
C'
I
59
I
!
Q
0-
%
-
(0
$ N
w
501
1 0
0
-2 0
-40
-60
31P6/ppm Fig. 9. Solid-state 2D heteronuclear 27Al-31Pcorrelation spectrum of hydrated VPI-5. (Reproduced with permission from E. R. H. van Eck and W. S. Veeman, J . Am. Chem. SOC., 1993, 115, 1168. 01993, American Chemical S~ciety.)"~
studies on AIPO4-11,136,159 AlP04-8 and -14,16' AlP04-18,'61*'62 and AIP0421 and -25.'63 Even though D O R removes the anisotropic part of the second-order quadrupole interaction, there still is a field-dependent shift of the resonance peaks so that even in D O R studies it is helpful to record the The "A1 DOR spectrum at more than one magnetic field spectra have been particularly useful in probing the structural changes that occur on adsorption of polar species into the molecular sieve. In the case of A1P04-18 for instance, a material which is isostructural with the natural zeolite chabazite, there are major changes in structure upon adsorption of methanol, ammonia and water (see Fig. The as-prepared sample contains two tetrahedral and one five-coordinate aluminium site in agreement with the crystallographic structure s01ution.l~~ There is a structural change upon calcination, and then further changes that are reversible upon adsorption of polar species. In the case of saturation with methanol, the D O R spectrum (Fig. 10) shows that there are now four sites present in the ratio 1:2:1:2 with the last being a five-coordinate species. It is interesting to note that the formation of five-coordinate aluminium in this material requires the presence of more than one methanol molecule per cavity.'64 In
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t
80
I
I
I
40
I
0
I
1
I
-40
/PPm Fig. 10. 27Al DOR NMR spectra of A1P04-18: (a) as prepared, (b) methanolsaturated, (c) ammonia-saturated and (d) water-saturated. Dots indicate spinning sidebands. (Reproduced with permission from J. Janchen et al., J . Phys. Chem., 1993, 97, 12 042. 01993, American Chemical Society.)161
contrast, loading with ammonia or water produces substantial amounts of octahedral aluminium instead of five-coordinate aluminium, and little change in the resonance positions of the tetrahedral aluminium sites relative to the as-prepared sample. 164 These results nicely show the use of 27AlDOR NMR for probing changes in structure in the presence of adsorbates. Two-dimensional 27Alquadrupole nutation has also been applied with some success to the study of A1PO4 materials, as has 27Al CP/MAS.16" However, a certain degree of caution is needed in the interpretation of spectra recorded using these techniques as the orientation dependence of the second-order quadrupole interaction can produce unexpected results.56
NMR APPLICATIONS TO POROUS SOLIDS
61
The 1 7 0 environment in some AlP04 molecular sieves has also been observed, and shown to have a rather larger quadrupole coupling than in zeolites or silicates.165
2.2.2. Studies of SAPO molecular sieves The SAPO molecular sieves are frequently considered to be aluminophosphate frameworks with some isomorphous substitution by silicon. The location of the silicon has been a major topic of interest, and three possible mechanisms for silicon substitution can be envisaged:
(1) substitution of silicon into aluminium sites; (2) substitution of silicon into phosphorus sites; (3) simultaneous substitution of two silicon atoms for an aluminiumphosphorus pair. Chemical analyses invariably show that the phosphorus content is less than the aluminium content so that the framework has a net negative charge. This indicates that mechanism 2 must dominate over mechanism 1. However, the amount of aluminium present is often less than that expected if mechanism 2 was occurring alone, so it appears that some painvise substitution (mechanism 3) can also occur. 31P MAS NMR spectra of SAPO materials are normally identical to that of the analogous AlP04 framework, indicating that all phosphorus sites are in P(OAl)4 environments.lM Hence there are no P-0-Si bonds present. 27Alspectra are more complex, and can have broad underlying peaks as well as narrower peaks due to tetrahedral and octahedral aluminium. 29Si MAS NMR spectra tend to be of low quality due to the lower sensitivity of this nucleus and the relatively small amounts of 29Si present. In a number of cases it is clear that the idealized silicon for phosphorus mechanism is obeyed and a single peak for Si(OA1)4environments is while in a number of others there are additional 29Si peaks due to more siliceous environment^.'^^^^^^'^^ These have been suggested to arise from “silica islands” within inhomogeneous crystallites indicating that some pairwise substitution (mechanism 3) is also occurring. 174~175,178However, there is also the complication that small amounts of amorphous silica coating the crystallites will also give rise to 29Sipeaks in this region and the elemental analyses observed. 182,183 As in the case of AlP04 molecular sieves, there may be modifications to SAPO structures in the presence of adsorbates such as water. For instance, water can cause the complete collapse of the structure of SAPO-37. In the case of SAPO-34, on the other hand, 29SiNMR has shown that water causes the opening of Si-0-A1 bonds giving Si-OH and A1-OH species, but this process is reversible on dehydration. lS4
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In an analogous fashion to work on zeolites, 'H MAS NMR spectroscopy has been used to probe Brmsted acid sites d i r e ~ t l y , ~and ~ ~ hydrocarbon ,'~~ transformations within the molecular sieve have been studied by 13C ~~~.169,185 2.2.3. Studies of other AIP04-based molecular sieves Solid-state NMR spectroscopy has provided some of the clearest evidence for the incorporation of metals into the frameworks of MeAPO species. In the case of a sample of MAPO-20 (the magnesium aluminophosphate analogue of sodalite) well-resolved 31P peaks corresponding to P(OA1)3(OMg) and P(OAl),(OMg), are observed for a sample containing 15% magnesium on the tetrahedral sites.'86 Only a single 27Al NMR peak is observed. This shows that the magnesium is present exclusively on the aluminium sites and allows the framework composition to be calculated from the relative areas. The areas also enable alternative ordering schemes for the framework elements to be distinguished. lS6 Other magnesiumcontaining MeAPO species have also been studied by NMR.lS7 However, a degree of caution is needed in using 31P spectra to gain information on the extent of metal substitution, as many of the MeAPO structures have more than one crystallographic site and so give rise to multiple peaks even in the absence of incorporated metal. In those cases where the metal is paramagnetic, the 27Al and 31P spectra show large anisotropies, manifested in an array of spinning sidebands, due to the paramagnetic interaction between the unpaired electrons on the metal and the 27Al and 31P nuclei in the vicinity. 188~189It is possible to simulate the spinning sideband patterns to obtain the paramagnetic coupling, and a calculation on MnAPO-5 suggested that manganese was present in both framework and non-framework positions. 190 2.3. Other microporous materials
2.3.1. Microporous frameworks There are a number of other inorganic microporous framework solids with novel compositions that have recently been synthesized; these include gall oars en ate^'^^ and gall opho~pha t e s,'~ '-'~alurnin~arsenates,'~~~~~ ~ beryllophosphates.2m There are also a range of titanosilicates which have structures related to zeolite^.^^^-^^^ One gallophosphate of significant interest is known as cloverite; its structure consists of large supercages with a body diagonal length of 29-30 A accessed through cloverleaf-shaped 20-membered ring windows (larger than any known zeolite or AIP04).193The large supercage may be of particular
NMR APPLICATIONS TO POROUS SOLIDS
63
use as a host for preparing nanosized particles of potential application in materials science. Several characterization studies of cloverite have now appeared which include the use of NMR. 194,204207 The 31PNMR results are in broad agreement, and indicate a range of tetrahedral phosphorus sites including P-OH environments in line with the crystal structure. 193 However, there are differing interpretations of the 71Ga NMR results. Five gallium sites are expected, including a Ga-OH environment. 'lGa MAS NMR spectra appear to give peaks due to two differently coordinated gallium environments. 194,205 However, static 71Ga spectra recorded on cloverite at two magnetic fields indicate that the second-order quadrupole broadening is so large that MAS is not appropriate.2M This is because the maximum achievable spinning rate is less than the linewidth due to the second-order quadrupole interaction. The quadrupole coupling constants for the 71Ga sites were estimated to be of the order of 12.8MHz from the static spectra.206 Changes in the 31P, I9F (fluorine is present from the synthesis conditions) and 'H NMR spectra with temperature have also been reported.204 An example of the use of NMR was recently provided by the structural determination of the titanosilicate ETS-10 by Anderson et a1.*08 This material was discovered in 1989 and has only been synthesized with a very small particle size (so single crystal techniques are inappropriate) and exhibits significant long-range disorder. The structure consists of cornersharing S i 04 tetrahedra and T i 0 6 octahedra linked through bridging oxygen atoms. A crucial aspect in the structure determination was establishing the local silicon environment by 29Si NMR, which could then be combined with electron microscopy and powder diffraction results to propose a structure. Figure 11 shows the 29Si MAS NMR spectrum of ETS-10 which shows that there are four Si(3Si,lTi) environments (two of which virtually overlap) and one Si(4Si) environment, and these can be related to the silicon locations in 12-membered rings or seven-membered rings of ETS-10. The pore system consists of 12-membered rings (size 7.6 X 4.9 A), and can be subject to considerable disorder. It is interesting to note that some of the ordered variants of ETS-10 are chira1.208
2.3.2. Layered microporous materials There are also a wide variety of microporous materials based on layered materials. Pillared and intercalated clays have been known for many years, and many have potential as catalysts.2w It is also possible to create microporous layered materials from phosphates, titanates and metal oxides using a variety of pillar^.^^^^^^ Early common pillaring agents were large organic cations, though these tend to have low thermal stability, and alumina and silica species. The use of more complex pillaring agents including organosilicon compounds such as NH2(CH&Si( OCzH5)3, the
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Si(3Si. ITi) 2
Fig. 11. 29Si MAS NMR spectrum of titanosilicate ETS-10. LReproduced with permission from M. W. Anderson et al., Nature, 1994, 367, 347.)’ *
aluminium Keggin ion [A11304(OH)24(H20)12]7+ and the zirconium tetramer [Zr(OH)2(H20)4],8f have led to microporous materials with relatively high thermal stabilities. Particular areas of importance are the composition of the intercalate before and after calcination, and the nature of the binding of the pillar to the layers. In the case of clays intercalated with the AlI3 complex it has been shown that the location of the charge in the clay has a critical effect in determining whether or not cross-linking occurs at high Recently an NMR study of pillared saponite has suggested that alumina-like pillars cross-link to silicon sites, while silica-like pillars in contrast may cross-link to aluminium sites in the layers.217 One of the most studied layer phosphate materials is ( Y - Z ~ ( H P O ~ ) ~ . H , O , which may readily be intercalated with a variety of compounds to give very high surface area materials. This is a particularly interesting system as there has been a report of a chiral intercalate binding with a significant enantiomeric excess, thus giving the possibility of chiral recognition.218 31P MAS NMR spectra show a number of different phosphorus environments within the layers upon intercalation of a-Zr(HPO,J2.H2O with various amines, and the chemical shifts reflect the extent of hydrogen bonding between the layers and the The changes with temperature that occur when a-Zr(HP04)2.H20is refluxed with NH2(CH2)3Si(OC2H5)3have been examined in detail by 29Si NMR (Fig. 12).220 The 29Si MAS NMR
NMR APPLICATIONS TO POROUS SOLIDS
65
-67.5
0
-80
-160
6 /PPm Fig. 12. 29Si MAS NMR spectra of ( Y - Z ~ ( H P O ~ ) ~ after . H ~ Ointercalation with NH2(CH2),Si(OC2H5),: (a) uncalcined sample, (b) after calcination at 450°C for 2 h and (c) after calcination at 600°C for 2 h. (Reproduced with permission from L. Li et al., J . Phys. Chem., 1991, 95, 5910. 01991, American Chemical Society.)’”
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spectrum of the uncalcined sample shows major peaks at -59.2 and -67.5ppm due to Q2and Q3 organosilicate units respectively, indicating that the organosilicon compound has undergone polymerization and partial dehydroxylation during intercalation into the interlayer space. Upon calcination at 450°C or 6OO0C, the organic moiety of the intercalate decomposes and Q 2 , Q3 and Q4 species of a silica-like species are produced. The pillared material is stable to over 700°C and can sorb species such as n-hexane.220 The 31P and 13C chemical shift tensors in closely related zirconium phosphonates have recently been determined,221and used to determine the geometry of the organic group in uniaxially oriented films of Zr(03PCH2COOH)2.222 27Al MAS NMR is a useful probe of the state of aluminium polyoxycations in the interlayer space. Thus the AlI3 Keggin ion intercalated in a layered titanate, for example, gives tetrahedral and octahedral 27Al signals in the approximate ratio 1:12 as expected.223 Upon calcination to 500°C there is dehydration and significant dehydroxylation to give a species giving a 27Al spectrum similar to that of y - a l ~ m i n a The . ~ ~ 27Al ~ spectrum from aluminium polyoxycations may, however, be extremely complicated as observed, for instance, in the case of the AIl3 Keggin ion intercalated into the layered lattice of Moo3. Here a range of different aluminium environments, with different chemical shifts and quadrupole coupling constants, are observed, indicating a change in the complex structure on intercalation with possible binding to the molybdenum layers even before calcination.224
3. NMR STUDIES OF MESOPOROUS MATERIALS
3.1. Silicas, aluminas, etc,
Mesoporous materials are of considerable importance as sorbents and catalyst supports. Unlike most of the microporous materials discussed above, these materials are not crystalline and thus have no well-defined pore structure. As a consequence, they give rise to fairly broad NMR peaks, reflecting the range of local environments present. 3.1.1. N M R of silicas
Silicas may be subdivided into solution-based silica gels and into pyrogenic silicas. The first category are porous materials, and the pore dimensions depend on the exact method of preparation. They can contain both micropores as well as mesopores and can have very high surface areas. Pyrogenic silicas on the other hand, typified by Aerosil, are non-porous.
NMR APPLICATIONS TO POROUS SOLIDS
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Q4
-00
- 100
- 120
6 /PPm Fig. 13. 2ySi NMR spectra of a silica gel: (a) MAS (3min recycle delay) and (b) CPiMAS (10 ms contact time, 2 s recycle delay).
Silicas have been widely studied by NMR since the pioneering work of Maciel and S i n d ~ r f . ~ ~ ~ Figure 13 shows typical 29Si MAS and CP/MAS NMR spectra of a silica gel. Signals are observed from Q2, Q3 and Q4 species at about -90, -100 and -110ppm respectively (where Q" denotes a silicon bonded to four oxygens, n of which are bridging). These correspond to geminal hydroxyl &(OH), single hydroxyl silanol groups, (=SiO)3 silanol groups %(OH), and bulk (=SiO)4&i species respectively. Provided that sufficient time is left between scans for relaxation (this normally needs to be at least
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2 min) the spectrum in quantitative, and spectral deconvolution allows the relative amounts of these species to be obtained. The small amount of geminal groups means that measurement of their proportion by this method is particularly suspect to error. The single pulse experiment does, however, give a reliable measurement of the fraction of Q2+ Q3 environments present. The 2’Si CP/MAS NMR spectrum, on the other hand, discriminates against Q4 sites as these have no nearby hydrogens from which to cross-polarize, while the Q2 and Q3 sites readily give a strong signal. The rates of cross-polarization of the Q2 and Q3 sites are normally fairly similar, and thus CP spectra at contact times greater than about 5 m s provide a reliable measurement of the relative amounts of Q2 and Q3 sites present. For more accurate measurements, a variable contact time study may be performed in order to correct intensities for CP dynamics e f f e ~ t s . ~Thu ~ ~S, ~ ~ ’ the combination of single pulse MAS and CP/MAS experiments on silica gels readily gives a quantitative analysis of the Q2, Q3 and Q4 sites present. Chemical changes at the silica surface during dehydration and rehydration are particularly important areas of study. Spectra of dehydrated samples give significantly larger linewidths due to the dispersion of chemical shifts in the absence of mobile molecular ~ a t e r . Reversible ~ ~ ~ , condensation ~ ~ ~ of hydroxyl groups is believed to occur at temperatures up to about 500”C, after which rehydration becomes increasingly difficult. Some studies have observed an initial decrease in the relative proportion of geminal hydroxyl sites during dehydration, followed by an increase in their relative proportion at higher temperatures indicating that complex chemical changes must be occurring at the surface.228On the other hand, another study found a similar proportion of geminal hydroxyl groups for a range of samples at various stages of dehydration and rehydration .227 Another question of interest is the nature and the number of interior hydroxyl groups which are not readily accessible. Hydroxyl groups at the surface may be fully deuterated after several cycles of exchange with D 2 0 (unless previously subjected to high temperatures). 2ySi CP/MAS NMR spectra on deuterated samples have recently shown that there are negligible amounts of internal geminal hydroxyl groups, and have measured the number of internal single hydroxyl groups.22y On the basis of the rates of cross-polarization for the internal single hydroxyl groups, and estimates of the dipolar coupling to hydrogen, it appears that the internal single silanols undergo rapid rotation about the Si-OH bond axis.22y The surface of silica gel may also be studied by ‘H NMR. In order to achieve good resolution it is necessary to remove ‘H-lH dipolar interactions either by extremely fast MAS, or by combining MAS with multiple-pulse line narrowing methods (CRAMPS). Some ‘H CRAMPS spectra are shown in Fig. 14.230The untreated sample shows two narrow signals and one broad one. The narrow peak at 3.5ppm is removed upon evacuation at room temperature and hence can be assigned to physisorbed water. The broad
(a2)
NMR APPLICATIONS TO POROUS SOLIDS
69
25°C Evac.
5 0 0 ° C Evac.
Fig. 14. 'H CRAMPS spectra of a silica gel: (a) untreated sample, (b), (c) and (d) after evacuation at the temperature indicated. (Reproduced with permission from C . E. Bronnimann et al., J . Am. Chem. Soc., 1988, 110, 2023. @ 1988, American Chemical Society.)230
peak centred at about 3.0 ppm is removed upon evacuation of the sample at 5OO0C, leaving only the narrow peak at 1.7ppm which may be assigned to isolated Si-OH silanol species. The broad peak is probably due to hydrogen-bonded silanol species, and the linewidth of this peak reflects a range of different chemical environments and hydrogen bond strengths. There are several methods of modifying the surface of silica. The hydroxyl
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groups may be replaced by methyl groups by treatment with methylchlorosilanes; this treatment completely changes the properties of the silica by making the surface hydrophobic. 29SiNMR peaks for the methylsilyl groups at the surface may readily be detected using CP/MAS, and a range of different environments may be seen depending on the extent of any hydrolysis or additional condensation reactions at the surface.231 Other silylating reactions have also been explored in detai1.232-234Other treatments include modification of surface acidity by introducing phosphorus, and of course metal and metal ions may be deposited on the surface, as is common for heterogeneous catalysts. 3.1.2. N M R of aluminas
Alumina is the other common catalyst support, and different forms of alumina can have widely different surface areas, and different strength Bronsted and Lewis acid sites. 27Al NMR is handicapped by the broad range of environments present coupled with the complications arising from the second-order quadrupole interaction. However, it is still straightforward to identify octahedral and tetrahedral aluminium species. Thus NMR can readily distinguish between a-alumina, which contains only octahedral aluminium, and y-alumina, which has a quarter of aluminium in tetrahedral sites. It is interesting to note that (static) 27Al NMR spectra of alumina have been observed recently using a field-swept NMR spectrometer at 15 T magnetic field strength and 4.2 K.235 One anomaly that has been observed in the 27Al MAS NMR spectra of aluminas is an apparent decrease in signal intensity with increasing surface area of sample. It has been suggested that this is a result of the surface layers experiencing very large electric field gradients and so being broadened beyond detection.236 Recently, however, results have indicated that while the loss in 27Al signal with increasing surface area is a real phenomenon, it is due to dynamic effects at the surface involving proton migration, and that surface aluminium can indeed be observed under appropriate conditions.237 One possible method of gaining surface selectivity in an NMR experiment is using cross-polarization to transfer magnetization from surface hydroxyl protons to give the 27Al spectrum. This successfully detects octahedral surface aluminium species and the CP intensity is diminished when the sample is subjected to any dehydroxylation t r e a t r n e n t ~ . ’ ~ However, ~ no tetrahedral Bronsted acid sites were detected, either because of long AI-H distances or complications arising from cross-polarizing quadrupolar nuclei under MAS condition^.^^ 27Al CP/MAS also has the potential to investigate Lewis acid sites at the surface as well as B r ~ n s t e dsites. The surface hydroxyls may be fully deuterated, and then a base such as pyridine adsorbed. In this case all the 27Al detected under CP conditions will come from those aluminium sites very close to bonded pyridine molecules.238
NMR APPLICATIONS TO POROUS SOLIDS
71
Probe molecules adsorbed on alumina may also be studied in the same way as probe molecules on zeolites. For instance, I5N MAS NMR may be profitably used to study ”N-enriched pyridine bonded to acid sites on the surface of y-alumina. Two resonances are observed, and dipolar dephasing experiments show that neither comes from a hydrogen-bonded or protonated pyridine molecule, indicating that there are two distinct Lewis acid It has been suggested that these arise from occupation of tetrahedral and octahedral anion vacancies on the surface.”’ The I5N shielding anisotropy of both sites could be obtained by simulating the MAS spinning sideband intensity pattern, and this gives a lower anisotropy than for solid pyridine, indicating that there is a degree of molecular motion. Static 2H experiments on deuterated pyridine indicate that there is a heterogeneous distribution of pyridine motions, and that major contributions arise from continuous diffusion or C2 flips about the twofold symmetry axis.239 Multinuclear NMR experiments have also been performed on amorphous silica-alumina catalyst supports, with results that are broadly similar to those expected from a combination of silica and alumina.24c243 The 29Si NMR spectra tend to be very broad and reflect a range of environments: the S i 0 4 tetrahedra can be essentially randomly distributed in samples prepared by coprecipitation, and there is also evidence for single silanol and geminal hydroxyl silanol 3.1.3. N M R us u probe of pore size
A recent elegant use of NMR on porous solids is to gain information on pore size. It is well known that the freezing temperature of a liquid within a pore is reduced by an amount which depends on the pore diameter. Static ‘H NMR spectroscopy can quantitatively measure the relative amounts of solid and liquid present. Thus cyclohexane can be adsorbed by silica and spectra obtained as a function of temperature using a spin-echo pulse sequence that has the effect of suppressing the signal from solid cyclohexane. Cyclohexane is a particularly favourable liquid to use as it shows a large melting point variation and forms a soft plastic crystalline phase on freezing that appears not to damage pore structure. The amount of liquid cyclohexane present as a function of temperature can then be used to calculate a pore size distribution plot.244 Figure 15 shows the results of this NMR analysis using cyclohexane on a porous silica with a nominal pore diameter of 200 A. Good agreement is observed with the results of gas adsorption and desorption measurements. The freezing of water adsorbed on porous solids including silica and activated charcoal has also been explored. Here there may be two distinct freezing processes: strong bonding to the surface, and normal freezing which occurs at a temperature predicted by the Kelvin equation and so depends on pore size. It has been suggested that
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Pore diameter / A Fig. 15. Pore size distribution of a silica with nominal pore diameter of 200 A. The solid line gives that determined from 'H NMR spectra of adsorbed cyclohexane, while the points give that determined by conventional gas adsorptioddesorption measurements. (Reproduced with permission from J. H. Strange et al., Phys. Rev. Lett., 1993, 71, 3589. @ 1993, American Physical Society.)244
measurements of water freezing with temperature can provide a estimate for the true pore volume than other techniques such mercury-intrusion method.245 Pore geometries may also be studied by relaxation time Analysis of relaxation curves can give pore size distributions, knowledge of surface relaxation interactions is needed to gain information, and the method is not always reliable.2473248
better as the
but a useful
3.2. Novel mesoporous materials
3.2.1. MCM-41 There has recently been considerable interest in a new family of mesoporous materials, designated MCM-41, which possess regular hexagonal arrays of uniform channels between 16 and 100 in diameter. Cubic phase mesopor-
NMR APPLICATIONS TO POROUS SOLIDS
73
ous analogues have also recently been prepared. MCM-41 is synthesized from aluminosilicate gels in the presence of quaternary ammonium surfactants, and appears to form by a liquid-crystal templating mechanism in which the silicate material forms inorganic walls around ordered surfactant r n i c e l l e ~ The . ~ ~pore ~ ~ ~diameter ~~ depends principally on the alkyl chain length of the quaternary ammonium surfactant used in the synthesis. The pore structure remains intact even at temperatures as high as 8OO"C, and MCM-41 can exhibit pore condensation without h y ~ t e r e s i s . ~As ' ~ ,well ~ ~ ~as its distinctive adsorption properties, MCM-41 materials have great possibilities as high surface area supports and potential applications in the preparation of nanosized particles. 13C MAS NMR studies of the asprepared material show narrow peaks, and only a very weak CP signal of the hydrocarbon end of the surfactant can be observed. This indicates that there is significant molecular motion, particularly at the hydrocarbon end, as anticipated for a micellar array with the quaternary ammonium end linked to the silicate/aluminosilicate wall and the hydrocarbon end free in the middle of the channels.25o29Si MAS NMR spectra of siliceous MCM-41 give a broad spectrum similar to amorphous and 29Si NMR has already shown that the hydroxyl surface groups may be functionalized by treatment with trimethylchloro~ilane.~~~~~'~ Recently, 27A1 NMR has confirmed that it is possible to synthesize MCM-41 with fairly high levels of aluminium, all of which are tetrahedrally coordinated in the framework.25s
3.2.2. Organosilicates There have recently been preparations of porous organosilicate materials consisting of hybrids between organic and inorganic networks. Thus hydrolysis and condensation of monomers such as (Et0)3Si-Ar-Si(OEt)3 by sol-gel processing forms polysilsesquioxane ~ e r o g e l s These . ~ ~ ~ novel materials exhibit both microporosity and mesoporosity and can have surface areas as high as 1000m2g-'. 29Si CP/MAS NMR spectroscopy of these organosilicates shows peaks due to Q', Q2 and Q3 organosilicon units. Quantification of these peaks allows the determination of the degree of condensation that has occurred, which depends on the exact synthesis Chlorosiconditions used and the size of the organic building lane precursors have also successfully been used and the products studied by "SSi NMR.257
3.3. Catalysts
There have been a large number of NMR investigations into heterogeneous catalyst systems supported on silica and/or alumina. It is not possible to discuss the wealth of useful NMR data recorded on these systems, but NMR
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has been used to study the surface of the catalyst with and without adsorbates.25a260 A recent advance in using NMR to study catalytic systems is the use of dipolar coupling between labelled I3C nuclei to give useful information including measurements of accurate bond lengths.2613262 Thus in the study of benzene on a Pt/q-A1203catalyst, a I3C dipolar study of doubly 13C-labelled benzene shows a single C-C bond length, implying the absence of a significant distortion of benzene which had been previously The dynamics of the benzene molecule were also explored and ring reorientation was found to occur even at temperatures as low as 6 K in contrast to bulk b e n ~ e n e . *In ~~ the ? ~same ~ ~ system, static *H spectra have been used to explore dipolar coupling to 19’Pt, and the structure in the spectrum indicates that the benzene adsorbs directly over a platinum atom. The coupling magnitude suggests that the Pt-benzene distance is 1.56 A; however, there will also be a contribution from pseudodipolar coupling which would increase this Another method of gaining structural information is to measure I3C--lH dipolar coupling using a SEDOR pulse sequence as used, for example, in studies of acetylene on platinum and other metal Such studies of adsorbed species on catalysts by NMR are highly dependent on the detailed nature of the catalyst (metal particle size and distribution, nature of the support, how ‘‘clean’’ the surface is before adsorption) and it is not uncommon for different research groups to obtain slightly different results. Also, it is not always possible to record good quality I3C CP/MAS spectra of chemisorbed species on metals due to metal susceptibility problems. For instance, ethylene on Ptly-A1203 gives only broad 13C CP/MAS peaks. However, the deuterated form could still be studied by static 2H NMR revealing that the dominant chemisorbed species was ethylidyne ( E C - C H ~ ) On . ~ ~the ~ other hand, I3C CP/MAS spectra of ethylene adsorbed on Ag/y-A1203 show that the major species is .rr-bonded ethylene with the C=C axis parallel to the silver surface. In this case the I3C shielding anisotropy and C-C distance have been measured by recording spectra at low temperature with the use of isotopic labelling.269At high temperature the dynamics of the weakly-bonded ethylene on the silver surface have also been e ~ p l o r e d . ~ In ” a I3C CP/MAS NMR study of ethylene on oxygen-covered Ag/77-A1203 a range of other peaks may be observed corresponding to carboxylate species, and these may be inferred to be intermediates in the complete combustion of ethylene.271 As well as studies on the geometry and dynamics of adsorbates, NMR has been used to follow reactions in situ in a similar fashion to that described for zeolites. Reactions studied include commercially important ones such as methanol synthesis over Cu/ZnO/AI2O3 catalysts,272and acetylene cyclotrimerization over Pt/A1203systems.273Probe molecules may also be useful, such as using 31P NMR of adsorbed trimethylphosphine to determine acid site concentrations on a commercial silica-alumina cracking catalyst.274
NMR APPLICATIONS TO POROUS SOLIDS
75
4. lz9Xe NMR STUDIES OF POROUS MATERIALS
4.1. ‘29Xe NMR of zeolites Pioneering 12’Xe NMR work by Ripmeester and co-workers on xenon trapped in ~ l a t h r a t e s and ~ ~ ~by. ~Fraissard ~~ and co-workers on the behaviour of ‘”Xe chemical shifts inside zeolites277has led to a considerable interest in using 12’Xe NMR spectroscopy as a sensitive inert probe of pore structure and a number of reviews have The major feature of the technique is that the 12’Xe NMR chemical shift of xenon inside microporous solids is intrinsically affected by pore size as well as xenon gas pressure, the presence of cations and possible strong adsorption sites. It was demonstrated early on that the I2’Xe chemical shift in zeolites Na-Y and H-Y varies approximately linearly with xenon concentration,277 and only has a small dependence on framework composition (%/A1 Other zeolite structures show similar behaviour but with a different value for the chemical shift extrapolated back to zero xenon concentration, here termed as (at which point there will be no effects from xenon-xenon collisions).283For instance isostructural A1P04-5, SAPO-5 and the purely siliceous analogue, SSZ-24, have identical Ss values, but different from that of zeolite Na-Y.284 It is generally found that the larger the dimensions of the cavity containing xenon, the smaller the value of 6s observed. Several empirical correlations of as against pore size were suggested but none of these is entirely sati~factory,~” and simple model calculations have indicated that no simple correlation is likely and that the temperature dependence must also be considered.285 The behaviour of 12’Xe chemical shifts for xenon inside zeolite Y with other cations is in fact rather more complicated than described in the previous paragraph. First of all, if large univalent cations are present, as in the case of zeolites K-Y and Rb-Y, then higher values of Ss than expected are observed, possibly because the cation reduces some of the effective pore volume.286 In the presence of divalent cations, such as Ca2+ and Mg2+, in zeolite Y there is further anomalous behaviour, as it is found that the 12’Xe chemical shift increases as the xenon concentration is reduced.286 This has been rationalized in different ways as being due to a distortion of the xenon electron cloud by strong electric fields278,286or to the presence of strong adsorption sites on the cations.287 More recently it has been found that in zeolites X and Y containing Ag+ or Cu+ cations a significant reduction in chemical shift occurs as the xenon concentration is reduced, in contrast to the behaviour with other univalent cations, or multivalent i ~ n s . ~ ~This ~ ’ is ’ illustrated in Fig. 16 which shows the ‘*’Xe chemical shift variation with xenon concentration for Cd2+-, Zn2+-, Na+-, Cu+- and Ag+-exchanged zeolite X. With the exception of Na+, all these cations have dl’ configurations. It has been argued that the reduction in chemical shift at lower
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0
5E+20
IE+21
N (Xe atoms /g 1 Fig. 16. Plot of '"Xe
chemical shift against xenon concentration for zeolite X containing different cations. (Reproduced with ermission from A. Gedeon and J. Fraissard, Chem. Phys. Lett., 1994, 219, 440.)2 9 9
pressures for the Cu+ and Ag' cases is due to a specific d'"-d" .rr-back donation from the metal to the xenon atom.288-290However, this interaction does not occur, or is masked by other effects, for the divalent d" cations. Thus it seems that the NMR behaviour of 129Xein the proximity to different cations is not yet fully understood. There will also be additional effects on the '29Xe chemical shift if the cation is paramagnetic. Despite this, there have been a number of studies using lZ9XeNMR to probe cation locations and metal clusters in zeolites with a certain degree of success.291-304 12'Xe NMR may also be useful in identifying more than one adsorption zone inside a zeolite as in the case of mordenite, offretite and zeolite rho,
NMR APPLICATIONS TO POROUS SOLIDS
77
provided that xenon exchange between the zones is not fast on the chemical shift t i m e s ~ a l e . ~ ~ ~ - ~ ~ ' One particular application to which '29Xe NMR is well suited is probing the homogeneity of the sample. For instance, upon adsorption of water into dehydrated zeolite Na-Y containing xenon, more than one 129XeNMR peak is observed as initially the water adsorbs strongly into exposed crystallites, leaving others bare. A single narrow '29Xe NMR peak can be observed after shaking or heating the sample to produce a homogeneous distribution of water.308 Indeed the change in lz9Xe NMR spectrum with time may be used to measure the rate of water d i f f u s i ~ n Similar . ~ ~ heterogeneous distributions of organic adsorbates in zeolites have also been o b ~ e r v e d . ~ ~ ~ , ~ ~ ~ One crucial aspect in the interpretation of 129Xe NMR spectra is the volume over which the xenon atoms undergo fast exchange on the NMR chemical shift timescale. This may be a single cavity (as discussed for zeolite Na-A below), many cavities or even intercrystalline. For instance, two distinct species are observed at room temperature for xenon adsorbed in a mixture of zeolite Na-Y and Ca-Y, but only a single average peak is observed upon thorough mixing of the different zeolite forms due to fast intercrystalline diffusion unless the temperature is lowered.312 Other examples of fast interparticle exchange in '29Xe NMR spectra have also been o b ~ e r v e d . " ~Because of this, the packing density of a powder sample can also have a significant effect on '29Xe NMR spectra.314 Thus 129Xe NMR may give both microscopic and macroscopic information depending on the system under investigation making useful spectral interpretation particularly difficult. In some cases it is helpful to cool the sample in order to slow down the diffusional processes occurring when microscopic information is desired, though this might of course also affect the chemical shift by altering the rate of exchange between xenon adsorbed at the surface and in the free volume.315 In the case of xenon adsorbed in zeolite Na-A, the window between a-cages is about 4.2 A in Na-A, which is slightly smaller than the diameter of xenon atoms (approximately 4.4 A). Xenon can, however, be forced into the cages of zeolite Na-A at elevated pressures and temperatures. Differing xenon concentrations can be obtained depending on the pressure applied. In this case diffusion between cages is slow on the chemical shift timescale and so this is a good model system for attempting to understand '29Xe chemical shift behaviour in more detail. Distinct peaks are observed corresponding to differing numbers of xenon atoms, n , present in each cage (Fig. 17).316318 Hence the distribution of xenon atoms in the a-cages may be measured. Interestingly the equilibrium distribution (which is reached after many days, though this may be shortened by heating) is found to deviate from random statistical models, indicating that there are attractive xenon-xenon interactions which favour clustering at low to medium loadings, together with higher energies associated with overcrowding of cages at higher loadings
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2
I
300
1
I
200
100 6 /PPm
I
0
Fig. 17. Xenon in zeolite Na-A occluded at 523 K at different equilibrium pressures: (a) 8 atm, (b) 40 atm, (c) 150 atm and (d) 210 atm. The numbers above the peaks indicate how many xenon atoms are in the a-cage giving rise to the peak. (Reproduced with permission from B. F. Chmelka et a l . , Phys. Rev. Lett., 1991, 66,
580. 01991, American Physical Society.)317
(particularly cages containing seven or eight atoms) .318 The overcrowding of the cages is also indicated by the observed chemical shifts: the difference in chemical shift between adjacent peaks increases slightly from 17.5 pprn (between n = 1 to n = 2) to 25.1ppm (between n = 5 to n = 6) at which point there is a large increase of 45.1 ppm between the n = 6 and n = 7 chemical shifts, and a further 43.7 ppm increase to the n = 8 resonance. The temperature dependences of the chemical shifts have also been explored.318 Interestingly '29Xe peaks at the same positions may be observed even after the adsorption of a small amount of water, together with an additional peak
NMR APPLICATIONS TO POROUS SOLIDS
79
at 185 ppm, indicating once again that adsorption is not necessarily homogeneous.319 In an attempt to understand the chemical shift behaviour, ab initio calculations on adsorbed 39Ar atoms have been performed, and the correspondence with the observed lz9Xe NMR data suggest that the theoretical aspects are gradually becoming better u n d e r ~ t o o d . ~While ~ " the rate of exchange between xenon atoms in neighbouring cages is slow on the chemical shift timescale, it still may be measured by NMR using twodimensional exchange spectroscopy. Cross-peaks are obtained as a function of mixing time, and these give a direct measure of the mass transport of xenon between the cages.321 It is found that the relative xenon adsorption separation energies are relatively constant for occupancies up to four xenon atoms in a cage, after which the separation energies decrease due to repulsive interactions as the cages become more crowded.321 It is interesting to note that in zeolite Ca-A the Ca2+ ions are not located near the windows between cages, and xenon can easily diffuse into neighbouring cages. Hence only a single 129Xepeak is observed in the NMR spectrum. Observations at high pressures have shown that the chemical shift does not vary linearly with xenon concentration, but depends on the detailed nature of the pore structure.322
4.2. '29Xe NMR of other porous solids There is a significant difference in the 12'Xe NMR chemical shift behaviour for mesoporous materials compared to microporous solids. It has been found that at room temperature the lZ9Xe chemical shift is approximately independent of xenon pressure for a range of silica gels.323 This has also been observed for xenon adsorbed in the pore structure created by compressing non-porous silica spheres.324 The observed chemical shift is comparable to that in zeolites, and reflects fast exchange between surface adsorbed and free xenon. An empirical correlation between the chemical shift and the average pore diameter has been suggested.323 At low temperatures the lZ9Xe NMR chemical shift does show a dependence on xenon c o n c e n t r a t i ~ nThis . ~ ~ dependence ~ is not, however, straightforward as there will be preferential adsorption of xenon into any micropores present; this will manifest itself as an increase in '29Xe chemical shift as the xenon concentration is reduced.325 One particular feature of lZ9Xe measurements on small amorphous particles is that the particle size may have a significant effect. Figure 18 shows lZ9XeNMR spectra obtained on a silica gel after grinding in a mortar. A broad peak is observed, unless all small particles are removed, in which case narrow peaks corresponding to adsorbed and free xenon gas are observed.323 This is probably due to the small particles having a range of free volumes and interparticle exchange effects becoming more important.
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65
(a)
t
200
I
*
1
100 0 WPPm
1
1
-100
Fig. 18. 129XeNMR spectra of adsorbed xenon in a silica gel: (a) after grinding the silica, (b) after removing all small particles leaving those with sizes in the range 150-250~m. (Reproduced with permission from V. V. Terskikh et al., J. Chem. SOC., Faraday Trans., 1993, 89, 4239.)323
Complicated broadening effects due to small particles have also been observed in other systems,314and it is clear that this factor has to be borne in mind when interpreting spectra. In principle, 129XeNMR spectra of porous layered materials should be affected by similar considerations to those described for zeolites,326 but another macroscopic factor must also be considered. Different preferred orientations of a powdered sample can give different 129XeNMR chemical shifts as is illustrated for a montmorillonite clay in Fig. 19, where vastly different spectra are obtained depending on the alignment of the clay A number of other porous systems have been studied by the lZ9XeNMR technique. It has been applied to study porous carbons, either as an attempt to gain information on pore dimension^,^^' or to observe the effect of acidic functional groups on the surface.328It has been used to probe the amount of hydrogen adsorption on platinum particles supported on alumina or other supports which is of importance in catalysis.3293330 It has also been used to confirm microporosity in certain heteropolyoxometallates.331One last application of 129XeNMR is two-dimensional exchange spectroscopy, which may be used to probe the rate of exchange between adsorbed xenon and free xenon gas, giving information on adsorptioddesorption rates.332
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aligned platelets
Fig. 19. lzYXeNMR spectra of xenon adsorbed in tetramethylammonium-exchanged montmorillonite: (a) powder spectrum, (b) and (c) spectra for platelets aligned parallel and perpendicular to the magnetic field. (Reproduced with permission from J. A. Ripmeester and C. I . Ratcliffe, Anal. Chim. Acta, 1993, 283, 1103.)314
It is thus clear from this discussion that there are a considerable number of factors, both microscopic and macroscopic, that can influence '29Xe NMR spectra of xenon adsorbed in porous solids and it is dangerous to draw conclusions from spectra on unknown systems without additional information. The theoretical factors behind '29Xe NMR chemical shifts are, however, gradually becoming better understood, and already '29Xe NMR spectroscopy is a useful probe of the homogeneity of porous systems.
5. NMR STUDIES OF MOLECULAR TRANSPORT IN POROUS SOLIDS
Various methods have been mentioned earlier of characterizing pore geometry by the influence on chemical shifts and relaxation times. In this section some experiments to measure the diffusion of adsorbed species within porous solids are discussed; these will give additional information on
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pore geometries, and on the important process of mass transport within porous solids.
5.1. Pulsed field gradient measurements
Diffusion measurements and the study of mass transport are particularly important in the understanding of catalysis. The possibility of interpreting and correlating molecular mass-transfer phenomena in solids depends critically on a knowledge of the surface structure and its regularity. In this respect, diffusion in zeolites and related materials are ideal systems to study as zeolites have well-defined pore structures. There have been a large number of studies on hydrocarbon diffusion in zeolites, particularly by Karger and co-workers, and these have recently been reviewed.3333334 Diffusion measurements on adsorbed species can be made by a variety of NMR methods normally based upon spin-echo pulse sequences.33s 'H or *H spin-lattice relaxation time measurements may also give diffusion coefficients in favourable circumstances. lo' The first NMR self-diffusion measurements of adsorbate-adsorbent systems were carried out in 1967 using the constant field spin-echo method, and it was found that methane adsorbed on silica gel had a similar diffusion rate to that of the free In contrast, results on systems where the pore diameters only slightly exceed the size of the adsorbate molecules show that self-diffusion coefficients are commonly lower by more than two orders of magnitude than in neat The current NMR method of choice to measure diffusion coefficients is a pulsed field gradient (PFG) spin-echo t e ~ h n i q ~ e , ~ ~ ~ , though alternative techniques are still being devised.339 In PFG NMR, magnetization is first dephased and then subsequently rephased under the influence of a spatially dependent magnetic field gradient. Observing the NMR signal intensity as a function of the applied field gradient pulses provides direct information about the diffusion of individual molecules. A major advantage of the NMR method of measuring diffusion rates is that it is a measurement performed under equilibrium conditions and so there is no interference from intrinsic mass transfer effects. A feature of the PFG technique is that it measures diffusion over distances of the order of a few micrometres. In the case of diffusion in zeolites, this is normally less than the size of the crystallites and we are thus observing only intracrystalline self-diffusion, without any complications from boundary or interparticle effects.340Cases of restricted self-diffusion, where molecular propagation is comparable with crystal size, and long-range self-diffusion, in which molecular propagation occurs over many crystallites during the measurement, may also be identified unambiguously by PFG NMR.340 Many PFG NMR experiments have measured diffusion coefficients which are up to five orders of magnitude higher than values obtained by traditional
NMR APPLICATIONS TO POROUS SOLIDS
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uptake methods. Such discrepancies are predominantly due to surface effects and interparticle transport processes affecting the values obtained by the sorption technique. PFG measurements may easily be checked for reproducibility as they are obtained on an equilibrium system, while sorption methods require repetition of the complete desorption/adsorption cycle to check the reproducibility of the measurement, and many of the discrepancies between PFG NMR and uptake measurements have now been removed by careful remeasurement of the sorption data. It should also be observed that the self-diffusion measurements obtained by the two techniques are not necessarily equivalent, as one represents an equilibrium measurement (on a system in which the structure of the solid may have been slightly altered by the presence of the adsorbate), while the other is a non-equilibrium measurement (reflecting adsorption into regions of the solid containing no adsorbate). It should also be borne in mind that PFG NMR measurements are normally performed at low temperatures and comparatively high loadings, and molecule-molecule collisions may have an Other methods for measuring intracrystalline self-diffusion include molecular dynamics calculations341 and quasi-elastic neutron ~ c a t t e r i n g , ~and ' ~ these give results very similar to those of PFG NMR. Both macroscopic and microscopic diffusion rates can be obtained by an NMR tracer exchange method in which the rate of exchange between protoncontaining molecules in the gas phase and deuterated adsorbed molecules is followed by 'H NMR, and then the sample studied by PFG NMR after attaining equilibrium. 333 One particularly interesting application of PFG NMR is that it can measure diffusion anisotropies for non-aligned crystallites by analysis of the shape of NMR signal attenuation as a function of the gradient amplitude. For instance, it has been used to estimate that for methane in zeolite ZSM-5, the diffusivities in the different channels present differ from each This measurement of diffusion anisotropy other by a factor of about is in good agreement with results obtained on oriented ZSM-5 crystallites. PFG NMR experiments at high temperature can allow diffusivities to be obtained that would otherwise be too slow to measure accurately by the technique, and it is found that the diffusivities of n-alkanes in ZSM-5 decrease monotonically with increasing chain length.344 Such studies have shown that the Si/Al ratio of ZSM-5 has no effect on the diffusion of n - a l k a n e ~ . ~ ' ~On . ~ 'the ~ other hand, the rates of water and benzene diffusion are affected, presumably because of interactions of the adsorbate with the charge-balancing ~ a t i o n s . ~While ~ ~ , ~'H ' ~nuclei have been most frequently studied by PFG NMR due to sensitivity reasons, other nuclei may also be measured. Thus I3C PFG NMR has recently been used to study CO and C 0 2 diffusion in zeolites.348 Another advantage of the PFG NMR technique is that it is possible to measure the diffusivities of different species in a multicomponent system if
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they have different chemical shifts. This has been demonstrated by the simultaneous measurement of the diffusivities of ethane and ethylene adsorbed in zeolite Na-X.349 It was found that ethylene has a smaller diffusivity by a factor of three to four, reflecting the interactions between unsaturated hydrocarbons and sodium cations, but it should be noted that this difference is significantly smaller than that observed if the components are present on their own. This implies that the mutual interaction between the two adsorbates is significant and shows that diffusivities in multicomponent systems, such as occur in catalytic conversions, are not necessarily the same as those measured for single-component systems. Another multicomponent system that has been studied is cyclopropane and propene in zeolite X.350 Here the catalytic conversion of cyclopropane to propene has been studied in sifu by PFG NMR, and it was found that the diffusivities were sufficiently large for this system that any effects of intracrystalline diffusion in a flow reactor could be n e g l e ~ t e d . ~ ” Diffusion in amorphous solids, such as silica gel, is more complicated than in zeolites due to variations in pore size, but it can still be measured by PFG NMR. In experiments on n-alkanes on silica gel, two distinct diffusion processes could be observed during the observation time, and these correspond to surface self-diffusion (associated with microporous regions) and long-range self-diffusion (associated with the mesoporous regions between particles) .351 Models describing the influence of pore morphology on PFG NMR studies of fluid-saturated porous solids including restricted diffusion measurements are gradually being d e ~ e l o p e d . ~ ~ * - ~ ’ ~ 5.2. Applications of NMR imaging
In many cases one is interested in diffusion over longer time periods than accessible by PFG NMR studies. These may now be measured by following the concentration of molecules with distance in real time using NMR imaging. Thus the transport of water from saturated to unsaturated parts of porous systems may be followed q ~ a n t i t a t i v e l y . ~It’ ~is~also ~ ~ possible to follow the diffusion of paramagnetic ions such as Ni2+ in porous media through their influence on relaxation times.359 There have not been as many studies of fluid flow in porous solids by NMR imaging as might have been expected considering its considerable industrial importance in processes such as oil recovery and ~ a t a l y s i s . ~ ’ ~ ~ ~ ~ This is caused in part by the large local magnetic field inhomogeneities caused by susceptibility differences between the solid and the liquid. This means that the effective transverse relaxation time, T;, is often very small. However, it is still possible to obtain rapid images using methods such as a modified echo-planar imaging technique.365 NMR imaging has also been used to attempt to resolve changes in pore size distributions during drying of materials made by a sol-gel process.3hh
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Recently, NMR imaging has successfully been applied to the study of water within alumina and silica catalyst support pellets, allowing both the pore structure and transport processes to be explored in the same experimental environment.367 Spin density, relaxation time and diffusion measurements within the catalyst support have been made. The results show that there is significant structural heterogeneity within the catalyst support, reflecting variations in pore size that arise during preparation of the support pellet, and these heterogeneities can be directly imaged.367 It is also now possible to combine NMR imaging with PFG NMR to obtain velocity and diffusion measurements on fluids in solid^.^^^^'^ For instance the adsorption and diffusion of n-hexane in a bed of zeolite Na-X has been monitored. It is found that intracrystalline diffusion is fast enough to ensure total adsorption of individual zeolite crystallites before the macroscopic adsorption front has moved significantly further into the bed.371 ACKNOWLEDGEMENT
I thank John Cresswell for redrawing many of the figures, and the University of London Intercollegiate Research Services (ULIRS) for financial support. REFERENCES 1. IUPAC Manual of Symbols and Terminology, Pure Appl. Chem., 1972, 31, 579. 2. J . Klinowski, Progr. NMR Spectrosc., 1984, 16, 237. 3. G. Engelhardt and D. Michel, High-Resolution Solid-state NMR of Silicates and Zeolites, Wiley, Chichester, 1987. 4. C. A. Fyfe, Y. Feng, H. Grondey, G. T. Kokotailo and H. Gies, Chem. Rev., 1991, 91, 1525. 5. J. Klinowski, Chern. Rev., 1991, 91, 1459. 6. J . Klinowski, Anal. Chim. Acta, 1993, 283, 929. 7. E. Lippmaa, M. Magi, A. Sarnoson, G . Engelhardt and A.-R. Grimmer, J. A m . Chem. Soc., 1980, 102, 4889. 8. E. Lippmaa, M. Magi, A. Samoson, M. Tarmak and G. Engelhardt, J. Am. Chem. Soc., 1981, 103, 4992. 9. W. Loewenstein, Am. Mineral., 1954, 39, 92. 10. G. Engelhardt, U. Lohse, E. Lippmaa, M. Tarmak and M. Magi, 2. Anorg. Allg. Chem., 1981, 482, 49. 11. J. M. Thomas, C. A. Fyfe, S. Ramdas, J. Klinowski and G . C. Gobbi, J. Phys. Chem., 1982, 86, 3061. 12. J. Klinowski, S. Ramdas, J. M. Thomas, C. A. Fyfe and J. S. Hartman, J. Chem. Soc., Faraday Trans. I I , 1982, 78, 1025. 13. D. W. Breck, Zeolite Molecular Sieves: Structure, Chemistry and Use, Wiley, London, 1974. 14. X. Liu, J. Klinowski and J. M. Thomas, J. Chem. Soc., Chem. Commun., 1986, 582. 15. H. Hamdan, B. Sulikowski and J. Klinowski, J. Phys. Chem., 1989, 93, 350. 16. P. J . Barrie, L. F. Gladden and J. Klinowski, J. Chem. Soc., Chem. Commun., 1991,592.
86
P. J. BARRIE
17. G. T. Kerr, J . Phys. Chem., 1967, 71, 4155. 18. H. K. Beyer and I. Belenykaja, in Catalysis by Zeolites (eds 8. Imelik, C. Naccache, Y. Ben Taarit, J. C. VCdrine, G . Coudurier and H. Praliaud), Stud. Surf. Sci. Catal., 1980, 5 , 203. 19. D. W. Breck and G . W. Skeels, U . S . Patent 4 503 023, 1985. 20. M. W. Anderson and J. Klinowski, J . Chem. Soc., Faraday Trans I , 1986, 82, 1449. 21. B. Chauvin, M. Boulet, P. Massiani, F. Fajula, F. Figueras and T. des Courikres, J . Catal., 1990, 126, 532. 22. B. Gil, E. Broclawik, J. Datka and J. Klinowski, J . Phys. Chem., 1994, 98, 930. 23. J. M. Thomas, J. Klinowski, S. Ramdas, B. K. Hunter and D. T. B. Tennakoon, Chem. Phys. Lett., 1983, 102, 158. 24. J. Klinowski and M. W. Anderson, J . Chem. Soc., Faraday Trans I , 1986, 82, 569. 25. M. W. Anderson, Magn. Reson. Chem., 1992, 30, 898. 26. G. Engelhardt and R. Radeglia, Chem. Phys. Lett., 1984, 108, 2711. 27. R. Radeglia and G. Engelhardt, Chem. Phys. Lett., 1985, 114. 28. 28. J. V. Smith and C. S . Blackwell, Nature, 1983, 308, 223. 29. J. M. Thomas, J. Kennedy, S. Ramdas, B. K. Hunter and D. T. B. Tennakoon, Chem. Phys. Lett., 1983. 102, 158. 30. S. Ramdas and J. Klinowski, Nature, 1984, 308, 521. 31. C. A. Fyfe, G. T. Kokotailo, J. D. Graham, C. Browning, G . C. Gobbi, M. Hyland, G . J. Kennedy, C. T. DeSchulter, J . Am. Chem. Soc., 1986, 108, 522. 32. J. A. Martens, Y. L. Xiong, E. J. P. Feijen, P. J. Grobet and P. A. Jacobs, J . Phys. Chem., 1993, 97, 5132. 33. J. H. Kwak and R. Ryoo, J . Phys. Chem., 1993, 97, 11 154. 34. C. A. Fyfe, H. Strobl, G . T. Kokotailo, G . J. Kennedy and G . E. Barlow, J . Am. Chem. Soc., 1988, 110, 3373. 35. J. Klinowski, T. A. Carpenter and L. F. Gladden, Zeolites, 1987, 7, 73. 36. C. A. Fyfe, H. Strobl, G . T. Kokotailo, C. T. Pasztor, G . E. Barlow and S. Bradley, Zeolites, 1988, 8, 132. 37. B. H. Toby. M. M. Eddy, C. A. Fyfe. G . T. Kokotailo, H. Strobl and D. E. Cox, J . Marer. Res., 1988. 3, 563. 38. C. A. Fyfe, H. Gies and Y. Feng, J . Chem. Soc., Chem. Cornmun., 1989, 1240. 39. C. A. Fyfe, H. Gies and Y. Feng, J . Am. Chem. Soc., 1989, 111, 7702. 40. C. A. Fyfe, Y. Feng and G . T. Kokotailo, Nature, 1989, 341, 223. 41. C. A. Fyfe, Y. Feng, H. Gies, H. Grondey and G. T. Kokotailo, J . Am. Chem. Soc., 1990, 112, 3264. 42. C. A. Fyfe, H. Grondey, Y . Feng and G . T. Kokotailo, J . Am. Chem. Soc., 1990, 112, 8812. 43. C. A. Fyfe, Y. Feng, H. Grondey. G . T. Kokotailo and A. Mar, J . Phys. Chem., 1991, 95, 3747. 44. C. A. Fyfe, H. Gies and Y . Feng, J . Am. Chem. Soc., 1989, 111, 7702. 45. W. Kolodziejski, P. J. Barrie, H. He and J. Klinowski. J . Chem. Soc., Chem. Commun., 1991, 961. 46. C. A. Fyfe, G. C. Gobbi, J. Klinowski, J. M. Thomas and S. Ramdas, Nature, 1982. 296, 530. 47. P. Massiani, F. Fajula, F. Figueras and J. Sanz, Zeolites, 1988, 8, 332. 48. H. Ernst, D. Freude and I . Wolf, Chem. Phys. Letr., 1993, 212, 588. 49. A. Samoson and E. Lippmaa, Phys. Rev. B , 1983, B28, 6565. 50. D. Fenzke, D. Freude, T. Frohlich and J. Haase, Chem. Phys. Lett., 1984, 111, 171. 51. P. P. Man and J. Klinowski, J . Chem. Soc., Chem. Commun., 1988, 1291. 52. A. Samoson, E. Lippmaa, G. Engelhardt, U. Lohse and H.-G. Jerschkewitz, Chern. Phys. Lett., 1987, 134, 589.
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87
53. J. Gilson, G. C. Edwards, A. W. Peters, K. Rajagopalan, R. F. Wormsbecher, T. G. Roberie and M. P. Shatlock, J. Chem. SOC.,Chem. Commun., 1987, 91. 54. L. Kellberg, M. Linsten and H . J. Jakobsen, Chem. Phys. Lett., 1991, 182, 120. 55. J. Rocha, S. W. Carr and J. Klinowski, Chem. Phys. Lett., 1991, 187, 401. 56. P. J. Barrie, Chem. Phys. Lett., 1993, 208, 486. 57. G. J. Ray and A. Samoson, Zeolites, 1993, 13, 410. 58. K. F. M. G. J. Scholle and W. S. Veeman, Zeolites, 1985, 5 , 118. 59. G. W. Haddix, M. Narayana, W. D. Gillespie, M. B. Georgellis and Y. Wu, J. A m . Chem. SOC., 1994, 116, 672. 60. H . Pfeifer, D. Freude and M. Hunger, Zeolites, 1985, 5 , 273. 61. D. Freude, in Recent Advances in Zeolite Science (eds J. Klinowski and P. J. Barrie), Stud. Surf. Sci. Catal., 1989, 52, 169. 62. H . Pfeifer, Nucl. Magn. Reson., 1994, 31, 31. 63. D. Freude, M. Hunger, H. Pfeifer and W. Schwieger, Chem. Phys. Lett., 1986, 128, 62. 64. H. Pfeifer, D. Freude and J . Karger, 2. Phys. Chem. (Leipzig), 1988, 269, 320. 65. E. Brunner, J. Chem. Soc., Faraday Trans., 1993, 89, 165. 66. D. Freude, J. Klinowski and H. Hamdan, Chem. Phys. Lett., 1988, 149, 355. 67. M. Hunger, D. Freude, D . Fenzke and H. Pfeifer, Chem. Phys. Lett., 1992. 191, 391. 68. N. P. Kenaston, A. T. Bell and J . A. Reimer, J. Phys. Chem., 1994, 98, 894. 69. L. A . Curtiss, H. Brand, J. B. Nicholas and L. E. Iton, Chem. Phys. Lett., 1991, 184,215. 70. P. Batamack, C. Dorernieux-Morin, R. Vincent and J . Fraissard, J. Phys. Chem., 1993, 97, 9779. 71. F. Haase and J. Sauer, J . Phys. Chem., 1994, 98, 3083. 72. M. W. Anderson, P. J. Barrie and J. Klinowski, J . Phys. Chem., 1991, 95, 235. 73. J. L. White, L. W. Beck and J. F. Haw, J. Am. Chem. SOC., 1992, 114, 6182. 74. D . Michel, A. Germanus, H. Pfeifer, J . Chem. Soc., Faraday Trans I , 1982, 78, 237. 75. W. L. Earl, P. 0. Fritz, A. A. V. Gibson and J. H . Lunsford, J. Phys. Chem., 1987, 91, 2091. 76. W. P. J. H. Jacobs, J. W. de Haan, L. J. M. van de Ven and R . A. van Santen, J . Phys. Chem., 1993, 97, 10394. 77. J. A. Ripmeester, J. Am. Chem. Soc., 1983, 105, 2925. 78. W. P. Rothwell, W. Shen and J. H. Lunsford, J . A m . Chem. SOC., 1984, 106, 2452. 79. J. H . Lunsford, W. P. Rothwell and W. Shen, J. A m . Chem. Soc., 1985, 107, 1540. 80. J. H. Lunsford, P. N. Tutunjian, P. Chu, E. B. Yeh and D. J . Zalewski, J. Phys. Chem., 1989, 93, 2590. 81. A. A. Kheir and J. F. Haw, J . A m . Chem. SOC., 1994, 116, 817. 82. H . K. C. Timken, G. L. Turner, J . P. Gilson, L. B. Welsh, E. Oldfield, J. A m . Chem. SOC., 1986, 108, 7231. 83. S. Yang, K. D. Park and E. Oldfield, J. A m . Chem. SOC., 1989, 111, 7278. 84. X. Liu, J. Klinowski and J. M. Thomas, Chem. Phys. Lett., 1986, 127, 563. 85. H. K. C. Timken and E. Oldfield, J. Am. Chem. Soc., 1987, 109,7669. 86. A. P. M. Kentgens, C. R . Bayense, J. H. C. van Hooff, J. W. de Haan and L. J. M. van de Ven, Chem. Phys. Lett., 1991, 176, 399. 87. C. R. Bayense, A. P. M. Kentgens, J. W. de Haan, L. J. M. van de Ven and J. H. C. van Hooff, J. Phys. Chem., 1992, 96, 775. 88. A. Tuel and Y. Bentaarit, J. Chem. Soc., Chem. Commun., 1992, 1578. 89. J. Caro, M. Biilow, M. Derewinski, M. Hunger, J . Karger, U. Kiirschner, H. Pfeifer, W. Storek and B. Zibrowius, in Recent Advances in Zeolite Science (eds J. Klinowski and P. J. Barrie), Stud. Surf. Sci. Catal., 1989, 52, 295. 90. G. Lischke, R. Eckelt, H.-G. Jerschkewitz, B. Parlitz, E. Schreier, W. Storek, B. Zibrowius and G. Ohlrnann, J. Catal., 1991, 132, 229. 91. W. Kolodziejski, V. Fornes and A. Corma, Solid State Nucl. M a p . Reson., 1993, 2, 121.
88
P. J. BARRIE
92. R. Jelinek, S. Ozkar and G. A. Ozin, J. Am. Chem. SOC.,1992, 114,4907. 93. R. Jelinek, S. Ozkar and G. A. Ozin, J. Phys. Chem., 1992, 96, 5949. 94. R. Jelinek, S. Ozkar, H. 0. Pastore, A. Malek and G. A. Ozin, J. Am. Chem. SOC.,1993, 115, 563. 95. M. Hunger, G. Engelhardt, H. Koller and J. Weitkamp, Solid State Nucl. Magn. Reson., 1993, 2, 111. 96. H. A. M. Verhulst, W. J. J. Welters, G. Vorbeck, L. J. M. van de Ven, V. H. J. de Beer, R. A. van Santen and J. W. de Haan, J. Chem. SOC., Chem. Commun., 1994,639. 97. P. A. Cybulski, D. J. Gillis and M. C. Baird, Znorg. Chem., 1993, 32,460. 98. R. R. Eckman and A. J. Vega, J. Phys. Chem., 1986, 90, 4679. 99. B. Zibrowius, J. Car0 and H. Pfeifer, J. Chem. SOC., Faraday Trans 1 , 1988, 84, 2347. 100. B. Boddenberg and R. Burmeister, Zeolites, 1988, 8, 488. 101. L. M. Bull, N. J. Henson, A. K. Cheetham, J. M. Newsam and S. J. Heyes, J. Phys. Chem., 1993, 97, 11776. 102. B. F. Chmelka, J. G. Pearson, S. B. Liu, R. Ryoo, L. C. de Menorval and A. Pines, J. Phys. Chem., 1991, 95, 303. 103. J. G. Pearson, B. F. Chmelka, D. N. Shykind and A. Pines, J. Phys. Chem., 1992, 96, 8517. 104. L. W. Beck, J. L. White and J. F. Haw, J. M a p . Reson., 1992, 99, 182. 105. M. W. Anderson and J. Klinowski, Nature, 1989, 339,200. 106. M. W. Anderson and J. Klinowski, J. Am. Chem. SOC., 1990, 112, 10. 107. J. L. White, N. D. Lazo, B. R. Richardson and J. F. Haw, J. Catal., 1990, 125,260. 108. E.J. Munson, D. B. Ferguson, A. A. Kheir and J. F. Haw, J. Catal., 1992, 136, 504. 109. E. J. Munson, D. K. Murray and J. F. Haw, J. Catal., 1993, 141,733. 110. F. G. Oliver, E. J. Munson and J. F. Haw, J. Phys. Chem., 1992, 96, 8106. 111. C. Tsiao, D. R. Corbin and C. Dybowski, J. Am. Chem. SOC., 1990,112,7140. 112. E.J. Munson, A. A. Kheir, N. D. Lazo and J. F. Haw, J. Phys. Chem., 1992, 96,7740. 113. M. W. Anderson and J. Klinowski, Chem. Phys. Lett., 1990, 172,275. 114. W. Kolodziejski and J. Klinowski, Appl. Catal., 1992, A81, 133. 115. E. J. Munson, N. D. Lazo, M. E. Moellenhoff and 3. F. Haw, J. Am. Chem. SOC., 1991, 113, 2783. 116. E. J. Munson and J. F. Haw, J. Am. Chem. Soc., 1991, 113, 6303. 117. E.J. Munson, A. A. Kheir and J. F. Haw, J. Phys. Chem., 1993, 97,7321. 118. J. F. Haw, B. R. Richardson, I. S. Oshiro, N. D. Lazo and J. A. Speed, J. Am. Chem. SOC., 1989, 111, 2052. 119. N. D. Lazo, B. R. Richardson, P. D. Schettler, J. L. White, E. J. Munson and J. F. Haw, J . Phys. Chem., 1991, 95,9420. 120. B. R. Richardson, N. D. Lazo, P. D. Schettler, J. L. White and J. F. Haw, J. Am. Chem. SOC., 1990, 112, 2886. 121. K. P. Datema, A. K. Nowak, J. van Baarm Houckgeest and A. F. H. Wielers, Catal. Lett., 1991, 11, 267. 122. N. D. Lazo, J. L. White, E. J. Munson, M. Lambregts and J. F. Haw, J. Am. Chem. Soc., 1990, 112,4050. 123. E. J. Munson, T. Xu and J. F. Haw, J. Chem. SOC., Chem. Commun., 1993, 75. 124. E. J. Munson and J. F. Haw, Angew. Chem. Int. Ed. Engl., 1993, 32,615. 125. T. Xu, E. J. Munson and J. F. Haw, J. Am. Chem. SOC., 1994, 116, 1962. 126. D.K. Murray, J.-W. Chang and J. F. Haw, J. Am. Chem. SOC., 1993, 115,4732. 127. V. Bosacek, J. Phys. Chem., 1993, 97, 10732. 128. G. A. Ozin and S. Ozkar, Chem. Muter., 1992, 4, 511. 129. G. D. Stucky and J. E. MacDougall, Science, 1990, 247,669. 130. S. T. Wilson, B. N. Lok, C. A. Messina, T. R. Cannan and E. M. Flanigen, J. Am. Chem. SOC., 1982, 104, 1146.
NMR APPLICATIONS TO POROUS SOLIDS
89
131. B. M. Lok, C. A. Messina, R. L. Patton, R. T. Gajek, T. R. Cannan and E. M. Flanigen, J . Am. Chem. SOC., 1984, 106, 6092. 132. E. M. Flanigen, B. M. Lok, R. L. Patton and S. T. Wilson, Pure Appl. Chem., 1986, 58, 1351. 133. J. M. Bennett, W. J. Dytrych, J. J. Pluth, J . W. Richardson Jr and J. V. Smith, Zeolites, 1986, 6, 349. 134. P. J. Barrie, in Spectroscopy of New Materials (eds R. J. H. Clark and R. E. Hester), Adv. Spectrosc., 1993, 22, 151. 135. D . Miiller, E. Jahn, G. Ladwig and U. Haubenreisser, Chem. Phys. Lett., 1984, 109, 332. 136. P. J. Barrie. M. E. Smith and J. Klinowski, Chem. Phys. Lett., 1991, 180, 6. 137. M. E. Davis, C. Saldarriaga, C. Montes, J . Garces and C. Crowder, Nature, 1988, 331, 698. 138. C. E. Crowder, J . M. Garces and M. E. Davis, Adv. X-ray Anal., 1988, 32, 507. 139. J. W. Richardson Jr, J. V. Smith and J. J . Pluth, J . Phys. Chem., 1989, 93, 8212. 140. M. E. Davis, C. Montes, P. E. Hathaway. J . P. Arhancet, D. L. Hasha and J . M. Garces, J . Am. Chem. SOC.,1989, 111, 3919. 141. L. B. McCusker, C. Baerlocher, E. Jahn and M. Biilow, Zeolites, 1991, 11, 308. 142. J. B. van Braam Houckgeest, B. Kraushaar-Czarnetzki, R. J . Dogterom and S. de Groot, J . Chem. SOC., Chem. Commun., 1991, 666. 143. L. Maistriau, 2. Gabelica and E. G . Derouane, Appl. Cafal. A: General, 1992, 81, 67. 144. Y. Wu, B. F. Chmelka, A. Pines, M. E. Davis, P. J . Grobet and P. A. Jacobs, Nature, 1990, 346, 550. 145. P. J. Grobet, A. Samoson, H. Geerts, M. Martens and P. A. Jacobs, J . Phys. Chem., 1991, 95, 9620. 146. C. A. Fyfe, H. Grondey, K. T. Mueller, K. C. Wong-Moon and T. Markus, J . A m . Chem. SOC.,1992, 114, 5876. 147. C. A. Fyfe, K . C. Wong-Moon, H. Grondey and K. T. Mueller, J . Phys. Chem., 1994,98, 2139. 148. A. J. Vega, J . Magn. Reson., 1992, 96, 50. 149. C. A. Fyfe, K. T. Mueller, H . Grondey and K. C. Wong-Moon, Chem. Phys. Lett., 1992, 199, 198. 150. E. R. H. van Eck and W. S. Veeman, J . Am. Chem. SOC., 1993, 115, 1168. 151. C. A. Fyfe, K. T. Mueller, H. Grondey and K. C. Wong-Moon, J . Phys. Chem., 1993,97, 13 484. 152. G. Engelhardt and W. Veeman, J . Chem. SOC., Chem. Commun., 1993, 622. 153. S. Prasad and R. Vitrivel, J . Phys. Chem., 1994, 98, 1579. 154. W. Kolodziejski, J. Rocha, H. He and J. Klinowski, Appl. Catal., 1991, 77, L l . 155. M. W. Anderson, J . M. Shi, D. A. Leigh, A. E. Moody, F. A. Wade, B. Hamilton and S. W. Carr, J . Chem. SOC., Chem. Commun., 1993, 533. 156. A. Gugel, K. Mullen, H. Reichert, W. Schmidt, G . Schon, F. Schuth, J. Spickermann, J. Titman and K. Unger, Angew. Chem. Znt. Ed. Engl., 1993, 32, 556. 157. M. J. Duer, H. He, W. Kolodziejski and J. Klinowski, J . Phys. Chem., 1994, 98, 1198. Li and M. E. Davis, J . Am. Chem. SOC., 1992, 114, 3690. 158. D. Goldfarb, H.-X. 159. M. P. J. Peeters, J. W. de Haan, L. J. M. van de Ven and J. H. C. van Hooff, J . Phys. Chem., 1993, 97, 5363. 160. J. Rocha, J. Klinowski, P. J. Barrie, R. Jelinek and A. Pines, Solid State Nucl. Magn. Reson., 1992, 1, 217. 161. J. Janchen, M. P. J. Peeters, J . W. de Haan, L. J. M. van de Ven, J . H. C . van Hooff, J . Phys. Chem.. 1993, 97, 12 042. 162. H. He and J. Klinowski, J . Phys. Chem., 1993, 97, 10385. 163. R. Jelinek, B. F. Chmelka, Y . Wu, A. Pines, P. J. Grandinetti, P. J . Barrie and J . Klinowski, J . Am. Chem. Soc., 1993, 113, 4097.
90
P. J. BARRIE
164. A. Simmen, L. B. McCusker, C. Baerlocher, W. M. Meier, Zeolites, 1991, 11, 654. 165. H. K. C. Timken, N. Janes, G. L. Turner, S. L. Lambert, L. B. Welsh and E. Oldfield, J. Am. Chem. SOC.,1986, 108, 7236. 166. C. S. Blackwell and R . L. Patton, J . Phys. Chem., 1988, 92, 3965. 167. I. P. Appleyard, R. K. Harris and F. R. Fitch, Chem. Lett., 1985, 1747. 168. L. S. de Saldarriaga, C. Saldarriaga and M. E. Davis. J . Am. Chem. Soc., 1987, 109. 2686. 169. M. W. Anderson, B. Sulikowski, P. J. Barrie and J. Klinowski, J . Phys. Chem., 1990, 94, 2730. 170. B. Zibrowius, E. Loffler and M. Hunger, Zeolites, 1992, 12, 167. 171. B. Zibrowius and U. Lohse, Solid State Nucl. Magn. Reson., 1992, 1, 137. 172. H.-L. Zubowa, E . Alsdorf, R. Fricke, F. Neissendorfer, J . Richter-Mendau, E. Schreier, D. Zeigan and B. Zibrowius, J . Chem. SOC.,Faraday Trans., 1990, 86, 2307. 173. G . H. Kiihl and K. D . Schmitt, Zeolites, 1990, 10, 2. 174. J . A. Martens, M. Mertens, P. J. Grobet and P. A. Jacobs, in Znnovation in Zeolite Materials Science (eds P. J. Grobet, W. J. Mortier, E. F. Vansant and G . Schulz-Ekloff), Stud. Surf. Sci. Catal., 1987, 37, 97. 175. J . A. Martens, C. Janssens, P. J. Grobet, H. K. Beyer and P. A . Jacobs, in Zeolites: Facts, Figures, Future (eds P. A. Jacobs and R. A. van Santen), Stud. Surf. Sci. Catal., 1989, 49, 215. 176. J. A. Martens, P. J. Grobet and P. A. Jacobs, J . Catal., 1990, 126, 299. 177. L. Maistriau. N. Dumont, J. B. Nagy, Z. Gabelica and E. G . Derouane, Zeolites, 1990, 10, 243. 178. P. P. Man, M. Briend. M. J. Peltre, A. Lamy, P. Beaunier and D . Barthomeuf, Zeolites, 1991, 11, 563. 179. E. Jahn, D. Miiller and K. Becker, Zeolites, 1990, 10, 151. 180. R. Khouzami, G . Coudurier, F. Lefebvre, J. C . VCdrine and B. F. Mentzen, Zeolites, 1990, 10, 183. 181. D . Hasha, L. S. de Saldarriaga, C. Saldarriaga, P. E. Hathaway, D . F. Cox and M. E. Davis, J . Am. Chem. SOC.,1988, 110, 2127. 182. D . Freude, H. Ernst, M. Hunger, H. Pfeifer and E. Jahn, Chem. Phys. Lett., 1988, 143, 477. 183. R. Wang, C. F. Lin, Y. S. Ho, L. J . Leu and K. J. Chao, A p p l . Cutal., 1991, 72, 39. 184. R. Vomscheid, M. Briend, M. J . Peltre, P. Massiani, P. P. Man and D. Barthomeuf, J . Chem. Soc., Chem. Commun., 1993, 544. 185. Y . Xu, C. P. Grey. J. M. Thomas and A . K. Cheetham, Catul. Lett., 1990, 4. 251. 186. P. J. Barrie and J. Klinowski, J . Phys. Chem., 1989, 93, 5972. 187. W.-L. Shea, R. B. Borade and A. Clearfield, J . Chem. SOC., Faruduy Trans., 1993. 89, 3143. 188. C. Montes, M. E. Davis, B. Murray and M. Narayana, J . Phys. Chem., 1990. 94, 6425. 189. C. Montes, M. E. Davis, B. Murray and M. Narayana, J . Phys. Chem., 1990, 94, 6431. 190. D. Goldfarb, Zeolites, 1989, 9, 509. 191. J. B. Parise, J . Chem. SOC., Chem. Commun., 1985, 606. 192. G . Yang, S. Feng and R. Xu, J . Chem. SOC.,Chem. Commun., 1987, 1254. 193. M. Estermann, L. B. McCusker, C. Baerlocher, A. Merrouche and H. Kessler, Nature, 1991, 352, 320. 194. A. Merrouche, J . Patarin, H. Kessler. M. Soulard, L. Delmotte, J. L. Guth and J. F. Joly, Zeolites, 1992, 12, 226. 195. Q. Huo and R . Xu, J . Chem. SOC.,Chem. Commun., 1992, 1391. 196. G. Yang, L. Li, J . Chen and R. Xu, J . Chem. SOC., Chem. Commun., 1989, 810. 197. J . Chen and R. Xu, J . Solid State Chem., 1989, 80, 149. 198. J. Chen, R . Xu, L. Li, Y. Xu and F. Zhou, J . Solid Stare Chem., 1990, 87, 152.
NMR APPLICATIONS TO POROUS SOLIDS 199. 200. 201. 202. 203. 204.
205. 206. 207. 208. 209. 210. 211. 212. 213. 214. 215. 216. 217. 218. 219. 220. 221. 222. 223. 224. 225. 226. 227. 228. 229. 230. 231. 232. 233. 234. 235. 236. 237. 238.
91
J. Chen. L. Li, G . Yang and R. Xu, J . Chem. Soc., Chem. Commun., 1989, 1217. Y . Long and P. Wenqin, J . Chem. Soc., Chem. Commun., 1990, 787. M. Taramasso, G. Perego and B. Notari, U.S. Patent 4 410 501, 1983. D. M. Chapman and A. L. Roe, Zeolites, 1990, 10, 730. R. C. Haushalter and L. A. Mundi, Chem. Muter., 1992, 4, 31. R. L. Bedard, C. L. Bowes, N. Coombs, A. J. Holmes, T. Jiang, S. J. Kirby, P. M. Macdonald, A. M. Malek, G . A. Ozin, S. Petrov, N. Plavac, R. A. Ramik, M. R. Steele and D. Young, J . A m . Chem. Soc., 1993, 115, 2300. S. M. Bradley, R. F. Howe and J. V. Hanna, Solid State Nucl. Magn. Reson., 1993, 2, 37. B. Zibrowius, M. W. Anderson, W. Schmidt, F.-F. Schiith, A. E. Aliev and K. D. M. Harris, Zeolites, 1993, 13, 607. C. Schott-Darie, L. Delmotte, H. Kessler and E. Benazzi, Solid State Nucl. M a p . Reson., 1994, 3, 43. M. W. Anderson, 0. Terasaki, T. Ohsuna, A. Philippou, S. P. MacKay, A. Ferreira, J. Rocha and S. Lidin, Nature, 1994, 367, 347. T. J. Pinnavaia, Science, 1983, 220, 365. M. E. Landis, B. A. Aufdembrink, P. Chu, I. D. Johnson, G. W. Kirker and M. K. Rubin, 1. A m . Chem. Soc., 1991, 113, 3189. S. Cheng and T.-C. Wang, Inorg. Chem., 1989, 28, 1283. A. Clearfield and B. D. Roberts, Inorg. Chem., 1988, 27, 3237. V. Soghomonian, R. C. Haushalter, Q. Chen and J. Zubieta, Inorg. Chem., 1994, 33, 1700. D. Plee. F. Borg, L. Gatineau and J. J. Fripiat, J . A m . Chem. Soc., 198.5, 107, 2362. T. J. Pinnavaia, S. D. Landau, M. S. Tzou, I. D. Johnson and M. Lipsicas, J . A m . Chem. Soc.. 1985, 107, 7222. J. Sterte and J. Shabtai, Clays Clay Miner., 1987, 35, 429. L. Li, X. Liu, Y. Ge, R. Xu, J. Rocha and J. Klinowski, J . Phys. Chem., 1993, 97, 10389. G. Cao, M. E. Garcia, M. Alcal6, L. F. Burgess and T. E. Mallouk, J . A m . Chem. Soc., 1992, 114, 7574. D. J. MacLachlan and K. R. Morgan, J . Phys. Chem., 1990, 94, 7656. L. Li, X. Liu, L. Ge, L. Li and J. Klinowski, J . Phys. Chem., 1991, 95, 5910. D. A. Bunvell, K. G. Valentine and M. E. Thompson, J . Magn. Reson., 1992, 97, 498. D. A. Bunvell, K. G . Valentine, J. H . Timmermans and M. E. Thompson, J . A m . Chem. Soc.. 1992, 114, 4144. M. W. Anderson and J. Klinowski, Inorg. Chem., 1990, 29, 3260. E. Lalik, W. Kolodziejski, A. Lerf and J. Klinowski, J . Phys. Chem., 1993, 97, 223. G . E. Maciel and D. W. Sindorf, J . A m . Chem. Soc., 1980, 102, 7606. A. R. Grimmer, R. Rosenberger, H. Burger and W. Vogel, J . Non-Cryst. Solids, 1988, 99, 371. S. Leonardelli, L. Facchini, C. Fretigny, P. Tougne and A . P. Legrand, J . A m . Chem. Soc., 1992, 114, 6412. D. W. Sindorf and G. E. Maciel, J , A m . Chem. Soc., 1983, 105, 1487. I.-S. Chuang, D. R . Kinney and G. E. Maciel, J . A m . Chem. Soc., 1993, 115, 8695. C. E. Bronnimann, R. C. Zeigler and G . E. Maciel, 1.A m . Chem. Soc., 1988, 110.2023. D. W. Sindorf and G. E. Maciel, J . A m . Chem. Soc., 1981, 103, 4263. D. W. Sindorf and G. E. Maciel, J . A m . Chem. Soc., 1983, 105, 3767. D. W. Sindorf and G. E. Maciel, J . Phys. Chem., 1982, 86, 5208. D. W. Sindorf and G . E. Maciel, J. Phys. Chem., 1983, 87, 5516. X. Wu, E. A. Juban and L. G. Butler, Chem. Phys. Lett., 1994, 221, 65. D. E. O’Reilly, Adv. Catal., 1960, 12, 31. B. A. Huggins and P. D. Ellis, J . A m . Chem. Soc., 1992, 114, 2098. H. D. Morris and P. D . Ellis, J . A m . Chem. Soc., 1989, 111, 6045.
92
P. J. BARRIE
239. P. D. Majors and P. D. Ellis, J . A m . Chem. SOC., 1987, 109, 1648. 240. M. McMillan, J . S. Brinen, J. D. Carruthers and G. L. Hailer, Colloids Surf., 1989, 38, 133. 241. C. DorCmieux-Morin, C. Martin, J . M. Bregeault and J . Fraissard, Appl. Catal., 1991, 77, 149. 242. C. Dorkmieux-Morin, P. Batamack, C. Martin, J. M. Bregeault and J. Fraissard, Cutul. Lett., 1991, 9, 403. 243. G. E. Maciel, J. F. Haw, 1 . 4 . Chuang, B. L. Hawkins, T. A. Early, D. R. McKay and L. Petrakis, J. A m . Chem. SOC.,1983, 105, 5529. 244. J. H. Strange, M. Rahman and E. G. Smith, Phys. Rev. Lett., 1993, 71, 3589. 245. K. Overloop and L. van Gerven, J. Magn. Reson., Series A , , 1993, 101, 179. 246. J. Klafter and J. M. Drake (eds), Molecular Dynamics in Restricted Geometries, Wiley, New York, 1989. 247. K. S. Mendelson, Magn. Reson. Imaging, 1991, 9, 651. 248. K. S. Mendelson, Magn. Reson. Imaging, 1991, 9, 877. 249. C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli and J. S. Beck, Nature, 1992, 359, 710. 250. J. S. Beck, J. C. Vartuli, W. J. Roth, M. E. Leonowicz, C. T. Kresge, K. D. Schmitt, C. T.-W. Chu, D. H. Olson, E. W. Sheppard, S. B. McCullen, J. B. Higgins and J. L. Schlenker, J. A m . Chem. SOC., 1992, 114, 10834. 251. P. J. Branton, P. G. Hall and K. S. W. Sing, J. Chem. SOC., Chem. Commun., 1993, 1257. 252. 0. Franke, G . Schulz-Ekloff, J . Rathousky, J. Starek and A. Zunkal, J . Chem. SOC., Chem. Commun., 1993, 724. 253. W. Kolodziejski, A. Corma, M.-T. Navarro and J. PCrez-Pariente, Solid State Nucl. Magn. Reson., 1993, 2 , 253. 254. P. Behrens and G. D. Stucky, Angew. Chem. Int. Ed. Engl., 1993, 32, 696. 255. R. Schmidt, D. Akporiaye, M. Stocker and 0. H. Ellestad, J . Chem. SOC., Chem. Commun., 1994, 1493. 256. K. J. Shea, D. A. Loy and 0. Webster, J. A m . Chem. SOC.,1992, 114, 6700. 257. P. J. Barrie, S. W. Cam, D. L. Ou and A. C. Sullivan, Chem. Mater., 1994, in press. 258. C. P. Slichter, Annu. Rev. Phys. Chem., 1986, 37, 25. 259. J.-P. Ansermet, C. P. Slichter and J. H. Sinfelt, Progr. NMR Spectrosc., 1990, 22, 401. 260. V. M. Mastikhin, I. L. Mudrakovsky and A. V. Nosov, Progr. NMR Spectrosc., 1991, 23, 259. 261. S . L. Rudaz, J . - P . Ansermet, P. K. Wang, C. P. Slichter and J . H. Sinfelt, Phys. Rev. Lett., 1985, 54, 71. 262. M. Engelsberg and C . S . Yannoni, J . Magn. Reson., 1990, 88, 393. 263. M. Engelsberg, C. S. Yannoni, M. A. Jacintha and C. Dybowski, J. A m . Chem. SOC., 1992, 114, 8319. 264. M. Engelsberg, C. S. Yannoni, M. A. Jacintha, C. Dybowski and R. E. de Souza, J. Phys. Chem., 1994, 98, 2397. 265. C. F. Tirendi, G. A. Mills, C. Dybowski and G. Neue, J. Phys. Chem., 1992, 96, 5045. 266. P.-K. Wang, C. P. Slichter and J. H. Sinfelt, Phys. Rev. Lett., 1984, 53, 82. 267. P.-K. Wang, C. P. Slichter and J. H. Sinfelt, J . Phys. Chem., 1985, 89, 3606. 268. P.-K. Wang, C. P. Slichter and J. H. Sinfelt, J. Phys. Chem., 1990, 94, 1154. 269. Y.-H. Chin and P. D. Ellis, J. A m . Chem. Soc., 1993, 115, 204. 270. J. Wang and P. D. Ellis, J. A m . Chem. SOC., 1993, 115, 212. 271. J. K. Plischke, A. J. Benesi and M. A. Vannice, J. Catal., 1992, 138, 223. 272. N. D. Lazo, D. K. Murray, M. L. Kieke and J. F. Haw, J. Am. Chem. SOC.,1992, 114, 8552. 273. M. J. Larnbregts, E. J. Munson, A. A. Kheir and J . F. Haw, J. A m . Chem. SOC., 1992, 114, 6875.
NMR APPLICATIONS T O POROUS SOLIDS
93
274. T.-C. Sheng and I. D. Gay, J. Catal., 1994, 145, 10. 275. J. A. Ripmeester, J. A m . Chem. SOC., 1982, 104, 289. 276. J. A. Ripmeester, C. I. Ratcliffe and J. S. Tse, J. Chem. SOC., Faraday Trans I , 1988, 84, 3731. 277. T. Ito and J. Fraissard, J. Chem. Phys., 1982, 76, 5225. 278. J. Fraissard and T. Ito, Zeolites, 1988, 8, 350. 279. P. J. Barrie and J. Klinowski, Progr. NMR Spectrosc., 1992, 24, 91. 280. C. Dybowski, N. Bansal and T. M. Duncan, Annu. Rev. Phys. Chem., 1991, 42, 433. 281. D. Raftery and B. Chmelka, Nucl. Magn. Reson., 1994, 30, 111. 282. K.-J. Chao and D.-S. Shy, J. Chem. Soc., Faraday Trans., 1993, 89, 3841. 283. T. Ito, L.-C. de Menorval, E. Guerrier and J. Fraissard, Chem. Phys. Lett., 1984, 111, 271. 284. M. J. Annen, M. E. Davis and B. E. Hanson, Catal. Lett., 1990, 6, 331. 285. J. A. Ripmeester and C. I. Ratcliffe, J. Phys. Chem., 1990, 94, 7652. 286. T. Ito and J. Fraissard, J. Chem. Soc., Faraday Trans. 1 , 1987, 83, 451. 287. T. T. P. Cheung, C. M. Fu and S. Wharry, J. Phys. Chem., 1988, 92, 5170. 288. R. Grosse, R. Burmeister, B. Boddenberg, A. Gedeon and J. Fraissard, J . Phys. Chem., 1991, 95, 2443. 289. A. Gedeon, J. L. Bonardet and J. Fraissard, J. Phys. Chem., 1993, 97, 4254. 290. A. Gedeon and J. Fraissard, Chem. Phys. Len., 1994, 219, 440. 291. E. W. Scharpf, R. W. Crecely, B. C. Gates and C. Dybowski, J. Phys. Chem., 1986, 90, 9. 292. R. Shoemaker and T. Apple, J. Phys. Chem., 1987, 91, 4024. 293. N. Bansal and C. Dybowski, J . Phys. Chem., 1988, 92, 2333. 294. A. Gedeon, J. L. Bonardet, T. Ito and J. Fraissard, J. Phys. Chem., 1989, 93, 2563. 295. L.-C. de Menorval, J. Fraissard, T. Ito and M. Primet, J. Chem. Soc., Faraday Trans. I , 1985, 81, 2855. 296. B. F. Chmelka, R. Ryoo, S.-B. Liu, L.-C. de Menorval, C. J. Radke, E. E. Petersen and A. Pines, J. A m . Chem. Soc., 1988, 110, 4465. 297. 0. B. Yang, S. I. Woo and R. Ryoo, J. Catal., 1990, 123, 375. 298. C. Tsiao, D. R. Corbin and C. Dybowski, J. Phys. Chem., 1990,94, 867. 299. S. J. Cho, S. M. Jung, Y. G. Shul and R. Ryoo, J. Phys. Chem., 1992, 96, 9922. 300. R. Ryoo, S. J. Cho, C. Pak, J.-G. Kim, S.-K. Ihm and J. Y.Lee, J. Am. Chem. Soc., 1992, 114, 76. 301. T. I. Koranyi, L. J. M. van de Ven, W. J. J. Welters, J. W. de Haan, V. H. J. de Beer and R. A. van Santen, Catal. Lett., 1993, 17, 105 302. G. Moretti and W. M. H. Sachtler, Catal. Lett., 1993, 17, 285. 303. E. Trescos, L.-C. de MCnorval and F. Rachdi, J. Phys. Chem., 1993, 97, 6943. 304. B. Boddenberg and J. Watermann, Chem. Phys. Lett., 1993, 203, 531. 305. J. A. Ripmeester, J. Magn. Reson., 1984, 56, 247. 306. T. Ito, M. A. Springuel-Huet and J. Fraissard, Zeolites, 1989, 9, 68. 307. T. Ito and J. Fraissard, Zeolites, 1987, 7, 554. 308. A. Gedeon, T. Ito and J. Fraissard, Zeolites, 1988, 8, 376. 309. N. Bansal and C. Dybowski, J. Magn. Reson., 1990, 89, 21. 310. L.-C. de Menorval, D. Raftery, S.-B. Liu, K. Takegoshi, R. Ryoo and A. Pines, J. Phys. Chem., 1990, 94, 27. 311. S.-B. Liu, L.-J. Ma, M.-W. Lin, J.-F. Wu and T.-L. Chen, J. Phys. Chem., 1992, 96, 8120. 312. R. Ryoo, C. Pak and B. F. Chmelka, Zeolites, 1990, 10, 790. 313. Q. J. Chen and J. Fraissard, J. Phys. Chem., 1992, 96, 1814. 314. J. A. Ripmeester and C. I. Ratcliffe, Anal. Chim. Acta, 1993, 283, 1103. 315. Q. J. Chen and J. Fraissard, J . Phys. Chem., 1992, 96, 1809.
94
P. J. BARRIE
316. M. G. Samant, L.-C. de Menorval, R. A. Dalla Betta and M. Boudart, J. Phys. Chem., 1988, 92, 3937. 317. B. F. Chmelka, D. Raftery, A. V. McCormick, L.-C. de Menorval, R. D. Levine and A. Pines, Phys. Rev. Lett., 1991, 66, 580. 318. C. J . Jameson, A. K. Jameson, R. Gerald I1 and A. C. de Dios, J. Chem. Phys., 1992, 96, 1676. 319. R. Ryoo, L . X . de Menorval, J. H. Kwak and F. Figueras, J. Phys. Chem., 1993, 97, 4124. 320. C. J. Jameson and A. C. de Dios, J. Chem. Phys., 1992, 97, 417. 321. R. G. Larsen, J. Shore, K. Schmidt-Rohr, L. Emsley, H. Long, A. Pines, M. Janicke and B. F. Chmelka, Chem. Phys. Lett., 1993, 214, 220. 322. C. J. Jameson, A. K. Jameson, R. Gerald I1 and A. C. de Dios, J. Phys. Chem., 1992,96, 1690. 323. V. V. Terskikh, I. L. Mudrakovskii and V. M. Mastikhin, J. Chem. SOC.,Faraday Trans., 1993, 89, 4239. 324. W. C. Conner, E. L. Weist, T . Ito and J. Fraissard, J . Phys. Chem., 1989, 93, 4138. 325. T. T. P. Cheung, J. Phys. Chem., 1989, 93, 7549. 326. P. J. Barrie, G. F. McCann, I. Gameson, T. Rayment and J. Klinowski, J. Phys. Chem., 1991, 95, 9416. 327. N. Bansal, H. C. Foley, D. S. Lafyatis and C. Dybowski, Catal. Today, 1992, 14, 305. 328. D. J. Suh, T.-J. Park, S.-K. Ihm and R. Ryoo, J. Phys. Chem., 1991, 95, 3767. 329. M. Boudart, L . X . de MenorVal, J. Fraissard and G. P. Valenca, J. Phys. Chem., 1988, 92, 4033. 330. M. Boudart, R. Ryoo, G. P. Valenfa and R. van Grieken, Catal. Lett., 1993, 17, 273. 331. J . L. Bonardet, G . B. Garvey, J. B. Moffat and J. Fraissard, Colloids Surfaces A: Physicochem. Eng. Aspects, 1993, 72, 183. 332. M. Mansfeld and W. S. Veeman, Chem. Phys. Lett., 1993, 213, 153. 333. J . Caro, M. Biilow, H. Jobic, J. Karger and B. Zibrowius, Adv. Catal., 1993, 39, 351. 334. J. Karger and D. M. Ruthven, Diffusion in Zeolites and Other Microporous Solids, Wiley, New York, 1992. 335. J . Karger, H. Pfeifer and W. Heink, Adv. Magn. Reson., 1988, 12, 1. 336. D. Beckert, Phys. Lett. A , 1967, 25A, 502. 337. E. 0. Stejskal and J. E. Tanner, J. Chem. Phys., 1965,42, 288. 338. P. Stilbs, Progr. NMR Spectrosc., 1987, 19, 1. 339. T. J. Norwood, J. M a p . Reson., Ser. A , 1993, 103, 258. 340. J. Karger and H. Pfeifer, Zeolites, 1987, 7, 90. 341. M. P. Allan and D. S . Tildesley, Computer Simulation of Liquids, Clarendon Press, Oxford, 1987. 342. R. K. Thomas, Progr. Solid State Chem., 1982, 14, 1. 343. J. Karger and H. Pfeifer, J. Chem. SOC., Faraday Trans., 1991, 87, 1989. 344. W. Heink, J . Karger, H. Pfeifer, K. P. Datema and A. K. Nowak, J. Chem. SOC., Furaday Trans., 1992, 88, 3505. 34s. K. P. Datema, C. J. J. den Ouden, W. D. Ylstra, H. P. C. E. Kuipers, M. F. M. Post and J. Karger, J . Chem. SOC., Faraday Trans., 1991, 87, 1935. 346. J . Caro, M. Biilow, W. Schirmer, J. Karger, W. Heink, H. Pfeifer and S. P. Zhdanov, J . Chem. SOC., Faraday Trans I , 1985, 81, 2541. 347. A. Zikanova, M. Biilow and H. Schlodder, Zeolites, 1987, 7, 115. 348. F. Stallmach, J. Karger and H. Pfeifer, J. Magn. Reson, Ser. A , 1993, 102, 270. 349. U . Hong, J. Karger and H. Pfeifer, J. Am. Chem. SOC., 1991, 113, 4812. 350. U. Hong, J. Karger, B. Hunger, N. N. Feoktistova and S. P. Zhdanov, J. Catal., 1992, 137. 243. 351. U. Rolle-Kampczyk, J. Karger, J. Caro, M. Noack, P. Klobes and B. Rohl-Kuhn, J. Colloid Interface Sci., 1993, 159, 366.
NMR APPLICATIONS TO POROUS SOLIDS
95
352. P. T. Callaghan, A. Coy, T. P. J. Halpin, D. MacGowan, K. J. Packer and F. 0. Zelaya, J . Chem. Phys., 1992, 97, 651. 353. P. T. Callaghan, A. Coy, D. MacGowan and K. J. Packer, J . Mol. L i q . , 1992, 54. 239. 354. P. P. Mitra and P. N. Sen, Phys. Rev. B , 1992, 45, 143. 355. P. N. Sen, L. M. Schwartz, P. P. Mitra and B. I. Halperin, Phys. Rev. B , 1994, 49, 215. 356. W. Heink, J. Karger and H. Pfeifer, Chem. Eng. Sci., 1978, 33, 1019. 357. M. A. Horsfield, E. J. Fordham, C. Hall and L. D. Hall, J . Magn. Reson., 1989, 81, 593. 358. S. Blackband and P. Mansfield, J . Phys. C - Solid State Phys., 1986, 19, L49. 359. Z. Pearl, M. Magaritz and P. Bendel. J . Magn. Reson., 1991, 95, 597. 360. P. A. Osment, K. J. Packer, M. J. Taylor, J. J. Attard, T. A. Carpenter, L. D. Hall, N. J. Herrod and S. J. Doran, Phil. Trans. R . Soc. Lond. A , 1990, 333, 441. 361. B. A. Baldwin and W. S. Yamanashi, M a p . Reson. Imaging, 1988, 6, 493. 362. L. D. Hall and V. Rajanayagam, J . Magn. Reson., 1987, 74, 139. 363. W. P. Rothwell and H. J. Vinegar, Appl. O p t . , 1985, 24, 3969. 364. P. D. Majors, D. M. Smith and P. J. Davis, Chem. Eng. Sci., 1991, 46, 3037. 365. D. N. Guilfoyle, P. Mansfield and K. J. Packer, J . Magn. Reson., 1992, 97, 342. 366. D. M. Smith, R. Deshpande. C. J. Brinker, W. L. Earl, B. Ewing and P. J. Davis, C a r d Today, 1992, 14, 293. 367. M. P. Hollewand and L. F. Gladden, J . Catal., 1993, 144, 254. 368. T. W. Redpath, D. G. Norris, R. A. Jones and J. M. S. Hutchinson, Phys. Med. Biol., 1984, 29, 891. 369. P. T. Callaghan, Principles of Nuclear Magnetic Resonance Microscopy, Clarendon Press, Oxford, 1993. 370. P. T. Callaghan and Y. Xia, J . Magn. Reson., 1991, 91, 326. 371. J. Karger, G. Seiffert and F. Stallmach, J . Magn. Reson., Ser. A , 1993, 102, 327.
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Miscibility, Morphology and Molecular Motion in Polymer Blends K. TAKEGOSHI Department of Chemistry, Faculty of Science, Kyoto University, Kyoto 606, Japan
1. Introduction 2. Miscibility 2.1. Spin-lattice relaxation experiments 2.2. Spin-diffusion experiments 2.3. Heteronuclear cross-relaxation experiments 2.4. Other experiments 2.5. Concluding remarks 3. Polymer-polymer interaction 3.1. Chemical shift 3.2. Nuclear Overhauser effect (NOE) 3.3. Molecular motion 4. Morphology 4.1. NMR imaging 4.2. Lineshape 4.3. Spin-lattice relaxation times and spin diffusion 4.4. Thermally induced morphological change 4.5. Microscopic heterogeneity 5. Molecular motion 5.1. Glass transition 5.2. Effect of blending on local motion 5.3. Motional heterogeneity Acknowledgement References
97 101 102 104 108 109 109 110 111 112 114 115 115 116 118 119 122 122 122 124 125 126 126
1. INTRODUCTION
To satisfy various engineering needs, polymer scientists have been trying to find new polymeric materials. A variety of new monomers and new polarization techniques have been exploited day by day. At the same time, chemical and physical modifications of existing polymers such as grafting, cross-linking, block-copolymerization, interpenetrating-network formation and blending have been widely examined. Much of the usefulness of these multicomponent materials derives from the inherent possibility to modify ANNUAL REPORTS O N NMR SPECIXOSCOPY VOLUME 30 ISBN 0-12-505330-4
Copyright 01995 Academic Press Limited AN rightr of reproduction in any form reserved
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macroscopic properties. Among these modifications, polymer blending provides a simple and economical means of combining useful properties of component polymers.' Whether a blend shows an average property of component polymers or keeps original properties of them depends on the degree of microscopic mixing and its phase structure.2 The degree of mixing has been described in terms of miscibility of molecular to macroscopic scales, domain size and phase structure, compositions of each domain, e t ~ . ~ Many instrumental methods have been applied to investigate structures of blend^.^ To name a few examples, differential scanning calorimetry (DSC) and dynamic mechanical spectroscopy (DMS) examine miscibility and motional behaviour. Scattering measurements (small angle X-rayheutron scattering (SAXS/SANS), light scattering and pulse-induced critical scattering (PICS)) concern the size and distribution of domains as well as the repeat period of a domain structure. Electron microscopy (for example, tunnelling electron microscopy (TEM) and scanning electron microscopy (SEM)) provides morphology of domains. Usually one method alone provides a limited view of a blend. The first application of solid-state nuclear magnetic resonance spectroscopy (NMR) to examine the microstructure of a blend is the work of Kwei and co-working on polystyrene/poly(vinyl methyl ether) (PS/PVME) .5 They measured 'H spin-lattice relaxation time ( Tl) and spin-spin relaxation time (T2) over a wide temperature range. The invention of high-resolution solid-state 13C NMR spectroscopy in 1976 by combining high-power proton decoupling and magic angle sample spinning (MAS)6 opened new possibilities to study solid materials. Nowadays, most polymer researchers employ high-resolution NMR in liquids and in solids to characterize what they obtain from reaction vessels. Not simply using NMR as an analytical tool, many researchers use NMR to provide a molecular interpretation of macroscopic properties of synthetic polymers in bulk.7 Several NMR techniques have been successfully applied to investigate phase structure, heterogeneity and molecular motion of pure polymers. Heterogeneity in a blend is much more easily appreciated than that in pure polymers, because each component polymer in a blend can be discriminated by its distinct peaks. This facilitates the study of the domain structures of the component polymers in a blend. The first high-resolution I3C NMR study on a blend is the work of Schaefer et al. on polystyrene/polystyrene-polybutadieneblock copolymer (PSIPS-PB)8 and PS/poly(2,6-dimethyl-l ,Cphenylene oxide) (PS/ PPO)' in 1981, and there are growing numbers of NMR studies of blends. In Table 1 are collected more than 100 NMR studies of polymer-polymer blends published in the literature up to the end of 1993. These are mainly collected from two journals, Macromolecules and Polymer, and one can see the increase of publications within these few years. In this review, the main discussion concerns I3C high-resolution solid-state NMR measurements applied to a blend of two polymers. Since miscibility is
MISCIBILITY, MORPHOLOGY A N D MOLECULAR MOTION
Table 1. Polymer pairs studied by NMR.'
Polymer I
Polymer I1
PAA PAC PAC PAEK PAr PB PB PB PBA PB I PB I PBMA PBT PBZMA PBZT PC PC PC PC PC PCHMA PChP PCL PCL PCL PDMA PDMA PDMA PDMA PDMA PDMS PDMS PDMS-PDPS PE PEA PEA-PMVPyl PEA-PMVPyI PECMA PEMA PEMAD PENDC PEO PEO PEO PES PES PET PET PET
PVA PS PE PEI PBT PIP PS SBR PVPh PEI PIm PS-PVPh PC PVC Nylon 66 PAN-PMA-PB PCHDMT PET PMMA PS PVC PIP PVC PVME PVPh PHMP PS PS-PSSA PS-PVPh PVPh Silicone PDMS-d Silicone PP PS PS-PSSA PS-PAAMA PNBEA PVF2 PAN-PMA-PB PENDC-PHBZA PMMA PVC PVPh PIm PPS PENDC PENDC-PHBZA Vectra
Reference
10 11 12 13 14, 15 16 17, 18 19 20 21, 22 23 24, 25 26 27 21 46 28 29, 30 28, 31 32 27 33 34 35a 20 36 37 37 37 37,38 39 40 39 41 42,43 43 43 44 45 46 47 48-50 51 52,53 54 55 47 47 56a
99
100
K. TAKEGOSHI
Table 1. (contd.) Polymer pairs studied by NMR.“
Polymer I
Polymer I1
Reference
PETA PETS PIP PIP PMA PMA PMMA PMMA PMMA PMMA PMMA PMMA PMMA PMMA PMMA PMMA PMMA- PVPy POT PPO PPO PPO PS PS PS PS PS PS PS PS PS-d PS-PSSA PS-PSSA PVA PVE PVMK PU PU
PVPh PVPh epo-PIP PVE PVAc PVPh PVA PMMA-d PS PS-PAN PS-PVPh PVAc PVC PVF2 PVPh PU PS-PSSA PPO P2MS P4MS PS Nylon 6 PS-d PVIZ PVIZ-PEA PVME PVPy PVPy-PEA PU PS-PB Nylon 6 PU PVP PVE-d PVPh PU-d Lignin
20 20 33 57 58 59 10 60 61, 62, 67, 87 63,64 65 66 27, 67, 68 45,64,6972 59,73 74 61,75 76 77 77 9,56b, 78-81 82 8, 83 42 42 5, 35, 67, 84-92 42 42 93 8 94,95 96 97,98 57b 99 40 100
“A copolymer is hyphenated and a deuterated polymer is denoted by “-d”. Abbreviations: Nylon 6, poly(s-caprolactam); PAA, poly(acry1ic acid); PAAMA, poly(tetraalkylammonium methacrylate); PAC, polyacetylene; PAEK, poly(ary1 ether ketone); PAN, poly(acrilonitri1e); PAr, polyarylate; PB, polybutadiene; PBA, poly(buty1ene adipate); PBI, polybenzimidazole; PBMA, poly(buty1 methacrylate); PBT, poly(buty1ene terephthalate); PBZMA, poly(benzy1 methacrylate); PBZT, poly(benz[a,d]dithiazol-2-6-diy1-1,4-phenylene); PC. polycarbonate; PCHMA, poly(cyclohexy1 methacrylate); PCHDMT, poly(cyc1ohexylenedimethylene terephthalate); PChP, polychloroprene; PCL, poly(s-caprolactone); PDMA, poly(N,N-dimethylacrylamide); PDMS, poly(dimethylsi1oxane); PDPS, poly(diphenylsi1oxane); PE, polyethylene; PEA, poly(ethy1 acrylate); PECMA, poly([N-ethylcarbazoI-3-yl]methyl methaacrylate); PEI, poly(ether imide); PEMA, poly(ethy1 methacrylate); PEMAD, poly(ethy1ene-co-maleic anhydride); PENDC, poly(ethy1ene naphthalene dicarboxylate); PEO,
MISCIBILITY, MORPHOLOGY AND MOLECULAR MOTION
101
very important for a blend, various NMR techniques have been developed, which are discussed in Section 2. Section 3 takes up the questions of how to specify the origin of interpolymer interactions between component polymers. Without such interactions, most of a polymer pair does not mix well (immiscibility). In Section 4, NMR approaches to study heterogeneity in a blend are discussed. It also includes the interface of domains and phase separation. Finally, in Section 5, molecular motion in a blend is discussed. For some polymer pairs, microscopic mixing at the molecular level is achieved. Some DSC studies have shown that microscopic mixing leads to averaging of the two Tg values of component polymers. Does microscopic mixing force component polymers to move together? We will see that chain dynamics of component polymers affect each other. However, there has been no apparent NMR evidence of a correlated motion of two dissimilar polymer chains. 2. MISCIBILITY
Macroscopic properties of a blend are influenced largely by its microscopic degree of mixing. The degree of mixing (i.e. miscibility) varies from very homogeneous mixing, where the blend acts like a single-phase system, to very heterogeneous mixing, for which a separated domain of a component polymer is dispersed in a matrix of the other polymer. If the size of a domain is smaller than the characteristic space scale of a particular observation, the blend appears to be homogeneous. Various methods have been used to examine miscibility, for example, dielectric and dynamical relaxation, lightheutron scattering and infrared and NMR spectroscopies with the characteristic space scales. For instance, an observation of a single glass transition at a composition-dependent temperature has been taken to show evidence of miscibility. However, the smallest domain size that can be studied by glass transition measurements is ca. 100
poly(ethy1ene oxide); PES, poly(ether sulphone); PET, poly(ethy1ene terephthalate); PETA, poly(ethy1ene adipate); PETS, poly(ethy1ene succinate); PHBZA, poly(p-hydroxyhenzoic acid); PHMP, poly([l-hydroxyl-2,6-phenylene]methylene);PIm, polyimide; PIP, polyisoprene; epo-PIP, epoxidized PIP; PMA, poly(methy1 acrylate); PMAA, poly(methacry1ic acid); PMMA, poly(methy1 metacrylate); PMVPyI, poly(N-methyl-4-vinyl pyridinium iodide); PNBEA, poly(2-[3,5-dinitrobenzoyl)oxy]ethyl methacrylate); POT, poly(3-octylthiophene); PP, polypropylene; PPO, poly(2,6-dimethyl-l,4-phenyleneoxide); PPS, poly(pheny1ene sulphide); PS, polystyrene; PSSA, polystyrene sulphonated; PU, polyurethane; PVA, poly(viny1 alcohol); PVAc, poly(viny1 acetate); PVC, poly(viny1 chloride); PVE, poly(viny1 ethylene); P W , poly(viny1idene fluoride); PVIZ, poly(N-vinylimidazole); PVME, poly(viny1 methyl ether); PVMK, poly(viny1 methyl ketone); PVP, poly(N-vinyl-2-pyrrolidone); PVPh, poly(4vinylphenol); PVPy, poly(4-vinylpyridine); E M S , poly(2-methyl styrene); P4MS, poIy(4methyl styrene); SBR, styrene-butadiene rubbers; Vectra, poly(p-hydroxylhenzoic acid-co-phydroxylnaphthoic acid).
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In most NMR methods discussed below, microheterogeneity manifests itself in the magnetic relaxation phenomena such as spin diffusion and spin-lattice relaxation. The relaxation phenomena in solids are mostly governed by a dipole-dipole interaction, which is a function of the distances between the spins concerned. In the following, we will see that in favourable cases, the spatial resolution of solid-state NMR reaches down to 20 A. 2.1. Spin-lattice relaxation experiments
Each 'H spin has its intrinsic spin-lattice relaxation rate. In solids, these different relaxation rates tend to be averaged by a mechanism called spin diffusion.' 0 2 Spin diffusion is the equilibration process of non-equilibrium polarizations of spin systems at each local site through mutual exchange of polarization. Since the efficiency of spin diffusion is governed by a strength of a dipoledipole interaction, the rate of spin diffusion among the 'H spins of component polymers in a blend would provide information about the domain size. In this section, the effects of spin diffusion on the spin-lattice relaxation process are discussed. The 'H spin-lattice relaxation is monitored via resolved 13C signals to enjoy higher resolution of 13C spectra. This enables us to observe the relaxation of a component polymer separately. Stejskal et al. studied the 'H spin-lattice relaxation process in the rotating frame of reference (Tl process) of PPOlPS via the 13C signal intensities of PPO and PS (Fig. 1).B Observed non-exponential decays were successfully explained by the following model. Firstly, the 'H spins are divided into two species, depending on the polymer they are part of (species A for PPO, species B for PS). One can simplify the problem by considering that both 'H spins A and B have their own relaxation rates K , and Kb, respectively. By assuming very fast spin diffusion among 'H spins within a same polymer chain, and moderate spin diffusion between A and B, the coupled equations for the decay may be derived as
+
-dAldt
=
(K,
-dBldt
=
(Kb+f,k,)B-fbk,A
fb
k,) A - f a k, B (1)
where k, is the spin-diffusion rate between A and B , and fa and fb are the ratios of the numbers of spins A and B, respectively. The observed decay is fitted satisfactorily by the values shown in the figure. k, can be related to the domain size and its structure, based on a proper model of morphology. lo3 From the 'H relaxation experiments, however, the value of k, can be obtained only when the characteristic non-exponential decay curves are observed. From numerical calculations of equation (l),one may note that only when k, is of the order of K , and Kb is such non-exponential behaviour appreciable. In many blends, k, is so fast that
MISCIBILITY, MORPHOLOGY AND MOLECULAR MOTION
103
10
PPO
PS (high MW) m m ( r ._
I
-
I n 1 m
_I 0
PPO i-PS
0.1
I
0
I
I
I
1
20
10 t, (SLL ms
Fig. 1. Observed T I , decay curves of PPO and PS in PPO/PS = 75/25 blends. The pair of calculated curves by using equation (1) with the fitting parameters indicated in the figure are shown as solid lines. (Reprinted with permission from ref. 9. Copyright 1981 American Chemical Society.)
the two decay curves from polymer A and polymer B are identical or k, is too slow to average the two decays. In these extreme cases, one cannot obtain the k, value. To estimate spatial information here, the diffusion equation is solved by assuming a proper model for a 'H spin system of a blend. For a heterogeneous polymer, one may assume lamellar morphology. Then a typical diffusion path length, x, for a short diffusion time in one dimension can be given as213104 x2 = 4Dtl3 (2) where D is the spin-diffusion constant. If one starts from a different model such as diffusion from a point the factor 4/3 in equation (1) may be different. Fortunately, however, such differences depending on the model chosen would not become serious in a deduced domain size. The
104
K. TAKEGOSHI
spatial resolution thus depends on the diffusion constant, D. Assink gave a simple relation between D and the spin-spin relaxation time, T2 asIo5
D = 2(r0)2/T2 (3) where ro is the proton van der Waals radius of 1.17 A. From this equation, the D value for T2 of 50 ps is 5.5 x cm2 s-'. For 'H spins in alkanes, D was calculated to be 6.2 X cm2 s-l;lo6 for PET, D was estimated to be 5X cm2 s - ' . ~By~ comparing the NMR results with SAXS and TEM data, Clauss et al. decided D for PSRMMA as 8 X cm2 s - ~ They . ~ ~ ~ postulated this value as a reference value for materials with pronounced mobility. All D values in the literature are in a range of cm2 to s-', and I adopt a value of 5 x cm2 s-'. For a diffusion time of 1s, the mean-square diffusive path length ( x ~ ) "is~ calculated to be ca. 200A. This means that if one observes the IH spin-lattice relaxation (TI) in the time scale of 1s, all 'H spins within 200 A appear to have an identical relaxation time. If we observe only one single T I of 1s for both component polymers and assume a diffusion time similar to the relaxation time,34'45,63,68 we can conclude that the domain size is smaller than 200 A.Since a typical Tlp value is of the order of milliseconds, the T I P experiment can be used to investigate the domain size on the scale of a few 10 A.Due to its facility, the 'H spin diffusion measured via the Tl and T1, relaxation times is frequently used to establish the length scale over which the blend is homogeneously mixed. Various factors affecting miscibility, such as molecular eight,^^,"^ side-chain d i f f e r e n ~ e , ~ number ~'~~,~ of~ , ~ ~ monomer units in the copolymer,25and ta~ticity,~' have been studied by the IH spin-lattice relaxation experiments. Also, many works examined composition dependence of miscibility. 2.2. Spin-diffusion experiments
Instead of monitoring spin-diffusion effects from relaxation, several experiments have been invoked to observe 'H spin diffusion directly. The spin-diffusion experiment consists of four periods: (1) the preparation of the non-equilibrium magnetization among the 'H spins of the component polymers or between different domains; (2) the variable spin-diffusion time, t, during which spin diffusion takes place;
(3) the observation of the resulting 'H magnetization; (4) the relaxation time during which the whole 'H spin system achieves the Boltzmann equilibrium. Note that these procedures are formally analogous to cross-relaxation and
MISCIBILITY. MORPHOLOGY AND MOLECULAR MOTION
105
chemical exchange NMR experiments in liquids. Various experimental methods for (1) and (3) are demonstrated. For (l), one may select 'H spins by their resonance frequencies. One can also use a T2 difference for mobile and rigid 'H spins. For (3), one may enjoy high sensitivity of 'H by observing 'H directly, or enjoy high resolution of 13C resonances. 2.2.1. Goldman-Shen spin-diffusion experiments One simple way to achieve non-equilibrium magnetizations for 'H spins in a heterogeneous system is to utilize mobility difference. Goldman and Shedo7 have developed an experiment that may be used to monitor spin diffusion between regions of a heterogeneous system described by significantly different spin-spin relaxation times (T2). The original Goldman-Shen experiment is modified to incorporate the high-resolution 13C d e t e c t i ~ n . ~ This ~ " ~ 'modified ~~ experiment is performed as follows. The free-induction decay (FID) of the 'H transverse magnetization of a heterogeneous system may be described by a sum of FIDs with different T2 values reflecting different mobilities of 'H atoms. After a certain delay time, a shorter T2 component of the 'H magnetizations vanishes, and only a longer T2 component remains. The remaining 'H magnetizations are flipped back to the z-direction by an r.f. pulse. For time t , the distribution of the magnetizations becomes gradually uniform through spin diffusion. The resulting 'H magnetizations at a time t are measured indirectly by transforming it to I3C by cross-polarization (CP). The longer T2 component may be attributed to one of the mobile component polymers or a side chain such as a fast reorienting methyl group. We are to observe spin diffusions from mobile to rigid parts. Figure 2 plots normalized deviations of 13C magnetizations, P(t) = ( M ( t )-Mo)/Mo, for PMA and PVPh versus the square of the spin-diffusion time,59c where M ( t ) is the magnetization after the diffusion time t and Mo is the magnetization at internal equilibrium. An effective spin-diffusion time te is defined as the intercept of the straight line with the abscissa,21 and the domain size can be calculated from equation (2). By this technique, miscibility of several blends has been studied: PEI/PBI and PBZT/nylon,21 PES/PP0,55 PS/PP0,79 PEO/PVPh,52a PMA/PVPh.59c There are further modifications made on the modified Goldman-Shen experiment. Instead of using the T2 difference, Zhang and Wang applied the spin-locking pulse during the delay time to select 'H spins by their TIP difference.55bClauss et al. applied the multiple-pulse dipolar filter during the delay time.62b The application of the multiple pulse renders the T2 difference and helps us to differentiate component polymers. Schmidt-Rohr et al. incorporated two-dimensional (2D) NMR techniques: the first dimension gives the 'H wideline spectrum and the second dimension the I3C high-resolution spectrum.92
106
K. TAKEGOSHI
-0.4
1
-- 1.2 O . Y
Fig. 2. Plot of P(t) versus square root of spin-diffusion time f1'2 for PMA/PVPh = li 1.5 blends at 361 K. Symbols represent data observed through the methoxy carbon of PMA (a), the aromatic carbons of PVPh (V)and the main-chain carbons of both PMA and PVPh (A)in the blend. Straight lines are drawn through the linear portion of the data at an early stage to determine the intercept time te. (Reprinted with permission from ref. 59c. Copyright 1992 The Society of Polymer Science, Japan.)
2.2.2. Exchange N M R experiments Caravatti et al. observed 2D 'H exchange spectra of PS/PVMEs6= (Fig. 3). High-resolution 'H NMR is achieved by applying a multiple-pulse technique and MAS. The cross-peaks between different 'H species represent spin diffusion among them. For immiscible PS/PVME obtained from chloroform (Fig. 3(a)), only intrapolymer cross-peaks within PS or PVME are observed. For miscible PS/PVME from toluene, interpolymer cross-peaks indicated by arrows appear (Fig. 3(b)), showing direct evidence of spin diffusion. Since the 2D experiment is time consuming, they also postulated two onedimensional (1D) spin-diffusion experiments.86b By changing the spindiffusion time in the 1D experiments, they determined the composition of the mixed phase and spin-diffusion rate constants. VanderHart et al. applied similar 1D spin-diffusion experiments to study miscibility and stoichiometry in a blend.21,22*24 For many blends, the resolution of 'H spectra is not enough to discriminate component polymers. As for the modified Goldman-Shen sequence, Spiess et al. combined a high-resolution 13C NMR technique with
MISCIBILITY, MORPHOLOGY AND MOLECULAR MOTION
PS -CH-CH,I
PVME
OCH, OCH
-CH-CH,-
aliph. ti
107
0 I CH,
f\
Fig. 3. Two-dimensional proton spin-diffusion spectra of PS/PVME in solids: (a) cast from chloroform; (b) cast from toluene. The mixing time is 100ms. Interpolymer cross-peaks between aromatic protons on PS and the methine and methoxy protons on PVME are indicated by arrows. (Reprinted with permission from ref. 86a. Copyright 1985 American Chemical Society.)
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K. TAKEGOSHI
the 1D spin-diffusion experiment. 13,62b They selected 'H magnetizations of one component polymer based on 'H chemical shift or mobility. The resulting 'H magnetizations after variable spin diffusion times are transferred to 13C spins by CP and observed. This method enables us to enjoy higher resolution of I3C. Henrichs et al. applied the lD/2D '3C-'3C exchange NMR to study PC/PET.*' Miscibility and the spin-diffusion rate can be deduced from the interpolymer cross-peaks between well-resolved 13C resonances. Since for 13C both natural abundance and gyromagnetic ratio are small, 13C-13C spin diffusion is much less efficient than that among 'H. To facilitate experiments, Henrichs et al. used 13C enriched polymers. Since isotopic enrichment is time consuming and expensive, the rotational resonance technique'" was adopted to recover the l3C--l3C dipole interaction averaged by MAS.56This realizes 2D 13C-13C exchange spectra without enrichment of I3c.
2.3. Heteronuclear cross-relaxation experiments
So far, NMR techniques utilizing homonuclear dipole interactions have been reviewed. In this section, we summarize techniques to examine crossrelaxation phenomena induced by heteronuclear dipole interactions. One of the typical cross-relaxation phenomena is the transient nuclear Overhauser effect (NOE), which is a function of interspin distance. The NOE between 'H and "F spins was observed to study miscibility of PMMA/PVF2.45White and Mirau observed interpolymer NOE between protons of PVME and carbons of deuterated PS.35cThis technique may be applicable to a mobile polymer blend. A cross-relaxation phenomenon frequently used to study miscibility is interpolymer CP from protons in one component to carbons of another deuterated component.8'47'57b,61,67,87 Without interpolymer CP, the 13C signal intensity of a deuterated polymer should be much smaller than those of the protonated ones. Therefore, an appreciable signal enhancement for the deuterated component is taken as evidence of miscibility. Since effective 'H-13C CP transfer is limited to about 10 A, the signal enhancement of the latter carbons by CP shows that at least parts of the protonated molecules are nearby. For the interpolymer 'H-I3C CP experiment, deuteration of one of the component polymers is not a prerequisite. Grinsted and Koenig undertook close examination of the CP rate upon blending and ageing.72 The observed decrease of the CP rate with ageing was explained by phase separation. Zhang et al. also examined the interpolymer CP effects for PVA/PVP.97 The CP rate of the non-protonated carbonyl carbon of PVP increases upon blending with PVA, showing closeness of the OH proton of PVA and the carbonyl carbon of PVP.
MISCIBILITY, MORPHOLOGY AND MOLECULAR MOTION
109
For blends with unresolved I3C resonances, Zumbulyadis et al. showed that proton to deuterium CP transfer is useful to investigate mis~ibility.~',~~ The interpolymer CP experiment was performed for PMMNPVF2 in which 19Fpolarizations of PVF2 are transferred to carbons of PMMA.71 2.4. Other experiments
Walton et al. demonstrated the use of '29Xe NMR to study miscibility of blends. 16,33 It employs a density-proportional 129Xechemical shift. If '29Xe atoms are dissolved in domains of a blend and the domain size is so large that '29Xe atoms in different domains cannot exchange rapidly, a 129Xe NMR spectrum shows multiple resonances reflecting different environments around the Xe atoms. The authors found that an upper bound for the domain size studied is about 600 A. There are a few studies to appreciate effects of the additional 'H dipole field on spectra upon blending. Delayed or non-decoupled 13C NMR can be utilized to envisage whether 'H dipole interactions increase/decrease by blending.8,47,83For deuterated PS, VanderHart observed broadening of residual 'H spins in 'H MAS spectra when protonated PS is i n t r ~ d u c e d . ~ ~ The increased 'H dipole interactions would indicate that the protons of one component polymer come close to the other component upon blending.
2.5. Concluding remarks In this section, we have reviewed several NMR techniques to monitor spin diffusion. All techniques rely on a dipole-dipole interaction, which is a function of the internuclear distance. It is worth noting here that a dipole interaction is also a function of the angle between the static magnetic field and the internuclear vector. Therefore, modulation of a dipole interaction by molecular motion must be carefully considered in interpreting spindiffusion results. One manifestation of motion frequently encountered is the discrepancy of the calculated and the observed relaxation rates of a miscible blend. In Section 2.1, it was stated that a fast spin-diffusion averages unequal spin-lattice relaxation rates of component polymers. The apparent relaxation rate Raveis given as a weighted average of the rates of component polymers A and B as follows:45263 Rave
= f a Ra -/-
f b Rb
(4)
where f a and f b are the fractions of protons of the polymers A and B, respectively. In evaluating equation (4), one may use the relaxation rate of a pure polymer A for R , and that of B for Rb. Many authors found discrepancy between the calculated Rave and the observed Rave. As these
110
K. TAKEGOSHI
authors pointed out, one cannot use R of the pure polymer, because blending sometimes changes molecular mobilities (Section 5). The averaging of Tg values upon blending also indicates alternations of molecular motion in the blend. MAS also modulates a dipole interaction. Haeberlen and Waugh reported that MAS has little effect on T I but has some effect on T2 and T1,."o TCkCly et al. reported that T2 of the mobile amorphous component becomes longer by MAS.'"8 Caravatti et al. noted that modulation of the dipole interaction by MAS becomes appreciable when the dipole interaction is partially averaged by fast molecular motion.86 Therefore, results of spin-diffusion experiments of mobile blends must be examined carefully. A temperature calibration is prerequisite to estimate the degree of molecular motion. From temperature calibrations using proton signals of methanol under spinning at 6 kHz, we found the temperature inside about 10°C higher than that for the driving/bearing gas of our spinning system. Both molecular motion and MAS may reduce spin diffusion, leading to overestimation of the domain sizes. Most of the above-mentioned techniques adopt the 13C detection in monitoring 'H spin diffusion. Despite the advantage of high resolution, one disadvantage may be anticipated. Although the spin-locking field suppresses spin diffusion partially,'" 'H spin diffusion occurs during the infinite CP period. This blurs heterogeneity and may lead to wrong conclusions. From our recent 2D 'H-13C heteronuclear correlation experiments' l 2 of PMA/ PVPh using CP, as for spin-diffusion/mixing, short CP times less than 200 ps may be sufficient to ignore the spin diffusion during CP.l13 However, such insufficient CP would lead to distorted 13C spectra.
3. POLYMER-POLYMER INTERACTION
According to modern thermodynamical theories of polymer b l e n d ~ , ' ' ~the Gibbs free energy of mixing is described by the following three contributions: (1) combinatorial entropy of mixing;
(2) free volume difference between the component polymers; (3) exchange interaction energy. Except for a few polymer pair^,^',^' the combinatorial entropy of mixing is too small to overcome the disadvantage of free volume difference and mixing is unfavourable for most polymer pairs. A certain exothermic interpolymer interaction should therefore be operative when dissimilar polymers are miscible. These interactions include charge transfer, dipoledipole, ion-dipole, ion-ion, acid donor-acceptor and hydrogen bonding. It
MISCIBILITY, MORPHOLOGY AND MOLECULAR MOTION
111
is of particular interest to investigate how and to what extent component polymers interact with each other. NMR spectroscopy provides information about such interpolymer interactions. In fact, most of the spin-diffusion experiments reviewed in Chapter 2 are potentially applicable to explore specific interactions. In this chapter, polymer interactions appreciated by chemical shifts, NOE and molecular motion are reviewed.
3.1. Chemical shift By comparing NMR spectra of component polymers with that of a blend, one can easily deduce any chemical-shift and/or lineshape change due to blending. The lineshape reflects morphology of a blend, and will be discussed in Section 4. Apparent chemical-shift change can be attributed to modifications of both chemical structure and polymer conformation upon blending, reflecting a specific interpolymer interaction. In solution, Djordjevic and Porter investigated the solvent-induced changes in chemical shifts of PPO/PS, and concluded that the driving force of miscibility of PPO and PS is the r-hydrogen bond between the electrodeficient methyl group in PPO and r-orbitals in PS.80 In solids, however, there have been no reports of apparent shifts in PPO/PS on blending, and the specific interaction was investigated by observing molecular motion (Section 3.3). In fact, many of the above-mentioned interpolymer interactions do not cause appreciable change in chemical shifts in solids. For example, Natansohn and Simmons examined 13C spectra of PECMA/PNBEA.44aModels for the structural units of the polymers show upfield shifts of 1-5ppm due to charge-transfer interaction. For polymer blends, however, the shift is less obvious due to a general broadening of signals. Grobelny et al. observed changes of the imide carbonyl lineshapes, which were attributed to increased polarity due to solvation of PIm by the PES chain.54 So far, only the hydrogen-bonding interaction is found to cause an apparent shift. Several blends show downfield shifts and changes of lineshapes due to hydrogen bonding. For example, Yang et al. found a broadening and a downfield shift of the carbonyl carbon resonance of PHMP in PHMP/ PDMA.36 Also Grobelny et al. found that blending PBI and PIm induces a broadening and a downfield shift of the aromatic phthalimide carbonyl resonance with respect to that of the pure material.23 This shift is interpreted as a result of the specific hydrogen bonding between the PBI imidazole amine group and the PIm carbonyl group. Kwei et al. closely examined the lineshapes of nylon 6/zinc salt of PS-PSSA to figure out the specific interpolymer intera~tion.’~ They found that the Zn2+ cation of the ionomer forms a complex with the amide nitrogen of nylon 6 and not with the carbonyl oxygen. Since the chemical shift of the phenolic carbon of PVPh is sensitive to
112
K. TAKEGOSHI
near-neighbour segment interactions, Belfiore et al.20~533yy and other via chemical shift/ g r ~ ~ pinvestigated ~ ~ ~ blends , ~ of ~ PVPh , ~ extensively ~ ~ lineshape changes. In these blends, PVPh is used as the proton donor and often a polymer having a carbonyl group as a side chain is used as a proton acceptor. Evidence for specific interaction is provided by a downfield shift of -3 ppm in the phenolic carbon resonance and shifthneshape changes of the carbons in the proton acceptor. Belfiore et al. examined the lineshape of the carbonyl carbons of several polymers in PVPh blends, and showed that the carbonyl lineshape is useful as a qualitative diagnostic probe of the polyester component's morphology and molecular mobility in partially miscible blends with PVPh.*' Another interesting proton donor is PVA. 10b,y7,98 The signal of the CHOH carbon of pure PVA shows the characteristic triplet lineshape due to hydrogen bonding. On blending with a proton acceptor such as PAA, rearrangement of hydrogen bonding occurs and the characteristic lineshape disappears. Such rearrangement also occurs in PAA and causes a shift for the carboxyl carbon. This clearly shows the formation of specific hydrogen bonding between the PVA hydroxyl group and the PAA carboxyl group. Contrary to the widely accepted statements that the hydrogen bonding brings a downfield shift, an upfield shift of about 3ppm is found for the carboxyl carbon of PMAA upon blending with PVA. lob The dissociation of the intrapolymer hydrogen bonding brings an upfield shift and the formation of blend causes a downfield shift. The observed highfield shift shows that the intrapolymer hydrogen bonding has a larger downfield shift effect than the interpolymer hydrogen bonding.
3.2. Nuclear Overhauser effect (NOE) Although the solid-state morphology is lost in solution, the specific interaction responsible for mixing in the solid state will be retained. The higher resolution in solution NMR enables us to investigate a specific region of interaction. In solution, dipoledipole interactions give rise to transient NOE between 'H spins. Since the strength of a dipole-dipole interaction is proportional to the inverse sixth power of the interproton distance, there occurs no appreciable NOE between protons separated by more than 5 A. NOE is, therefore, a sensitive probe to investigate whether component polymers are in close contact on a microscopic scale. Application of 2D NOE spectroscopy may reveal the interacting regions as interpolymer cross-peaks. Natansohn and E i ~ e n b e r gcarried ~~ out one- and two-dimensional (2D) NOE experiments and showed that the ionic interactions are operative between PMMA-PVPy and partially sulphonated PS (PS-PSSA). They found interpolymer NOE between the aromatic protons of PS and the methoxy protons of PMMA. Crowther et ~ 1 and. Mirau ~ ~ et ~ 1 . ~applied '
113
MISCIBILITY, MORPHOLOGY AND MOLECULAR MOTION PYME
PS m , ~0 0.00
! PSIPYME
2.0a
I*
$
CH
PYME
4.00
6.00
PS
1
13
P
8.00 I
I
I
I
I
8.00
6.00
4.00 PPM
2.00
0.00
Fig. 4. Two-dimensional phase-sensitive NOESY spectrum of PS/PVME (60 wt%) in toluene. The mixing time is 200 ms. Interpolymer cross-peaks between aromatic protons on PS and the methine and methoxy protons on PVME are circled. (Reprinted with permission from ref. 88. Copyright 1988 American Chemical Society.)
NOE experiments t o PS/PVME (Fig. 4). It was pointed out that interpolymer NOEs become appreciable only when the polymer concentration is more than 25 wt%. Above 40 wt% the interpolymer NOE between the aromatic protons and the methoxy protons of PVME is of the same magnitude as intrapolymer NOEs, indicating a specific i n t e r a ~ t i o n . ~ ~ However, for PCL/PVME, a polymer-polymer interaction is less specific. Similar NOE studies may be found in refs 10a, 37, 58, 59b, 69, 75. There are two factors that make it difficult to specify the interacting regions. One is the intrapolymer spin diffusion that redistributes magnetizations among protons nearby. If the spin diffusion rate is slower than the NOE rate, the initial build-up rate reflects only the NOE. In 1D N OE
114
K. TAKEGOSHI
experiments of PMNPVAc, Takegoshi et ~ 1 . ~found ' that the NOE between the methine protons of PMA and PVAc becomes appreciable only when irradiation times are longer than 500ms. The lag period indicated that the NOE peak of the former is caused by intrapolymer spin diffusion from the methoxy protons of PMA. The other factor may be the forcing contact of polymers at higher polymer concentrations. The increase in concentration reduces non-specifically the average interpolymer distance. Zhang el al. examined concentration dependence of the NOE value for PMA/PVPh.59b At higher concentrations than 40 wt%, the interpolymer NOE value between the OCH3 protons of PMA and the O H of PVPh is similar to that between the OCH3 of PMA and the phenolic ring protons of PVPh. Thus, it is difficult to specify interacting regions. However, they found that the former NOE does not have significant concentration dependence and below 20wt% only the NOE of the OH proton of PVPh is appreciable. This clearly indicates that PMA and PVPh is bound by hydrogen bonding. Concentration also influences mobility of polymers, and effects of molecular weight and concentrations are examined.35b The lack of intermolecular NOEs does not prove that the polymers are not in proximity, because NOE depends not only on a distance but also on the correlation time of motion of the interproton vector. If the correlation time of the motion is close to the inverse of the proton Larmor frequency, NOE is very weak and may not cause appreciable NOE cross-peaks. One may conduct experiments at different temperatures to shorten or lengthen the correlation time. Alternatively, the rotating frame Overhauser experiment (ROESY) may be helpful. As suggested by Kelts et ~ l . , ~ ROESY ' is also useful to differentiate cross-peaks from spin diffusion and NOE. It is worth noting here that the appearance of intermolecular NOEs does not guarantee homogeneous mixing in solutions. Zhang et al. showed that even in a phase-separated solution, NOEs between PMA and PVPh appear.59b The interpolymer NOE only indicates that a miscible phase exists, but not that the whole system is miscible. In solids, White and Mirau studied interpolymer NOE between the 'H spins of PVME and the 13C spins of deuterated PS to conclude that the phenyl ring of PS is much closer to the methoxy group of PVME than to the main-chain carbons of PS.35cIn fact, most of the spin-diffusion experiments discussed in Section 2 are potentially applicable to explore specifically interacting regions. However, the fast spin diffusion in solids may blur the specific regions.
3.3. Molecular motion
If there is a specific interpolymer interaction between component polymers, molecular motion of the interacting region of the individual polymer in the
MISCIBILITY, MORPHOLOGY AND MOLECULAR MOTION
115
mixture is expected to be different from that of pure solution. de Araujo et af. examined a possible specific interaction between the ether linkage of PPO and the phenyl group of PS by observing deuterium('H) spectra of the deuterated phenyl group of P S g l Such a specific interaction should reduce the fraction of mobile phenyl groups as compared with pure PS, due to less space available for conformational rearrangements. From experimental results, they concluded that such a specific interaction is not appreciable. On the other hand, Feng et al. found that after mixing, the aromatic carbons of PPO and PS come to have almost the same 13C spin-lattice relaxation times.79 They concluded that due to the strong r-7r conjugation interaction between the aromatic rings of PPO and PS, they move cooperatively. Bovey et af. have studied effects of blending on molecular motion in PMMA/PVF2 by 13C-T1 experiments in solutions.69 Both 13C-T1 values for pure polymers and for a mixture are the same. They concluded that the compatibility of these polymers, at least in solution, does not arise from complex formation between them. Comparison of the temperature dependence of l3C--T1 values has been made by Asano et al. for PC/PMMA.31a Compared to those of pure polymers, only the Tl-temperature curves of phenyl carbons of PC and that of the methoxy carbon of PMMA in the mixture shift toward high temperatures. The 13C-T1 curves of other carbons are not influenced by mixing. These results indicate that there is a specific interaction between the phenyl group of PC and the methoxy group of PMMA for PC/PMMA in solutions. Takegoshi et al. also applied 13C-T1 measurements to P M A / P V A C ~and ~ the effects of blending on TI curves are non-specific. 4. MORPHOLOGY
4.1. NMR imaging
The most comprehensive information about the morphology of a blend has come from microscope studies. For instance, the domain size and shape of the order ranging from 100 to 10 000 A can be visualized by TEM. Similar visualization may be possible by NMR imaging. In fact, NMR imaging has been a valuable tool in medical science to determine human morphology by locating water. In solids, the additional line-broadening due to the dipole interaction and the chemical shift interaction blurs the NMR image of the material. Therefore, the techniques used in medical imaging may not directly be applied to solid materials, and certain line-narrowing techniques such as multiple-pulse and MAS or large field gradient should be applied. However, for a mobile component whose 'H resonances are already narrowed by motion, extensive use of sophisticated line-narrowing techniques may not be necessary.
116
K. TAKEGOSHI
Cory et al. employed MAS for line narrowing of PB in PB/PS." The spinning speed of 5 kHz was enough to reduce the 'H linewidth of the mobile PB, and the NMR image of PB was obtained with spatial resolution of 50 pm. To realize imaging under MAS, one has to spin the field gradient synchronously with the sample. Sarkar and Komoroski applied conventional NMR imaging techniques to obtain images of elastomeric components of several tyre sections with resolution of 100-200 pm.I9 By applying strong (20 G cm-'), actively shielded gradients capable of fast switching (50100 ps), they could obtain images of 'H spins with T2 of a few milliseconds. 4.2. Lineshape
There are a few polymers that show different lineshapes for different morphology. One such polymer is nylon 6 , and it shows different lineshapes for the a- and y-crystalline and mesomorphous phases. By simulating the 13C spectrum of PShylon 6 from the three lineshapes, Schmidt et al. determined the fractions of the nylon 6 forms in the blend.82 Alternations in morphology of component polymers may occur on blending. For example, suppose we mix a crystalline polymer with an amorphous one. The blend may be miscible, that is, the crystalline phase is destroyed, and the whole blend becomes amorphous. Or the blend may be composed of a miscible amorphous phase and a crystalline phase. Such blending-induced alternations in morphology would be reflected in chemical shifts, linewidth and relaxation behaviour. Huo and Cebe found that for the melt-crystallized PBT/PAr, the NMR linewidth decreases as the PAr content increases, indicating more perfect crystals appear in the blends compared with that in pure PBT." They attributed this to the much slower crystallization of PBT in the blends. Belfiore et al. showed that the lineshape of the carbonyl 13C resonance reflects the polyester component's morphology and mobility in partially miscible blends with PVPh.*' The carbonyl signal in the crystalline domains exhibits a full width at half height of 1-2ppm when Tg is below the temperature of the NMR experiment. For a PVPh-rich blend in which no crystallization of the polyester component occurs and Tg is above the temperature of the NMR experiment, the linewidth increases to ca. 5-6 ppm. When the blends are completely amorphous, the carbonyl lineshape reveals at least two morphologically different microenvironments. Dumais et al. analysed solid-state 2H NMR spectra of deuterated PAC in PAc/PS to estimate the fraction of crystallinity." Molecular motion of PAC in PS is similar to pure PAC, indicating that domain structures are present in the blend. When the morphological difference does not cause an apparent shift, one still can reflect morphology from spectra by using the difference of relaxation times in different domains. Zhang et al. examined the T I , process
MISCIBILITY, MORPHOLOGY A N D MOLECULAR MOTION
I 90°*Y
117
DEC
9oox
PVPh/ P€0
Fig. 5. (a) Pulse sequence for selective measurement of a crystalline domain of PEO, and the resulting 13C CP/MAS spectra for (b) PVPNPEO = 58/42 and (c) 40/60. The signal from the crystalline PEO is indicated by an arrow. (Reprinted with permission from ref. 52a. Copyright 1992 American Chemical Society.)
in PEO/PVPh, and concluded partial miscibility for an excess of crystalline PE0.52a The blend consisted of the amorphous and crystalline phases of pure PEO and the miscible PEO/PVPh phase. The existence of crystalline PEO was confirmed by 13C spectra as follows. Since the 13C spin-lattice relaxation time of crystalline PEO (cu. 15 s) is much longer than those of amorphous phases (ca 0.1s), it is possible to observe the 13C spectrum of crystalline PEO selectively (Fig. 5(a)). Figure 5(c) shows the 13C-T1 selected spectrum of PVPh/PEO = 40/60, in which the signal of crystalline PEO is indicated by an arrow. On the other hand, for the PVPh-rich blend (PVPh/PEO = 58/42), the crystalline-PEO peak is not appreciable (Fig. 5(b)). There are reports describing the observation of 13Csignals of different domains separately using the variations of the dipolar field between the domain^.^,^' Due to the low sensitivity of NMR, observation of interfacial regions of a blend has been a formidable task. Yet, two groups observed the interface selectively with an enhanced signal-to-noise ratio. 12z3* Both groups employed highly polarized electron spins in one component polymer. The electron polarization is transferred to the 'H spins of the other component polymer at the interface region. The enhanced 'H polarization can be
118
K. TAKEGOSHI
observed directly12 or further transferred to the 13C spins for better r e s ~ l u t i o n .The ~ ~ electron spin was introduced by doping a radicalcontaining molecule to one component polymer,32 or the component polymer itself carried the unpaired electrons. l2 Even though the signal enhancement achieved is much less than that expected from simple theory ,12 Afeworki et af. observed the aromatic carbon signals of PC at the interface of It was also shown that the interfacial PC chains have less motion than PC chains in the To avoid leakage of polarization from the interface by the fast 'H spin diffusion, Afeworki attempted to transfer the electron polarization in the PS domain directly to the 13C spins of PC."'
4.3. Spin-lattice relaxation times and spin diffusion
Several studies have been done on immiscible blends to figure out the phase structure. McBrierty measured the temperature variation of 'H T I of PE/PP, which is i m m i ~ c i b l e The . ~ ~ observed increase of the TI minimum for the methyl group of PP and the concomitant slight decrease of the T I for PE was attributed to a weak PE-PP coupling via spin diffusion among two domains of component polymers. From T I and TI P results, Natansohn et af. concluded that PU/lignin is immiscible. However, they also found some interactions between two phases, which allow the interpolymer CP transfer from lignin to PU.'O0 A n immiscible blend of two dissimilar polymers A and B consists of three phases: two domains of polymer A and B and the interface. The 'H relaxation decay curves of an immiscible blend containing the three-domain structure has been examined by a direct 'H observation. For PB/PS, Segre et af. observed that the 'H FID consists of a fast- and slow-decaying component." The fast-decaying component was attributed to rigid PS, whereas the slow-decaying component shows the presence of two TI relaxations. These were attributed to the interface and to pure rubbery PB. For PU in a PMMA network, Parizel et af. observed that the 'H FID consists of three components, which were attributed to rigid PMMA, the intermediate region and mobile PU.74 In increasing temperature, they observed that the amounts of the latter two regions increase. For PMA/PVAc, the 'H T1 and T I , relaxation curves were analysed by a three-component superposition, and compositions of each domain were evaluated for P M N P V A C . Percec ~~ and Hammond observed the 'H TIP decay curves of component polymers of PUPAN-PMA-PB through the resolved I3C signals.46 The 'H T I , decay shows doubleexponential character, and the two TIPdecays of component polymers have one TIPcomponent in common. The common TIPcomponent was attributed to the interface. A blend of a crystalline polymer and an amorphous polymer tends to be immiscible when the crystalline component is excessive. The immiscible 18366774
MISCIBILITY, MORPHOLOGY AND MOLECULAR MOTION
119
crystalline-rich amorphous/crystalline blend consists of the miscible amorphous phase and the crystalline phase of one component polymer. TCkCly et al. observed a double-exponential decay for PMMA carbon resonances in PMMA/PVF2 when PVF2 is in excess. This is attributed to partial crystallization of PVF2.” Zhang et al. observed similar double-exponential T I or T1, decay curves for the crystalline component and a single exponential decay for the amorphous one.’0b,52b,55b,97 The relaxation time for the amorphous component is in agreement with one of the crystalline components, showing the existence of the miscible phase. By analysing the curves, the phase composition of PVA/PVP was evaluated.97
4.4. Thermally induced morphological change Thermodynamically, a polymer blend is rather unstable. Thus, its thermal history is an important factor in determining miscibility. In other words, heat-treatment is a simple technique to modify a phase structure of a blend. 4.4.1. Lineshape By annealing a crystalline/amorphous blend, one would expect a crystalline component polymer to recrystallize. The characteristic lineshape/resonance of a morphology can be used to monitor thermally induced morphological changes. By monitoring a peak characteristic of the a-crystalline phase of nylon 6, Gao et al. found that thermal annealing reproduces the crystalline phase in nylon 6/PS-PSSA.94 The methylene carbon resonance of PET in the trans conformation is narrower than that in the gauche form and appears at a higher field. By monitoring these resonances, Tang et al. found that the relative amount of the gauche conformer in PET/vectra is reduced greatly upon annealing, and its linewidth becomes Some studies use lineshapes to examine phase separation. At higher temperatures, the free-volume difference becomes too large to overcome the hydrogen-bonding interaction, and the phase separation occurs. Since the amount of the downfield shift is roughly proportional to the strength of the hydrogen bonding, it is possible to monitor phase separation of a blend by observing the spectra. Zhang et al. showed that when heating a PVA/PAA blend above its T g , the chemical shift of the carboxyl carbon of PAA shows a high-field shift. This high-field shift is attributed to dissociation of hydrogen bonding between PVA and PAA.”“ The 129XeNMR was applied to monitor the phase-separation process of PB/PIP. l 6 For a phase-separated, two-component blend, the 12’Xe NMR spectrum exhibits two resonances, whereas the homogeneous morphology of a miscible blend leads to a single peak. Although reactionldegradation is not a morphological change, I would
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like to include the works on these topics here. By examining l3C spectra of PC/PBT after heating at 270°C, Velden et al. concluded that transesterification occurred in a blend.26 Similarly, for PAr/PBT14 and PC/PET,30 transesterification at high temperatures has been found by 'H NMR in the solution state. These works may indicate a suitable arrangement for interpolymer reaction of dissimilar polymers in a blend. By examining TI values for annealed PC/PET, Henrichs et al. showed that, although PC and PET are not inherently miscible, at least at 2 W C , miscibility is induced by chemical reaction between polymers.29b With the hope of observing transesterification between PVA and PAA, Zhang et al. undertook heat treatment of PVA/PAA.lO" They observed dehydration of PAA. The products are similar to those from homopolymers, but the reaction temperatures for the blends are lower than those for homopolymers. 4.4.2. Relaxation behaviour The relative proportion of the phases in a blend may be reflected in relaxation decay curves. Annealinglageing of PMMA/PVF2 has been studied extensively. Grinsted and Koenig observed an increase of T l p and the cross-relaxation time between 'H and 13C with ageing of PMMMPVF2, indicating a subtle separation in the amorphous phase.72 By analysing the double exponential Tlp decays of PMMA/PVF2, TCktly et al. determined the degree of crystallinity as a function of annealing d ~ r a t i o n . ~From ' the Tl, values, they suggested that the crystalline phase is mainly the build-up of nuclei and lamellae of small dimensions. Papavoine et al. applied a triple-resonance 1H-13C-'9F CP technique to PMMA/PVF2.71dThey compared the crystalline fraction obtained by DSC and the isolated fraction of PVF2 measured by NMR as a function of the annealing time. They observed different crystallization behaviour depending on annealing temperatures, and suggested an upper critical solution temperature (UCST) for PMMA/ PVF2. Heating of PET/PC above the melting point of PET, followed by slow cooling, produced crystalline PET, as was indicated by the longer T I value for the PET proton after heating and by appearance of a slowly relaxing component of Segregation of domains in PMMA/PVAc after annealing at temperatures higher than Tg of PVAc was detected by analysis of T1,. 66 As shown above, stoichiometries of phases in an immiscible blend may be deduced by analysing multi-exponential relaxation decay curves. This approach was applied to study a phase-separation process. After spinodal phase separation, a two-mixed-phase morphology is assumed. Namely, two phases consist of both component polymers (A and B), but their stoichiometries are different. By assuming a fast spin diffusion within each phase, and a negligible spin diffusion between the two phases, one expects a double exponential decay for the 'H spins of polymer A. The fraction of the
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two exponential functions should reflect the stoichiometry of the two separated phases. The decay of the 'H of polymer B is also a double exponential. Nishi et al. observed that a single exponential T I decay of PS/PVME becomes double exponential when annealed at 130"C.5.s4 The fraction of the two relaxations does change gradually with a phaseseparation period, leading them to conclude a spinodal decomposition at 130°C. Since they observed 'H directly, it was difficult to analyse fully the observed 'H decays by using the two-mixed-phase model. This has been overcome by extending the approach using I3C techniques. Asano et al. showed that stoichiometries of both major and minor components in a phase-separated domain can be obtained by analysing two 'H T I decay curves, selectively observed for component polymers via 13C.31b They determined the compositional change during a spinodal decomposition of PC/PMMA during the first 15 min (Fig. 6). Further heat-treatment does not cause any appreciable change in T1 curves. This shows that after a completion of the initial fluctuation in concentration, the morphological change occurs on a scale of more than 200-300 A, which does not affect the TI decays. A plot of the coexistent composition at each heat-treatment temperature versus the temperature gives us a phase diagram viewed from T I or T l p . Such phase diagrams are presented for PS/PVMEs9 and PC/PMMA.3'b VanderHart et al. applied a direct 'H observation using multiple-pulse methods and MAS to monitor spin diffusion in annealed PEI/PBI. From the spin diffusion results, they estimated the minimum Sinale Phase
-
0.50
J
-
Phase Separated 10190
+
0.51
1
+
Spinodal Decomposition
+-Q.484
0.52
5
3 1 8
\
-0.564
10
Fig. 6. Schematic illustration of the compositional change during heat-treatment of PC/PMMA = 50/50. The composition of PC is indicated by the underlined numbers. (Reprinted with permission from ref. 31b. Copyright 1992 The Society of Polymer Science, Japan.)
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domain dimensions in the annealed blends that display phase separation.22b Detailed discussions regarding the SAXS and NMR results are given. 4.5. Microscopic heterogeneity
Even for a miscible blend, conformational and packing heterogeneity would bring deviations of the isotropic chemical shift and local dynamics. Grobelny et al. studied miscibility of PBI/PIm by measuring T1p.23The TIPvalues for component polymers are similar; thus the blend is homogeneous as far as spin diffusion is concerned. The carbonyl carbon resonance, however, exhibits broadening. This broadening was attributed to different hydrogenbonding strength and distances in a blend. The lineshape was decomposed by assuming two carbonyl groups. The downfield resonance was attributed to the carbonyl group forming hydrogen bonding with PBI and the highfield one to the free PIm. Similar distribution of the resonance by different hydrogen bonding in a blend was found for the phenolic carbon of PVPh in PVMWPVPh99 and PEO/PVPh.53 The works exploiting microheterogeneity of local dynamics will be treated in the next section.
5. MOLECULAR MOTION Macroscopic properties of a blend, such as impact strength and ductility, are influenced largely by molecular motion of component polymers. Therefore, it is of importance to characterize motions in a blend, especially because blending affects molecular motions. In several blends, such effects of blending are appreciable in the relaxation phenomena. If both component polymers have the same Tlp value, it indicates miscibility. The observed T1, value for the blend can be calculated from the intrinsic T I P values for component polymers by using equation (4). Since it is difficult to measure the intrinsic T I , values for component polymers in the blend, one uses the T I , values for pure polymers. For several miscible blends, the calculated T1, values show apparent deviations from those expected from equation (4), showing that the TIPrelaxation values for respective component polymers are altered by blending. The effects of blending on motion may be caused from the different free volume of the blend compared with that of pure polymers, or specific interpolymer interactions between component polymers. 5.1. Glass transition
For an immiscible blend, one would expect that the component polymers keep their original mobilities, while for a miscible blend, entanglement on a
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segmental scale would affect the motion of component polymers. Largescale chain motion in particular may be prone to being affected. In fact, the traditional mechanical and dielectrical experiments show that large-scale segmental motion of component polymers, which are related to the glass transition, are affected by blending. Moreover, for a miscible blend, a composition-dependent glass transition occurs at a temperature between the two Tg values of the respective component polymers. In NMR, the onset of large-scale chain motion at the glass transition affects 'H lineshapes. For PVME/PS = 50/50, Kwei et al. observed a transition of 'H T2 from 15 ps to 3 ms at ca. 50"C, which was ascribed to the onset of large-scale motion at the glass t r a n ~ i t i o n .The ~ FIID is composed of two T2 components, and each shows a different transition temperature. They are different from those observed for pure PS and PVME, showing effects of blending on large-scale motion, responsible for the glass transition. For PEO/PMMA, Brosseau et al. found that the temperature dependence of T2 of PE O obeys a Williams-Landel-Ferry equation with a temperature reference shifted 50 K higher than Tg.'' The molecular weight dependence was also studied. T o observe PEO in PEO/PMMA selectively, they deuterated PMMA. The transition of 'H T2 or the change in linewidth occurs when the frequency of motion exceeds the 'H linewidth, so that an averaging of the 'H-'H dipole interactions becomes appreciable. Similar motional narrowing occurs for a dilute spin such as 13C and 29Si. The linewidth of a dilute spin is governed by the anisotropic chemical shift interaction and the heteronuclear dipole interaction between 'H. The linewidth of a13C spin is typically a few 10 kHz for a rigid solid, therefore, the linewidth of a dilute spin is also sensitive to motion of a few 10 kHz. Newmark and Copley measured *'Si NMR spectra of silicone in P D M S / ~ i l i c o n e .The ~ ~ linewidth decreases gradually as the temperature is increased beyond Tg from 1200Hz at -100°C to 450 Hz at 150°C. The linewidths have been correlated with Tg and rheological data. For high-resolution solid-state 13C NMR using 'H dipolar decoupling (DD) and MAS, however, the heteronuclear dipole interaction between 'H and the anisotropic chemical shift interaction are effectively averaged. Thus, effects of motion on linewidth are rather complicated. Instead of motional narrowing, motional broadening is observed for a 13C spin under D D and MAS.'" It is because random molecular motion interferes with the artificial coherent averaging ( DD and MAS). When the motional frequency is close to the MAS frequency, the chemical shift anisotropy is reintroduced. While the heteronuclear dipole interaction is reintroduced, when the motional frequency is close to the 'H decoupling field strength in hertz. With a conventional static magnetic field of ca. lOT the former is negligible for anisotropic motion. Therefore, the observed broadening of 13C lines above the glass transition temperature has been attributed to the interference between motion and DD. For most glassy polymers below T g , the linewidth of a 13C resonance is
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K. TAKEGOSHI
temperature independent and is about 2-3 ppm. In increasing temperature over T,, the line broadens, and reaches a maximum width. Further increase of temperature narrows the line to a few 10Hz. This behaviour was explained as follows:9o below Tg, the linewidth reflects a distribution of the isotropic chemical shifts arising from a variety of local conformations of the polymer in the glassy state. It is averaged by the motion associated with the glass transition to show motional narrowing. On the other hand, the interference occurs when the motional frequency comes close to the decoupling frequency, and the line shows maximum broadening. At much higher temperature, motional narrowing becomes effective, and the line becomes narrower even without D D and MAS. Takegoshi and Hikichi gave a quantitative equation to analyse the temperature dependence, and applied it to the C H carbon of PVME in PS/PVME.90 Menestrel et al. investigated the 13C resonance of PS in PS/PVME.91 Miller et al. observed temperature dependence of the 13C linewidths for PIP/PVE.57a The maximum linewidths for pure PVE and pure PIP occur at 302 and 250K, respectively. The difference is 52 K for pure polymers, while that for the blend becomes about 25 K, even though the blend exhibits a single Tg. Similar behaviour has been found for PEO/PVPh52aand PMA/PVPh.59aThese studies show that despite the thermodynamical homogeneity, the component polymers exhibit distinct glass transitions. The large-scale motions associated with the glass transition of the two component polymers affect each other appreciably. However, the chain dynamics of the two polymers are not correlated and still have different characteristic temperature dependences.
5.2. Effect of blending on local motion The lineshape studies described above concern motions of a few tens of kilohertz. There are several works exploiting effects of blending on local motions in the megahertz range by measuring the spin-lattice relaxation times of 13C. Feng et al. measured I3C-T1 for PPO/PS.79 The l3C-TI values for the aromatic carbons of PPO and PS become similar for a blend, suggesting that the aromatic rings of PPO and PS move with the same frequency. An analysis of the observed 13C-T1values led them to conclude that the blending increases the motional frequency of PS nearly 10 times. In addition to this, changes of mobility of PS were related to the improved impact strength. For a partially miscible POT/PPO, Schantz and Ljungqvist found that I3C-T1values of alkyl side-chain carbons increase considerably in blends of POT concentrations less than 30%, reflecting an increased flexibility for POT on blending.76 They suggested that the increased mobility is caused by thermal stresses in the material. Landry and Henrichs applied dynamic mechanical spectroscopy and 2H NMR to investigate sub-T, motion in PC/PMMA and PC/PCHDMT.28 Examination of *H NMR spectra and
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relaxation times led them to conclude that local motions in the PC backbone are slower in the miscible blends than they are in pure PC, while local motions of PMMA are relatively unaffected by blending.
5.3. Motional heterogeneity As discussed in Section 4.5, conformational and packing heterogeneity exist in a miscible blend. This heterogeneity would manifest itself as a distribution of correlation times or motional frequencies. It is worth while to note here that there is another type of distribution of correlation time T . To treat the spin-lattice relaxation of anisotropic motions of a neat polymer, the correlation function of the orientation of an internuclear vector, Y(t), may be given as116
1'
Y ( t + T ) Y ( t ) = I Y ( t ) - Y ( t ) l G(T)exp(-dt)dt
(5)
where G(T)is the distribution function. Note that this distribution does not mean that there are several spins having different T , and the 13C spin-lattice relaxation of the whole spin system is described by a single exponential. This approach may be applicable to appreciate motions of polymer chains in a blend without defining a clear motional mode. It is difficult to differentiate the origin of the distribution in polymer materials. Jones et al. studied glass transition dynamics of PPO/PS, which is miscible.78 Chain motion of the I3C labelled PPO was investigated by I3C 2D exchange powder patterns.78b Further, chain motion of the deuterated PS was studied by 2H exchange powder patterns.78cThe motion of PPO of a few kilohertz commenced at a temperature of ca. 10°C below Tg,in contrast to the pure PPO glasses which only show such motion at temperatures above Tg. Both motions exhibited the characteristics of rotational Brownian diffusion with an associated broad distribution of correlation times. The distribution is a bimodal distribution and considerably broader than that typical for the pure polymer. They employed a statistical lattice model to evaluate local concentration fluctuations and explained the observed relative ratio of the modes. Schmidt-Rohr et al. applied the 2D version of the extended Goldman-Shen experiment to PS/PVME.92 From the cusps of the 'H wide-line spectrum of PS, they showed a certain amount of PS has intermediate or high mobilities. These studies and those in Section 4.5 show that miscibility found by the spin-diffusion studies does not necessarily guarantee homogeneity of local environments. A distribution of correlation times in a blend has not been appreciated in the studies in Sections 5.1 and 5.2. For example, the 13C linewidth studies on PS/PVME90.91do not show any asymmetric temperature dependence,
126
K. TAKECOSHI
which would be a consequence of equation ( 5 ) . Further, a 13C NMR lineshape under MAS and DD at higher temperatures above Tg can be satisfactorily simulated by a Lorentzian. Signals from fast- or slow-moving I3C spins appear as a sharp peak at the centre or a broad signal at the envelope of the signal. Therefore, 13C high-resolution NMR spectra are not sensitive to motional heterogeneity.
ACKNOWLEDGEMENT The preparation of this review was facilitated by the cooperation of Dr A. Asano who kindly helped me to survey references.
NOTE ADDED IN PROOF I notice that I have omitted several works. Maunu et al. studied miscibility of PAA/PVP, PANPEO, PEO/PMAA, and PMAA/PVP by the 'H relaxation times and 13C lineshapes. 11' Nzudie et al. examined PB/PMMA by the 'H TlP.lI8 Ageing and phase separation of PIP/PS have been investigated by 'H NMR imaging."' A 129Xe2D exchange NMR experiment has been applied to PS/PVME and PVC/PVME12' and also to PP/PP-PE. 12'
REFERENCES 1.
2. 3. 4.
5. 6.
7. 8. 9. 10a lob I oc 11.
D. R. Paul and S. Newmann (eds), Polymer Blends, Vols 1 and 2, Academic Press, New York. 1979. R. A. Dickie, in ref. 1, Vol. 1, p. 353. 0. Olabisi, L. M. Robeson and M. T. Shaw, Polymer-Polymer Miscibility, Academic Press, New York, 1979. L. M. Robeson, in Polymer Compatibility and Incompatibility, Principles and Practices (ed. K. Solc), MMI Press Symp. Ser. 2, p. 177. Hanvood Academic, New York, 1982. T. K. Kwei, T. Nishi and R . F. Roberts, Macromolecules, 1974, 7 , 667. J . Schaefer and E. 0. Stejskal, J. Am. Chem. Soc., 1976, 98, 1031. R. A. Komoroski (ed.), High Resolution NMR Spectroscopy of Synthetic Polymers in Bulk, VCH, Deerfield Beach, 1986. J. Schaefer, M. D . Sefcik, E. 0. Stejskal and R. A. McKay, Macromolecules, 1981, 14, 188. E. 0. Stejskal, J. Schaefer, M. D. Sefcik and R. A. McKay, Macromolecules, 1981, 14, 275. X. Zhang, K. Takegoshi and K. Hikichi, Polym. J . , 1991, 23, 79. X. Zhang, K. Takegoshi and K. Hikichi, Polym. J . , 1991, 23, 87. X. Zhang, K. Takegoshi and K. Hikichi, Polymer, 1992, 33, 718. J. J . Dumais, L. W. Jelinski, M. E . Calvin, C. Dybowski, C. E. Brown and P. Kovacic, Macromokcules, 1989, 22, 612.
MISCIBILITY, MORPHOLOGY AND MOLECULAR MOTION
127
12. G. G. Maresch, R. D. Kendrick, C. S. Yannoni and M. E. Calvin, Macromolecules, 1988. 21, 3523. 13. K. Schmidt-Rohr, J. Clauss, B. Bliimich and H. W. Spiess, Magn. Reson. Chem., 1990. 28, s3. 14. M. Valero, J. J. Iruin, E . Espinosa and M. J. Fernhdez-Berridi, Polym. Commun., 1990, 31, 127. 15. P. P. Huo and P. Cebe, Macromolecules, 1993, 26, 5561. 16. J. H. Walton, J. B. Miller, C. M. Roland and J. B. Nagode, Macromolecules, 1993. 26, 4052. 17. D. G. Cory, J. C. de Boer and W. S. Veeman, Macromolecules, 1989, 22, 1618. 18. A. L. Segre, D . Capitani, P. Fiordiponti, P. L. Cantini, A. Callaioli, A. Ferrando and R. Nocci, Eur. Polym. J . , 1992, 28, 1165. 19. S. N. Sarkar and R. A. Komoroski, Macromolecules, 1992, 25, 1420. 20. L. A. Belfiore, C. Qin, E. Ueda and A. T. N. Pires, J . Polym. Sci., Part B, Polymer Phys., 1993, 31, 409. 21. D. L. VanderHart, Makromol. Chem., Macromol. Symp., 1990, 34, 125. 22a G. C. Campbell and D. L. VanderHart, J . Magn. Reson., 1992, 96, 69. 22b. D. L. VanderHart, G . C. Campbell and R. M. Briber, Macromolecules, 1992, 25, 4734. 23. J. Grobelny, D. M. Rice, F. E. Karasz and W. J. MacKnight, Macromolecules, 1990, 23, 2139. 24. G . C. Campbell, D. L. VanderHart, Y. Feng and C. C. Han, Macromolecules, 1992, 25, 2107. 25. L. Jong, E. M. Pearce, T. K. Kwei and L. C. Dickinson, Macromolecules, 1990, 23, 5071. 26. G. v. d. Velden, G . Kolfschoten-Smitsmans and A . Veermans, Polym. Commun., 1987, 28, 169. 27. J. F. Parmer, L. C. Dickinson, J. C. W. Chien and R . S. Porter, Macromolecules, 1989, 22. 1078. 28. C. J. T. Landry and P. M. Henrichs, Macromolecules, 1989, 22, 2157. 29a. M. Linder, P. M. Henrichs, J. M. Hewitt and D. J. Massa, J . Chem. Phys., 1985, 82, 1585. 29b. P. M. Henrichs, J. Tribone, D . J. Massa and J. M. Hewitt, Macromolecules, 1988, 21, 1282. 30. W. G. Zheng, Z. H. Wan, Z. N. Qi and F. S. Wang, Polymer, 1993, 34, 4982. 31a. A. Asano, K. Takegoshi and K. Hikichi, Polym. J . , 1992, 24, 473. 31b. A. Asano, K. Takegoshi and K. Hikichi, Polym. J . , 1992, 24, 555. 32a. M. Afeworki, R. A. McKay and J. Schaefer, Macromolecules, 1992, 25, 4084. 32b. M. Afeworki and J. Schaefer, Macromolecules, 1992, 25, 4092. 32c. M. Afeworki and J. Schaefer, Macromolecules, 1992, 25, 4097. 33. J . H. Walton, J . B. Miller and C. M. Roland, J . Polym. Sci., Part B, Polym. Phys., 1992, 30, 527. 34. B. Albert, R. JkrBme, P. Teyssie, G . Smyth and V. J. McBrierty, Macromolecules, 1984, 17, 2552. 35a. P. A. Mirau, H. Tanaka and F. A . Bovey, Macromolecules, 1988, 21, 2929. 35b. P. A. Mirau and F. A. Bovey, Macromolecules, 1990, 23, 4548. 3%. J. L. White and P. Mirau, Macromolecules, 1993, 26, 3049. 36. T. P. Yang, E . M. Pearce, T. K. Kwei and N. L. Yang, Macromolecules, 1989, 22, 1813. 37. L. W. Kelts, C. J. T. Landry and D. M. Teegarden, Macromolecules, 1993, 26, 2941. 38. T. Suzuki, E. M. Pearce and T. K. Kwei, Polym. Commun., 1992, 33, 198. 39. R. A. Newmark and B. C. Copley, Macromolecules, 1984, 17, 1973. 40. P. Sotta, B. Deloche, J. Herz, A. Lapp, D. Durand and J.-C. Rabadeux, Macromolecules, 1987, 20, 2769.
128
K. TAKEGOSHI
41. V. J. McBrierty, D . C. Douglass and P. J. Barham, J . Polym. Sci., Polym. Phys. E d . , 1980, 18, 1561. 42. D . W. Crick and S . D . Alexandratos, Macromolecules, 1993, 26, 3267. 43. X. Zhang and A. Eisenberg, J . Polym. Sci., Part B, Polym. Phys., 1990, 28, 1841. 44a. A. Natansohn and A. Simmons, Macromolecules, 1989, 22, 4426. 44b. A. Simmons and A. Natansohn, Macromolecules, 1991, 24, 3651. 45. D. C . Douglass and V. J. McBrierty, Macromolecules, 1978, 11, 766. 46. S. Percec and T. Hammond, Polymer, 1991, 32, 1252. 47. M. Guo and H . G. Zachmann, Polymer, 1993, 34, 2503. 48. E. Martuscelli, G. Demma, E. Rossi and A. L. Segre, Polym. Commun., 1983, 24, 266. 49. C. Marco, J. G . Fatou, M. A . Gomez, H. Tanaka and A. E . Tonelli, Macromolecules. 1990, 23, 2183. 50a. C . Brosseau, A . Guillermo and J. P. Cohen-Addad, Polymer, 1992, 33, 2076. 50b. C. Brosseau, A. Guillermo and J. P. Cohen-Addad, Macromolecules, 1992. 25. 4535. 51. C. Marco, M. A. Gomez, J. G . Fatou, A . Etxeberria, M. M. Elorza and J. J. Iruin, Eur. Poly. J . , 1993, 29, 1477. 52a. X. Zhang, K. Takegoshi and K. Hikichi, Macromolecules, 1992, 25, 2336. 52b. X. Zhang, K. Takegoshi and K. Hikichi, Macromolecules, 1993, 26, 2198. 53. C. Qin, A. T. N. Pires and L. A . Belfiore, Polym. Commun., 1990, 31, 177. 54. J. Grobelny, D . M. Rice, F. E . Karasz and W. J. MacKnight, Polym. Commun., 1990, 31, 86. 55a. Y . Wang, Q. Chen and X. Zhang, in Interfaces in Polymer, Ceramic, and Metal Matrix Composites (ed. H. Ishida), Elsevier Press, New York, 1988, p. 249. 55b. X. Zhang and Y. Wang, Polymer, 1989, 60, 1867. 56a. P. Tang, J. A. Reimer and M. M. Denn, Macromolecules, 1993, 26, 4269. 56b. G . Pavlovskaya, M. Hansen, A . A . Jones and P. T. Inglefield, Macromolecules, 1993, 26, 6310. 57a. J . B. Miller, K. J. McGrath, C. M. Roland, C. A . Trask and A. N. Garroway, Macromolecules, 1990, 23, 4543. 57b. C. M. Roland, J. B. Miller and K. J. McGrath, Macromolecules, 1993, 26, 4967. 58. K. Takegoshi, Y. Ohya and K. Hikichi, Polym. J . , 1993, 25, 59. 59a. X. Zhang, K. Takegoshi and K. Hikichi, Macromolecules, 1991, 24, 5756. 59b. X. Zhang, K. Takegoshi and K. Hikichi, Macromolecules, 1992, 25, 4871. 59c. X. Zhang, K. Takegoshi and K. Hikichi, Polym. J., 1992, 24, 1403. 60. N. Zumbulyadis and J. M. O’Reilly, J . Am. Chem. Soc., 1993, 115, 4407. 61. X. Zhang, A . Natansohn and A. Eisenberg, Macromolecules, 1990, 23, 412. 62a. H . W. Spiess, Makromol. Chem., Macromol. Symp., 1991, 50, 241. 62b. J. Clauss, K. Schmidt-Rohr and H . W. Spiess, Acra Polymer, 1993, 44,1. 63. V. J. McBrierty, D. C. Douglass and T. K. Kwei, Macromolecules, 1978, 11, 1265. 64. V. J. McBrierty, Faraday Discuss. Chem. Soc., 1979, 68, 78. 65. L. Jong, E. M. Pearce and T. K. Kwei, Polymer, 1993, 34, 48. 66. W. Schenk, D . Reichert and H. Schneider, Polymer, 1990, 31, 329. 67. J. F. Parmer, L. C. Dickinson, J. C. W. Chien and R. S . Porter, Macromolecules, 1987, 20, 2308. 68. B. Albert, R. JerBme, P. Teyssie, G . Smyth, N. G. Boyle and V. J. McBrierty, Macromolecules, 1985, 18, 388; 1640 (correction). 69. F. A. Bovey, F. C. Schilling, T . K. Kwei and H . L. Frisch, Macromolecules, 1977, 10, 559. 70. P. TCkCly, F. Laupretre and L. Monnerie, Polymer, 1985, 26, 1081. 71a. C . H. K. Douwel, W. E . J. R. Maas, W. S. Veeman, G . H . W. Buning and J. M. J. Vankan, Macromolecules, 1990, 23, 406. 71b. W. E. J. R . Maas, W. A. C. van der Heijden, W. S . Veeman, J. M. J . Vankan and G . H. W. Buning, J . Chem. Phys., 1991, 95, 4698.
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71c. A. P. A. M. Eijkelenboom, W. E. J. R. Maas, W. S. Veeman, G . H . W. Buning and J. M. J. Vankan, Macromolecules, 1992, 25, 4511. 71d. C. H. M. Papavoine, W. E. J. R. Maas, W. S. Veeman, G. H. W. Buning and J. M. J. Vankan, Macromolecules, 1993, 26, 6611. 72. R. A. Grinsted and J. L. Koenig, J . Polym. Sci., Part B, Polym. Phys., 1990, 28, 177. 73. N. Zumbulyadis, C. J. T. Landry and T. E. Long, Macromolecules, 1993, 26, 2647. 74. N. Parizel, G. Meyer and G . Weill, Polymer, 1993, 34, 2495. 75. A. Natansohn and A. Eisenberg, Macromolecules, 1987, 20, 323. 76. S. Schantz and N. Ljungqvist, Macromolecules, 1993, 26, 6517. 77. L. C. Dickinson, H. Yang, C.-W. Chu, R. S. Stein and J. C. W. Chien, Macromolecules, 1987, 20, 1757. 78a. R. P. Kambour, J. M. Kelly, B. J. McKinley, B. J. Cauley, P. T. Inglefield and A. A. Jones, Macromolecules, 1988, 21, 2937. 78b. Y. H. Chin, C. Zhang, P. Wang, P. T. Inglefield, A. A. Jones, R. P. Kambour. J. T. Bendler and D. M. White, Macromolecules, 1992, 25, 3031. 7%. Y. H. Chin, P. T. Inglefield and A. A. Jones, Macromolecules, 1993, 26, 5372. 79. H. Feng, Z. Feng, H. Ruan and L. Shen, Macromolecules, 1992, 25, 5981. 80. M. B. Djordjevic and R. S. Porter, Polym. Eng. Sci., 1983, 23, 650. 81. M. A. de Araujo, D . Oelfin, R. Stadler and M. Moller, Makromol. Chem., Rapid Commun., 1989, 10, 259. 82. P. Schmidt, J. Dybal, J . Straka and B . Schneider, Makromol. Chem., 1993, 194, 1757. 83. D. L. VanderHart, W. F. Manders, R. S. Stein and W. Herman, Macromolecules, 1987, 20, 1724. 84. T. Nishi, T. T. Wang and T. K. Kwei, Macromolecules, 1975, 8, 227. 85. S. Kaplan, ACS Polym. Prep., 1984, 25, 356. 86a. P. Caravatti, P. Neuenschwander and R. R. Ernst, Macromolecules, 1985, 18, 119. 86b. P. Caravatti, P. Neuenschwander and R. R. Ernst, Macromolecules, 1986, 19, 1889. 87. G. C. Gobbi, R. Silvestri, T. P. Russell, J. R. Lyerla, W. W. Fleming and T. Nishi, J . Polym. Sci., Part C, Polym. Lett., 1987, 25, 61. 88. M. W. Crowther, I. Cabasso and G. C. Levy, Macromolecules, 1988, 21, 2924. 89a. C. W. Chu, L. C. Dickinson and J. C. W. Chien, Polym. Bull., 1988, 19, 265. 89b. C. W. Chu, L. C. Dickinson and J. C. W. Chien, J . Appl. Polym. Sci., 1990, 41, 2311. 90. K. Takegoshi and K. Hikichi, J . Chem. Phys., 1991, 94, 3200. 91. C. L. Menestrel, A. M. Kenwright, P. Sergot, F. Laupretre and L. Monnerie, Macromolecules, 1992, 25, 3020. 92. K. Schmidt-Rohr, J. Clauss and H. W. Spiess, Macromolecules, 1992, 25, 3273. 93. T. P. Russell, D. S. Lee, T. Nishi and S. C. Kim, Macromolecules, 1993, 26, 1922. 94. Z . Gao, A. Molnar, F. G. Morin and A. Eisenberg, Macromolecules, 1992, 25, 6460. 95. T. K. Kwei, Y. K. Dai, X. Lu and R. A. Weiss, Macromolecules, 1993, 26, 6583. 96. A. Natansohn, M. Rutkowska and A . Eisenberg, Polymer, 1987, 28, 885. 97. X. Zhang, K. Takegoshi and K. Hikichi, Polymer, 1992, 33, 712. 98. H. Feng, Z. Feng and L. Shen, Polymer, 1993, 34, 2516. 99. C. Qin, A. T. N. Pires and L. A. Belfiore, Macromolecules, 1991, 24, 666. 100. A. Nathansohn, M. Lacasse, D . Banu and D. Feldman, J . Appl. Polym. Sci., 1990, 40, 899. 101. D. S. Kaplan, J . Appl. Polym. Sci., 1976, 20, 2615. 102a. J. E. Anderson and W. P. Slichter, J . Phys. Chem., 1965, 69, 3099. 102b. U. Haeberlen, Phil. Trans. R. Soc. Lond., 1981, A299, 497. 103. Ref. 62b and works cited therein. 104. J. R. Havens and D. L. VanderHart, Macromolecules, 1985, 18, 1663. 105. R. A. Assink, Macromolecules, 1978, 11, 1233. 106. D. C. Douglass and G. P. Jones, J . Chem. Soc., 1966, 45, 956. 107. M. Goldman and L. Shen, Phys. Rev., 1966, 144, 321.
130
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P. Tekely, D. Canet and J.-J. Delpuech, Mol. Phys., 1989, 67, 81. D. P. Raleigh, M. H . Levitt and R. G. Griffin, Chem. Phys. Left., 1988, 146, 71. M. G. Colombo, B. H. Meier and R. R. Ernst, Chem. Phys. Lett., 1988, 146, 189. W. E. J. R. Maas and W. S. Veeman, Chem. Phys. Lett., 1988, 149, 170. M. H. Levitt, D. P. Raleigh, F. Creuzet and R. G. Griffin, J . Chem. Phys., 1990, 92, 6347. 110. U. Haeberlen and J. S. Waugh, Phys. R e v . , 1969, 185, 420. 111. K. Takegoshi and C . A. McDowell, J . Chem. P h y s . , 1987, 86, 6077. 112. P. Caravatti, G. Bodenhausen and R. R. Ernst, Chem. Phys. Lett., 1982. 89, 363. 113. K. Takegoshi and K. Hikichi, Polym. J . , 1994, 26, 1377. 114a. P. J. Flory, J . Am. Chem. Soc., 1965, 87, 1833. 114b. D. Patterson, Macromolecules, 1969, 2, 672. 115a. D. L. VanderHart, W. L. Earl and A. N. Garroway, J . M a p . Reson., 1981, 44,361. 115b. W. P. Rothwell and J. S. Waugh, J . Chem. P h y s . , 1981, 74, 2721. I l k , D. Suwelack, W. P. Rothwell and J. S. Waugh, J . Chem. Phys., 1980, 73, 2559. 116a. A. Miyake, J . Polym. Sci., 1958, 117, 476. 116b. D. W. McCall, D. C. Douglas and E. W. Anderson, J . Chem. Phys., 1959, 30, 1272. 116c. T. M. Connor, Trans. Faraday SOC.,1964, 60, 1574. 116d. F. Heatley and A. Begum, Polymer, 1976, 17, 399. 116e J. Schaefer, Macromolecules, 1973, 6, 882. 117. S. L. Maunu, J. Kinnunen, K. Soljamo and F. Sundholm, Polymer, 1993, 34, 1141. 118. D. T. Nzudie, L. Delmotte and G . Riess, Makromol. Chem., Rapid Cornmun., 1991, 12, 251. 119. P. Bliimler and B. Bliimich, Macromolecules, 1991, 24, 2183. 120. M. Tomaselli, B. H. Meier, P. Robyr, U. W. Suter and R. R. Ernst, Chem. Phys. Lett., 1993, 205, 145. 121. M. Mansfeld and W. S. Veeman, Chem. Phys. Letf., 1993, 213, 153. 108. 109a. 109b. 109c. 109d.
One-bond 13C-13C Spin-Spin Coupling Constants K. KAMIENSKA-TRELA Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44, Warsaw 01-224, Poland
1. 2. 3. 4. 5. 6. 7.
8. 9. 10. 11. 12. 13.
Introduction Theoretical considerations Unsubstituted hydrocarbons Substituent effects on one-bond CC spin-spin couplings across single, double and triple bonds One-bond CC spin-spin coupling constants in derivatives of benzene One-bond CC coupling constants in heteroaromatic systems One-bond CC couplings in substituted aliphatic cyclic and heterocyclic systems 7.1. Three-membered ring compounds 7.2. Four-membered ring compounds 7.3. Five-membered ring compounds 7.4. Six-membered ring compounds 7.5. Large ring and polycondensed cyclic compounds The lone pair effect One-bond CC couplings in structural studies of complexes One-bond CC couplings in charged molecules and some related compounds One-bond CC couplings in biological studies Experimental methods Application of the INADEQUATE method in structural elucidations References
131 132 140 144 153 157 161 161 169 172 172 176 180 186 196 200 212 216 222
1. INTRODUCTION Lynden-Bell and Sheppard' and Graham and Holloway2 were the first to determine one-bond l3C-I3C couplings in ethane, ethylene and acetylene using 13C enriched samples, over 30 years ago. Developments in NMR instrumentation combined with the introduction of the Fourier transform (FT) pulse technique now allow one to measure 13C-13C couplings at natural abundance of 13C isotope. The pulse sequences, such as the one- and two-dimensional INADEQUATE (Incredible Natural Abundance DoublE ANNUAL REPORTS ON NMR SPECTROSCOPY VOLUME 30 ISBN 0-12-505330-4
Copyrighi 0I995 Academic Press Limited A / / rights of reproduction in any form reserved
132
K . KAMIENSKA-TRELA
QUAntum Transfer Experiment) technique and its further improvements and/or substitutes, simplify interpretation of the spectra considerably. This has made 'J(CC) couplings easily accessible, even in the case of large molecules, and revived interest in this unique parameter. It has occurred that in spite of initial assumptions, one-bond carbon-carbon couplings undergo strong variations upon substitution and complexation, and are in this way a sensitive measure of the electronic structure of carbon-carbon bonds. It is therefore not surprising that they have become a subject of lively interest, and a steady increase in the number of the papers devoted to 'J(CC) has been observed since the early 1980s. The present review covers the results which were published between 1987 and the end of 1993, with special attention paid to the factors which determine the 'J(CC) magnitude. The earlier results were covered in several exhaustive reviews written by M a ~ i e l M , ~a r ~ h a l lHansen ,~ and Wray,'-* and by Krivdin and Kalabin' and It is worth while to mention that the 13C-13C couplings across more than one bond were recently also reviewed by Krivdin and Della. l7 2. THEORETICAL CONSIDERATIONS A general theory of spin-spin coupling was developed in the early 1950s by Ramsey,ls*" who showed that indirect magnetic coupling between nuclear spins A and B results from three types of interactions:
J
= 'JoD
+ 'JsD +'JFC
(1)
those involving nuclear spin and electron orbital magnetic moment, 'JoD, dipole-dipole interaction between nuclear and electron spins, 'JsD, and the Fermi contact interaction, 'JFC, between the latter spins. Thus, electrons are involved in all interactions as a transmitting medium for the indirect coupling between nuclear spins. McConnell,20~21 Pople and c ~ - w o r k e r s , ~and ~ - ~Blizzard ~ and further developed Ramsey's theory and applied it to larger molecules. Though the theory was applied at an approximate level only, involving, among others, the so-called average excitation energy approximation, it afforded a successful interpretation of the FC, SD and OD contributions in terms of commonly used characteristics of the ground electronic states of the molecules under study. Thus, it has been shown that the contact contribution depends on the product S2(A).S2(B) of the electron densities at the coupled nuclei; the orbital and dipolar interactions are proportional to the product of the one-centre integrals, (rA-3)and (rB-3) for the coupled nuclei, where (rF3) is the expectation value of the inverse cube of the valence p electron radii. The first large sets of theoretical one-bond CC spin-spin coupling
ONE-BOND 13C-13C SPIN-SPIN COUPLING CONSTANTS
133
constants were published in the early 1970s by Maciel et a1.,27p30who calculated the SCF INDO values of one-bond CC couplings, 'J(CC), for a variety of organic molecules. In spite of the fact that the computations were performed for the Fermi contact term only, the agreement between the theory and experiment was in most cases satisfactory. The values of non-contact terms for CC spin-spin couplings have also been obtained by Blizzard and Santry26 from SCF perturbation theory calculations at the INDO level, and by Schulman and Newton.31 The older results have been collected and discussed by Kowalewski in his excellent review on calculations of nuclear spin-spin coupling constants.32 Furthermore, the mechanism of the spin-spin coupling has been a subject of continuing interest and in recent years there have been numerous papers on this t o p i ~ . ~ ~ Among - ~ l them, those devoted to the density functional calculations are of special interest. Recently, the first set of spin-spin coupling constants calculated by the use of this method has been published by Malkin et al.33 It includes one-bond carbon-carbon spin-spin coupling constants in acetylene, ethylene, propene, butadiene, benzene and pyridine. In the case of large molecules, especially those bearing the atoms of the second and the third row at the carbon-carbon bond involved, the INDO calculations still remain the method of choice. 34-50 The ab initio calculations are still rather time-consuming and require access to powerful computers. As a consequence only rather small molecules can be calculated by means of these methods. Nevertheless, the number of the papers devoted to the couplings calculated by these methods constantly i n ~ r e a s e s . ~ l -Recently, ~l the finite-field perturbation theory combined with the quadratic configuration interaction has been applied by C a r m i ~ h a e to l~~ calculate the Fermi contact contribution to the indirect CC spin-spin coupling constants across one bond in ethane, cyclopropane, cyclobutane and bicyclo[l.l.O.]butane. The computed 'J(CC) values matched the experimental ones very well. The ab initio data for cyclopropene have been recently published by Fronzoni and gal ass^^^ and by Barszczewicz et al.,60 and the ab initio value of 'J(CC) in vinyl lithium has been calculated by Ruud et a1.6' The most relevant data for the simplest molecules, i.e. ethane, ethene, ethyne and some cyclic unsubstituted compounds are collected in Table 1. The following general conclusions can be drawn from these data: (1) In all cases, without any exception, the Fermi contact term is the dominant factor. This also includes the coupling across central bond in bicyclobutane. The ab initio calculations performed by Galasso5' and by C a r m i ~ h a eshow l ~ ~ that even in the case of this unique bonding the coupling mechanism is controlled by the Fermi interaction, whose sign is, in this case, exceptionally negative. This leads to a negative sign of the 'J(CC) coupling constant, in agreement with the experimental
134
K. KAMIENSKA-TRELA
Table 1. Contributions from different mechanisms to the carbon+arbon couplings in ethane, ethene, ethyne and some alicyclics calculated by various semiempirical and ab initio methods; all values are in hertz.
Contact
Dipolar
35.6 41.5 41.5 43.24 30.24 34.1
0.7 1.6
CH3-CH3 SCPT INDO SCPT INDO SCF INDO FOPPA INDO/MCI EHMO Ab initio QCISD(T)
-
-1.45 0.18
Orbital -2.9 -2.9 -
0.59 0.04
Experimental HzC=CH2 SCPT INDO SCPT INDO SCF INDO FOPPA INDO/MCI EHMO Density functional results F32 F64 Ab initio results FPMC + CI" SOPPA".b SOPPA".' EOM Experimental
Ref.
33.4 40.2 41.5 42.38 30.46
26 50 27 43 42 58
34.6 70.6 82.1 82.2 84.22 74.90
81.9 98.6 78.8 86.99
HC-CH SCPT INDO 140.8 SCPT INDO 136.1 SCF INDO 163.6 FOPPA/INDO/MCI 164.49 EHMO 157.13 Density functional results F32 F64 A b initio results 173.81 FPMC + CI" SOPPA",' 194.2 SOPPA".' 186.7 SOPPA' 183.34 ECCDPPA 180.83 EOM 210.05 Experimental
Total
3.9 7.8 -
2.09 1.64
-
2.5 2.3 1.85
-18.6 - 18.6 -
-6.96 -3.97
-10.0 -9.3 -9.0 -6.48
55.9 71.3 82.2 79.35 79.57
26 50 27 43 42
70.8 61.2
33 33
71 .9 91.8 72.1 82.37
51 52 52 56
67.6 8.3 16.6
23.6 23.6
-
-
3.79 5.30
1.09 10.32
-
6.4 6.6 7.24 7.25 5.20
15.3 1.8 2.5 5.82 5.40 1.74
1
1
172.7 175.8 163.6 169.37 172.75
26 50 27 43 42
250.8 249.1
33 33
189.1 202.4 177.8 196.4 193.5 216.99
51 52 52 54 54 56
171.5 170.6
1 2
ONE-BOND I3C-l3C SPIN-SPIN COUPLING CONSTANTS
135
Table l-cont’d Contact Cyclopropane SCPT INDO A b initio QCISD(T)
23.6 13.9
Dipolar -3.6
Orbital
Total
Ref.
-0.6
19.4
50 58
12.4
62
Experimental Cyclobutane Ah initio QCISD(T)
27.4
58
Experimental (for methylcyclobutane) Bicyclobutane (edge) SCPT INDO A b initio QCISD(T)
25.2 24.3
-3.3
-0.5
29.1 28.9
63 64
21.4
31 58
Experimental Bicyclobutane (bridge) SCPT INDO A b initio EOM Ab initio QCISD(T)
65 -1.4 -7.0 -13.6
-1.3 -0.5 -
-2.9 -0.27
-5.6 -7.77 -
31 57 58
-17.5
66
-
Experimental (in 2,2,4 ,4-tetramethylbicyclobutane-dl 4) Cyclopropene (double bond) SCPT INDO 64.5 69.76 A b initio EOM Ab initio MC TDHF 72.8
9.2 -4.0 3.8
-6.5 1.8 -5.3
67.2 67.6 71.2
50 59 60
Cyclopropene (single bond) 25.0 SCPT INDO Ab initio MC TDHF 18.7
-1.0 -0.4
-2.7 -0.5
21.3 17.8
50 60
“Re-calculated from the reduced coupling constants K . bDZ basis. ‘DZP basis. Acronyms SCPT, Self-consistent perturbation theory; SCF, Self-consistent field theory; LMO, Localized molecular orbitals; EHMO. Extended Hiickel molecular orbital theory; FOPPA/INDO/MCI, First-order polarization propagator approach (multicentre integrals); FPMC CI, Finite perturbation-multiconfiguration SCF method plus configuration interaction; SOPPA, Secondorder polarization propagator approximation; ECCDPPA, Extended coupled-cluster doubles polarization propagator; EOM, Equations of motion; QCISD(T), Quadratic configuration interaction with the space restricted to single, double (triple) substitutions; MC TDHF, Multiconfiguration time-dependent Hartree-Fock approach.
+
136
K. KAMIENSKA-TRELA
Table 2. FFT INDO-calculated values of one-bond CC coupling constants in the derivatives of acetylene (in hertz).
Compound HC=CLi HC=CBeH HCECBH~ HCzCCH3 HGCNH2 HC=COH HC-CF HC=CNa HC=CMgH HC-CAlH2 HC=CSiH3 HCECPH~ HC-CSCH3 HC-CC1 LiCICLi HBe-C=CBeH H~B-CECBH~ H~CCECCH~ HZNGCNH2 HOC=COH FC=CF H3SiC=CLi H3SiCECBeH H3SiC=CBHz H3SiC=CCH3 H3SiC=CNH2 H3SiC=COH H3SiC=CF H3SiC=CSiH3
Contact
Dipolar
Orbital
Total
Ref.
51.6 86.0 125.5 162.0 179.7 190.6 200.0 56.5 69.9 93.6 125.2 145.5 164.6 180.9 31.4 47.1 102.5 161.0 202.0 235.3 275.5 41.6 65.8 97.3 123.2 132.6 135.8 135.1 96.2
4.8 4.4 4.8 5.7 5.7 6.0 6.0 5.1 4.9 5.1 5.7 5.0 6.1 6.3 2.1 0.7 5.5 7.5 9.3 10.5 11.1 4.6 4.4 4.5 5.5 5.5 5.8 5.9 5.5
5.0 4.4 6.1 7.9 8.4 9.3 9.8 5.8 5.5 6.2 7.7 7.6 9.7 10.6 3.7 3.5 4.8 5.6 6.0 6.4 6.4 4.7 3.8 5.1 7.2 7.8 8.8 9.3 7.4
61.4 94.8 136.4 175.6 193.8 206.0 215.8 67.4 80.3 104.9 138.6 158.1 180.5 197.8 37.2 51.3 112.8 174.1 217.3 252.2 293.0 50.9 74.0 106.9 135.9 145.9 150.4 150.3 109.1
45 45 45 45 45 45 45 49 49 49 44 49 49 49 45 45 45 45 45 45 45 49 49 49 49 49 49 49 44
result reported by Finkelmeier and Luttke for perdeutero-2,2,4,4tetramethylbicyclobutane.66 In all remaining cases known so far the couplings across one CC bond are positive. (2) The orbital and dipolar terms are negligible for single CC bonds. For the double CC bond the non-contact terms are of mutually opposite signs and partly cancel each other. Only in the case of the triple CC bond, the orbital as well as the dipolar terms are large and positive. In Tables 2-4 the INDO 'J(CC) values calculated for substituted acetylenes, ethylenes, allenes and diacetylenes, where substituents were systematically vaned, are displayed, and some of these results are additionally shown in Figs 1 and 2. Though the agreement between the calculated and experimental coupling constants (the latter values are
137
ONE-BOND 13C-'3CSPIN-SPIN COUPLING CONSTANTS
Table 3. The I N D O FPT total 'J(CC) values in variously substituted ethenes, allenes and diacetylenes; for H,C=CHLi the ab initio 'J(CC) value taken from ref. 61 is included.
XCH=CHz XC'H=C2=C3H2 Substituent X
'J( C C ) ~ ~ 'J( c1c 2 y 7
14.6 Li 51.3" Li" 35.4 BeH 68.5 BH2 82.1 CH3 93.3 NH, 96.8' OH 95.0" OH 99.6 F Range of O D contribution -5.4to -6.5 0.9 to 1.0 Range of S D contribution ~~
XC'd?-C3zC4X l ~~(
1
~
I J (2 ~
) 2 ~ ~ ~3 ) ~
27.3
43.2
104.0
55.1 75.7 107.5 120.1 128.8' 125.4' 130.8 --3.7 to -4.4 1.6 to 2.9
93.5 137.5 178.9 202.1 216.5
118.3 135.3 154.0 165.0 170.7
-
~
-
-
-
-
233.3 176.1 3.0 to 10.1 -0.1 to 0.3 4.1 to 6.0 -0.3 to 1.0
~
"Ab inrtio value ('J(FC) 57 83. 'J(0D) 9 53, 'I(SD) 3 07) 's-cry arranged OH group 's-trans arranged OH group
Table 4. Calculated total INDO FPT and FOPPA INDO/MCI one-bond CC couplings in fluoroethenes; all values in hertz.
Compound
H2C=CF2 FCH=CHF cis FCH=CHF trans FCH=CF2 F,C=CF, Range of OD contribution Range of S D contribution
FOPPA INDO/MC143
INDO FPP7
116.4 109.8 121.3
119.2 113.5 129.4 146.6 196.4 -3.6 to -4.8 2.5 to 3.3
-
-5.6 to -6.2 2.4 to 2.8
collected and discussed in Section 4) is not always satisfactory, some general trends emerge from the data collected. Thus, in all cases, without exception, a strong influence of electronegativity of substituent is observed. The largest calculated values have been found for fluorosubstituted compounds, the smallest for derivatives of lithium and sodium. The dramatic changes observed can be interpreted mainly in terms of the changes occurring in the Fermi contact term. The contribution of orbital-dipole and spin-dipole interactions, though not negligible, is considerably smaller than that introduced by the FC interaction. This is in agreement with the semiempirical data published earlier by Maciel et for some substituted
138
K. KAMIENSKA-TRELA
___c_c_c_.
(OD+SD)
0 L i B e B C
N
O
0 F
(atomic number) Fig. 1. Plot of the total, the Fermi contact (FC) and the sum of orbital and dipolar terms vs. atomic numbers of the first atom of the substituent for 'J(CC) coupling constants in disubstituted acetylenes.
ethenes and acetylenes and with the ab initio results published by Fronzoni and Galassos9 for monoheteroanalogues of cyclopropane and cyclopropene. The theoretical calculations of one-bond CC coupling constants performed at both semiempirical and ab initio levels predict for them a dependence on both conformation and configuration of the compounds. Thus, variations by as much as 5-6Hz were noted by Barfield and co-workers68 in the INDO values of 'J(CC) couplings as the dihedral angle 4 was varied in butane, butanol and butanoic acid. A very strong 'J(CC) vs. the valence angle dependence has also been observed by Krivdin et ~ 1 . ~who ' performed the calculations for the model CH2CH2CH2fragment using the SCPT INDO method. The ab initio calculations performed by Carmichael et al.69 at the
ONE-BOND I3C-l3C SPIN-SPIN COUPLING CONSTANTS
139
H 3SiCCX
150 -
100
-
50 -
0
L i B e B C
N
O
F
(atomic number) Fig. 2. Plot of the total, the Fermi contact (FC) and the sum of orbital and dipolar terms vs. atomic numbers of the first atom of the substituent for 'J(CC) coupling constants in silyl-substituted acetylenes.
QCISD(T) level for ethylene glycol revealed that 'J(CC) coupling in this compound depends on both the C-C and C - 0 torsions. The coupling is largest when the hydroxyl substituents are trans and smaller for gauche geometries; the coupling reaches a maximum when the hydroxyl proton is anti to a carbon and a minimum in gauche configurations. Thus, in addition to the relative C-C torsion one should also take into account the conformational behaviour of the C - 0 bonds. 'J(CC) values found for trans 1,2-difluoroethene were substantially greater than those calculated for the cis-difluoro i s ~ m e r . ~ ~ ? ~ '
140
K. KAMIENSKA-TRELA
3. UNSUBSTITUTED HYDROCARBONS
A large number of the 'J(CC)couplings have been collected for a variety of unsubstituted hydrocarbons and thoroughly discussed in two recent reviews.9310Therefore, in this section only some of the most important data are included in order to allow the reader to become quickly familiar with the general trends prevailing in this group of the compounds. Two factors have to be taken into consideration in order to estimate the unknown one-bond CC coupling value. These are (i) hybridization of the bonding orbitals involved and (ii) the ring size of the compound. With the increasing s characters of carbon atoms involved the magnitude of the corresponding coupling increases. The couplings across endo-cyclic carbon-carbon bonds increase with increasing ring size, while the reverse trend is observed for the couplings across em-cyclic bonds which decrease upon passing from smaller to larger rings: 'J(Csp3Csp3)< 'J(Csp3Csp2)< 'J(Csp2Csp2) (single bond) = 'J(Csp2Csp2)(aromatic bond) = 'J(Csp3Csp)< 'J(Csp2Csp) (single bond) < 'J(Csp2Csp2) (double bond) < 'J(Csp2Csp)(allenic bond) < 'J(CspCsp) (single bond) < J(CspCsp) (triple bond) 'J(CC) endo in C3H6< 'J(cc) endo in C4Hs< 'J(CC) endo in CSHlo= 'J(CC) endo in C6H12 and 'J(CC) ex0 in C3H5CH3>'J(CC) ex0 in C4H7CH3='J(CC) ex0 in C5H9CH3= 'J(cC) ex0 in C6HllCH3
Table 5 and Fig. 3 illustrate these trends. The results obtained recently by Eckert-Maksic et d7' for allenes substituted with a cyclopropyl ring provide a particularly elegant illustration of the above trends. The couplings of 151.8Hz, 142.2Hz and 142.0Hz observed in (1) bis(cyclopropy1idene)methane (2) bis(tetramethylcyclopropy1idene)methane
(3) 1-(dimethyletheny1idene)cyclopropane
across cyclopropyl substituted allenic bonds are greater by ca. 44-54 Hz than the coupling in unsubstituted allene (98.7 Hz):
B=-.==q 4
3
2 '
1
2 1
3
141
ONE-BOND I3C-l3C SPIN-SPIN COUPLING CONSTANTS
151.8Hz
'J(C2C3) 'J( C3C4)
(3)
(2) 23.0 Hz 142.2 Hz 142.2 Hz
(1) 24.6 Hz
'J( ClC2)
151.8 Hz
45.0 Hz 109.0 Hz 142.0 Hz
Thus in the absence of strongly influencing factors such as complexation, electron-donating o r electron-attracting substituents, the hybridization of
Table 5. Relationship between 'J(CC) couplings and hybridization.
Hybridization of carbons involved
Compounds
3 3 SP3> S P , SP , S P
CH3CH3 CH3CH=CH2 CH2=CH-CH=CH2 C6H6
sp:, sp2 (single bond) sp ,sp2 (aromatic bond)
H2C=CH2 H~C-CECH H,C=CH-C-CH H&=C=CH2 HCEC-CECH HC=CH
I(ClC2)
12.4
SP2, SP2
sp3, sp (single bond) sp2,sp (single bond) S P 2 , sp sp, sp (single bond) S P , SP
32.7
!J(C 1c 1,)
refs
62
62
'J(CC)
Ref.
34.6 41.9 53.7 55.95 55.88 67.6 67.4 83.9 98.7 154.8 171.5
1 29 70 71 72 1 73 73 74 75 1
13.3
29.1
43.4
36.1
36.2
35.7
40,64
64
64
64,76
33.3
lJ(CIC1')
95 2
73 1
73 8
72 3
lJ(C1C 2)
23 2
33 6
39 6
39 7
28 5
33 3
31 9
78
78
78
'J(C2C3) refs
77
Fig. 3. Influence of ring size on one-bond CC coupling constants.
142
K. KAMIENSKA-TRELA
Table 6. Collection of the coefficients in the modified versions of equation (2). Coefficients U
576 598 621 658 637
'J(CC)values applied
Ref.
Experiment Experiment
80 77 81 62 15
b
3.4 3.5 10.2 7.9 11.0
INDO
Experiment Experiment
bonding carbon orbitals is the factor which dominates the magnitude of carbon-carbon spin-spin coupling. The corresponding equation of the form where sA and sB are the s characters of intervening carbon atoms was derived by Frei and Bernstein in 1963;80since then several slightly differing values of numerical coefficients entering this equation have been proposed. The authors used either theoretical or experimental sets of 'J(CC) couplings. The corresponding a and b values are collected in Table 6. Some of the authors have modified the equation (2) including overlap integrals (,SAB) calculated using the maximum overlap
The Frei-Bernstein relationship has been recently applied by Jarret and C u ~ u r n a n o ~in~ order to estimate the orbital hybridization in [l.l.l]propellane (4). The one-bond C1C2 coupling of 9.9Hz was found in indices for the C-CH2 bond, in good this compound leading to sp8.6-~p4.8 agreement with the earlier theoretical treatment. Finally, it should be added that determination of carbon-carbon coupling constants for such basic molecules like benzene, cyclohexane, cyclopropane, etc. is by no means a trivial task. Different approaches were applied in order to overcome difficulties arising from the symmetry of the spin systems.9 have applied the method of isotopic Recently, Roznyatovsky et perturbation of symmetrical spin systems by H/D substitution in order to measure one-, two- and three-bond CC couplings for benzene and cyclohex-
143
ONE-BOND 13C-13C SPIN-SPIN COUPLING CONSTANTS
Table 7. One-bond spin-spin couplings across one-, two- and three-bonds in benzene and cyclohexane; all values are in hertz. Compounds
'J(CC)
'J( CC)
3J(CC)
Ref.
Benzene Benzene" Benzeneb Cyclohexane Cyclohexane
55.88 55.3 0.5 55.95 k 0.04 33.10 32.7
2.46
10.04 10.08 0.10 10.01 k 0.03 2.05
72 86 71 72 62
*
-
2.12 -
*
-
"Measured from the nematic phase. bThe method of measurements not reported.
Tables. One-bond carbon<arbon pentadienes.88 All values in hertz.
No. 6
7 8 9
couplings in polymethylsubstituted
cyclo-
R
'J(ClC2)
'J(ClC.5)
'J(ClC1')
'J(C2C2')
'J(C5C5')
H D CH3 NO2
71.0 71.4 71.4
40.7 40.7 40.7 43.3
47.8 47.5 47.5 48.7
45.4 45.3 45.3 45.3
33.6 33.1 33.1 37.4
-
ane. The measurements using double quantum filtration and subsequent analysis of the spectra were performed for monodeuterated derivatives of these two compounds giving the very precise 'J(CC) values. The results reported by Roznyatovsky et aL7' (Table 7 ) for benzene are in agreement with those reported earlier by Diehl et ~ 1and. by~Wray ~ et ~ 1 .the ; ~'J(CC) ~ coupling for cyclohexane is in accord with that published by Luttke and his co-workers.62 An interesting result has been reported by Gay et U I .who ~ ~ have recorded the INADEQUATE spectrum of adamantane (5) in the solid state. The one-bond CC coupling of 31.4 k 0.5 Hz observed in this spectrum was in good agreement with the value of 31.5 Hz obtained by the same authors in benzene solution.
144
K. KAMIENSKA-TRELA
H
H Finally, 'J(CC) couplings have been published by Borodkin et aZ.** for some polymethyl substituted cyclopentadienes (Table 8). 4. SUBSTITUENT EFFECTS ON ONE-BOND CC SPIN-SPIN COUPLINGS ACROSS SINGLE, DOUBLE AND TRIPLE BONDS
The electronegativity of substituents is a second important factor which, as theoretical data presented in Section 2 showed, determines the magnitude of one-bond CC couplings. In particular, the experimental 'J(CC) data obtained for a large number of variously substituted acetylenes fully corroborated the theoretical predictions made for this group of compounds. The data collected in Tables P-11 show that indeed the couplings across the triple bond are extremely sensitive towards substitution. They extend over more than 170Hz varying from 56.8 Hz in (C2H5)3SiC=CLiS9to 230.4 Hz in m-CH30C6H50C=CCH3.90 A lack of the corresponding data for the couplings across single and double bonds led some authors to somewhat hasty conclusions that the couplings across triple CC bonds are an exception, whereas all the remaining ones are much less affected by substituent effects. However, the most recent data obtained for halogenosubstituted ethanes by Gornb1e1-l"~ and for variously substituted ethenes by Kamienska-Trela et al. lo5 and by Wrackmeyer et al. ,lo6 revealed that these coupling constants also undergo a dramatic change upon substitution. The 'J(CC) coupling across double CC bond of 30.9Hz only has been found in (Me3Sn),C=C(Et)BEt2 by Wrackmeyer et al. ,lo6 and 'J(CC) of 172 Hz for trifluorochloroethene by Kamienska-Trela et al. lo5 leading to the total range covered by these couplings larger than 140Hz. A very small 'J(CC) coupling constant of ca. 36Hz only, has been reported recently for vinyllithium by Kamienska-Trela et af.lo7 and by Bauer and Griesinger. The coupling of 85Hz in F3CCC13 is the largest 'J(CC) value across a single Csp3Csp3bond reported so far.104This, combined with the value of 22.9Hz in (CH3)2CHLi,109 gives the total range of ca. 60Hz. Similar changes are observed for the couplings across Csp3Csp2 (0)bonds as shown
ONE-BOND l3C-I3C SPIN-SPIN COUPLING CONSTANTS
145
Table 9. One-bond CC coupling constants, 'J(CC), across triple bonds in XC=CY acetylenes; all values are in hertz.
Y Substituent X ~~
=
J
Ph
Y Ref.
OMe NEt2 Br Ph EtCO,CH=CH" SMe I Et SeMe PPh2 PBu~ TeMe' SiMe3 GeEt, SnEt, PbEt, Li Y X OEt NEt, %Me3 SnMe3 PbMe3 PbPh3 m-CH30C6Hs
Y = Me3Si
J
Ref.
J
Ref.
-
-
-
-
216.0 204.3 202.5 185.0
45, 89 48, 89 45, 89 92
204.8 -
89
-
166.7 155.3
89 45, 89
190.6
45, 89
143.2
45, 89
-
-
-
-
184.2 179.7 177.6 173.2 157.0 154.1 154.4 136.9
45, 91 45 89 89, 91 48 48, 89 89, 91 89
175 175.0 169.5 170.7
93 89, 91 45, 89 45, 89
-
=
-
-
-
-
134.2 126.6 133.3'
89 45, 89 45
115.26
48, 89
-
-
-
-
-
-
130.6 131.5 120.5 111.9
45 94 94 16
101.4'
89, 95
-
CH3
-
94.0
-
45 -
-
56.8
45, 89
J
Ref.
216.5 175.9 175.0 131.8 132.5 125.7 119.8 113.0
94 80 94 45 89 97, 98 95 96, 97
Y = H
J
Ref.
224.3 204.0 136.7 127.6 120.0 122.6 230.4
96 96 45 96, 97 96, 97 16 90
Y = SnBu3
SnBu3
C(CH3)3
~
c1
X
=
J
Ref.
81.0
95
"The trans compound. bMeasured for Et,Si derivative. 'In ref. 89, erroneously CH,TeC=CH was given.
X OEt Ph Me SiEt3 GeEt, HgMe SnBu3 PbEt,
146
K. KAMIENSKA-TRELA
Table 10. One-bond CC coupling constants, 'J(CC), in derivatives of diacetylene XIC-C-C=CX2; all values are in hertz.
xi
x2
'J(C=C)
Ref.
188.3 146.4 146.8 134.5 124.5 145.7b
75 100 101 101 101
99
"Couplings across central CC bond are given in Table 15 'Coupling in (CH,),SiC=C fragment.
Table 11. Influence of values are in hertz.
p substituents on 'J(CC) coupling constants in acetylenes; all
Compounds
'J(CC) Ref.
HOCHZCECH (CH,)*C(OH)C=CH (CH3)2C(OH)C=CCl (CH3)*C(OH)C=CBr C~HSOCH~CECH CHzCICeCH CH2BrC=CH CSF1 ICECH
169.3 166.3 202.2 188.4 173.1 178.6 179.3 188.5
90 90 90 90
90 90 90 96
Compounds
'J(CC) Ref. 146.0 150.6 136.0 133.3 131.3 130.4 174.0 170.7 177.0
90
90 102 102 102 102 102 102 103
-
by the data obtained by G ~ m b l e r "for ~ trifluoroacetic acid and its chloride (see Table 16). The experimental data available in the literature for substituted allenes are rather scarce and originate from two papers by Krivdin et aZ."O and Afonin et d.'" who measured the couplings for two series of alkoxysubstituted allenes. Also in this group of compounds with the formal Csp'Csp hybridization the expected sensitivity towards substitution is revealed by the one-bond CC couplings (Table 12). The following general conclusions and remarks can be made upon a careful inspection of the most recent data collected in Tables 9-17, as well as those presented in earlier reviews. Thus, within a given type of CC bond the electronegativity of asubstituent is the main factor controlling the magnitude of 'J(CC) coupling. The 'J(CC) values increase with increasing electronegativity of substituent, and diminish when the electronegativity of substituent decreases.
ONE-BOND l3C-I3C SPIN-SPIN COUPLING CONSTANTS
N
100.0
N
90.0
I
0 I
-0 F
147
1
-J
-0
c
0
n I
a,
5
30.0
1
I
I
I
I
I
I
I
0.5
1 .o
1.5
2.0
2.5
3.0
3.5
4.0
Pauling's electronegativity of substituent Fig. 4. The 'J(CC) vs. Ex relationship in monosubstituted ethylenes. The Pauling electronegativities Ex of the first atom of the substituent are taken from R. McWeeny, Coulson's Valence, p. 163, Oxford University Press, London, 1979.
An equation which has a multiplicative form has been derived for the couplings across the triple bond:89
' J ( X C = C Y ) = 23.23 (f0.51)ExEy+ 15.45 (f3.32)
( n = 27; r
=
(4)
0.99; s.d. = 4.2Hz)
where Ex and Ey denote Pauling's electronegativities of substituents attached at the triple bond. The substituents involved in the correlation represented a wide range of electronic interactions (C1, Br, I, Li, O R , SR, NR2, PR2, C(CH3)3, SiR3 and GeR3) and therefore one can expect that the validity of equation (4) should be quite general.89 Attempts to apply an additivity rule to these couplings have also been made' but they led to rather dubious results, since large deviations from this scheme have been found when strongly influencing substituents such as SiAlk3, SnAlk3, C1 and Br have been attached to the triple bond simultaneously. The 'J(CC) vs. Ex dependence in monosubstituted ethenes is obviously non-linear (see Fig. 4) and in the case of di-, tri- and tetrasubstituted ethenes also steric effects, i.e. configuration of the compound and conformation of substituents have to be taken into a c c o ~ n t . ~ ~ ' ~
148
K. KAMIENSKA-TRELA
Table 12. One-bond CC couplings (in hertz) in alkyl-, ROC'H=C2=C3H2(1&18), and vinylalkoxyallenes, H2Cp=CaH-O-C'R=C2=C3H2 (19-26).
Compound no. 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26
R CH3 C2H5 n-C3H7 i-C3H7 i-C4Hy CH2CH=CH2 t-C4Hy HC=CH2 C6H5
CH3 C2Hs n-C3H7 n-C4H9 i-C3H7 i-C4Hy 2;ec-C4H9 t-C,H,
' J ( ClC2)
'J( C2C3)
113.8 114.1 113.7 114.0 113.7 114.8 118.2 117.8 117.7 118.6 118.5 118.0 118.3 117.8 118.2 117.8 118.0
101.7 101.8 101.4 101.9 101.4 101.1 102.2 101.9 102.1 102.1 102.2 102.0 102.1 102.0 102.2 102.1 102.1
' I (CcuCp)
Ref.
-
110 110 110 110 110 110 110 110 110 111 111 111 111 111 111 111 111
-
-
-
81.2 -
81.5 82.0 82.4 82.1 81.7 82.2 82.1 82.2
Table 13. One-bond CC coupling constants, 'J(CC), in some selected monosubstituted ethenes H2C=CHX; all values are in hertz. ~
Substituent Li
'J(CC)
Ref.
35.8"
107 107 108 108 112 113 114 113 112 114 114
35.9h
36.3' 35.0d 54.7 58.8 58.2 58.2 60.6 60.3 61.3
Substituent
'J(CC)
Ref.
70.0 72.3 72.4 72.9 76.3 77.6 78.6 78.4 82.2
113 112 112 112 112 115 112 113 112
"Saturated solution of tetramer in EtZO (measured at ambient temperature). '3 M solution of tetramer in EtzO (measured at ambient temperature). '2.3 M solution of tetramer in THF-$ (measured at +30"C). d3.4M solution of dimer in C,D6 with 1.5 equiv. of TMEDA (measured at 3OOC).
ONE-BOND 13C-13CSPIN-SPIN COUPLING CONSTANTS
149
Table 14. 'J(CC) in trans- and cis-substituted ethenes (in hertz).
Substituents FHC=CHBr cis FHC=CHBr trans CIHC=CHCl cis ClHC=CHCI trans BrHC=CHOC2HStrans BrCH=CHOC2Hs cis BrPhC=CHBr cis BrPhC=CHBr trans BrHC=CHBr cis BrHC=CHBr trans IHC=CHI cis IHC=CHI trans C1((CH&Si)C= CHCl cis CI((CH3)3Si)C=CHCltram Br((CH&Si)C= CHBr cis Br((CH3)3Si)C=CHBrtrans (CH3)3SiCI=CHIcis (CH3)3SiCI=CHI tram CH3CH=CHBr cis CH3CH=CHBr trans (CH3)3SiCH=CHClcis (CH3)3SiCH=CHCltrans (CH&SiCH=CHBr cis (CH3)$iCH=CHBr trans CI(CH3)2SiCH=CHCIcis Cl(CH3)2SiHC=CHCItram C13SiCH=CHCI cis Cl3SiCH=CHC1trans (C2HsO)(CH3)2SiCH=CHClcis (C2Hs0)(CH3)2SiCH=CHCltrans (C2H50)2(CH3)SiCH=CHCI cis (C2Hs0)2(CH3)SiCH=CHCI trans (C2H50)3SiCH=CHClcis (CH30)3SiCH=CHClcis (C2Hs0)3SiCH=CHCl trans (CH30)3SiCH=CHCltram C6Hl CH=CHSi(CH& cis C6H1'CH= CHSi(CH3)3trum
'J(CC)
Ref.
87.9 96.0 84.5 91.9 91.5 k 0.5 88.3 k 0.5 87.0 89.5 82.2 86.4 78.7 78.3 67.5 77.5 64.9 72.4 62.5 66.3 78.0 77.0 70.9 65.5 k 0.5 69.9 64.5 0.5 71.1 67.0 72.3 69.7 70.9 65.1 70.3 64.9 70.8 70.7 65.4 65.4 61.4 60.6
105 105 116 116 105 105 105 105 117 117 118 118 117 117 117 117 117 117 105 105 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 114 119 119
*
150
K. KAMIENSKA-TRELA
Table 15. One-bond CC coupling constants in variously substituted ethylenes; all values are in hertz.
Compounds F2C=CFCI F2C=CC12 PhCHzCFZ CI3SiCCI=CCl2 CI2(CH3)SiCCI=CCl2 (C2H50)3SiCC1=CC12 (CH3)3SiCCI=CC12 CI3SiCH=CCl2 C12(CH3)SiCH=CC12 Cl(CH3)2SiCCI=CC12 (C2H50)3SiCH=CC12 (C2H50)2(CH3)SiCH=CC12 CH3CBr=CH2 (CH3)3CC-CCH=CHCN trans ( CH&CC-CCH=CHC02Et trans PhCH=CHC02Me (C2H5)3SiCH=CHCOOC2H5 trans (CH3)$KBr=CH2 (CH30)3SiCH=CHCItrans (CH3)2HSi(CH3)C=C(B(C2H5)2)C2H5 cis (CH~).~S~(C~HI~)C=C(B(C~H~)~)C~H~ cis (CH3)3SnCH=C(B(C2H5)2)C2H5 cis (CH3)3SnCH=C(Sn(CH3)3)C2Hs cis C5Hll((CH3)3Si)C=CHSi(CH3)3trans
(CH3)3Si((CH3)3Sn)C=C(B(C2H5)2)C2H.iU
((CH3)3Si)2C=C(B(C2H5)2)C2H5 ( (CH3)3Si)2C=CHSi(CH3)3 ((CH3)~Sn)2C=C(B(C2H5)2)c2HS
'J(CC)
Ref.
172 k 1 154 2r 0.5 115.3 90.0 88.1 84.5 82.4 82.5 80.7 79.5 79.6 78.2 79.0 k 0.5 77 74 72 65.3 62.8 2r 0.5 65.4 56.1 57.2 54.6 54.6 53.2 k 0.5 51.5 50.8 45.3 k 0.5 30.9
105 105 47 114 114 114 114 114 114 114 114 114 105 93 93 93 114 105 114 120 120 106 106 105 106 106 105 106
"Silyl and ethyl substituents trans.
The data obtained for cis and trans 1,2-dihalogenoethene~~~"~~~ and for cis and trans l-trimethylsilyl-l,2-dihalogenoethene~~~~ showed that 'J(CC) couplings in trans compounds are larger than those in cis ones, but the difference diminishes with decreasing electronegativity of halogen, and becomes negligible for iodine substituent. In l-trimethylsilyl-2halogenosubstituted and in 1-trimethylsilyl-2-alkylsubstituted compounds the opposite trend is ~ b s e r v e d ; "the ~ couplings in cis compounds are greater than those in trans ones. The data available in the literature indicate that cis dihalogenosubstituted ethenes are more stable than trans ones, but the difference, AE, decreases in order 1,2-difluoro- (3.9 kJ/mole), 1,Zdichloro(2.7 kJimole), 1,2-dibromo- (1.3 kJ/mole) ethene and is close to zero for
ONE-BOND 13C-'3CSPIN-SPIN COUPLING CONSTANTS
151
1,2-diiodoethene~.'~~~~~~ No theoretical justification could be offered for the observed relationship between A'J(CC) and AE. Since, however, 'J(CC) coupling constants depend on the contributions of the s electrons to the corresponding bonding orbitals, the parallel decrease in A'J(CC)s and AEs can be tentatively associated with the s-electron densities at the bonding orbitals of the cis and trans isomers. It can be also concluded that, by analogy, the larger 'J(CC) value indicates the more stable isomer when two analogous compounds are compared. An influence of strongly electronegative substituents in the P position to the CC bond is considerably smaller than that of a-substituent. Moreover, as the studies performed by Krivdin et ~ 1 . ~ for ' a series of substituted acetylenes showed, no simple correlation exists between the nature of the P-substituent and its influence on the 'J(CC) coupling concerned. An average increase of 3 to 5 Hz in 'J(CC) is observed upon the introduction of one chlorine or bromine atom, but a decrease of similar magnitude is found when hydroxy or phenoxy groups are introduced. A small but systematic decrease in 'J(CC) has been observed upon the introduction of subsequent P-methyl groups in the alkyl substituent in triethylsilyl acetyleneslo2 (Et3SiC= CAlk), but no analogous regularity is revealed by t-butylacetylenes (t-BuCECAlk) (see Table 11). Particular attention is invited by the results obtained by Lambert and Singer,13' who measured the 'J(CC) couplings for a series of the benzyl derivatives of the type X-C6H4CH2M(CH3)3 (M = Sn, Ge, Si, C and X = H, Me, OCH3, CN) (Table 18). The 'J(CipsoCH2) couplings in these compounds decrease in order Sn > Ge > Si > C (ca. 43 Hz, ca. 43 Hz, ca. 41 Hz, 36 Hz, respectively). This result has been invoked by the authors as evidence for the presence of hyperconjugation in the neutral ground state in agreement with the double-bond, no-bond valence structure: X--CgHd=CH2 +M(CH3)3 However, among the results reported, those obtained for XC6H4CH2C(CH3)3draw attention. All previously reported 'J(CC) couplings for analogous compounds are in the range 43 to 45Hz: PhCH3 (44.2 H z ) , ~ PhC2H5 (45.5 H z ) , ~ PhCH(CH3)2 (43.3 H z ) , ~ PhC(CH,), (43.3 Hz) .5 This includes 'J(CipsoCHz) coupling in PhCH2CH(CH3)2 (43.5 Hz) (measured in our laboratory). Therefore, the values of 36 Hz found by Lambert and Singer for the series XC6H4CH2C(CH3)3(X = H, OMe, Me, NO2) seem to be rather improbable and obviously require re-investigation. The decrease of these couplings by comparison with all others is even less understandable in the light of the authors' statement'37 that the CHZC(CH3), group does not hyperconjugate while the other three, i.e. CH2Si(CH3)3, CH2Ge(CH3)3 and CH2Sn(CH3)3, where the rather typical 'J(CC) values are observed, do. See also "Note added in proof" on p. 221.
Table 16. One-bond CC coupling constants across single bonds; all values are in hertz.
Compound
'J(CC) Ref. Compound
Csp3Csp2bonds CH3CH=CH2 CH3CH=CHCHO CH3COCH2CH2CH=CH2 HOCH2CH=CH2 CH3CCl=CHp CH3CCl=CC12
'J(CC) Ref.
22.9 28.4 31.7 32.8 33.0 33.1 33.8 37.6 38.2
109 109 6 124 97 97 97 69 123
CH3CHOHCH20H HOCH2CH(OH)2 (CH3)3CF CC13CH3 CF3CD3 CF3CH3 CF3(CH2)30H CF3CBr3 CF3CC13
41.3 48.7 40.3 42.7 60.5 60.5 60.3 73.0 85.0
69 69 109 104 104 104 104 104 104
41.9 41.2 41.2 45.4 48.5 50.3
5 125 125 41 29 115
ClCH2CCl=CC12 C12CHCCl=CC12 C13CCCl=CC12 CF&H=CHZ CF,CCl=CCICF3
55.2 60.8 68.6 75.7 74.4
115 115 115 104 104
Csp3C(0) bonds CH3C(0)CH2Ra CH3C(0)CH2Ra CH3C(O)CH3 CH3C(0)ONa CH$(O)Cl CHSC(0)OH CH3(CH2)13C(O)ONa CF3C(0)CF3 CF&(O)OH CF3C(O)CI
38.6'." 125 40.4'~~ 125 40.44 5 +54' 126 56.1 5 56.7 5 +58 126 82.4 104 103.4 104 105.6 104
CH3COCH(CH3)C02GH5 56.6 CH3COC(CH3)2C02CH3 56.8 C H ~ C H O H C H ~ C O ~ C ~ H57.0 S C6HsCH2C02CH3 57.8 BrCH2CH2C02CH3 58.3 C H ~ C O C H ~ C O ~ C ~ H S 59.0 CH3C02CH3 59.8 59.7 CH3COC2HS 60.9 CH3CH(OH)C02C2HS NCCH2C02C2H.j 61.4 62.2 HSCH2C02CH3 CH3CHBrC02C2HS 64.4 ClCH2C02CzHs 64.7 BrCH2C02C2H5 65.0
127 127 127 127 127 127 127 127 127 127 127 127 127 127
Csp3Crp bonds CF3-C-CCF3 BrCH2-C=CH ClCH,-C=CH HOCH,-C=CH CH~-C=COC~HS CH3-C=CN(C2H5)2 CH3- C=CSi(CH3)3 CH3-C=CSi(C2Hs)3 CH3-CzCSn(CH3)3 CH3-C-CPb(CH3)3
133.9 78.0 77.5 71.5 74.8 70.0 63.5 63.2 62.2 59.0
(CH3)3C-C=CCl 68.5 (CH3)3C-C=CCZHS 68.3 ( C H ~ ) ~ C C E C - C H ~ C H ~ 68.0 (CH~)~C-CGCSCH~ 67.1 (CH&C-C=CBr 67.0 (CH3),CC=CCH=CHCO,Et 67.0 (CH3)3C-C=Cl 65.1 (CH3)3C-C-CSi( CH& 62.0 61.8 (CH3)3C-C-CSi(C2H5)3 (CH3)3C-C-CGe(CH3)3 62.5 (CH&C- C-CSn( C2H5)3 61.4 (CH3)zCH- C=CSi(C ~ H S ) ~62.1 CH3CH2-CZCSi(C2H& 62.3
129 45 45 91 45 93 45 45 45 129 129 45 45
104 128 128 128 96 96 45 45 96 96
ONE-BOND I3C-l3C SPIN-SPIN COUPLING CONSTANTS
153
Table 16-contd. Compound
Csp2Cspzbonds (CH3)2NC5H=C4H-C3H=C2H-C'Hd
_
_
'J(CC) Ref.
60.3
130
58.5 73.4 73.7 74.7 76
130 127 127 127 93
~
Csp2Csp bonds (CH3)3CC=C-CH=CHCO&HS (CH~)~CCEC-CH=CHCN
CspCsp bonds (CzHS),SiC=C-C=CSi(C2Hs)3 (CZH,)~G~C=C-C=CG~(C~H~)~
92 93
93 93
127.7 119.3 126.2 123.0
131 131 131 131
137.2 137.7
75 100
"R = CH2CH=CH2. bFor the C(0)CH2 fragment. "J(ClC2) = 69.5 Hz, 'J(C3C4) = 35.6 Hz. dFor the CH,C(O) fragment. 'Measured in the solid state. flJ(C2C3) = 66.0 Hz, 'J(C4CS) = 71.8 Hz.
5. ONE-BOND CC SPINSPIN COUPLING CONSTANTS IN DERIVATIVES OF BENZENE
As was shown for substituted acetylenes and ethylenes, the changes effected by substituents on 'J(CC) magnitudes dramatically exceed those caused by a change in the formal hybridization of the coupled nuclei. Also in substituted benzenes the influence of substituents upon 'J(CC) is very strong (Tables 19-23). The 'J(ClC2) coupling of 29.5Hz (in Et20)136 and 27.8Hz (in THF)138 was found for phenyllithium, which is the smallest one-bond CC coupling determined so far for derivatives of (Table 19). A somewhat larger 'J(CC) value of 34.7 Hz (in THF) and 36.1 Hz (in Et,O) was observed in phenylmagnesium bromide. 136~139The largest coupling of 82.3 Hz was found in 1,2-difluorosubstituted benzene across the C1C2
154
K . KAMIENSKA-TRELA
Table 17. One-bond CC spin-spin couplings across Csp2(arom)Csp3, Csp2(arom)Csp2and Csp2(arom)Csp bonds in derivatives of benzene; data for substituent at C1. All values are in hertz.
Substituents at carbon X c1 CH3 CH2N02 CH2N02 CH3
c2
c3
C4
C5
C6
NO2 NO2 H H
H H NO2 H
H H H CN
H H H H
H H H H
'J(Csp2(arom)Csp3) Ref. 44.1 50.1 47.4 43.4
132 132 132 133
'J(Csp2(arom)Csp2 CH=CHC02Ettrans
CHO CHO COOH COOH COOCH3 COOCH3 COOCH3 COOCH, COOCH, COOCH, COOCH3 COOCH3 COOCH3 COOCZHS COOC2HS COOCH3 N(CH312 COOCH, COOCH, COOCH3 COOCH, COOCH3 COOCH3 COOCH3 COOCH3 COOCH3 COOH COOH COF COF COF
H-
56
CH3
H
H H H NO2 H H H H H H H H H H H H H H H H H H H H H H H H H H H
H H H H H H H H H H H H H H H H H CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3 H H H H H
52.0 50.5 73.6 74.3 74.5 75.0 74.8 74.7 74.7 75.6 75.7 76.4 77.2 77.1 77.9 78.1 78.5 73.4 74.1 73.7 74.3 74.6 74.7 75.8 76.4 76.7 71.9 72.0 80.6 80.8 81.6
93
132 132 132 132 134 134 134 134 134 134 134 134 134 127 127 134 134 134 134 134 134 134 134 134 134 134 135 135 135 135 135
155
ONE-BOND 13C-13CSPIN-SPIN COUPLING CONSTANTS
Table 17-continued 'J( Csp2(arorn)Csp(N)) H H H H H H H H H H H
CN CN CN CN CN CN CN CN CN CN CN
H NO2 OCH3 H CH3 H
NO2 H H H H OCH3 H H H H CF3
c1
Br F CF3 H
H H H H H H H H H H H
H H H H H H H H H H H
83.9 82.0 83.7 80.3 81.5 80.6 84.0 83.1 83.0 80.8 82.6
136 136 133 133 133 133 133 133 133 133 133
-
'J( Csp2(arorn)Csp) Compound
'J
Ref.
Compound
Table 18. One-bond spin-spin couplings across ~ U ~ U - X - C & I ~ - C H ~ M ( CallHvalues ~ ) ~ ; in hertz.'37 Substituents
'J(CC)
X
M
Me0 Me0 Me0 Me0 Me Me Me Me
C Si Ge Sn C Si Ge Sn
36.0 41.5 43.2 43.5 36.0 41.1 42.7 43.0
'J
Ref.
Csp3Csp2(arorn) bonds
Substituents
'J(CC)
x
M
H H H H CN CN NO2
C Si Ge Sn Si Sn C
"43.8 Hz (measured in our laboratory, see Note added in proof). b42.6 Hz (measured in our laboratory, see Note added in proof).
36.0" 40.9 42.5 42.8 40.3 40.4 36.Ob
in
156
K. KAMIENSKA-TRELA
b ~ n d . ' ~ ~ Ne , ' ~xt' to it are the C1C2 couplings in l-fluoro-2-nitrobenzene, l-fluoro-2-methoxybenzene, 1-methoxy-2-nitrobenzene and l-fluoro-2bromobenzene, where the corresponding 'J(ClC2) values are 80.2 Hz, 79.7 Hz, 77.6 Hz and 77.4 Hz136 (Table 20). The influence of substituents in substituted benzenes is limited practically to the couplings across Cipso-Cortho bonds. This close-range character is typical of inductive effects which are assumed to be concerned with an appropriate redistribution of s-electron densities. This was observed for the first time by Wray et a/." for monosubstituted benzenes and by others for multisubstituted aromatic rings.' The most illustrative example of this phenomenon is provided by 4-fluorophenylmagnesium iodide'36 in which the effects produced by the substituents are of a similar magnitude but of the opposite sign, negative for the MgI substituent and positive for fluorine. As a consequence, three very different 'J(CC) values are found in this small molecule. These are 37.0 Hz, 52.0 Hz, and 70.4 Hz (see below and Table 21):
Q
37.0 Hz
52.0 Hz
70.4 Hz
F The results obtained for Li and MgBr (or MgI) derivatives extend considerably the region covered by 'J(CC)s (over 50 Hz), which allows one a reliable estimate of the influence of substituent electronegativity upon the parameter concerned. As can be seen from Fig. 5 , the relationship is evidently non-linear: 136 'J(CC)
=
30.57
+ 29.82 In Ex
(5) It should be stressed that no particular meaning can be assigned to this form of relationship; the important feature is its strong non-linearity . This contradicts some reports in the literature where the linear relationship for ' J ( CC) vs. Ex was suggested for benzene derivatives. 14c-142 H owever, the 'J(CC) range discussed in these references was rather narrow, i.e. of ca. 25 Hz only. It should also be mentioned that a correlation of 'J(CC) couplings with the bond polarity index in benzenes has been investigated by Reed and Allen,'43 but no meaningful relationship has been found by these authors.
157
ONE-BOND I3C-l3C SPIN-SPIN COUPLING CONSTANTS
Table 19. One-bond CC couplings in rnonosubstituted benzenes (in hertz).
~~
~
~
Compound Substituent Solvent Concentration 'J(ClC2) 'J(C2C3) 'J(C3C4) Ref. no.
'J(CC) in phenyllithiurn (27) and phenylrnagnesiurn bromide Et20 Saturated 29.5 27 Li 27.8 27 Li THF -a 28 MgBr Et20 1.00 M 36.1 28 MgBr Et20 2.00 M 35.3 28 MgBr THF 1.00 M 34.7 'J(CC) in silyl and boryl substituted benzenes (29-33) 49.5 H3Si 29 49.2 30 Ph2(H2C=CH)Si 31 Ph2(2'-CH3-c-C3H2)Si 48.8 32 Ph2(2'-C5Hll-c-C3H2)Si 48.6 33 BH2 48.4
(28) 51.4 50.3 52.0 52.3 51.9
55.8 56.0 56.0 56.0 55.9
136 138 136 136 136
54.7 54.7 54.8 55.0
55.4 55.6 55.4 55.4 -a
71 119 119 119 144
57.5
56.0
145
-a
'J(CC) in benzyl bromide, C6H5CH2Br(34)
34
58.6
aNot reported.
The low value of 'J(CC) in phenyllithium (29.5 Hz) was attributed by von Schleyer and c o - ~ o r k e r s ~ ~to* ,a' ~shortening ~ of the Cipso-Cortho bond accompanied by the contraction of the ips0 angle when compared with the remaining phenyl derivatives. The changes observed were interpreted by the authors in terms of re-hybridization which occurred at the carbon atom involved upon substitution. 6. ONE-BOND CC COUPLING CONSTANTS IN HETEROAROMATIC SYSTEMS
The data published for heteroaromatic systems during the period reviewed include a collection of the couplings for unsubstituted five-membered heteroaromatic ring systems measured by Witanowski and Biedrzycka14' (Table 24), a large set of 'J(CC) couplings measured by Gronovitz et al. 148,349 for thieno[c]quinolines and thieno[c]isoquinolines'48 (Table 25) (Table 26) and some new data for indole and dithien~[b,d]pyridines'~~ derivative^'^^^'^^ (Table 27).
158 1
N
I
K . KAMIENSKA-TRELA
75 7
1 1
N
0 I
65
7
-0 7
-0
c
55
0
n I
a,
6
45
35
25
I 0.5
I
I
I
I
I
I
1
1.o
1.5
2.0
2.5
3.0
3.5
4.0
Pa uli ng 's e l e c t r o n e ga t ivi t y of subs t it uen t Fig. 5. The 'J(CC) vs. Ex relationship in monosubstituted benzenes. The Pauling electronegativities Ex of the first atom of substituent are taken from R. McWeeny, Coulson's Valence, p. 163, Oxford University Press, London, 1979. (Reprinted with permission from ref. 136.)
Table 20. One-bond CC spin-spin coupling constants in ortho and meta disubstituted benzenes; substituent X at C1; all values in hertz.
Substituents
x ortho F F F OCH3 F OCH3 NO2 OH NO2 CH3 MgI
'J(CC)
Y
CIC2
C2C3
C3C4
F OCH3
82.3 79.7 80.2 77.6 77.4 75.2 73.0 71.8 67.6 67.0
72.3 67.5 67.4 66.3 64.6 66.2 60.7 67.4 58.7 68.2 54.4
57.2 57.7 56.8 57.8 56.0 55.0 54.7 58.6 55.9 56.9 56.3
NO2 NO2 Br Br I NO2 CHO NO2 CH3
-a
C4C5
C5C6
C6C1 Ref.
-
55.7 55.0 55.5 56.5 56.0 55.2 53.8 56.3
57.2 56.7 56.9 57.9 57.5 58.0 57.3 58.7 56.3
72.3 73.7 71.7 66.2 71.7 66.3 66.2 67.5 67.7
56.4
51.6
38.0
-'
-a
-a
136 136 136 136 136 136 136 132 132 132 136
ONE-BOND I3C-l3C SPIN-SPIN COUPLING CONSTANTS
159
Table Zkontinued Substituents X
J( CC) Y
NO2 CN NO2 NO2 Br Br I CH2N02
C1C2
C2C3
C3C4
C4C5
C5C6
C6C1
Ref.
73.5 70.1 70.1 69.4 67.0 68.8 66.5 68
69.9 62.4 70.1 69.4 66.9 65.1 62.6 56
67.2 59.5 67.8 68.0 64.3 63.2 60.1 56
57.0 57.1 55.6 56.8 55.6 55.0 54.5 56.6
58.3 56.0 55.6 58.4 58.7 57.2 56.6 62.1
71.0 67.6 67.8 66.9 67.5 68.1 67.6 68
136 136 132 136 136 132 136 132
“Not determined.
Table 21. One-bond CC spin-spin coupling constants in para-substituted benzenes; substituent X at C1; all values in hertz. Substituents
X
‘J(CC)
Y
F F F F OCH3 OCH3 NO2 NO2 COCH3 CH2N02 OCH3 OCH3 OCH3 OCH3 CH3 CH3 CH3 CH3 CN CN “Not determined.
ClC2/ClC6 72.5 72.1 70.9 70.4 68.0 66.2 67.9 68.3 58.1 59.1 67.6 67.6 67.6 67.6 56.9 57.3 57.3 57.3 60.3 60.8
C2C3/C5C6
C3C4K4C5
Ref.
-a
72.5 62.0 67.9 37.0 65.0 68.1 60.7 68.3 67.5 67.9 57.0 57.0 57.3 57.3 56.4 56.8 56.8 56.8 55.9 55.9
136 136 136 136 136 136 136 132 132 132 137 137 137 137 137 137 137 137 137 137
55.9 59.1 52.0 57.6 54.3 57.3 -
56.6 56.8 58.0 58.6 58.6 58.7 56.6 57.2 57.2 57.2 58.0 58.0
160
K. KAMIENSKA-TRELA
Table 22. One-bond CC spin-spin coupling constants in multisubstituted benzenes; all values are in hertz. ~~~~
~
Substituent at carbon
c1
C2
NO2 NO2 NO2 c1 NO2 COOH H NO2 OH NO2 H
CHO OH F
Coupled nuclei
C3
C4
C5
C6
C1C2 C2C3 C3C4 C4C5 C5C6 C6C1 Ref.
H H H H NO2 NO2 NO2
NO2 NO:, NO2 NO:, H H H
H H H H NO2 NO2 NO:,
H H H H H H H
69.3 70.6 70.6 68.9 72.4 72.1 72.1 66.2 80.6 71.1 72.1 67.8 -a 71.3 70.3 69.4 60.2 69.3 70.5 70.5 77.0 77.0 72.7 71.7 70.5 70.5 70.5 70.5
54.3 59.7 132 60.5 67.6 132 58.4 72.1 132 57.3 68.7 132 69.3 60.2 132 71.7 72.7 132 70.5 70.5 132
"Not determined.
Table 23. One-bond CC couplings in trans and cis '3C-labelled azobenzenes; all values are in hertz. 14'
q
N=N
NEN
db
3 43
(
trans
cis
'J(ClC2) ~
~
'J(C2C3)
'J(C3C4)
~~
[ 1,1'-13c2]trans [4,4'- I3C2]trans [2,2',6,6'-I3C4]trans 4,4'-dichlor0[4,4'-'~C:,] trans 4,4'-diiodo[4,4-13C2]trans
-
56
-
65 61 58
2,2'-dirnethoxy[4,4'-l3C2] trans [ I , I ' - ' ~ c ~cis ]
-
[4,4'-''C2] cis 4,4'-diiod0[4,4'-'~C~] cis
52 61
The compounds studied by Witanowski et al. 147 represent all relevant diazole, triazole, oxazole, oxadiazole, thiazole and thiadiazole systems. The couplings measured for them show a clear distinction between carbon-carbon bonds which are formally double and single, respectively. Those across the formally single C3-C4 bonds vary from 45.6 to 52.2Hz, whereas the couplings across the double bonds range from 58.9 to 70.7 Hz.
ONE-BOND I3C-l3C SPIN-SPIN COUPLING CONSTANTS
161
This is at variance with the situation in pyridine where both couplings in question are of almost the same value, 'J(C2C3) = 54.3Hz and 'J(C3C4) = 53.7 Hz.lS2It is of interest to note that these values lie almost in the centre of the gap between the two subranges mentioned above. The authors attempted to correlate the obtained 'J(CC) values with the corresponding bond lengths but in spite of some apparent trends no general correlation has emerged. This is in agreement with the observation made recently by Kamienska-Trela et al. lS3 for 9aH-quinolizine-l,2,3,4tetracarboxylate and some of its alkyl derivatives. A multivariate principal components data analysis has been applied by Gronovitz et al. 149 in order to estimate 'J(CC) in dithieno[b,d]pyridines from shift data, the azomethine C-H coupling constant and MNDO bond orders, and the calculated values have been compared with experimental ones. Good results have been obtained for the couplings of the pyridine subunit. It is of interest, however, that the last parameter gave only a minor contribution to the coupling variability.
7. ONE-BOND CC COUPLINGS IN SUBSTITUTED ALIPHATIC CYCLIC AND HETEROCYCLIC SYSTEMS
7.1. Three-membered ring compounds
One-bond CC spin-spin couplings in substituted aliphatic cyclic compounds deserve a special attention. Among them those in substituted cyclopropanes and cyclopropenes are of special interest. A set of coupling constants for a series of 1,l-dihalogeno-2-alkoxysubstitutedcyclopropanes has been recently reported by Krivdin et ~ 1 . ' and ~ the data for lithium-substituted compounds have been published by Seebach and co-workers'" (Table 28). The for 2,3,3-triphenylcouplings measured by Krivdin et cyclopropene-l-carboaldehyde represent the first set of 'J(CC) couplings measured for substituted cyclopropene (Table 29). The data for a few silyl-substituted cyclopropenes have been obtained by Jankowski et a/. l9 In all these compounds the couplings across the endo-cyclic bonds are substantially smaller, whereas the couplings across the exo-bonds are much greater than the corresponding couplings in analogously substituted openchain compounds. The 'J(CC) couplings collected for substituted cyclopropanes in Table 28 vary from 16.55 Hz in 1,l-dichlorocyclopropane (85),76 to < 0.5 Hz in l-phenyl-2-lithiocyclopropane(72).Is' Thus, the range covered by these couplings is quite large. However, out of the substituents involved only Li exerts the strong influence of ca. 12 Hz on the magnitude of 'J(CC) in these compounds. As a consequence, the value of 'J(CC) across the bond with the
'
162
K. KAMIENSKA-TRELA
Table 24. One-bond I3C-l3C coupling constants (in hertz) in five-membered heteroaromatic systems. 4
50 0 3
2
F 0 N
36
35
0
37
38
F N N
N
1h3
0
p
S
41
42
46
47
43
N S’
44
45
CH,
48
CH,
7-7 49
Compounds 35 Furan 36 1,2-0xazole (isoxazole) 37 1,3-oxazole
38 1,2,5-oxadiazole (furazan) 39 1-Me-pyrrole 40 1-Me-pyrazole 41 1-Me-imidazole 42 1-Me-1,2,5-triazole 43 l-Me-1,2,3-triazole 44 Thiophene 45 1,2-thiazole 46 1,3-thiazole 47 1,2,5-thiadiazole 48 1,2,3-thiadiazole 49 4,5-dimethylfuroxan 50 4,5-diethylfuroxan “Not determined.
50
IJ(3,4)
‘J(2,3)
Ref.
-a
69.1 67.7 70.7
9 147 147 146 9 147 147 147 147 9 147 147 147 147 154 154
48.7 -
45.6
-
51.5
66.3 64.6 66.5
-a -
51.6
-
-
64.5 64.2 62.2 61.1
-a
52.5 -
48.1
-
-
58.9
63.0 62.0
ONE-BOND l3C-I3C SPIN-SPIN COUPLING CONSTANTS
163
Table 25. One-bond CC spin-spin coupling constants (in hertz) in thieno[c]quinolines and thieno[c]isoquinolines. Reprinted from ref. 148 by permission of John Wiley & Sons Ltd.
51
54
Carbons coupled
Cl,C9b c1,a C2,C3 C3,C3a C3a,C9b C3a,C4 C5,CSa C5a,C9a C5a,C6 C6,C7 C7,C8 C8,C9 C9,C9a C9a,C9b
53
52
55
56
Positions of nitrogen and sulphur atoms (compound no.) N5,S3
N5,S2
N5,Sl
N4,S3
N4,S2
N4,Sl
58.9 65.3
67.7
-
60.6 64.6
68.8
-
-
55.1 57.9 -
55.1 65.5 58.7 53.4 59.9 58.4" 57.6
-
65.2 52.1 52.9
-
56.3 66.8 57.4 54.5 58.8 58.5" 57.1
"Calculated from the inner lines only.
65.9 58.4 54.8 54.9 -
54.5 65.7 58.8 53.3 60.4 57.7 60.9
-
59.7
76.8 55.3
66.6 67.3 58.3
-
-
55.0 53.7 56.9 59.6 53.5 59.7 56.7 58.1
52.3 54.5 58.1 58.2 54.6 58.6 58.6 57.3
54.4 53.9 57.1 59.6 53.5 60.1 57.7 61.6
-
-
164
K. KAMIENSKA-TRELA
Table 26. One-bond CC couplings in dithieno[b,d]pyridines (in hertz).'49
59
58
57
62
61
60
63
rn
64
65
Position of S atoms (compound no.)
Coupling
c1c2 ClC8b C2C3 C3C3a C3aC8b C5C2a C5aC6 C5aC8a C6C7 C7C8 C8C8a C8aC8b
1,6
3,6
1,8
3,8
2,6
1,7
2,8
3,7
2,7
(57)
(58)
(59)
(60)
(61)
(62)
(63)
(64)
(65)
-
64.8 60.2
-
65.3 61.1
-
-
-
-
68.5
-
69.9
64.3 61.1
60.9
-
67.9 67.2 56.1 61.2
57.0 62.2
54.1
57.5
-
-
65.8 59.2 69.9
-
-
-
65.5 58.3 58.2
68.2 62.2 55.2 58.1 58.2 53.0 66.8
57.5 58.7 58.3 53.7 66.9
-
-
-
-
-
-
68.5
69.9
"Calculated from the inner lines only
-
76.4 54.4 58.5
-
56.5
-
64.6 59.4 59.7
66.6 67.9 59.5 55.0 64.6 53.3"
-
68.7 63.8
-
76.5 53.9 55.1 58.7 56.3 67.7 -
63.2
-
61.1 55.7 64.8 51.6
-
77.5 54.7 53.7 65.6 -
-
-
67.3 60.3
68.8 59.9
ONE-BOND I3C-l3C SPIN-SPIN COUPLING CONSTANTS
165
Table 27. (a) One-bond CC spin-spin couplings (in hertz) in dimethyl l-acetyl-6hydroxy-4,5-indoledicarboxylate(66).150 COOCH, I
COCH,
'J(C2C3)
'J(C3C9)
'J(C5C6)
'J(C6C7)
'J(C7C8)
'J(C8C9)
71.5
55.9
69.5
67.7
62.4
54.3
'J(C4C9) 53.5
'J(C4COO) 'J(C5COO) 74.4
75.1
(b) One-bond CC spin-spin couplings (in hertz) in tryptophane (67).15' COOH
H H O
'J(C2C3)
'J(C3C9)
'J(C3C10)
70.3
55.8
48.4
lithium substituent attached is close to zero (< 0.5 Hz). An influence of the remaining substituents, including the strongly electronegative ones, such as OAlk, CI and Br, is of few hertz only, and clearly non-additive. Small 'J(CC) values in derivatives of cyclopropane and their rather weak and non-typical sensitivity towards substitution can be explained in terms of small contribution of the s electrons to the orbitals forming a CC bond in the cyclopropane ring. This explanation is in accord with the theoretical results of Eckert-Maksic and M a k ~ i c who l ~ ~ calculated the following hybridization indices for unsubstituted cyclopropane:
n
C-C 3.69-3.69; C-H 2.49
166
K. KAMIENSKA-TRELA
Table 28. One-bond CC coupling constants in substituted cyclopropanes: all values are in hertz. 3
Substituents Compound no. 68 69
X
Y
H H Sesquiterpene globulol"
70 71 72 73 74 75 76 77 78 79
H C6H5 C6HS COOH H C6H5 C(CH,)=NOH C6HS
Z H
CH3 Br H H COOH Br H Br H
OC2Hs
c1
CH3 Li Li H COOH H H Br H
80
O(CH&CH3
Cl
c1
81
OCH(CH3)z
C1
c1
82
O(CH&CH3
C1
c1
c1
c1
83
c1
84
c1
85
H
c1
c1
Coupled nuclei
'J(CC)
Ref.
12.4 14.6 14.6 15.8 <0.5 <0.5 9.8 9.55 12 12.4 13 13.9 15.8 15.9 14.1 15.9 15.7 14.1 15.7 15.8 13.9 15.8 15.8 13.8 15.8 15.8 16.0 16.2 13.4 16.55
62 159 159 158 155 155 158 158 155 50 155 76 50
c1c2 C2C3 c3c4 c1c2 c1c2 c1c2 c1c2 c1c2 c1c2
c1c2 c1c2 c1c2 c1c2 C1C3 C2C3 ClC2 ClC3 C2C3 ClC2 ClC3 C2C3 c1c2 ClC3 C2C3 c1c2 C1C3 c1c2 C1C3 C2C3 c1c2
"Formula and remaining 'J(CC) couplings are given at the end of this section.
50
50 50
50 50 76
ONE-BOND 13C-13C SPIN-SPIN COUPLING CONSTANTS
167
Table 29. 'J(CC) couplings in silyl-substituted cyclopropenes (31, 32, 86) and in 2,3,3-tri-phenylcyclopropene-l-carboaldehyde (87); for a comparison also 'J(CSi) and 'J(CH) couplings measured for silyl compounds are included. All values are in hertz.
Rl = CH3 Rl = C5Hll R1 = CH3 R1 = CHO
31 32 86 87
R2 = R2 = R2 = R2 =
SiPh3 R3 = R4 = H SiPh3 R3 = R4 = H SiMe3 R3 = H R4 = CH20CPh3 R3 = R4 = Ph
Compound 'J(ClC2) 'J(ClC3) 'J(C2C3) 'J(ClC4) no. ~
'J(C3H)
Ref.
~
86
50.0 49.9 49.0
11.0 11.8 12.8
<3 (3 <3
54.9 55.0 55.8
87
48.8
32.0
33.5
85.2
31 32
'J(C2Si)
119 89.5 167.0 89.6 167.0 119 119 78.0 n.m. 'J(C2Cipso) 'J(C3Cipso) 80.3 58.4 50 156
The data collected in Table 29 for silyl-substituted cyclopropenes reveal that also in this group of the compounds the ring closure exerts a considerable influence on all the 'J values, but these changes are not equally distributed. Cis-1-Trimethylsilyloctene-1(TMSO) may serve as a good
reference compound in this respect. While the coupling across the double bond in all three silyl-substituted cyclopropenes of ca. 50Hz is only moderately smaller, by ca. 12 Hz, than that in TMSO (61.4 Hz,l19 Table 14), the couplings across the single bonds are greatly lowered. Thus, 'J(CC) of ca. 12Hz only has been found for the C1C3 bond bearing an alkyl substituent (42.0Hz in TMSO). The coupling across the C2C3 bond which bears a silyl substituent has not been observed at all, and is most probably close to zero (at least smaller than 3 Hz). The couplings across the exocyclic CH, CC and CSi bonds are, on the other hand, substantially larger than the corresponding couplings in ethenes and ethanes. Thus, 'J(C3-H) of 167 Hz was found in compounds 31 and 32 (125.6Hz in p r ~ p e n e ' ~ )'J(Cl-C4) , of
168
K. KAMIENSKA-TRELA
ca. 55 Hz in all three compounds (42.0 Hz in TMSO) and 'J(C2-Si) of 89.5 Hz in 31 and 32 and of 78.0 Hz in 86 (66.3 Hz in TMSO). 'J(ClC3) = 11 .O Hz
'J(C2C3) < 3 Hz
SiPh3
H3C 31
'J(ClC2) = 50.0 Hz
It is of interest to note that there is quite a good agreement between these experimental data and the ab initio 'J(CC) values published recently by Fronzoni and G a l a s ~ oand , ~ ~Barszczewicz et ~ 1 . ~ for ' unsubstituted cyclopropene if the influence of a silyl substituent is taken into account. It has been shown by both groups of authors that the 'J(CC) couplings are dominated by the Fermi contact contribution, while the orbital-dipole (OD) and spin-dipolar (SD) contributions, which are related to the density of p-electrons, play a minor role. This is a significant observation since it allows one to interpret the experimental 'J(CC) values in terms of changes of the s-characters of the carbon orbitals involved. Thus, the small 'J(ClC3) and 'J(C2C3) coupling constants indicate that there is a large contribution of p-electrons to the C1C2 and C2C3 bonds. The large couplings across the exocyclic bonds, on the other hand, should be interpreted as favouring a large contribution of s-electrons to these bonds. This is in agreement, as in the case of cyclopropane, with the data of Eckert-Maksic et ~ l . , ' ~ ~ who calculated the following hybridization indices for unsubstituted cyclopropene: 1
2
A,
Cl-C2 (3.68-2.65), C2=C2 (1.88-1.88), C1-H (2.49) and C2-H (1.64). The above interpretation is confirmed by the behaviour of cyclopropenes and cyclopropanes in numerous chemical reactions. However, in the case of these compounds an alternative interpretation can be offered for the observed low 'J(CC) values. Thus, it is now well accepted that in such cases when more than one coupling pathway is possible, the resulting coupling constant is the algebraic sum of the expected J values for the pathways that contribute to the coupling constant in question. According to this, the J(CC) coupling constant between two adjacent carbon atoms in cyclopropanes and cyclopropenes is the sum of one-bond and two-bond couplings. The latter contribution is assumed to be relatively large and negative,'58 which is reflected in the small 'J(CC) values observed. The oxiranes are representatives of three-membered ring compounds with heteroatom (oxygen) included. A large set of 'J(CC) data has been recently
ONE-BOND l3C-I3C SPIN-SPIN COUPLING CONSTANTS
169
published for this group of compounds by Krivdin et ~ 1 . (Table ' ~ 30). The couplings vary from 25 to 33Hz and are by ca. 10-20Hz larger than the couplings found in cyclopropane (68) itself ( 1 2 . 4 H ~ ) ~and * in 1,ldimethylcyclopropane (70) (14.5 H z ) , ' ~but ~ on the other hand, considerably smaller than, for example, the couplings in the open-chain alcohols (39-41 Hz).'~' An observed increase in 'J(CC) couplings measured in oxiranes by comparison with those observed for cyclopropanes can be, at least in part, interpreted in terms of electronegativity of heteroatom (oxygen) involved. However, as in the case of cyclopropanes, the two-path coupling mechanism should be taken into consideration in oxiranes. 160 One-bond CC couplings of ca. 29 Hz were found across the C1C8 bond in 7-cyano-3-azaoctabisvalene (98) and syn-3,7-diazaoctabisvalene (99) providing an example of 'J(CC) coupling in three-membered ring with a nitrogen atom involved'62 (Table 31). 7.2. Four-membered ring compounds
Very few data have been published recently for the 'J(CC) couplings in four-membered ring compounds. In the paper by Buddrus et ~ 1 . the ' ~ ~ 'J(CC) couplings have been measured for two products of photodimerization of maleic acid anhydride and of 2-chloroindene, respectively, both of which involve the cyclobutane ring. The couplings of ca. 30 Hz typical of the couplings across endo-cyclic bonds in four-membered rings were found in both compounds (see below):
' CO,CH, 11
A
CO,CH,
2
100
3 1 CO,CH,
'J(ClC2) = 'J(C2C3) = 29.8 Hz; 'J(ClC7) = 61.3 Hz; 'J(ClC5) = 34.6Hz; 'J(C2C6) = 61.7Hz
'J(ClC2) = 'J(C2C3) = 31.3Hz; 'J(C2C11) = 42.8Hz; 'J(ClC.5) = 38.1 Hz; '(C5C6) = 41.8Hz
170
K. KAMIENSKA-TRELA
Table 30. One-bond CC coupling constants in cyclic oxiranes (in hertz).Im 4
88
3Qt75
c1c5 c1c2 c2c3
30.3 36.5 27.9
C1C6 c1c2 c2c3
31.8 43.1 33.0
C1C7 c1c2 c2c3 c3c4
30.3 43.2 32.1 33.0
c2C8 c1c2 C1C6 C1C7 c2c3 c3c4 c4c5 C5C6
32.7 42.8 31.2 31.1 40.3 31.9 35.5 31.9
C2C9 c1c2 C1C6 C1C7 c2c3 c3c4
31.2 43.1 32.0 32.0 40.4 31.9
C1C6 c4c5
41.7 33.0
C1C7 c4c5
43.1 33.8
0
89
‘k6 3
90 4
b
7
&.)
91
5
4 8
92
6 &
5
9
6
93 5
94
’
Oo 4
ONE-BOND I3C-l3C SPIN-SPIN COUPLING CONSTANTS
171
Table 3O-continued
&/
95
6
96
O
c1c2 C1C7 C1C8
40.5 30.6 31.5
C1C3 ClCll c3c4 c4c5 C5C6 C5C11 C6C7 C9C1 ClOCll
28.0 41.9 41.2 34.4 33.0 32.3 42.1 42.9 35.9
C1C3 ClCll c3c4
27.4 44.5 41.9
4
37
R5
4
12
4
Table 31. One-bond CC couplin constants in 7-cyano-3-azaoctabisvalene(98), and syn-3,7-diazaoctabisvalene(99)16F (in hertz). Compound 98
99
'J(ClC2)
'J(C2C4)
'J(Cl(37)
'J(ClC8)
'J(C8C7)
'J(C7C=N)
56.1
29.8 29.2
22.3
21.5 29.8
16.4
103.8
-
-
-
98 4
7
3 99
8
4
-
172
K. KAMIENSKA-TRELA
7.3. Five-membered ring compounds A series of cyclic derivatives of silicon, germanium and tin have been recently measured by Wrackmeyer and his (Table 32). The 'J(CC) coupling constants have been measured for alkyl-, boryl- and silylsubstituted siloles, germoks and stannoles, and for the related spiro[4.4]1,3,6,8-tetraenes (Table 32). A typical sensitivity towards electronegativity of substituents and upon complexation (see also Section 9) has been observed also in this interesting group of compounds.
7.4. Six-membered ring compounds
Steric effects on 'J(CC) couplings in derivatives of cyclohexane have been recently thoroughly discussed by Krivdin and Kalabin in their review .~ new interesting results published in Progress in N M R S p e c t r o ~ c o p ySome have been obtained since then. One of the most crucial results, which seems to have been overlooked by other authors, has been obtained by Booth and Everett, 168 who measured the CC coupling constants in [ 13C-l-methyl]-cis1,4-dimethylcyclohexane (113a) and its isomer trans (113b) at about 180 K. This allowed them to determine 'J(CC) coupling constants for the equatorial and axial methyl groups separately, 'J(CC) (eq) of 35.40 Hz and 'J(CC) (ax) of 34.64. It is of interest to note that a similar stereospecificity is revealed by 'J(CH) coupling constants. 169 The difference between 'J(CH) (eq) and 'J(CH) (ax) is, as should be expected, about four times greater than that for the relevant 'J(CH) constant, ('J(CH) (eq) = 126.44Hz and 'J(CH) (ax) = 122.44 Hz). Two effects have been invoked by Booth and Everett in order to rationalize the observed data. One of them was a greater electronegativity of the equatorially oriented methyl group, compared with
T =
'J(CC)(ax) = 34.64HZ T =
T = 173 K
1ao K
'J(CC)(eq) = 35.40Hz
300 K
'J(CC)av. = 35.55 HZ
'J(CC) = 35.64 Hz T = 300 K
'J(CC) = 35.89 Hz
ONE-BOND 13C-13C SPIN-SPIN COUPLING CONSTANTS
1
J(C2C2') = 37.6 Hz
cis 1
J(C2C2') = 39.3 Hz
173
'J(C2C2')= 33.8Hz
trans J(C2C2')= 35.3 Hz
the axial one, the other a slight flattening of the ring.'68 The 'J(CC) (eq)'J(CC) (ax) difference considerably increases when a heteroatom or a carbon-heteroatom bond are introduced in the neighbourhood. This was reported for the first time by Barna and Robinson for anancomeric derivatives of cyclohexanone and derivatives of piperidine. 170 A large set of data has been recently reported by Aliev1713172 for variously substituted piperidine-4-ones (Tables 33, 34). The conformation of many of these compounds has been already established by means of other spectral methods. This allowed the author to interpret the 'J(CC) data rather unequivocally and to use them for elucidation of the ratio of conformers in the compounds of the unknown structure. The trans compounds 117 to 119 (Table 33) are conformationally homogeneous and consist of the chair conformer only with a fixed equatorial orientation of both methyl substituents. The couplings across C2C2' and C5C5' bonds in these compounds are consistently larger than the corresponding couplings in all the remaining compounds listed in Table 33. The 'J(C2C2') couplings are of 39.0Hz and those across C5C5' bond of 37.0Hz. The smallest 'J(C2C2') coupling has been found in the cis compound 121, which is supposed to exist almost entirely in the chair form with substituents at carbons 2 and 5 oriented axially and equatorially , respectively. The remaining compounds presented in this table are the mixtures of various conformers whose ratio can be
174
K. KAMIENSKA-TRELA
Table 32. One-bond CC coupling constants (hertz) in organosubstituted h i l a - , and some related compounds. 5-germa and 5-~tannaspiro[4,4]nonatetraenes
102, 103 M = Si 104 M = Sn
105, 106 M = Si 107 M = Ge 108-112 M = Sn
R, = R4 == Rs = R,j = CH3; R2 = H; R3 = C2Hs R I = R4 = Rs = R,j = CH3; R2 = B(C2Hs)z; R3 = C2Hs Rl = R4 = Si(CH&; Rs = R6 = CH3; R2 = B(C2Hs)2; R3 = C2H5 Rl = R4 = R,j = R, = CH3; R2 = R7 = H; R3 = R8 = C2H5 Rl = R4 = R,j = R, = CH3; R2 = R7 = B(C2Hs)Z; R3 = R8 = C2Hs Rl = R4 = R,j = R9 = CH3; R2 = R7 = B(C2HS)Z; R3 = Rs = C2HS Rl = R4 = R6 = R, = Si(CH3)3;R2 = R7 = B(C2H5)2;R3 = RR = C2Hs R, = R4 = R6 = R, = Si(CH3),; R2 = R7 = B(C3H7)2;R3 = R, = C3H7 R1 = R4 = R6 = R9 = Si(CH3),; R2 = R7 = B(i-C3H7)2;R3 = R8 = i-C3H7 R, = R4 = R6 = R9 = Si(CH3)3;R2 = R7 = H; R3 = R8 = C2H5 112 R, = R4 = R6 = R, = n-C3H7; R2 = R7 = B(C,H,),; R3 = RR = C2H5
102 103 104 105 106 107 108 109 110 111
Compound no.
C1C2
C2C3
C3C4
102 103 104 105 106 107 108 109 110 111 112
58.9 52.1 48.9 59.6 52.0 56.6 48.4 49.0 49.5 54.7 56.2
54.1 43.1
61.0 60.1 58.6 60.1 59.5 65.5 58.2 57.8 58.7 55.4 65.1
C1CH2 c3cff2
c4cff2 B(CH2CH3)2 Ref. ~~
-
54.7 47.5 47.4 -
-
49.0
41.6 40.4
41.8 42.2
41.6 40.4
42.1 43.0
41.3 43.1 42.1
42.1 42.1 42.6
-
-
-
-
-
-
34.1 -
34.0 33.7
-
-
-
-
-
-
-
-
42.2
41.8
41.4
33.7
-
-
~
-
-
-
164 164
165 166 166 166 165 165 165 165 167
ONE-BOND 13C-’3C SPIN-SPIN COUPLING CONSTANTS
175
Table 33. One-bond CC couplin constants in cis and trans isomers of N-substituted 2,5-dimethylpiperidine-4-ones. 1 7 8
R
2‘
119 R = CH2CH2CbH5 120 R = CH(CH3)C6H, 121 R = C(CH3)3
116 R = H 117 R = CH3 118 R = CH2C6H5
Coupled nuclei Compound 116 117 118 119 120a 120b 121 116 117 118 119 120a 120b 121
trans trans trans trans trans‘ transb trans cis cis cis cis cis‘ cisd cis
C2C2’
C2C3
c3c4
C4C5
C5C5’
C5C6
38.2 38.9 39.0 39.0 38.5 38.3 37.8 37.9 36.8 36.4 36.4 36.5 36.6 35.5
31.5 33.7 33.6 33.6 34.4 34.0 33.0 31.6 32.9 32.5 32.5 32.4 32.3 32.0
37.9 38.2 38.1 37.8 38.0 37.9 37.5 37.8 37.8 38.1 37.9 38.1 38.0
38.2 37.4 38.1 37.6 37.7 37.8 36.6 37.9 37.4 38.1 38.0 38.0 37.9 37.4
37.5 37.6 37.2 37.4 36.9 36.7 34.7 35.0 36.2 37.1 37.0 37.1 37.2 37.5
31.4 33.4 33.2 33.1 34.0 33.6 35.0 31.5 32.2 32.3 32.3 32.2 32.2 33.5
-e
“Stereoisomer (I’S,2S, 3R), ‘J(C1’CH3) = 36.2 Hz, lJ(C1’Cipso) = 47.6 Hz. ’Stereoisomer (l’S, 2R, 5S), ‘J(C1’CH3) = 39.1 Hz, ‘J(C1’Cipso) = 43.9Hz. “Stereoisomer (l’S, 2 S , 5s);‘J(C1‘CH3) = 37.3 Hz, ‘J(C1’Cipso) = 47.7 Hz. “Stereoisomer (l’S, 2R, 5R) ‘J(Cl’CH,) = 37.4 Hz, lJ(C1’Cipso) = 47.7 Hz. ‘Not determined.
estimated using these border values. Thus, for example, the presence of the twist-boat (2a, 5e) and chair (2a, 5a) conformers has been suggested for compound 121 trans.
2a. 5a
2a, 5e 121 trans
176
K. KAMIENSKA-TRELA
Table 34. One-bond, 'J(CC), couplings in some variously substituted piperidones.17' 0
0
CH,
CH,
122 R = CH,CH,CN
123
R = CH,CH,CN
124
R = CH,CH,COOCH,
____~
Compound no.
C2C2'
C2C3
c3c4
c4c5
C5C5'
C5C6
122 trans 122 cis 123' 124"
38.7 38.4
34.5 34.4 34.7 34.9
31.6 38.4 38.0 38.1
37.7 38.0 38.0 38.1
37.6 34.2
34.9 34.5 33.8 34.0
-
-
"'J(C3C3') 36.1 Hz, and 36.7 Hz in 123 and 124, respectively.
7.5. Large ring and polycondensed cyclic compounds
In this section the results obtained for several large ring and polycondensed compounds have been gathered (Tables 35-38). Out of these, a study of Luttke and c o - w ~ r k e r s ' on ~ ~ 'J(CC) coupling constants in two highly strained molecules, cyclooctyne (125) and 1-sila-4-cycloheptyne (126), deserves a special comment. The 'J(C=C) values found in both compounds (166.0 and 159.4Hz, respectively) are lower than in the corresponding open-chain dialkylacetylenes (174.9 Hz in 4-methylpentyne-2 and 177.0 Hz in 2,2-dimethyl-5-methyl-hexyne-3).The experimental value of 'J(CC) for octyne was compared with those calculated by means of INDO method for
36.5
166.0
7 64.4 32.5 37.2 7 -0.
64.3
32.2
32.4
37.2 125
126
13c-13c SPIN-SPIN
ONE-BOND
COUPLING CONSTANTS
177
Table 35. Carbon-carbon coupling constants, 'J(CC) of tetramethyl 9aHquinolizine-1,2,3,4-tetracarboxylateand its methyl and dimethyl derivative^;'^' all values in hertz. 11
H
COOMe
I
COOMe
HI 127 128 129 130 131 132
14
tetramethyl 9aH-quinolizine-l,2,3,4-tetracarboxylate 9a-methyl 7,9-dimethyl 7,9a-dimethyl 8,9a-dimethyl 9,9a-dimethyl 'J(CC)
Compound no.
C1C2
C2C3
C3C4
C6C7
C7C8
127 128 129 130 131 132
73.7 72.2 73.3 74.7 72.0 72.4
59.1 57.7 58.1 57.9 57.6 58.0
76.5 75.5 73.6 77.2 75.6 75.0
73.7 73.5 77.2 77.6 73.6 73.8
50.5 51.0 51.2 50.6 50.7 52.2
C,Meb 127 128 129 130 131 132
-
36.5 45.3 49.5 44.9 45.6
C,Me" -
45.4 37.2 36.6 38.8
'
C8C9
C9C9a C9aC1
-*
-'
67.5 70.8
44.9 43.5 45.6 45.9 44.6
-'
70.5 71.6
46.7 46.4 46.8 47.8 46.8 45.1
ClClO
C2Cll
C3C12
C4C13
78.2 77.1 78.8 77.7 77.9 76.6
76.4 77.4 75.8
85.2 85.0 85.5 86.1 84.7 83.5
81.5 79.9 79.9 79.7 79.9 81.5
-
(1
77.5 76.5
"Not determined. 'Denotes the 9a-, 7-, 7-, 8- and 9-position of methyl substitution for 128, 129, 130, 131 and 132, respectively. 'Denotes 9-methyl substitution for 129 and 9a-methyl substitution for 130, 131 and 132.
178
K. KAMIENSKA-TRELA
Table 36. One-bond CC coupling constants in [di-'3C]norborn-2-ylderivatives; all values are in hertz.'"
7
Derivative Alcohol Tosylate
Chloride Acetate
Coupled carbons
ex0
endo
C2C3 c1c2 C2C3 c1c2 C2C3 c2c1 c2c3 c1c2 C1C6 C1C7 c3c4 c4c5 C5C6
34.8 35.0 34.1 36.2 31.9 33.6 34.4 36.7 31.9 31.3 31.4 32.3 31.5
35.5 35.4 36.0 36.0 34.1 33.9 36.4 36.4 32.3 30.5
-
32.2 31.5
2-butyne, where the geometry of the C-C=C-C system was forced out of linearity into both planar and non-planar structures. The authors came to the conclusion that the experimental 'J(CC) value corresponds to a distorted model of 2-butyne with an in-plane cis distortion combined with a subsequent twist from planarity. This result has been confirmed by gas electron diffraction measurements. The 8 C-C=C-C dihedral angle was estimated to be cu. 40", while the < C-C=C: angle amounted to about 155". In this way cyclooctyne represents the first reported example of a highly bent and twisted CC triple bond. One-bond CC couplings have been measured by Kamienska-Trela et ul. 153 for 9aH-quinolizine-l,2,3,4-tetracarboxylate (127) and several of its methyl derivatives (Table 35). For two of these compounds an X-ray analysis has been performed. This allowed the authors to check if a 'J(CC) vs. rcc relationship exists. The existence of such a relationship has been postulated and discussed in the literature (for the corresponding references see r e ~ i e w s ~Since ~ ~ ~ one-bond ). CC coupling constants are now fairly readily accessible, and can be measured with high accuracy, a 'J(CC) vs. rcc equation derived using a reliable set of data could be a valuable source of information on the bond length in compounds for which either X-ray or
ONE-BOND 13C-13C SPIN-SPIN COUPLING CONSTANTS
Table37. One-bond CC couplings in sesquiterpene globulol (69) (isomer of viridiflorol which was isolated from niaouli (Meluleuca viridifiora) essential oil;" values are in hertz.
179
+
2;
OH
H
\
I
69
Coupled carbons
'J(CC)
Coupled carbons
'J(CC)
Coupled carbons
'J( CC)
c1c2 C2C3 C3C15 C6C7 C8C9 CllC12
45.3 14.6 44.9 37.8 33.4 36.1
ClC8 c3c4 c4c5 C7C8 ac10
32.3 14.6 43.3 38.3 32.7
ClCll C3C14 C5C6 C7C13 ClOCll
33.3 43.3 33.3 40.6 32.8
8
501
, O
:;
40 1.32
1.42 rm
1.52
(4
Fig. 6. Variation of 'J(CC) with the CC bond length for 9a-methyl- (128), ( 0 ) and 7,9-dimethyl-9aH-quinolizine(129), (m). The data in the upper left cluster correspond to CC double bonds in rings A and B, those in the upper right cluster are due to C(O)C,, (n = 1-4), and those in the lower right cluster correspond to CC single bonds in rings A and B. (Reprinted with permission from ref. 153.)
180
K.KAMIENSKA-TRELA Table 38. One-bond CC couplings in cembrene (133) (in hertz).173 18
5
4/
133
Coupled nuclei c1c2 c3c4 c4c5 C5C6
'J(CC)
Coupled nuclei
'J(CC)
Coupled nuclei
' J ( CC)
43.4 53.1 71.9 42.8
C6C7 C7C8 C8C9 C9C10
42.8 73.8 42.9 33.8
ClOCll CllC12 C12C13 C13C14 C15C16 c17c15
44.3 73.4 42.9 34.5 35.6 35.7
microwave and electron diffraction measurements are difficult to perform. A plot (Fig. 6 ) of the 'J(CC) values against bond lengths, rcc, derived from an X-ray crystallographic study shows three distinct clusters. However, the changes in the one-bond CC coupling constants do not follow those in rcc, and no general 'J(CC) vs. rcc relationship can be derived on this basis. The only exception is for the C3-Cl2 bond; this is the shortest of all C(O)Csp* bonds and, correspondingly, the largest 'J(CC) value of all the couplings has been found for it. 8. THE LONE PAIR EFFECT
The first observation concerning the lone pair effect on the magnitude of one-bond CC spin-spin couplings was made by Wray and Ernst, who measured 'J(CC) for a large series of syn ( Z ) and anti (E) oximes.s Invariably, 'J(CC) (anti) greater than 'J(CC) (syn) has been observed. The relationship seems to be of a general character, and as further experimental and theoretical studies have shown, applies to both oximes and imines. The problem has been thoroughly discussed by Gil and P h i l i p ~ b o r n , 'Krivdin ~~ and Kalabin' and most, recently, Contreras et al. '75 The most recent experimental data obtained by various authors for oximes, imines17&179 and some related compounds18' are collected in Table 39. The couplings for the series of oximes of sugars have been measured by Snyder (Table 4O).l8l
ONE-BOND 13C-13C SPIN-SPIN COUPLING CONSTANTS
181
c 1c 2 J
(cc)
40.5 Hz
42.3 Hz
48.4 Hz
C1 C3 42.5 Hz
refs
5
5
9
Table 39. One-bond CC couplings in oximes and some related compounds; all values
are in hertz.
140 a
134 -139
:N
141 ,142
.N:
'OH OH
140 b ~~~~
Substituents Compound no. 134 135 136 137 138' 139a 139b 140a 140b 141 142
'J( CC)
R1
R2
R3
CH3 CH3 OH CH3 CH3 OC2H5 CH3 CH3 p-C6HsC02CH3 CH3 CH3 (CH212C6H5 CH3CO CH3CO OH (CH3)3Si0 CH3 OSi(CH& CH3 (CH3)3Si0 OSi(CH3)3 C6HS C6HS
CH3 C6H5
CiS"
49.8 49.6
'J( CC) trans"
-C
41.2 40.9 38.0 38.0 48.1 53.4
61.3 60.3d
-
47.9
49.0 58.5
-C 60.0 60.0
47.6d 40.0 52.0
Ref. 176 176 176 179 177 180 180 178 178 179 178
"In respect to the lone pair. bRernaining 'J(CC) couplings: in the CH3C0 cis fragment, 44.4Hz;in the CH3C0 trans fragment, 42.6 Hz. 'Not concerned. dCouplings across C1C2 bond.
182
K. KAMIENSKA-TRELA
Table 40. One-bond CC coupling constants for aldose oximes measured in *H,O; all values in hertz, accuracy k O . 1 Hz.'*l
Oxime D- Arabinose
D-Lyxose D-Ribose D-Xylose
'.I CC) ( cis"
'J(CC) trans"
53.6 53.6 53.8 53.6
45.8 45.3 45.3 45.3
"In relation to the lone pair
Table41. The FC, OD and SD contributions to 'J(CC) cis and 'J(CC) frans, in
acetoxime and its protonated form calculated by means of SCPT INDO method;" all values are in hertz.'*' H3C
H3C\/CH3
cis
C
I1
cis
trans 134 a
ON\o I H
CH3
\/
trans
C
II
A
H
134 b
O
I
H
cis
FC OD SD Total
Exp.
trans
134a
134b
134a
134b
58.84 -3.08 1.84 57.60 49.3
43.47 -4.97 0.94 39.44 41.5
53.12 -3.08 1.94 51.98 42.2'
42.18 -5.06 0.94 38.06 41.9'
"Calculations were carried out using MNDO-optimized geometries: S:(O) = 3.6762 was used in the FC calculations. 'Measured in CF,COOH (3.0 M).
The INDO calculations have been performed by Zinchenko et al. 176 and Krivdin et al. 185 for acetoxime itself and variously substituted imines (Tables 42 and 43). They showed that the CC coupling across bond cis arranged to the lone pair is larger than that across the trans bond. In other words the lone pair contribution to 'J(CC) (cis) is positive, and to 'J(CC) (trans), negative. This is corroborated by the results obtained for protonated acetoxime where very similar 'J(CC) values have been found for the couplings across both anti (E) and syn (2) CC bonds1'* (Table 41). It has also been concluded by Zinchenko et ~ 1 . '(Table ~ ~ 42) that it is mainly the
183
ONE-BOND 13C-'3C SPIN-SPIN COUPLING CONSTANTS
Table42. The IPPP INDO values of FC,SD and OD contributions to one-bond spin-s in CC couplings calculated for variously substituted imines; all data in
hertz.P,,
/GH3
H3c\ cis C
trans
II
a\ N
X
transa
Cis"
Substituent
x
FC
OD
SD
Total
FC
OD
SD
Total
H
70.6 69.2 75.2 76.1 72.4
-3.0 -3.1 -3.1 -3.1 -3.1
1.7 1.8 1.8 1.8 1.7
69.3 67.9 73.9 74.8 71.0
59.4 64.8 61.4 59.3 56.8
-2.9 -3.1 -3.1 -3.0 -3.1
1.8 1.8 1.9 1.9 1.8
58.5 63.5 60.2 58.2 55.5
CH3 NH2 OH
F
"In relation to the lone pair.
Table43. One-bond CC coupling constants (in hertz) for isomers 143a-c of N-( 1,2,5-trimethylpiperidilidene-4)aniline.
Isomer 143a trans E 143b cis E 143c cis Z
C2C2'
C2C3
C3C4
C4C5
C5C5'
C5C6
39.1 37.0 38.8
34.5 34.2 34.9
36.7 36.1 45.5
45.3 45.4 36.1
37.5 35.9 33.9
34.4 34.0 34.4
Fermi contact interaction which is responsible for this lone pair effect, while two remaining terms, i.e. OD and SD contributions, are irrelevant in this respect. An elegant example of the application of 'J(CC) coupling constants in structure elucidation has been published by Aliev et ~ 1 . , ' * who ~ studied the condensation product of 1,2,5-trimethylpiperidine-4-0neand aniline (143). The compound can exist in the form of four isomers - isomers cis (E) and cis ( Z ) , and isomers trans (E) and trans ( Z ) , with configurations E and Z with respect to the C=N bond. The product obtained consisted of three isomers 143a-q and the set of 'J(CC) couplings has been measured for each of them (Table 43). The 'J(C3C4) couplings of ca. 36 Hz and the 'J(C4C5) couplings of ca. 45 Hz were found for isomers 143a and 143b. This provided evidence that both these isomers exist in the form E. The couplings
184
K. KAMIENSKA-TRELA
143
'J(C3C4) = 45.5 Hz and 'J(C4C.5) = 36.1 Hz observed for compound 143c indicate that it has configuration Z . Also the 'J(C5C5') couplings of 37.5 Hz and 33.9 Hz found for isomers 143a and 143c, respectively, revealed the typical orientational dependence: 'J(C5CS'eq)> 'J(C5C5'ax). The 'J(C5C5') constant of 35.9 Hz found for isomer 143b provided evidence that this compound exists as a mixture of two conformers: cis(E) (2eq, 5ax) and cis(E) (2ax, 5eq). A presence of small amount of an imine form (143d) has also been postulated by the authors in order to explain 143a2143b 3 1 4 3 ~interconversion.
143 b
143 c
Reprinted with permission from ref. 183 An influence of the nitrogen lone pair of ca. 6-8 Hz on the corresponding 'J(CC) couplings has been also reported for numerous aza-aromatic compounds including a-picolines, pyridazines, pyrazines and pyrimidines. The relevant data have been collected in Krivdin and Kalabin's review.' The in order to lone pair effect has also been invoked by Afonin et rationalize the results obtained for a large series of vinylazoles, where the 'J(CC) couplings across the double bond of the vinyl group have been measured. Some of these compounds exist as the mixtures of s-trans and s-cis conformers with respect to the N(2) nitrogen, and the equilibrium shifts towards s-cis conformer upon alkyl substitution in position 5. This is
ONE-BOND 13C-13CSPIN-SPIN COUPLING CONSTANTS
185
Table 44. Lone pair contribution, ZIP,to 'J(CC) cis" and 'J(CC) trans' in monoprotonated (144a) and non-protonated acetone (144b) and in non-protonated acetoxime (134).
"
Compound lUab
144b' 134
'J(CC) cis
'J(CC) trans
1.28 1.54 2.48
-1.03 -0.99 -2.14
A(&
-
trans)
2.31 2.53 4.62
Exp. 4.5
-
7.8
9,,stands for the sum of all J,o,,b contributions in equation (6), where i or j corresponds to the unprotonated oxygen lone pair in monoprotonated acetone or to the nitrogen lone pair in acetoxime. bCorresponds to the 6-31G**/MP2 optimized geometry of protonated acetone. 'Corresponds to the 6-31G**/MP2 optimized geometry of unprotonated acetone with the 0 - H - length and bond angle taken from the standard model of Pople and Gordon.
accompanied by a small increase (ca. 2Hz) in the 'J(CC) value. Thus, for example the coupling across the vinyl bond, 'J(CC) = 77.7 Hz was found in 1-vinylpyrazole and 79.7 Hz in l-vinyl-3,5-dimethylpyrazole.
s - trans
s
- cis
The influence of the oxygen lone pairs on 'J(CC) is also substantial. In an interesting study by Krivdin et aZ.ls5 on the effects of protonation on acetone, a difference of ca. 5 Hz was observed between the coupling across the bond cis arranged to the oxygen lone pair and the trans one, the cis coupling being the greater one (Table 44).
cis
'J(CC) = 40.0 Hz
CH3
CH3
\C/
II
O+
\
H
'J(CC) in acetone = 40.5Hz
trans 35.5Hz
186
K. KAMIENSKA-TRELA
Calculations performed by the CLOPPA (Contributions for Localized Orbitals within the Polarized Propagator Approach) method allowed the authors to rationalize the results obtained in terms of the lone pair effect, though the other effects, such as the net positive charge effect and the geometry effect, have been discussed by them. In particular, a substantial positive charge which appears on the carbonyl carbon atom upon protonation of one oxygen lone pair should yield a reduction of both 'J(CC) cis and 'J(CC) trans couplings at the rate of 1.5-2Hz per O.le of positive charge. The calculations have been performed by the use of equation ( 6 ) , where the indirect spin-spin coupling constant is presented as a sum of MO contributions, each of them depending on, at most, two occupied and two vacant localized molecular orbitals (LMOs) (Table 44):
The above results are in agreement with the results of the earlier experimental studies performed by Krivdin et u Z . ~ on 'J(CC) couplings in a large series of vinyl and phenyl ethers, sulphides and selenides. Also the theoretical studies performed by the same group of authors for 'J(CC) in H2C=CHR and CH3CH2R where R = OH, NH2, SH and PH2,1g6and for protonated and non-protonated furane and some methyl-substituted furanesIg7 corroborate the conclusion that an influence of the lone pair has always to be taken into account.
9. ONE-BOND CC COUPLINGS IN STRUCTURAL STUDIES OF COMPLEXES
One-bond CC couplings have been measured by many authors for a variety of complexes with a hope that they should provide an insight into the structure of this most interesting group of compounds. Indeed, the changes occurring in 'J(CC) couplings upon complexation are often very strong and are the source of valuable information on the electron re-distribution which takes place within a carbon-carbon bond upon coordination of the ligand to the metal. One of the most intriguing results obtained in this field concerns the couplings measured by Chisholm et al. ,1883189 for the alkynes bonded to hexaalkoxides of dimolybdenum and ditungsten. The couplings range from 10.3 Hz in W2(0-t-Bu)6(py)(p-C2H2) to 43.4Hz in CP~MO~(CO)~(~-C (Table ~ H ~45). ) ~ *A~coupling of 55.9 Hz was observed by Aime et in C O ~ ( C O ) ~ ( ~ - C ~These H ~ ) .are the smallest values reported so far for the couplings across the triple CC bond. They are accompanied by the low 'J(CH) coupling of 192 Hz observed by Chisholm in
ONE-BOND I3C-l3C SPIN-SPIN COUPLING CONSTANTS
187
Table 45. One-bond CC coupling constants (in hertz) in M ~ ( O R ) ~ ( P Y ) ~ ( P - C ~ H ~ ) complexes and related carbonyl derivatives, with the CC distances, rcc. Compound
Type
'J(CC)
rcc(A)
Ref.
I
28.2 26.9 23.2 15.8 11.4 19.0 10.3 55.9 43.4
1.368(6)
189 189 189 188 189 189 189 190 189
I I I1 I11 P2
112
-
-
-
1.39(2) 1.39(2) 1.44(1) 1.327(6) 1.337(5)
W2(0-t-Bu)6(CO)(p-C2H2) (lJ(CH) in ethyne = 249 Hz);lS8 both coupling constants have been invoked as evidence for the dimetallatetrahedrane paradigm for the compounds under study. A rough inverse correlation between 'J(CC) values and the corresponding rcc distances has been noted by the authors for these complexes. However, since the carbon-carbon distances in complexes are measured with rather poor rsd the relationship mentioned above should be, as the authors themselves emphasized, treated l ~ ~ with great caution. It is also rather surprising that Chisholm et ~ 1 . have found that 'J(CC)s in the compounds studied by them are proportional to AE = &(LUMO)- &(HOMO). According to McConnell's average energy approximation all contributions to the couplings are inversely proportional
I R
R I
188
K. KAMIENSKA-TRELA
to the average energy AE.32 However, in spite of some inconsistencies in theoretical interpretation, Chisholm's results are certainly very interesting and shed new light on the electronic structure of alkyne complexes. A new, rather unusual, type of compound, 144, in which a diorganotin dication is stabilized by n- coordination to two C=C bonds has been reported by Wrackmeyer et ~ 1 . lAn ~ ~interaction between the Sn2+ cation and the triple bond is reflected by the substantial decrease in the 'J(CC) coupling across this bond (101.0 Hz only). For a comparison 'J(CC) of 119.2 Hz was found in sodium triethyl-1-propynylborate[CH3C=CB(C2H5)3]- Na+.
Quite a number of papers have been devoted to various complexes of olefins (Tables 46-50). Philipsborn and c o - ~ o r k e r s ' ~ 'ha - ~ve ~ ~reported the 'J(CC) data for a series of q4-diene, q3-allyl and q2-ene complexes of Fe, Ru and 0 s ; Benn and R ~ f i n s k a ' ~have ~ ' ~measured ~ the 'J(CC) couplings for a series of q2-olefin-Ni(I1) complexes; and Yamamoto et ~ 1 . lhave ~ ~ published the 'J(CC) values for (q-pentamethylcyclopentadienyl) titanium-diene complexes. The 'J(CC) couplings for olefin complexes of Rh(1) were published by Fitch et ~ 1 . Further ~ ' ~ examples include the data for various complexes of unsubstituted ethylene studied by Huffman and c o - ~ o r k e r s , ' ~ *Bender ~ ' ~ ~ et al. ,200 and others2"',202 (Table 50). Finally, 'J(CC) couplings in complexes of heterocyclic dienes and ethenes have been measured by Wrackmeyer and c o - w ~ r k e r s . ' ~ ~ ~ ~ ~ , ~ ~ ~ In all cases the 'J(CC) values are significantly smaller (by ca. 20 to 30 Hz) than the coupling constants in a free ligand. This remains in striking contrast to the behaviour of one-bond hydrogen-carbon coupling constants whose values slightly (by ca. 2Hz) increase upon complexation and lie between those in ethylene ('J(CH) = 157 Hz) and cyclopropane ('J(CH) = 160 Hz). The large decrease in 'J(CC) occurring upon complexation has been invoked by many authors as evidence that the complexes are best described as metallacyclopropanes (IV) rather than n--complexes (V). Thus, for example, the osmacyclopropane structure V has been assigned to the O S ( C O ) ~ ( C ~ H ~ ) complex by Bender ef ~ 1 . ~ " The magnitude of the decrease in 'J(CC) upon complexation varies upon the nature of the metal involved and depends on the geometry of a given complex, but remains constant within a given series.
ONE-BOND l3C-I3C SPIN-SPIN COUPLING CONSTANTS
189
Table 46. The typical 'J(CC) couplings in the s-cis complexes of butadiene; all values in hertz.
Fe
Co
Ru
0s
W
Th
Zr
Hf
43.9
43.5
42.4
38.8
38.5
38.0
37.4
34.2
The following trend emerges when the 'J(ClC2) data available for the s-cis complexes of butadiene are compared (Tables 46 and 47):
Fe = Co > Ru > 0 s = W = Th = Z r > Hf As far as the geometry of the complex is concerned, the 'J(ClC2) coupling reported for (q4-s-truns-C4H6)ZrCp2 is considerably greater than that for (v4-s-cis-C4H6)ZrCp2 complex, 45.9 Hz and 38.6 Hz, respectively. Furthermore, the C1C2 coupling in the endo titanium-diene complex is greater (ca. 43 Hz) than in the corresponding ex0 complex (39.1 Hz), while
. M <
1 -complex IV
,
metallacyclopropane V
the reverse relationship occurs for the coupling across the C2C3 bond, the 'J(C2C3) in the endo complex being smaller than that in the ex0 one, 45.0 Hz and 51.3 Hz, respectively. By analogy to the one-bond CC couplings in free ligands also the 'J(CC) couplings in complexes are governed by the electronegativity of substituent attached to the double bond involved. This has been demonstrated for the first time by Fitch et ~ 1 . l(Table ~ ~ 50), who measured 'J(CC) couplings in a series of v2-alkene complexes of rhodium (I). It has been emphasized by these authors that the constant decrease, AIJ(CC) of ca. 22Hz, occurring upon complexation is a more accurate guide to the nature of the metalolefin interaction than is the 'J(CC) value for the complex alone. The substituents involved in this study were the silyl, alkyl and alkoxy groups. The similar difference of ca. 23 Hz is observed for the cuprate complexes of enynes and methyl cinnamate measured by Krause et d9'It is of interest to
190
K. KAMIENSKA-TRELA
Table 47. One-bond CC coupling constants (in hertz) for ligated dienes in transition metal complexes.a Couplings across the bonds Complexes 1 2 3 4 Fe(C0)3(CH2=CH-CH=CH2) 5 1 2 3 4 Fe(C0)3(CHz=CH-CH=CH-CH3) Fe(C0)3(CH2=CH-C(CH3)=CHZ) Fe(C0)3(cyclo-hexadiene) Fe(CO)(CH2=CH-C( CH3)=CH2)2 Fe(PMe3)(CH2=CH-CH=CH2)2
Fe(PEt)3(CH2=CH-CH=CH2)2
RU(CO)~(CH~=CH-CH=CHZ) Ru(CO)3(CHZ=CH-CH=CH-CH~) Ru(C0)3(cycfo-hexadiene) Os(CO),( CH2=CH-CH=CH2) Os(CO),( CH2=CH-CH=CH-CH3) COC~CH~=CH-CH=CH~ COCP(CH,=CH-C( CH3)=CH2) Zr(Cp),(CH2=CH-CH=CH2)s-trans Zr(t-BuCp)2(CH2=CH-CH=CH2) Zr( Cp2)(CH2=CH-C(CH3)=CH2) ZJ(t-BuCp)z(CH,=CH-C( CH3)=CH2) Zr(Cp2)(CH2=C(CH3)-C(CH3)=CH2) H~(~-BUCP)Z(CH~=CH-CH=CH~)
Hf(t-BuCp)z(CH2=CH-C(CH3)=CH2)
Th(MeSCp)2(CH2=CH-CH=CH2) Mo((CH2=C(CH3)-C(CH3)=CH2)3 W(CH,=CH-CH=CHZ), W(CH2=CH-C(CH3)=CH2)3 W(( CH2=C(CH3)-C(CH3)=CH2)3 TiC1Cp(CH2=CH-CH=CH2) prone TiC1Cp(CH2=CH-CH=CH-CH3) prone TiCICp(CH2=CH- C(CH3)=CH2supine
C1C2
C2C3
43.9
-
-
-
192
43.3 44.3 42.7 46.7 46.2 46.0 42.4 42.1 40.8 38.8 38.0 43.5 42.4 45.9 37.4 37.5 37.5 37.5 34.2 34.0 38.0 42.0 38.5 38.5 38.0 43.5 42.9 39.1
43.5 45.0
46.2 45.1
-
-
43.0 43.6
46.5
46.6
44.4
192 195 192 195 195 195 192 192 192 192 192 195 195 195 195 195 195 195 195 195 195 195 195 195 195 197 197 197
-
42.5 -
40.2 -
44.5 -
57.3 57.6
C3C4 C(X)C5 Ref.
-
-
-
-
44.4
41.5
-
-
42.5
40.5
-
-
-
42.4
42.4
-
_.
-
38.0 37.5
-
-
42.6 42.2 41.6
60.5
34.0
-
-
42.0
-
-
-
-
-
48.8
37.8
43.7 43.6
-
-
-
-
43.5 45.1 39.0
45.0 51.3
-
-
-
-
“s-cis conformation if not otherwise stated
note that the couplings across the remaining bonds measured in these complexes differ only slightly from those in the corresponding free ligands. The same has been observed for the couplings across the RC(O)CH= bond in the (tricarbonyliron) complexes of the functionalized dienes of the type CH2=CH-CH=CHCOR (R = H , CH3, OEt) studied by Adams et ~ 7 l . (Table 48). According to the authors, the latter result indicates a loss of conjugation of the diene system with the functional group. It is striking that also in the complexes of heterocyclic dienes and ethenes
l ~ ~
ONE-BOND 13C-'3C SPIN-SPIN COUPLING CONSTANTS
191
Table 48. One-bond CC coupling constants (in hertz) for complexes of functionalized 1,3-dienes. Coupled nuclei
'J(CC)
Ref.
c1c2 C2C3 c3c4 c4c5 C5C6
54.6 67.2 54.8 69.6 42.4
193
50.8 44.7 44.8 45.1 42.1
193
CHO
c1c2 C2C3 c3c4 c4c5 C5C6
73.6 45.9 44.3 45.2 41.5
193
C02Et
c1c2 C2C3 c3c4 c4c5 C5C6 c1c2 C2C3 c3c4 c4c5
-U
193
45.9 43.7
c1c2 C2C3 c3c4 c4c5
51.2 43.4 44.0 42.8
Complexes 6 5 4 3 2 1 CH,CH=CH-CH=CHCHO
'/J' '/1 ' I I
-U
193
"Not reported.
Table49. One-bond CC couplings (in hertz) and CC bond lengths for ethylene complexes.
192
K. KAMIENSKA-TRELA
Table50. One-bond CC couplings (in hertz) in derivatives of ethene and some enynes; for comparison, the data for the corresponding ligands are included (in parentheses).
'J( CC) (acac)Rh(CH2=CHSiMe3)2 CpRh(CH2=CHSiMe3), (~c~c)(CH,=CHS~(OE~)~), (~c~c)R~(CH,=CHCH,)~S~M~~ (acac)Rh(CH2=CHCMe& (acac)Rh(CH,=CHOEt), trans-PtCl(py)(CH2=CHOEt) (t-Bu2Cu(CN)Li,)(t-BuC=CCH= CHC0,Et)
(Me,CuLi-LiI)(t-BuC=CCH=CHCN)
(t-Bu2CU(CN)Li2)(PhCH=CHCO2Me)
38.6 f 0.9 38.0 f 1.2 38.0 f 3 46.8 -t 1.7 45.9 f 1.5 56.6 f 1.6 51.0 f 1.3 51" 54 49
(58.8 k 1.3) (58.8 -t 1.3) (58.2 f 1.2) (69.7 -t 1.3) (70.0 f 1.2) (78.4 f 1.3) (78.4 f 1.3) (74Y (77) (72)
Ref. 113 113 113 113 113 113 113 93 93 93
"Remaining couplings in this compound: 'J(ClC2) 78 Hz, 'J(C3C4) 92 Hz, 'J(C4C5) 174 Hz, 'J(C5C6) 70 Hz. bRemaining couplings in unsubstituted compound are given in Section 4.
prone (endo)
s-1ra ns
supine (exo)
s-cis
studied by Wrackmeyer and his g r o ~ p ~ the ~ ~AIJ(free , ~ ~ lig~ , ~ ~ ~ and - complex) difference is only moderately larger than that observed for the open chain compounds, and varies from ca. 25 to 30 Hz (Table 51). A substantial (ca. 8 Hz) decrease upon complexation has been reported by Mole et a1.,204 for the couplings across the single Csp3Csp3 bond in (diph0sphine)platinum ethyl cations (Table 52). A similar decrease has been
ONE-BOND l3C-I3C SPIN-SPIN COUPLING CONSTANTS
193
145
CH+C -H,
4L-t I
38.3 Hz
19.2 Hz
H3
( i n ligand 63.0 Hz)
Reprinted from ref. 203 with permission of VCH Verlagsgesellschaft observed by Jordan and ~ o - w o r k e r s , ~for ' ~ a series of the zirconium complexes. In both cases the agostic structures have been invoked in order to explain the changes observed. In contrast to the above findings the 'J(CC) couplings in [1,4,8,11-tetrakis(2-hydroxyethyl)-1,4,8,ll-tetraazacyclotetradecane)cadmium(II), called subsequently [Cd(THEC)I2+, are very close to those observed in analogously substituted acyclic compounds. The 'J(CC) of 39.0 Hz and 39.3 Hz were found by Clarke et uZ.'06 for the bidentate and monodentate CH2CH20H arms of this complex. It is of interest to note that the corresponding two I3C AB quartets could be observed only under slow intramolecular exchange conditions, i.e. at low temperature (ca. 213 K). At higher temperatures the exchange rates become larger and the coalescence of the quartets follows. A complete lineshape analysis performed by the authors gave the full set of thermodynamical parameters of the pairwise exchange of the hydroxyethyl arm between the monodentate and bidentate environments of Cd(THEC)2+.
[1,4,8,11 -tetrakis(2-hydroxyethyI)-l,4,8,11-tetraazacyclotetradecane] cadmium (11) [Cd(THEC)](CIO&
194
K. KAMIEGSKA-TRELA
Table 51. One-bond CC couplings in cobalt and iron complexes of some siloles and spirobisiloles (in hertz).'
H3 H3TcH H3C\SJcH3
H3C\
Fe(CO), H2CH3
(CH3-CH,)zB
c o c p CH,CH,
Fe(CO),
CH,CH,
kCH
102a
103a
H3cx H3
F e ( W 3HZCH,
105a
Couuled nuclei Cornpound no. C1C2 C2C3 C3C4 C1CH3 B(CH2CH2),C3CH2C3(CH2CH3)C4CH3 Ref. 102a 103a
105a
37.9 29.5 35.0
41.3 35.7 44.1
36.7 34.5 34.1
40.7 39.2 39.4
43.5 42.9 42.7
-
32.6 -
32.9 33.3 33.5
39.6 39.8 39.1
164 164 166
" ' J ( C C )for the ligands are given in Section 7
The exceptionally low value of 'J(CspCsp) (44 Hz) observed by Caulton et a1.207 in . (t-BuO),W=C-C=W(O-tBu), is almost certainly a reflection of the greater affinity of C2s bonding to tungsten (relative to its other neighbour carbon atom) and parallels the extremely small value of 1J(13C-1H) in (t-Bu0)3W=CH (150 Hz) compared to that of HC=CH ('J(CH) = 250 Hz). Extraordinarily small 'J(CC) values, of only a few hertz, have been observed by Mashima et and Meinhart et ~ 1 . for ~ ' the ~ C(0)-cSp3 couplings across the C(0)-CH2 bond in (77'-acy1)titanium complexes. These values are in sharp contrast with those of acyl compounds of rhenium (see Table 53) which showed coupling constants by ca. 10-20Hz ~
1
.
~
~
~
3
~
~
~
ONE-BOND I3C-l3C SPIN-SPIN COUPLING CONSTANTS
195
Table52. One-bond CC couplings (in hertz) across single Csp3Csp3 bonds in complexes of platinum, zirconium and cobalt. Complex
Moiety
PtCH2CH3 [(~-(~-BU~PCH~)ZC~H~)P~(C~H~)~B H~ [ ( ( ~ - B ~ ) ~ P ( C H ~ > Z P ( ~ - B U ) ~ ) P ~ ( C ~ H S ) I BPtCHzCH3 H~ ZrCHzCH3 Cp$Zr(CH2CH3)(THF)BPh4 ZrCH2CH3 Cp$Zr(CHzCH3)(CH3CN)BPh4 ZrCH2CH3 Cp$Zr(CH2CH3)(CD3CN)BPh4 ZrCH2CH3 Cp$Zr(CHzCH3)(PMe3)BPh4 ZrCHzCH3 CpbZr(CHzCH3)C1BPh4 ZrCH2CH3 CphZr(CH2CH3){ (CH3),CCN)}BPh4 ZrCHzCH3 Cp$Zr[N=C(CH3)(CH2CH3)](CH3CN)BPh4 COCHCH~ Cp*Co{P(OMe)3}CHRCH; COCHzCH2 Cp*Co{P(OMe)3}CH2CH2R+ NCH2CHzOH [Cd(THWI(C104)2
'J(CC)
Ref.
29 26 32.9 26.9 33 28.5 32.3 26.9 36.0 29 36-39 39.0a 39.36
204 204 205 205 205 205 205 205 205 205 205 206
"For bidentate hydroxyethyl arm. bFor monodentate hydroxyethyl arm. Table 53. One-bond CC couplings (in hertz) in RCO complexes of titanium and rhenium (RCO = CH3C0 or C6H5CO). Ref.
-
210 208 209 209 210 212 211 21 1 212 212 "R = CH2Si(CH-J3
larger.211.2'2 Th e corresponding C(O)-Gp'(arom.) couplings across C(0)-Cipso bond in Re complexes are of 26 to 30 A CC coupling constant of ca. 20 Hz has been observed by Coffin et aL2I3 in an adduct of rhodium octaethyl porphyrin ( 0 E P ) R h dimer and two C O units, which provided clear evidence of CC formation. The relatively small value of this coupling, combined with the large value of 2J(CRh), has been invoked by the authors as evidence for a multicentred interaction between the ( 0E P ) Rh and C(O)C(O) units. One-bond CC couplings have been measured also for ((3,4,5,8,9-v5)tricyclo[5.2.1.O2.qdeca-3,8-dien-5-yl)( ~5-cyclo-pentadienyI)iron (DICP)
196
K. KAMIENSKA-TRELA
Table 54. One-bond spin-spin CC coupling constants (in hertz) for DICPFeCp?l4 for comparison, the data for DICP215are included.
' J in Coupled carbons c1c2 C1C9 ClCl0 C2C3 C2C6 c3c4 c4c5 C5C6 C6C7 C7C8 C7C10 C8C9
DICP
DICPFeCp
28.9 38.9 32.2 43.5 36.6
35.1" 36.8" 31.1" 41.0"
-b -b
36.9 29.9 38.1 31.8 66.0
-b
41.7" 41.7" 41.O" 35.1" 36.8" 31.1" -b
"Couplings across bonds C1C2 and C6C7, C1C9 and C7C8, ClClO and C7C10, C2C3 and C5C6, C3C4 and C4C5 are equivalent. 'Not observed due to symmetry problem.
10/
(DICP)FeCp
FeCp) .214 The couplings observed do not differ significantly from those measured for endo-dicyclopentadiene (DICP) itself215(Table 54).
10. ONE-BOND CC COUPLINGS IN CHARGED MOLECULES AND SOME RELATED COMPOUNDS
The older results on 'J(CC) couplings in charged molecules have been thoroughly reviewed by Krividin and Kalabin,' and some recent 'J(CC) data have been included by Saunders and Jimenez-Vazquez216 into their review covering the most relevant papers on carbocations published recently. Numerous spectroscopic methods have been already applied in order to gain insight into the electronic structure of fulvenes. According to these
ONE-BOND
13c-13c SPIN-SPIN COUPLING CONSTANTS
197
investigations, in the parent molecules a strong alternation of the bond lengths occurs, as it does in non-aromatic polyenes. A delocalization of the T electrons accompanied by charge separation may take place in pentafulvenes upon substitution with the exocyclic electron donating substituents. The same occurs in heptafulvenes when the exocyclic electron withdrawing groups are involved.
3
2
4
3
Recently, extensive NMR studies on these two groups of compounds have been performed by Neuenschwander and c o - w o r k e r ~These . ~ ~ ~included ~~~~ analysis of the substituent effects on the 'J(CC) values in p e n t a f ~ l v e n e s ~ ~ ~ and heptafulvenes.218 The data obtained for heptafulvenes have been compared for those obtained for the tropylium ion (154). Large changes R
154
have been observed, as can be expected, for the couplings across the directly substituted C5C6 bond in pentafulvenes (AIJ = 15.8 Hz), whose values vary from 66.6Hz in 6-ONa-substituted compounds to 82.4Hz in 6-OAc derivatives (Table 55) (no corresponding data were obtained for heptafulvenes). The remaining couplings are less influenced by substituents though some regular trends upon substitution are revealed for both groups of the compounds (see Tables 55, 56). The clear 'J(CC) alternation occurs in both groups of the compounds, and in particular in non-polar heptafulvenes the couplings resemble closely those in unsubstituted butadiene. In pentafulvenes the couplings across formally double bonds decrease upon increasing electronegativity of substituent attached to the carbon 6, whereas a decrease for those across single CC bonds is observed. These changes have been interpreted by the authors in terms of the equalizations of the corresponding CC bonds of the fulvene ring system. However, no corresponding trends were found for the 'J(CC) couplings in heptafulvenes. Extensive studies have been recently performed by Hoffmann et af.lU on N , N , N ' , N' ' , N' '-pentamethyldiethylenetriamine-solvated complexes of
198
K. KAMIENSKA-TRELA
Table 55. One-bond CC coupling constants (in hertz) in pentafulvenes.a
Carbons coupled Compound no.
Substituent Ph i-Bu t-Bu AcO MeS Me0 Me2N NaO
146 147 148 149 150 151 152 153
C1C2
C2C3
C3C4
C4C5
C1C5
C5C6
65.2 65.6 65.1 65.4 65.1 64.4 62.3 60.3
48.2 48.4 48.2 48.7 48.9 49.5 50.7 52.8
65.7 65.8
49.7 50.0 49.1 51.1 51.2 51.8 52.7 54.6
50.4 50.5
69.6 69.0 69.0 82.4
-
65.8 65.5 64.9 62.6 61.0
50.1 50.7 50.5 51.4 54.4 55.1
b -
78.2 70.9 66.6
“Measurements were performed in acetone-d, with an exception of compound 153 whose spectrum was measured in pyridine-d,; accuracy f 0 . 3 Hz. hNot determined.
Table 56. Coupling constants in tropylium ion (154), cycloheptatriene (155), and in a series of substituted heptafulvenes (156-159) (in hertz).’”
4
3 Carbons coupled
Compound no. 154 155 156 157 158 159
R’
CF3CO CN Ph Me2N
“Not determined.
R2
1,2/5,6
2,314,5
1,716,7
CN CN Ph Me3Si0
58.9 67.0 61.5162.0 65.2 68.1 69.4169.4
52.3 54.0
60.9 38.8 50.01.51.0 53.2 52.8 55.2155.0
-a
53.2 53.8 54.1154.1
7,8 -
54.0 67.5 -a -a
-a
ONE-BOND l3C-I3C SPIN-SPIN COUPLING CONSTANTS
199
For benzylrubidium C6H5CH2Rb and benzylpotassium C ~ H S C H ~(160). K the latter compound the one-bond carbon-proton and carbon-carbon couplings have also been measured and analysed. The values of 'J(CH) = 151.1 Hz (in the CH, group), were found and interpreted in terms of changes occurring in the hybridization of the carbons involved. The high value of 'J(CH) coupling of 151.1 Hz found for the CH, group (125 Hz in toluene) led the authors to conclusion that the benzylic carbon atom is approximately sp2.3 hybridized which is in accord with a nearly planar configuration of this fragment observed in the solid-state structures of PhCH2M with M = Li-K. The influence of the CH2- group on the CC couplings within the phenyl ring is rather substantial ('J(Cipso,Cortho) = 49.5 Hz and 'J(Cortho,Cmetu) = 60.1 Hz) though considerably smaller than that of Li and Mg, for example. 'J(CC) of 29 Hz'36,138 and 36 HZ'".'~~ were found in phenyllithium and in phenylmagnesium bromide, respectively (see also Section 4). Removal of two electrons from 1,8-bis[(4-methyIphenyl)thio]-9-(2,6dimethoxyphenyl-l'-'3C)-10-phenylanthracene provides rather an unusual pentacoordinate carbon species, a stable cation (161), whose structure is given below:21y 4
+
n
3
161
The coupling constants, 'J(Cl'C2') of 61.9 Hz and 'J(CI'C9) of 56.3 Hz, measured for this compound suggest that the carbon 1' is sp2 hybridized. The trigonal bipyramidal geometry has been postulated around this carbon centre. The pH dependence of 13C-enriched barbituric acid (162), has been studied by Franken et ~ 1 . ~The ~ ' smallest 1J(C4C5)l'J(C5C6) coupling of 48.9Hz has been found for pH = 1.9. Its value increases upon the
162
0
200
K. KAMIENSKA-TRELA
deprotonation of the methylene group, 'J(CC) = 74.5 Hz, and decreases with the ionization of the imide group, 'J(CC) = 69.7 Hz.
11. ONE-BOND CC COUPLINGS IN BIOLOGICAL STUDIES
The importance of 13C NMR spectroscopy in studies on biologically important compounds such as sugars and proteins, as well as on biological processes, is constantly increasing. On the one hand, many new procedures have been developed which make the 13C-enriched biologically important compounds more easily accessible and less expensive. On the other hand, the fast development in instrumentation makes the measurements for large and complex biological molecules easier. Simpson221provides a useful review on the application of stable isotope labelling and multinuclear NMR to biosynthetic studies which also includes data on one- and two-bond CC couplings. One-bond I3C-l3C coupling constants observed in biosynthetic experiments have been collected by Horak et ~ 1 . ~ ~ ' Extensive structural studies on carbohydrates and their derivatives, and on biologically important compounds which contain carbohydrate units have been performed by Serianni and his g r o ~ p .This ~ includes ~ , ~ studies ~ ~ ~on~ ~ 13C-enriched (Table 57), 13C-enriched d i s a ~ c h a r i d e s ~ ~ ~ ~ ~ ~ ~ ~ ~ , 59), ~~~ (Table 64), 1-'3C-alditols228(Table 58), some p e n t u l o ~ e s (Table deoxygenated and alkylated f u r a n ~ s e s ~(Table ~l 60) and D-penturonic (Table 61). Some papers have been devoted to the conformational studies on the sugar moieties of 13C-enriched ribo- and erythron u c l e o ~ i d e s(Table ~ ~ ~ 62). ~ ~ ~Bossennec ~ et al.235 have synthesized totally "C-enriched glucopyranose and two of its derivatives. Using a combination of 1D COSY and RELAY techniques they have determined ail one-bond and most long-range carbon-carbon couplings for all three compounds. A set of 'J(CC) couplings has been published by Dhawan and G o u x for ~ ~ per-0~ benzylated methyl furanosides. In all these papers, the relationship between one-bond CC couplings and the structure of sugars is analysed. One of the most recent papers has been devoted to the theoretical treatment of the problem.69 Calculations of 'J(CC) couplings have been performed at ab initio level, and ethane, ethanol, ethylene glycol, glycolaldehyde hydrate and D-mannopyranose were used as the model compounds. Results obtained revealed that 'J(CC) coupling increases with the number of OH groups attached to the CC bond. Furthermore, the coupling is larger in the rotamer with the hydroxyl groups trans arranged than in the rotamer gauche. In addition, the authors also observed that the conformational behaviour of the C - 0 bonds cannot be neglected. The coupling is the largest when the hydroxyl proton is anti to a
ONE-BOND l3C-I3C SPIN-SPIN COUPLING CONSTANTS
OH OH a-furanose
(*
* CH,OH 42'5Hz
H
0
?*
D-ribose
*
CH20H 53.OHz OCH3
201
*Hv OH OH fi-furanose
* CH20H 42.3Hz
40.8Hz 48.4Hz OH H methyl a-D-
0
OCH3 T i g i H z
41.1 Hz 46.7Hz OH H methyl fi-0-
Fructofuranosides
Reprinted with permission from ref. 6 9 , o 1993 American Chemical Society
carbon and the smallest when a compound adopts gauche configuration. The latter finding is of special importance since it indicates that an application of 'J(CC) as a structural probe for carbohydrates is limited, and conclusions based on it must be treated with great caution if additional information is not available. The following experimental data corroborate these theoretical results: (i) the 'J(CC) values increase in ethane, ethanol, 1,2-dihydroxypropane and glycolaldehyde hydrate upon the increasing number of the hydroxyl groups attached to the CC bond involved (34.6 Hz, 37.6 Hz, 41.3 Hz and 48.7 Hz, respectively).69 In agreement with this observation 'J(ClC2) of 52.7 Hz k 0.3 Hz in methyl-a-D- and methyl-P-D-fructofuranosides is greater (three oxygens involved, 01, 0 2 , 0 5 ) than 'J(C5C6) of 42.4 k 0.1 Hz (two oxygens only attached, 0 5 , 0 6 ) . Similarly, 'J(C2C3) is larger than 'J(C3C4) with values ca. 47 Hz and 41 Hz, respectively. (ii) 'J(ClC2) in aldofuranoses, aldopyranoses and 2-ketofuranosyl rings with 01 and 0 2 trans arranged are consistently larger than in their cis counterparts. Thus, for example, 'J(ClC2) in a-anomers of D-manno-, D-talo- and D-lyxopyranoses is considerably larger than in P-anomers. The same is observed for a- and P-anomers of per-0-benzylated methyl furanosides (Table 63). It is also worth while to mention that the above findings, both theoretical and experimental, are in line with general rules governing the behaviour of 'J(CC) couplings and observed in other groups of compounds. Thus, the relationship between the number of substituents and the value of 'J(CC) has been observed for substituted ethylenes and acetylenes; the couplings larger
202
K . KAMIENSKA-TRELA
Table 57. One-bond CC couplings in 13C-enriched aldoses, some model compounds, and some of their derivatives; all values are in hertz.
Coupled nuclei Compound
C1C2 C2C3 C3C4 C4C5 C5C6 C6C1
Glycolaldehyde hydrate Glyceraldehyde hydrate
48.7 48.5
-
-
-
-
-
69 223
46.1 42.5
-
37.2 37.6
-
-
-
-
223, 224 223, 224
-
-
-
-
223, 224 223, 224 223, 224
Aldotetroses D-Threose a-Furanose P-Furanose D-Erythrose a-Furanose P-Furanose Hydrate Aldopentoses D-Arabinose a-Pyranose P-Pyranose D-Lyxose a-Pyranose P-Pyranose D-Ri bose a-Furanose P-Furanose a-Pvranose P-PGranose D-Xylose a-Pyranose P-Pyranose Aldohexoses D- Allose a-Pyranose P-Pyranose D-Altrose a-Furanose ,B-Furanose a-Pyranose P-Pyranose D-Galactose a-Pyranose P-Pyranose D-Glucose a-Pyranose a
P-Pyranose a
-
Ref.
43.2 46.8 48.2
-
45.7 45.7
-
-
37.8 37.5
-
-
223, 224 223, 224
47.1 43.2
-
-
38.9 39.6
-
-
223, 224 223, 224
42.6 46.1 43.2 47.0
-
-
-
-
42.4 42.0 38.5 39.7
-
223, 224 223, 224 223, 224 223, 224
46.1 45.9
-
-
39.1 39.7
-
-
223, 224 223, 224
45.4 47.3
-
-
-
-
-
43.4 43.1
-
223, 224 223, 224
46.3 43.8 46.2 43.9
-
-
-
41.1 41.2 42.2 42.9
-
223, 223, 223, 223,
46.0 45.9
-
-
-
44.9 44.6
-
223, 224 223, 224
43.6 43.2 43.0 43.2
-
223, 224 235 223, 224 235
46.2 46.1 46.0 45.8
-
-
-
-
-
-
38.3
38.5
-
-
40.4
38.8
38.9
40.8
-
-
-
224 224 224 224
ONE-BOND I3c-l3c SPIN-SPIN COUPLING CONSTANTS
203
Table 57-continued Coupled nuclei Compound D-Gulose a-Pyranose P-Pyranose D-Idose a-Furanose P-Furanose a-Pyranose P-Pyranose D-Mannose a-Pyranose P-Pyranose D-Talose a-Furanose P-Furanose a-Pyranose P-Pyranose
C1C2 C2C3 C3C4 C4C5 C5C6 C6C1
Ref.
45.9 47.7
-
-
-
-
44.5 44.5
-
223, 224 223, 224
-
46.2 43.8
-
-
-
40.8 41.5 42.0 44.3
-
224 224 224, 225 224, 225
46.7 42.7
-
-
-
43.3 43.3
-
223, 224 223, 224
46.1 42.3 46.5 42.3
-
-
-
-
-
41.3 41.8 45.0 45.0
-
223, 224 223, 224 223, 224 223, 224
Derivatives of ' 3 C 6 - ~ - g l u ~ ~ s e 33.6 44.1 C 33.6 43.5
37.0 38.7
48.0 48.7
34.5 34.5
-
235 235
-
b
a13C6-D-glucose.
bl,2:5,6-di-O-isopropylidene-a-~-[ 1 ,2,3,4,5,6-'3C6]glucofuranose. "1,2:5,6-di-O-isopropylidene-3-O-benzyl-c~-~-[1 ,2,3,4,5,6-'3C,]-glucofuranose
Table 58. One-bond CC couplings in some alditols measured in D 2 0 (all values in hertz).228 Compounds Glycerol D-Arabinitol
Ribitol Xylitol
Coupled nuclei c1c2 41.2 42.3 41.4 41.6
Compounds
Coupled nuclei c1c2
D-Glucitol D-Talito1 D-Mannitol
41.3 41.4 41.5
for trans compounds than for cis ones were observed for substituted cyclopropanes and cyclohexanes (see relevant sections). Amino acids, peptides and proteins are another group of biologically important compounds extensively studied by means of 13C NMR. The older 'J(CC) data for neutral and protonated amino acids have been collected by Krivdin and Kalabin.'
204
K. KAMIENSKA-TRELA
Table 59. One-bond CC coupling constants for the pentuloses, pentos-2-doses and derivatives thereof; all values in hertz.
Coupled nuclei Compound
C1C2
2-Pen tulofuranoses a-D-Erythro 51.8 P-D-Erythro 51.3 a-D-Threo 51.8 P-D-Threo 51.2 Acyclic 2-pentuloses Keto-erythro 41.2 Keto-threo 41.3 Pentos-2-ulopyranose hydrates a-D-Erythro 52.0 P-D-Erythro 53.4 a-D-Threo 54.9 P-D-Threo 51.4 Ketofuranose exocyclic hydrates of pentos-2-uloses a-Erythro P-Threo Aldofuranose endocyclic hydrates of pentos-2-uloses a-Erythro P-Erythro ~-Pentos-2-ulopyranoses a-Erythro P-Erythro -
C2C3
C3C4
C4C5
C5C6
C6C1
46.8 47.1 47.0 44.7
-
229 229 229 229
43.3 43.1
-
229 229
44.1 44.7 43.1 43.8
-
230 230 230 230
44.0 44.0
-
46.1 45.7
-
230 230
38.8 39.0
-
230 230
-
Ref.
230 230
-
Table 60. One-bond CC coupling constants in deoxyfuranoses and alkyl-substituted furanoses (in hertz) .231
Compounds
'J(ClC2) 42.5
45.2 48.3 42.1 47.1 43.4 47.6 46.5 42.2
ONE-BOND '3C-'3C SPIN-SPIN COUPLING CONSTANTS
205
Table 61. One-bond CC spin-spin couplings in the D-penturonic acids (in hertz).232
'J( C1C2)
Compounds
46.1 46.9 43.5 46.3 46.9 43.7 42.5 42.9 46.5 46.0 46.8 40.7 45.3
a-~-Arabinuronicacid Methyl a-arabinofuranosiduronic acid P-D-Arabinuronic acid a-DLyxuronic acid Methyl a-D-lyxofuranosiduronic acid P-D-Lyxuronic acid a-D-Riburonic acid a-D-Riburonate (pH 4.7) P-D-Riburonic acid P-D-Riburonate (pH 4.7) Methyl P-ribofuranosiduronic acid a-D-Xyluronic acid P-D-Xyluronic acid
Table 62. One-bond CC couplings in some '3C-enriched erythro- and ribonucleosides (in hertz). Compounds
9-P-o-Erythrofuranosyladenine 1-P-o-Erythrofuranosylcytosine 1-P-D-Erythrofuranosyluracil 9-P-D-Ribofuranosyladenine 1-P-D-Ribofuranosylcytosine 9-P-u-Ribofuranosylguanine 1-P-o-Ribofuranosyluracil
'J( ClC2)
'J(C2C3)
Ref.
43.4 43.9 43.9 42.5 42.9 42.9 43.0
-
233 233 233 234 234 234 234
37.9 37.8 37.8 37.8
Table 63. One-bond CC couplings (in hertz) in some D-furanosides. Coupled carbons Compounds
C1C2C2C3 C3C4C4C5 C5C6 Ref.
47.6 Methyl-P-furanoside Methyl-a-ribofuranoside 46.7 37.2 Me thyl-P-ribofuranoside 44.6 37.2 - _ 52.4 46.7 41.1 Methyl-a-fructofuranoside Methyl-P-fructofuranoside 53.0 48.4 40.8 Methyl 2,3,5-tri-O-benzyl-a-xylofuranoside 44.8 42.6 39.6 45.3 Methyl 2,3,5-tri-O-benzyl-P-xylofuranoside 47.6 42.0 38.3 44.6 Methyl 2,3,5-tri-O-benzyl-a-arabinofuranoside48.3 42.3 39.0 44.6 Methyl 2,3,5-tri-O-benzyl-/3-arabinofuranoside 45.0 41.9 40.1 44.1 Methyl 2,3,5-tri-O-benzyl-P-ribofuranoside 46.8 39.2 39.6 43.6 Methyl 2,3,5-tri-O-benzyl-a-lyxofuranoside 47.7 38.9 - 45.9 Methyl 2,3.5-tri-O-benzyl-aY-fucofuranoside 44.6 39.8 40.4 43.7 Methyl 2,3.5-tri-O-benzyl-P-fucofuranoside 48.3 42.6 - 44.8
233 234 234 226 226 236 236 236 236 326 236 236 236
206
K . KAMIENSKA-TRELA
have measured 1J(i3C-L3CO) couplings for Recently, Grehn et s-trans (E) and s-cis ( Z ) isomers of two derivatives of the simplest amino acid glycine, i.e. for 13C-enriched tert-butoxycarbonylglycine and glycine amide. The compounds can be used as precursors providing access to most backbone-labelled a-amino acids, which makes studies on their structure particularly important. A very weak influence of conformation on 'J(CC) value has been observed in the amide only:
I
LH,COR
H
R = O H or NH
2
Flavodoxins are a group of relatively small flavoproteins (14-23 kDa) consisting of one polypeptide chain and containing a single molecule of non-covalently bound riboflavin 5'-phosphate. One-bond CC coupling constants have been recently determined by Vervoort et ~ 1 . ~for~ riboflavin ' 5'-phosphate in the oxidized (FMN) , two-electron-reduced neutral (FMNH2) and anionic state (FMNH-). For a comparison, the couplings in tetraacetylriboflavin in the oxidized and two-electron-reduced state, T A R F and TARFH2, respectively, have also been measured. The data obtained for these model compounds have been used to interpret the results obtained for the flavodoxins derived from Megasphaera elsdenii, Clostridium MP, Azotobacter v i n e l ~ n d i iand ~ ~ ~Desulfovibrio vulgaris.239 The electronic environment and conformation of the isoalloxazine ring in Anabaena 7120 flavodoxin were investigated by Markley and c o - w o r k e r ~ ~(Table ~' 66). One-bond CC coupling constants can be also applied in a different way, i.e. for the assignments of protein carbon spectra. As was demonstrated by R ..
R
1
oxidized
and
reduced
forms of the isoalloxazine ring of flavin nucleotides
u
ONE-BOND 13C-13C SPIN-SPIN COUPLING CONSTANTS
207
Table 64. One-bond CC coupling in some disaccharides (in hertz).
Coupled nuclei Compounds
C1C2 C2C3 C3C4 C5C6 Ref.
/3-D-Fructofuranosyla-1,-glucopyranoside (sucrose) 0-a-L-Fucopyranosyl-(1---f 2-methylP-I)-galactopyranoside
52.6
46.1
39.4
42.5
226
48.1
-
-
-
227
Table 65. 'J(CC) in derivatives of glycine t-BuOCONHCH2COR (in hertz).237
Substituent R
Conformation
'J(CC)
E Z E Z
58.9 58.9 51.3 52.5
OH OH NH2 NH2
Table 66. One-bond CC coupling constants of free and protein-bound [4,4a,10a13C3]flavinin the oxidized and reduced state (in hertz, k0.5).
'J(C4C4a) Compound TARF (TARFH2) FMN (FMNHZ) (FMNH-) C.M P flavodoxin M. elsdenii flavodoxin D . virlgaris flavodoxin A . vinelandii flavodoxin Anabaena 7120 flavodoxin" "'J(CX7'a)
=
'J( C4aClOa)
Oxidized
Reduced
Oxidized
Reduced
Ref.
75.5 75.4
79.1 82.0 84.0 85.5 85.2 86.7 87.9
53.3 55.9
84.5 81.6 74.4 73.2 73.2 72.8 72.0
238 238 238 238 238 239 238 240
-
76.3 76.5 76.9 76.3 74.9
44.4 Hz f 0.5 Hz; 'J(C8C8'a)
-
=
-
56.2 56.5 57.3 56.5 56.9
-
41.6 Hz k 0.5 Hz.
Markley and c o - ~ o r k e r s ~ entire ~ ~ -carbon ~ ~ ~ spin systems for amino acid residues and prosthetic groups can be identified by recording modified double quantum INADEQUATE spectra of uniformly 13C enriched compounds. The method has been among others applied in order to outline the carbon spin system of Anabaena 7120 flavodoxin, ferredoxin and some other proteins. A biosynthetic 13C labelling technique combined with analysis of the carbon-carbon scalar coupling patterns that facilitates complete stereo-
208
K. KAMIENSKA-TRELA
\/ CH
YH3
I
H3C\ CH
V:
I
-13CH
I
' 3 ~ ~ 2
-
o
!
o
n Y'
I
011'3C)
HA3C\ /CH3
13CH
I
/CH3
13CH
CHz
I
V:
II
L: -CH-
I
-CH-
L:
0 0
-CH-
O] 'J 0
u
~
>
I
~
I
I
1J>3C'H ~
B
0 2
(l H)
Fig. 7. Schematic representation of the dominant multiplet fine structures expected for the methyl 13C-lH cross-peaks of Val and Leu in [I3C, 'H COSY spectra recorded with a protein preparation fractionally labelled with C. The arrows indicate the coherence transfer that is relevant in the present context. (a) For $CH3 of Val or 62CH3of Leu the multiplet consists of two components along w2 separated by the 'J(CH) coupling constant. No splitting is observed along wl.This pattern is the same as for methyl groups in a protein with natural abundance of 13C. (b) In addition to the 'J(CH) splitting along y,y'CH3 of Val and @CH3 of Leu have a splitting of 'J(CC) along q. (Reprinted with permission from ref. 245, 1989 American Chemical Society.)
3-
specific assignments of the methyl groups of valine and leucine at an early stage of a protein structure determination has been proposed by Wutrich.244 In this approach the microorganisms which produce the required proteins are fed with a mixture of roughly 10% ['3C6]glucose and 90% unlabelled glucose as the sole carbon source. The isopropyl groups in both Val and Leu are formed from a two-carbon unit which originates from one pyruvate
ONE-BOND 13C-13CSPIN-SPIN COUPLING CONSTANTS
209
molecule, and since the process is stereoselective, the methyl groups in this case are always pro-R. The second methyl group is transferred from another pyruvate molecule and is always p r o 3 in both valine and leucine. This, according to probability calculus, leads to two different results, namely in 'H-decoupled 13C NMR spectra the 13C resonance of the pro-R methyl group appears as a doublet with 'J(CC) of ca. 33Hz, and the 13C NMR signal of the pro-S methyl group as a singlet. This is reflected in the corresponding diagrams of two-dimensional 'H-detected heteronuclear correlation experiments (["C, 'HI-COSY) which are easy to interpret (Fig. 7). This novel method, biosynthetically directed fractional 13C labelling, has been applied by Wutrich and co-workers to stereospecific 'H and 13C NMR assignments for the two diastereotopic methyl groups of the 14 valyl and leucyl residues in the DNA-binding domain 1-69 of the 434 repressor,245for the NMR assignment of the diastereotopic methyl groups of the valyl and leucyl residues in a cyclic peptide and in two globular proteins,246 and in the cyclic peptide cyclosporin A obtained from Tolypocladium i n J l ~ t u m . ~ ~ ' The method has been further developed by Szyperski et al. ,248 and applied in studies on the three samples obtained using the Escherichia coli overexpression system W3110 lac lQ/pTP125 for high-level production of the P22c2 repressor, which consists of a polypeptide chain with 216 amino acid residues, including all 20 proteinogenic amino acids. The authors found that the 59 aliphatic carbon positions in the latter compounds exhibit 16 different types of 13C-'3C coupling fine structures. These provided support for the assignment of the resonances of all methyl groups in the proteins studied and, in addition, because of the large values of the 13C-'3C coupling constant with the C ( 0 ) carbon involved the C(y) resonances of glutamine and glutamic acid have been identified by them. The great advantage of the method described lies in the fact that due to the high inherent sensitivity of the ['3C,1H]-COSY experiment for observation of methyl groups, only a small amount of protein enriched to about 10% in 13C is needed for these assignments, corresponding to 0.5 ml of an approximately 0.1 mM protein solution. All of the expected 13C-13C interactions, including those to quaternary ' A from Lactococcarbons, have been identified by Sailer et ~ 1 . ~for~ Nisin cus luctis by the use of the 2D INADEQUATE method, thereby giving the full carbon connectivity pattern for all individual amino acids. This food-preserving bacteriocine has been isotopically I3C and 15N enriched using a soluble peptone derived from enzymatic hydrolysis of Anabaena sp. ATCC 27899 cells grown on sodium ['3C]bicarbonate and sodium [''Nlnitrate. The I3C chemical shifts and I3C-l3C coupling constants are also a valuable ~ ' tool for studying enzyme transformations. Rajagopalan et ~ 1 . ~ have described the preparation of [U-13C]chorismate starting from [U'3C]glucose by the use of Klebsiella pneumoniae and its further enzymatic
210
K. KAMIENSKA-TRELA
163 a chorisrnic acid
163 b chorisrnate
164 prephenate
7 coo-
OH 165 hydroxyphenylpyruvate
transformation to [U-13C]prephenate and [U-13C]hydroxyphenyl pyruvate (Table 67). An extensive use of 13C-13C coupling patterns has been made in in vivo and in vitro studies on the metabolism of [1,2-13C2]acetatein rat brain,251in analyses of urinary metabolites of [ 1,2,3-13C3]acrylonitrile252 and [1,2,3'3C3]acryloamide253in rats and mice and in analysis of tricarboxylic acid cycle of the heart.254Further examples include identification and comparison of the urinary metabolites of [1,2,3-'3C2]acrylic acid and [1,2,3'3C2]propionic acid in the rat,255 the study on the metabolism of [ '3C]propionate in wild-type Escherichia coli and cells lacking citrate synthase .256 Evidence for nonregiospecific incorporation of [1,2-13C2]acetate during biosynthesis of 6p-hydroxytropine in Datura stramonium has been presented by Hemscheidt and S p e n ~ e r , ~the ~ ' incorporation of sodium [l-13C2]acetate and sodium [1,2-13C2]acetate into a number of polyketide metabolites produced by the fungus Arthropsis truncata has been examined by Ayer and Craw,25s (Table 68) and biosynthesis of the A/B/C/D-ring system of the rotenoid amorphigenin by Amorpha fruticosa seedlings starting from phenylalanine has been reported by Bhandari et ~ 1 . ~ ~ ~ 13C NMR spectroscopy including analysis of one-bond CC couplings has been applied to on-line monitoring of the Krebs cycle in isolated rat heart mitochondria during respiration2a (Table 69), to following the metabolism of glucose to glycogen in vivo and in vitro in the liver of fasted and well-fed rats261and to studying the stimulatory effect of acetate and propionate on aspergillic acid formation by Aspergillus oryzae A 21.262
ONE-BOND l3C-I3C SPIN-SPIN COUPLING CONSTANTS
21 1
Table 67. One-bond spin-spin CC couplings (in hertz) in chorismic acid (163a) and chorismate (163b), in prephenate (164) and hydroxyphenyl pyruvate (165).250 Compound no. C1C2 C2C3 C3C4 C4C5 C5C6 C1C6 163a 163b" 164 165
69.4 69.8 38.1 57.7
44.6 44.6 69.1 57.7
~~~
44.6 44.2 44.9 65.3
44.6 44.9 44.9
65.3
67.2 67.2 69.1 57.7
C1C9
ClClO C7C8 C8C9
53.6 51.7 38.1 33.0-37.5 44.9 57.7
72.4 64.9 45.3 -
81.5 74.3 61.9 62.6
81.5 80.4 37.4 37.4
~~
"[U-'3C]chorismate in 20 mM kP, buffer (pH 7.0) containing 0 5 mM EDTA and 2.5 mM P-mercaptoethanol.
Table68. Satellite multiplicities in the I3C NMR spectrum of arthropsadiol A diacetate (166) after incorporation of one molecule of Na[l,2-13C2]acetate (a) and after multiple incorporation (b); all data are from ref. 258, rather large discrepancies observed for 'J(C2C3), 'J(C6C7) and 'J(C7C8) have not been commented upon by the authors. All data are in hertz. 0
~~
Coupling
c1c2
C2C3 c3c4 c4c5 C5C6 C6C7
(a)
(b)
42, 41
42 72, 68 44,45 38, 38 62, 62 53, 62
-
44,43 -
62, 62 -
~~
Coupling C7C8 C8C9 c9c4 c9c10 ClOCll CllC12
(a)
(b)
43, 43
38 35 35-40 35,35 43, 43
-
35,35 -
A simple 13C NMR method has been developed by Sherry et al.263which allows one direct determination of substrate oxidation in tissue for up to three competing 13C-enrichedsubstrates. It has been applied by the authors to studying the alterations in substrate utilization in the reperfused myocardium.
212
K. KAMIENSKA-TRELA
12. EXPERIMENTAL METHODS Spin-spin coupling between carbon nuclei can be observed only in the spectra of isotopomers containing a pair of 13C atoms. Since the natural abundance of such isotopomers is very low (less than 0.01% of total), the corresponding spectra appear as doublets of low intensity located around the strong signals of non-coupled carbon atoms. The satellite lines are about 200 times weaker than the main signals of a 13C spectrum. This, combined with an unfavourable sensitivity of the 13C nucleus to NMR detection, caused a formidable challenge for 13C-13C studies, since for a long time 13C enrichment, expensive and often difficult experimentally, was an absolute requirement. With the introduction of high-field magnets and pulsed Fourier transform (FT) technique, it became feasible to record 13C-13C satellite spectra at the natural abundance of I3C isotope. Analysis of such spectra is straightforward since the satellites represent AB spin systems and the coupling constants can be extracted by inspection. The population of triply labelled isotopomers is a hundred times lower than that of doubly labelled ones and the corresponding ABC or ABX spectra never appear in the spectra registered at the natural concentration of 13C isotope. A breakthrough took place when INADEQUATE was introduced by Bax et aL2@ in 1980. This technique using double-quantum filtering suppresses signals of singly labelled molecules and allows one to observe the 13C NMR spectra of doubly labelled isotopomers. Since its discovery, INADEQUATE has gained a well-deserved popularity and both its one- and two-26s,266 dimensional versions have been widely applied in order to elucidate the carbon<arbon connectivities in organic molecules and to measure carboncarbon spin-spin couplings. The main drawback of the original INADEQUATE pulse sequence is its inherent low sensitivity, and numerous attempts have been made in order to overcome it. In several excellent reviews and books the theoretical background of the method, its experimental details and further improvements and editing techniques have been thoroughly d i s c ~ s s e d , ~ ~and ~-~~' only the most recent techniques are included in the present review, the older methods being only shortly mentioned here. The initial heteronuclear polarization transfer takes advantage of the higher proton polarization and the usually shorter proton longitudinal relaxation times, which allow shorter intervals between subsequent scans. This approach has been applied by Sorensen et Sparks and Ellis,271 and quite recently P o d k ~ r y t o v . 'The ~ ~ advantage of the higher sensitivity of proton detection, incorporated in inverse techniques via the final polarization transfer, has been used in the inverse INADEQUATE (INSIPID) experiment by Keller and V ~ g e l eThe . ~ ~main ~ disadvantage of the methods mentioned above is that they are not applicable in the case of quaternary
213
ONE-BOND l3C-I3C SPIN-SPIN COUPLING CONSTANTS
Table69. One-bond CC couplings (in hertz) recorded on model solutions if not otherwise stated in the 13C NMR spectra of suspensions containing isolated heart mitochondria.2m
Coupling across the bonds
1 2 3 4 HOZCCH2CH2C02H 1 2 3 4 H02CCH(OH)CH2C02H 1 2 3 4 H02CCOCH2COOH H20 1 2 3 4 H02CCH( NHz)CH2C02H 1 2 3 4 5 HO~CCH(NH~)CHZCH~CO~H
1 2 3 4 5 H02CCOCH2CH2C02H
C1C2
C2C3
C3C4
C4C5
52; 52
-
52; 52
-
60; 60 39; 39 55; 53" 38"
56; 56 52"
-
65; 65
46; 43
55; 54
-
54; 54 52"
37; 37 36"
-
-
53; 53 57"
34; 34 35"
35; 35 34; 34"
-
-
-
-
-
39; 40 37; 37 52; 52 39; 39" 37; 37"
~~
1 2 3 4 5 H02CCH2C(OH)CHZC02H 61
55
-
39; 39 38"
-
59; 60'
55; 55
35; 36
33; 33
52; 52
-
co2
1 2 3 4 5 HOZCCH(OH)CH(CO~H)CH~COZH "Recorded on preparations. 'Corresponds to 'J(C3C6).
carbons, i.e. those without hydrogens attached. These carbons are missing in the spectrum. More sensitive, selective variants of the INADEQUATE experiment have been proposed by several authors. In general, these methods allow one to elucidate the carbon-carbon connectivities but first of all highly accurate CC coupling constant values are available in this way. The selective INADEQUATE method called SELINQUATE in which a selective pulse converts the double quantum coherence into observable magnetization of those carbons which are coupled to the selectively excited carbon has been
214
K. KAMIENSKA-TRELA
developed by Berger.274This method, however, cannot be applied to older types of instruments which are not equipped with a selective excitation unit. This limitation does not concern the method devised by Canet et ~ 1 . ~ ~ ' where the selective polarization transfer was achieved by properly varying the delay around the value [U(CC)]-' and co-adding the corresponding free induction decays. An alternative method where the selectivity is achieved by a chemical shift selective filter leaving the evolution delay constant has been proposed by Kover et ul.276 The same approach has been applied by these authors to the H-C-C- relay experiments. Ma and Big1e1-I~~ have applied a series of selective 180" pulses instead of one selective pulse as in SELINQUATE. In this case not just one but several carbon spins are sequentially perturbed and the corresponding responses are detected simultaneously. The method is a valuable alternative to the basic INADEQUATE experiment provided that only a part of spectrum is of interest. The method has been furthermore applied in order to measure the connectivities and both one-bond and long-range carbon-carbon coupling constants in a 14membered ring compound, cembrene. L73 A selective version of the seven-pulse DEPT-INADEQUATE experiment was devised by Podkorytov and L ~ b n i n This . ~ ~ pulse ~ sequence gives a spectrum analogous to that obtained by Berger's SELINQUATE technique but with a gain in sensitivity due to polarization transfer. This pulse sequence differs from SELINQUATE in that it uses a selective DANTE read pulse and does not require equipment for the generation of a soft Gaussian pulse. In order to eliminate the off-resonance effects, composite pulses have been implemented in a one-dimensional version of the INADEQUATE experiment by Lewitt and E r n ~ t and ~ ~in ~a ,two-dimensional ~ ~ ~ one by Lambert et ~ 1 . ~ "This allowed the authors to overcome the problem of unequal signal intensities in the INADEQUATE spectra and to increase the sensitivity of the method. A method for improving both the S/N ratio and the sensitivity of 2D INADEQUATE spectra by considering the symmetry and the isotopic shifts has been proposed by Lambert and Buddrus.281The procedure is applied to phase-sensitive spectra taken with QUAD detection in both dimensions. The predicted and observed improvement of the S/N ratio is by a factor of 2, equivalent to a reduction in experimental time by a factor of 4. The INADEQUATE method can be also improved by the use of compensated delays and pulses as has been shown by Torres el ~ 1 . ' ~ 'A J-compensated homonuclear spin-echo sequence was developed by these authors from the composite pulses using a product-operator analogy between homonuclear spin-spin coupling and r.f. pulses, and applied to construct a J-compensated INADEQUATE sequence. The sequences CINADEQUATE, which incorporates composite pulses, and JCINADEQUATE, which includes both offset and J-compensation,
ONE-BOND ‘%-I3C SPIN-SPIN COUPLING CONSTANTS
215
have a sensitivity considerably higher than that of conventional INADEQUATE. 125 Strongly coupled spin systems, i.e. those with couplings that are large by comparison with the chemical shift difference, always present difficulties in attempts to register their spectra and/or evaluate their time evolution. In particular, in 1988 Kay and McC1ung282showed that also in the case of these systems the very convenient ordinary product operators can be applied, only with somewhat complicated coefficients. Kay and McClung’s formalism has been further developed by Nakai and M ~ D o w e l l and ’ ~ ~ applied in order to estimate the time evolution for extremely strongly coupled spin AB systems. This approach is much more convenient than the formerly applied density matrix. As an example the refocused INADEQUATE spectrum of benzyl bromide, in which two one-bond l3C--l3Cpairs are very strongly coupled, has been measured by the use of this newly developed method. The signals attributable to these spin pairs were detected with reasonably large intensities and the corresponding couplings including one-bond and longrange ones have been determined. The same group of authors developed the new refocused INADEQUATE method, which yields in-phase J doublets arising from 13C-13C pairs.283 The procedure designed for obtaining 2D pure absorptive INADEQUATE allows one to determine J couplings with accuracy higher than that in magnitude-mode spectra. A further advantage of the refocused method is that it allows one to avoid the accidental cancellation of positive and negative signals in crowded INADEQUATE spectra. The authors, however, stressed that tl quadrature detection in the method devised by them is not as simple as that in the standard INADEQUATE experiment, where the read pulse with a flip angle of 120°-135” can virtually distinguish the echo components from the antiecho ones in the 2D signals. Another inconvenience is that the delay time, 47, required to create and refocus the double quantum coherence is twice that for the ordinary sequence. Another great disadvantage of INADEQUATE lies in the fact that a correct delay time 7 = 1/(4J(CC)) must be set before starting the experiment. Its correct estimation may be quite difficult since the magnitude of ‘J(CC) may vary very strongly. A new technique which allows one to circumvent the difficulty connected with an appreciable spread of J(CC) values was proposed by Blechta and Freeman.284 The method uses the band-selective uniform-response pure phase (BURP) pulses which may be used for excitation or spin inversion, and achieves full sensitivity without the need to “tune” for the expected value of the coupling constant. Nevertheless, two separate experiments should be run in order to measure usually rather large one-bond and always small long-range CC couplings. The detection of carbon-carbon connectivities in the solid state is of great interest though it is a rather difficult task. This can be accomplished via the observation on 13C NMR spectra of solids rotated at the magic angle. The
216
K. KAMIENSKA-TRELA
spectra exhibit intensity and line width contributions due to homonuclear dipolar couplings. Such residual direct dipolar couplings, those across 13C-13C bonds, can be exploited in a double-quantum experiment in order to establish C-C connectivities in a given sample. The first INADEQUATE spectrum for a solid sample was recorded by Benn et ul.285 They used camphor as a model compound whose C P MAS (cross-polarization magic angle spinning) INADEQUATE spectrum provided the first example of the two-dimensional solid-state NMR spectrum from which the CC connectivities were derived using the homonuclear indirect CC scalar coupling constants. Nakai and McDowell have described the spinning spectra of the homonuclear two-spin systems, using the Floquet theory instead of the average Hamiltonian theory.286,287This new approach has allowed them to determine the spin parameters for homonuclear two-spin systems from the magic-angle spinning (MAS) and off-magic-angle spinning (OMAS) spectra.'26 Doubly 13C2-labelled sodium acetate, 13CH313COONa, and palmitic acid, CH3(CHJ1313CH213C00H, were used as model compounds. As a result, 'J(CC) couplings including their signs (positive ones) were determined for both compounds (see Table 16). Several new three-dimensional experiments have been described, all of which involve one-bond I3C- 13C coupling ons st ants.^^^"^^ 13. APPLICATION OF THE INADEQUATE METHOD IN STRUCTURAL ELUCIDATIONS
One of the most useful applications of both one- and two-dimensional INADEQUATE experiments concerns the determination of carbon-carbon connectivities of the carbon network. A variety of structures has been solved by the use of this method which is very often referred to as the X-ray of solutions. Among others the technique has been frequently applied in order to elucidate the structure of the compounds of biological origin, such as peptides, saccharides, metabolites, etc. In 1987 Christie and Munk included the INADEQUATE information into their structure solving program, CASE2" and its successor SESAMI (Systematic Elucidation of Structure Applying Machine In tellig en ~ e).'~In~ 1989, a program for applying 2DINADEQUATE data was introduced by Funatsu et al.292to their automated structure elucidation system, CHEMICS. A short review on this topic has been written by Massiot and N ~ z i l l a r d . ~ ~ ~ However, there are some inherent snags in the method which until now quite severely limit its widespread application. One of them is its low sensitivity which requires a rather large amount of the sample, and good solubility. Another problem is that before starting the experiment the value of 'J(CC) has to be well estimated. In order to overcome the sensitivity
ONE-BOND I3C-l3C SPIN-SPIN COUPLING CONSTANTS
217
problem and to take full advantage of this elegant experiment, two different approaches have been proposed. In one of them synthetically I3C-enriched samples are used. This approach has been widely applied by Markley and his for identification of individual peptides in uniformly 13Clabelled (up to 26%) proteins (see also Section 11 and references cited therein). The spectra have subsequently been analysed using a "semiautomated graphics package". A completely different approach was presented in 1990 by Dunkel et a f .,2y5,2y6 who designed a computer program capable of extracting bond information from low signal-to-noise ratio (S/N) 2D INADEQUATE spectra in a fully automated fashion. After substantial improvements of the original version of this program,2y7 which eliminated all manual manipulation of the data, it is possible now to perform an analysis of the spectrum with modest digital resolution and an S/N as low as 2.5. The procedure consists of two steps. In the first step the program localizes INADEQUATE responses in a 2D map within the general noise level of the spectrum, and appropriate signal treatment follows. Once correlations are known, a rather simple program is used to establish the connectivity of the carbon atoms. Using this strategy, Dunkel et af.298,2" were able to analyse the 2D INADEQUATE spectrum of bistramide A (167), a compound extracted from a Fijian Lissocfinum sponge, having only 50mg (20pmole!) of the compound at their disposal. It is worth while to emphasize that not only was the correct (revised) structure of the compound established, but that also most of the C C couplings were determined (Table 70). One should add, however, that data acquisition took 12 days and data processing required 27 h using three IBM RS/6000-520 computers. Revised assignments of the I3C-NMR spectra, based on 2DINADEQUATE experiments have recently been published for five derivatives of bicyclo[3.1. llheptane, cis-pinane, trans-pinane, cis-myrtanol, transmyrtanol and m y r t e n 0 1 . ~Although ~ numerous indirect techniques such as DEPT, COSY and HETCOR have previously been applied to assign the 13C spectra of these molecules, the results were dubious, and only the INADEQUATE technique allowed one unambiguous assignment of all 13C signals. Further examples of the application of the INADEQUATE technique to structure elucidation include azithromycin, a ring-expanded derivative of the important antibiotic erythromycin A,301 a ~ t e l l a t o l , ~a' ~ new complex sesterpene isolated from Aspergiffus variecofor, forskolin, isolated from the Indian medicinal herb Cofens forskohfii Briq. (Labiattae) ,303 which is a unique adenylate cyclase inhibitor, and the algal metabolite balearone, one of the marine meroditerpenoids in which the side chain incorporates a bicyclo[3.2.0]heptane ring system.304 The INADEQUATE technique has been applied in order to elucidate structures of p a x i ~ t e r o l , ~a' ~ sterol isolated from Penicillium paxiffi, an orally active cardiosteroid a ~ r i h e l l i n , ~ " ~ novel antibiotics aurantinis A and B produced by Bacillus aurantinus, b h a r a n g i ~ ~ a, ~diterpenoid '~ quinonemethide from Pygmacopremna herbacea
218
K. KAMIENSKA-TRELA
167
I
40
bistrarnide A (revised)
(Roxb.) M ~ l d e n k e , ~cyclonerodiol,309 "~ a metabolite isolated from corn infested by Fusarium moniliforme Sheld and phenylbutan-2-one p-Dg l u c o s i d e ~isolated ~~~ from raspberry fruit. An application of the INADEQUATE method in structural studies on 13C-substituted carbohydrates has been discussed thoroughly by Wu and S e ~ i a n n i Use . ~ ~ of ~ 2D 13C-13C and 13C-15N correlation spectroscopy in sequencing the amino acid units has been described by Moore et al.,312who studied puwainaphycin C , a cardioactive cyclic peptide isolated from the blue-green alga Anabaena BQ- 16-1. Polymers are the group of the compounds which have been extensively Table 70. One-bond CC couplings (in hertz) in bistramide A (167).2y8
Coupled nuclei
'J(CC)
Coupled nuclei
'J(CC)
Coupled nuclei
'J(CC)
c1c2 C2C3 c4c5 C5C6 C6C7 C7C8 C8C9 C9C10 C9C11 CllC12 C12C13 C14C15 C15C16
41.7 53.8 41.0 41.8 36.5 32.5 33.1 35.4 36.2 35.8 51.0 39.8 36.2
C16C17 C16C18 C19C20 c20c21 c21c22 C22C23 C23C24 C23C25 C26C27 C27C28 C28C29 C29C30 C30C31
34.5 49.0 36.1 35.2 40.7 36.7 35.4 33.0 45.2 45.6 33.0 32.6 36.9
C31C32 C32C33 c33c34 C34C36 C37C38 C34C35 c37c39 C39C40
40.5 35.5 34.5 43.7 43.5 34.8 45.7 38.7
ONE-BOND '%-I3C SPIN-SPIN COUPLING CONSTANTS
219
studied by means of the INADEQUATE method. The assignments of the 13C NMR spectra by the use of the 2D INADEQUATE technique have been performed for regioirregular polypropylene containing up to 40 mol% of the inverted propylene unit,313 for an ethylene-propylene c o p ~ l y m e r , a~ ~ butene-propylene ~.~~~ copolymer,316 some stereoirregular p ~ l y o l e f i n sand ~ ~ ~regioirregular poly( 1-butene) containing many inverted units,318 and p o l y v i n y l a l ~ o h o l ~ and ~ ~ p o l y ~ i n y l c h l o r i d e .The ~ ~ ~ 2D INADEQUATE technique has been successfully applied to the 13C NMR assignment of rn-cresol novolak d i m e r ~that , ~ ~of~linear trimers of buta-l,3diene obtained from the Ziegler-Natta process,322 and of the non-ioniccationic surfactant N-dodecyl-N,N-dimethylamine A new monomer, ethyl a-[(allyoxy)methyl]acrylate, has been polymerized by Thompson et al. ,324 to give a polymer consisting exclusively of five-membered rings with a ratio of trans to cis ring configuration in the polymer backbone of approximately 2.2. The structure of this novel cyclopolymer was conclusively confirmed by 2D INADEQUATE technique. Other examples of the application of 2D-INADEQUATE technique involve analysis of the structure of some catalytic products obtained from 1,3-butadiene and phenyl isocyanate in which two, three or four 1,3-diene molecules are coupled with one cyanate ,325 the adducts of diazocyclopentadiene derivatives with dimethylacetylenedi~arboxylate,~~~ and studies on maleopimaric acid, the Diels-Alder adduct of levopimaric acid and maleic anhydride, and of abietic The complete I3C NMR chemical shift assignment based on 2D 13C INADEQUATE and heteronuclear 13C,'H-COSY experiments of a new chiral pentacyclic pinocarvone dimer published by Kolehmainen et d.328 provides another elegant example of the application of two-dimensional methods. The compound, 6,6,6',6'-tetramethyl-3,4,5,6,7 ,&hexahydro5,7methanospiro-{2H-l-benzopyran-2,2'-bicyclo[3.l.l]heptan}-3'-onewas obtained as the SO2 oxidation product of (lS)-(-)-P-pinene, and in some earlier works an incorrect structure was assigned to it. Finally, several papers have been recently devoted to fullerenes, the most intriguing discovery of the last few year^.^^"'^^ The INADEQUATE technique has been used to confirm which carbons in C70are adjacent. The 'J(CC) couplings measured for this fullerene are in the range 55-68Hz, which is in accord with that expected for a six- and five-membered ring system.329 The large 'J(CC) values provide evidence against proposed structures for fullerenes involving three-membered rings.
NOTE ADDED IN PROOF Some new results have appeared since this review was submitted for publication. They are mentioned briefly below.
220
K. KAMIENSKA-TRELA
One of the most striking results obtained recently in the field of one-bond 13C-13C coupling constants is that obtained by Bocian et al. (W. Bocian, J. Jazwinski, L. Stefaniak and G. A . Webb, J . Chem. Soc., Perkin Trans. 2, 1994, 1467) for a series of mesoionic 3-phenyl-l-thia-2,3,4-triazol-3-ium-5ylmethanides with various exocyclic groups.
Pi Z
=
CN, C 0 2 E t , COMe, COPh
The 1J('3C-'3C) coupling values measured across formally single C(5)-C(6), C(6)-C(7) and C(6)-C(8) bonds were unusually large in comparison with *J('3C-'3C) values observed in other compounds. Thus, for example, for Z = CN, 'J(CSC6) = 92.7Hz, 'J(C6C,) = 97.2Hz and 'J(C6C8) = 99.1 Hz were found, whereas a typical 'J(CSp3C=N) value is of ca. 60Hz only, and that for Csp3-Csp2bond of 40Hz. This large increase observed for all the 13C-13C couplings in the exocyclic fragment of mesoionic compounds can be interpreted in terms of the increased s character of the central C6 atom, and provides clear evidence for a planar structure around this atom. The latter conclusion is in good agreement with the X-ray results obtained for these compounds. One-bond coupling constants between two carbonyl carbons of 66.9 to 84.0Hz have been measured for a series of the doubly 13C enriched compounds of a general formula, P - O ~ N C ~ H ~ ( C H ~ ) ~ N H - ' ~ C O ' ~ C O R , R = O H , OCH3, OC2Hs, OC6H4C2H5and SC2Hs (S. J. Weiner, S. M. Holl and D. F. Covey, M a p . Reson. Chem., 1994, 32, 122). For a compound with R=NHC3H7 an evidently incorrect 'J=0 Hz has been published. Most probably the authors overlooked the fact that in this particular compound the two C ( 0 ) carbons represented very tightly coupled AB system, and very weak outer lines of this spectrum were difficult to observe. The compounds obtained in this work were further used as the model a-dicarbonyl adducts to study the inactivation of cytochromes P-450 by dichloroacetamidecontaining mechanism-based inactivators. A sample of totally enriched '3C18-meso hexestrol, the oestrogen receptor
ONE-BOND l3C-I3C SPIN-SPIN COUPLING CONSTANTS
22 1
ligand (98 at.% of I3C enrichment at every position), has recently been synthesized by Kochanny et al. (M. J. Kochanny, T. Hard and J. A. Katzenellenbogen, Magn. Reson. Chem., 1993, 31, 977). Its complex 13C NMR spectrum was analysed by homonuclear decoupling and ZD 13C COSY experiments, and the estimated 1J('3C-13C) values refined via iterative simulation. The authors expect that l3C-enriched samples will be used more frequently in the future in studying receptor-ligand interactions by polarization transfer methods. The 13C labelling followed by an analysis of the 13C-13C coupling patterns has been especially useful in an investigation of the carbon fixation in the phototropic eubacterium Chloroflexus aurantiacus (W. Eisenreich, G. Strauss, U. Werz, G. Wechs and A. Bacher, Eur. J. Biochem., 1993, 215, 619). This bacterium does not use any of the known autotrophic C 0 2 fixation pathways, and some suggestions have been made that a new cyclic autotrophic pathway in which acetyl-CoA is converted to 3hydroxypropionate and further to succinate and malate. In order to test this hypothesis the growing cultures of the C. aurantiacus have been fed during several generations with 3-hydroxy[ l-13C]propionate,[l-13C]acetate, or [213C]acetate. Subsequently, a full 13C NMR analysis has been performed for the amino acids and nucleotides isolated from the cells of the bacterium. The data obtained confirm that a novel carbon fixation pathway via 3-hydroxypropionate is highly probable. One-bond '3C(0)-13C(O) coupling constants of 73 Hz have been measured for T13+/oxalate adducts of the half-molecules of ovotransferrin, found in an avian egg white, and the N-terminal lobe of serotransferrin, a prominent serum protein (J. M. Aramini, P. H. Krygsman and H. J. Vogel, Biochemistry, 1994, 33, 3304). The ethynyl-bridged complex W2(p-CCH)(OSiMe2t-Bu)5 reacts in hydrocarbon solvents with xylyl isocyanide 2,6-Me2C6H3NC7 to give W2(pcomplex; 'J( 13C-13C) of C( 1)C(2)C(3)NHXyl)(OSiMe2t-Bu)5(CNXyl)4 53 Hz has been found across the C(l)-C(2) bond and that of 36 Hz across the C(2)-C(3) bond (M. H. Chisholm, C. M. Cook, C. J. Huffman and J. D. Martin, Organometallics, 1993, 12, 2354). The 'J(CH2-Cipso) coupling constants have been measured for C6H5CH2C(CH3)3and p-02NC6H4CH2C(CH3)3.The values obtained were 43.8 and 42.6 Hz, respectively (K. Kamienska-Trela, accepted for publication in Magn. Reson. Chem.) instead of 36.0Hz for both compounds as reported by Lambert and Singer (see Table 18 and ref. 137). Thus, 1J(CI12-Cipso)coupling constants in the compounds studied by Lambert and Singer (see discussion on p. 151), not only fail to increase upon passing from C to Sn derivatives but even show a slight decrease. This means that there is no support from 'J(CC) coupling constants for the idea of hyperconjugation in a neutral ground state.
222
K. KAMIENSKA-TRELA
REFERENCES 1. R. M. Lynden-Bell and N. Sheppard, Proc. R. SOC., London, Ser. A . , 1962, 269, 385. 2. D. M. Graham and C. E . Holloway, Can. J . Chern., 1963,41, 2114. 3 . G . E. Maciel, in NMR Spectroscopy of Nuclei other than Protons (eds T. Axenrod and G. A. Webb), p. 187. Wiley-Interscience, New York, 1974. 4. J. L. Marshall, Carbonxarbon and carbon-proton NMR couplings: Applications to Organic Stereochemistry and Conformational Analysis Methods in Stereochemical Analysis. Vol. 2 (ed. A. P. Marchand), Deerfield Beach, Verlag Chemie Int., 1983. 5. V. Wray, in Progress in NMR Spectroscopy (eds J. W. Emsley, J. Feeney and L. H. Sutcliffe), 1979, Vol. 13, p. 177. Pergamon, Oxford. 6. V. Wray and P. E. Hansen, in Annual Reports on NMR Spectroscopy (ed. G . A. Webb), Vol. l l a , p. 99. Academic Press, London, 1981. 7. P. E. Hansen in Annual Reports on NMR Spectroscopy (ed. G . A. Webb), Vol. 11A, 65, Academic Press, London, 1981. 8. P. E. Hansen and V. Wray, Org. Magn. Reson., 1981, 15, 102. 9. L. B. Krivdin and G. A. Kalabin, in Progress in NMR Spectroscopy (eds J. W. Emsley, J. Feeney and L. H. Sutcliffe), 1989, Vol. 21, p. 293. Pergamon, Oxford. 10. K. Kamienska-Trela, in Isotopes in the Physical and Biomedical Sciences (eds E . Buncel and J. R. Jones), 1991, Vol. 2, p. 297. Elsevier, Amsterdam. 11. J.-R. Llinas, E.-J. Vincent and G. Peiffer, Bull. SOC. Chim. Fr., 1973, 3209. 12. J. B. Stothers, Carbon-I3 NMR Spectroscopy, Academic Press, New York, 1972. 13. V. F. Bystrov, in Progress in NMR Spectroscopy (eds J. W. Emsley, J. Feeney and L. H. Sutcliffe); 1976, Vol. 10, p. 1. Pergamon, Oxford. 14. R. E . Wasylishen, in Annual Reports on NMR Spektroscopy (ed. G . A. Webb), Vol. 7, 245. Academic Press, London, 1977. 15. H . - 0 . Kalinowski, S . Berger and S . Braun, ‘-’C-NMR Spektroskopie, Georg Thieme Verlag Stuttgart, New York, 1984. 16. B. Wrackmeyer and K. Horchler, Progress in NMR Spectroscopy (eds J. W. Emsley, J . Feeney and L. H. Sutcliffe), 1990, Vol. 22, 209. Pergamon, Oxford. 17. L. B. Krivdin and E. W. Della, Progress in NMR Spectroscopy (eds J. W. Emsley, J. Feeney and L. H. Sutcliffe), 1991, Vol. 23, p. 301. Pergamon, Oxford. 18. N. F. Ramsey and E. M. Purcell, Phys. Rev., 1952, 85, 143. 19. N. F. Ramsey, Phys. Rev., 1953, 91, 303. 20. H. M. McConnell, J . Chem. Phys., 1955, 23, 760. 21. H. M. McConnell, J . Chem. Phys., 1956, 24, 460. 22. J. A. Pople and D. P. Santry, Mol. Phys.. 1964, 8, 1. 23. J. A. Pople, J. W. McIver, Jr and N. S . Ostlund, Chem. Phys. Lett., 1967, 1, 465. 24. J. A. Pople, J. W. McIver, Jr and N. S . Ostlund, J . Chem. Phys., 1968, 49, 2960, 2965. 25. A. C. Blizzard and D. P. Santry, Chem. Conzmun., 1970, 87. 26. A. C . Blizzard and D. P. Santry, J . Chem. Phys., 1971, 55, 950; 1973, 58, 4714. 27. G . E. Maciel, J. W. McIver, Jr, N. S. Ostlund and J . A. Pople, J . A m . Chem. Soc., 1970, 92. 11. 28. V. J. Bartuska and G . E. Maciel, 1.Magn. Reson., 1971, 5 , 211. 29. V. J. Bartuska and G . E. Maciel, J . Magn. Reson., 1972, 7 , 36. 30. K . D. Summerhays and G. E . Maciel, J . Am. Chem. SOC., 1972, 94, 8348. 31. J. M. Schulman and M. D . Newton, J . A m . Chem. Soc., 1974, 96, 6295. 32. J. Kowalewski, Progress in NMR Spectroscopy (eds J. W. Emsley, J. Feeney and L. H. Suttcliffe), 1977, 11. p. 1. Pergamon, Oxford. 33. V. G. Malkin, 0. L. Malkina and D. R. Salahub, Chem. Phys. Lett., 1994, 221, 91. 34. C. Van Alsenoy, H. P. Figeys and P. Geerlings, Theor. Chim. Acta, 1980, 55, 87. 35. T. J. Venanzi, J . Chem. E d . , 1982, 59, 144.
ONE-BOND
36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46.
47. 48. 49. 50. 51. 52. 53. 54. 55. 56. 57. 58. 59. 60.
61. 62. 63. 64.
65. 66. 67. 68. 69. 70. 71. 72. 73. 74. 75. 76. 77. 78.
l3c-I3cSPIN-SPIN
COUPLING CONSTANTS
223
H . Fukui, T. Tsuji and K. Miura. J . Am. Chem. Soc., 1981, 103, 3652 H . Fukui, K. Miura, K. Ohta and T. Tsuji, J . Chem. Phys., 1982, 76, 5169. A . R . Engelmann, G. E . Scuseria and R. H. Contreras, J . Magn. Reson., 1982, 50, 21. M. F. Tufro and R . H. Contreras, 2. Phys. Chem., Leipzig, 1986, 267, 873. M. Stocker, Org. Magn. Reson., 1981, 16. 319. M. Stocker, Acta Chem. Scand., 1983, 37B. 166. F. A. A. M. de Leeuw, C . A. G . Haasnoot and C. Altona, J . A m . Chem. Soc., 1984, 106, 2299. J . C . Facelli and M. Barfield, J . A m . Chem. Soc., 1984, 106, 3407. K. Kamienska-Trela and B. Knieriem, J . Organomet. Chem., 1980, 198, 25. K. Kamienska-Trela, Z . Biedrzycka, R . Machinek, B. Knieriem and W. Luttke. Org. Magn. Reson., 1984, 22, 317. K. Kamienska-Trela and P. Gluzinski, Croafica Chem. Acta, 1986, 59, 883. K . Kamienska-Trela and Z. Biedrzycka, Bull. Pol. Acad. Sci. Chem., 1988, 36, 285. K. Kamienska-Trela, 2. Biedrzycka, R. Machinek and W. Luttke, Bull. Pol. Acad. Sci. Chem., 1988, 36, 105. Z. Biedrzycka and K. Kamienska-Trela, Wiadom. Chem., 1988, 42, 93. L. B. Krivdin, A. B. Trofimov, C. V. Zinchenko, H. G. Glukhikh, S. V. Piestunovich, I. N. Domnin, T. V. Akhachinskaya and N. A . Donskaya, Zh. Org. Khim., 1991, 27, 1369. A. Laaksonen, J. Kowalewski and V . R. Saunders, Chem. Phys., 1983, 80, 221. G . E. Scuseria, Chem. Phys. Lett., 1986, 127, 236. J. Geersten and J. Oddershede, Chem. Phys., 1986, 104, 67. J. Geersten, Chem. Phys. Lett., 1987, 134, 400. H. Fukui, K. Miura and T. Sakurai, J . Chem. Phys., 1988, 88, 7040. V. Galasso and G . Fronzoni, J . Chem. Phys., 1986, 84, 3215. V. Galasso, Chem. Phys., 1987, 117, 415. I. Carmichael, J . Phys. Chem., 1993, 97, 1789, and refs therein. G . Fronzoni and V. Galasso, J . M a p . Reson., 1987, 71, 229. A. Barszczewicz, M. Jaszunski, K. Kamienska-Trela, T. Helgaker, P. Jorgesen and 0. Vahtras, Theor. Chim. Acta, 1993, 87, 19. K. Ruud, T. Helgaker, P. Jorgensen and K . L. Bak (personal communication). J. Wardeiner, W. Luttke, R. Bergholz and R . Machinek, Angew. Chem.. Znt. Engl. E d . , 1982, 21, 872. M. Stocker and M. Klessinger, Org. Magn. Reson.. 1979. 12, 107. W. Luttke, G . Becker, R. Machinek, J. Wardeiner and R. B. Bergholz, private communication cited in H. Egli and W. von Philipsborn, Tetrahedron Lett., 1979, 4265. R . D. Bertrand, D. M. Grant, E. L. Allred, J. C. Hinshaw and A. B. Strong, J . Am. Chem. Soc., 1972, 94, 997. H . Finkelmeier and W. Luttke, J . Am. Chem. Soc., 1978, 100, 6261. K. Kamienska-Trela, P. Gluzinski and B. Knieriem, unpublished data. M. Barfield, I. Burfitt and D . Doddrell, J . A m . Chem. Soc., 1975, 97, 2631. I. Carmichael, D . M. Chipman, C. A. Podlasek and A. S. Serianni, J . Am. Chem. Soc., 1993, 115, 10863. G . Becher, W. Luttke and G . Schrumpf, Angew. Chem., 1973, 85, 357. V. Wray, L. Emst, T. Lund and H . J. Jakobsen, J . Magn. Reson., 1980, 40, 55. V. A. Roznyatovsky, N. M. Sergeyev and V. A . Chertkov, Magn. Reson. Chem., 1991, 29, 304. W. Luttke and R. Machinek, personal communication. G. Gray, Ph.D. Thesis, University of California, 1967, quoted in ref. 28. K. Kamienska-Trela, Org. Magn. Reson., 1980, 14, 398. F. J . Weigert and J . D . Roberts, J . Am. Chem. Soc., 1972, 94, 6021. H. Gunther and W. Herrig, Chem. Ber., 1973, 106, 3938. R . Hubers, M. Klessinger and K. Wilhelm, M a p . Reson. Chem., 1986, 24, 1016.
224
K. KAMIENSKA-TRELA
79. M. Eckert-Maksic, S. Zollner, W. Gothling, R. Boese, L. Maksimovic and A. de Meijere, Chem. Ber., 1991, 124, 1591. 80. K. Frei and H . J. Bernstein, J . Chem. Phys., 1963, 38, 1216. 81. M. D. Newton, J. M. Schulman and M. M. Manus, J. A m . Chem. Soc., 1974, 96, 17. 82. Z. B. Maksic, M. Ekert-Maksic and M. Randic, Theor. Chim. Acta (Berl.) 1971, 22, 70. 83. C . G . Zhan and Z.-M. Hu, Theor. Chim. Acta, 1993, 84, 511. 84. Z.-M. Hu and C.-G. Zhan, Theor. Chim. Acta, 1993, 84, 521. 85. R. M. Jarret and L. Cusumano. Tetrahedron Lett., 1990, 31, 171. 86. P. Diehl, H. Boesiger and J. Jokisaari, Org. Magn. Reson., 1979, 12, 282. 87. I. D. Gay, C. H. W. Jones and R. D. Sharma, J . Magn. Reson., 1991, 91, 186. 88. G . I. Borodkin, I. R. Susharin, M. M. Shakirov, V. G. Shubin, Yu. A . Ustyniuk, E. I. Lazko and V. Amman, Zh. Org. Khim., 1989, 25, 132. 89. Z. Biedrzycka and K. Kamienska-Trela, Spectrochim. Acta., 1986, 42A, 1323. 90. L. B. Krivdin, A. G. Projdakov, B. N. Bazhenov, S. V. Zinchenko and G . A . Kalabin, Zh. Org. Khim., 1988, 24, 1595. 91. K. Kamienska-Trela, Z. Biedrzycka, R. Machinek, B. Knieriem and W. Luttke, J. Organomet. Chem., 1986, 314, 53. 92. P. E. Hansen, 0. K. Poulsen and A. Berg, Org. Magn. Reson., 1975, 7, 405. 93. N. Krause, R. Wagner and A. Gerold, J. Am. Chem. Soc., 1994, 116, 381. 94. K. Kamienska-Trela, J. Mol. Struct., 1982, 78, 121. 95. K. Kamienska-Trela, J. Organomet. Chem., 1978, 159, 15. 96. A. Sebald and B. Wrackmeyer, Spectrochim. Acta, 1981, 37A, 365. 97. B. Wrackmeyer, Spectrosc. Znt. J., 1982, 1, 201. 98. A. Sebald and B. Wrackmeyer, Spectrochim. Acta, 1982, %A, 163. 99. F. Holzl and B. Wrackmeyer, J. Organornet. Chem., 1979, 179, 397. 100. K. Kamienska-Trela, H. Ilcewicz, H. Baranska and A. Labudzinska, Bull. Pol. Acad., Sci., Chem., 1984, 32, 143. 101. B. Wrackmeyer and K. Horchler, J. Magn. Reson., 1990, 90, 569. 102. K. Kamienska-Trela, J. Mol. Struct., 1982, 78, 121. 103. M. Traetteberg, W. Liittke, R. Machinek, A. Krebs and H. J. Hohlt, J. Mol. Struct., 1985, 128, 217. 104. W. Gombler, Magn. Reson. Chem., 1990, 28, 553. 105. K. Kamienska-Trela, Z . Biedrzycka and A. Dgbrowski, Magn. Reson. Chem., 1991, 29, 1216. 106. B. Wrackmeyer, K. Wagner, A. Sebald, L. H. Merwin and R. Boese, Magn. Reson. Chem., 1991, 29, S3. 107. A. Dgbrowski and K. Kamienska-Trela, J. Organomet. Chem., 1993, 460,C1. 108. W. Bauer and C. Griesinger, J. A m . Chem. Soc., 1993, 115, 10871. 109. T. Spoormaker and M. J. A . de Bie, Rec. Trav. Chim. Pays-Bas, 1979, 98, 380. 110. L. B. Krivdin, V. V. Shcherbakov, A . G. Projdakov, G. A. Kalabin, B. A. Trofimov, 0. A. Tarasova and S. V. Amosova, Zh. Org. Khim., 1988, 24, 1023. 111. A. V. Afonin, L. B. Krivdin, B. A . Trofimov, 0. A. Tarasova, L. M. Sinegovskaja, S. V. Eroshchenko and S. V. Amosova, Zh. Org. Khim., 1991, 27, 1214. 112. L. B. Krivdin, V. V. Shcherbakov and G. A. Kalabin, Zh. Org. Khim., 1987, 23, 2070. 113. J. W. Fitch, E. B. Ripplinger, B. A. Shoulders and S. D. Sorey, J. Organomet. Chem., 1988, 352, C25. 114. E. Lieping, I. Birgele, E. Lukevics, V. D. Sheludyakov and V. G. Lahtin, J . Organomet. Chem., 1990, 385, 185. 115. H. Bauer, J. Buddrus, W. Auf der Heyde and W. Kimpenhaus, Chem. Ber., 1986, 119, 1890. 116. S. Berger, J . Magn. Reson., 1986, 66, 555.
ONE-BOND 13C-13C SPIN-SPIN COUPLING CONSTANTS
225
117. K. Kamienska-Trela, L. Kania, J . Sitkowski and E. Bednarek, J. Organomet. Chem., 1989, 364, 29. 118. G . E. Maciel, P. D . Ellis, J. J. Natterstad and G . B. Savitsky, 1. Magn. Reson., 1969, 1. 589. 119. P. Jankowski, K. Kamienska-Trela, K. Minksztym and J. Wicha, J. Organomet. Chem., 1993, 460, 11. 120. R. Koster, G . Seidel and B. Wrackmeyer, Chem. Ber., 1989, 122, 1825. 121. N. C. Craig, L. G. Piper and V. L. Wheeler, J. Phys. Chem., 1971, 75, 1453. 122. H . G . Viehe and E . Franchimont, Chem. Ber., 1963, 96, 3153. 123. J. C. J. Barna and M. J. T . Robinson, M a p . Reson. Chem., 1985, 23, 192. 124. L. B. Krivdin, V. V. Shcherbakov, N. G . Glukhikh and G . A. Kalabin, Zh. Org. Khim., 1988, 24, 2276. 125. A. M. Torres, T. T. Nakashima, R. E. D . McClung and D. R. Muhandiram, J. Magn. Reson., 1992, 99, 99. 126. T. Nakai and C. A. McDowell, Bull. Magn. Reson., 1993, 15, 149. 127. R. M. Janet, L. Cusumano, M. Dinztner, M. Fortin, K. Pothier. J. Connolly, M. Biondi and T. Morrison, Microchem. J., 1993, 47, 187. 128. G. A. Kalabin, L. B. Krivdin, A. G. Projdakov and D . F. Kushnarev, Zh. Org. Khim., 1983, 19, 476. 129. Z. Biedrzycka, Ph.D. Dissertation, Warsaw, 1987, Institute of Organic Chemistry, Polish Academy of Sciences. 130. R. Radeglia and Th. Steiger, J. Prakt. Chem., 1991, 333, 505. 131. P. A. Chaloner, J. Am. Chem. SOC., Perkin Trans. 2, 1980, 1028. 132. W. Domalewski, L. Stefaniak and G. A. Webb, J. Mol. Struct., 1993, 295, 19. 133. G. A. Olah, P. S. lyer, G. K. Surya Prakash and V. V. Krishnamurthy, J. Am. Chem. Soc., 1984, 106, 7073. 134. C. Dell’Erba, A. Mele, R. Musio, M. Novi, G . Petrillo, F. Sancassan, 0. Sciacovelli and D . Spinelli, J. Org. Chem., 1992, 57, 4061. 135. P. E. Hansen, A. Berg and K. Schaumburg, Magn. Reson. Chem., 1987, 25, 508. 136. K. Kamienska-Trela, A. Dpbrowski and H . Januszewski, Spectrochim. Acta, 1993, 49 A, 1613. 137. J. B. Lambert and R . A. Singer, J. Am. Chem. Soc., 1992, 114, 10246. 138. S. Harder, P. F. Ekhart, L. Brandsma, J. A. Kanters, A. J. M. Duisenberg and P. von R. Schleyer, Organometallics, 1992, 11, 2623. 139. K. Kamienska-Trela, A. Dgbrowski and H. Januszewski, J. Mol. Struct., 1993, 293, 167. 140. S. Marriott, W. F. Reynolds, R. W. Taft and R. D . Topsom, J . Org. Chem., 1984, 49, 959. 141. J. Mullay, J. Am. Chem. Soc., 1985, 107, 7271. 142. D . Datta and S. N. Singh, J. Phys. Chem., 1990, 94, 2187. 143. L. H . Reed and L. C. Allen, J. Phys. Chem., 1992, 96. 157. 144. D . Hoffmann, W. Bauer, F. Hampel, N. J. R . van Eikema Hommes, P. von Rague Schleyer, P. Otto, U. Pieper, D. Stalke, D . S. Wright and R. Snaith, J. Am. Chem. Soc., 1994, 116, 528. 145. T. Nakai and C. A. McDowell, Mol. Phys., 1993, 79, 965. 146. H. J. Shine and W. Subotkowski, Magn. Reson. Chem., 1991, 29, 964. 147. M. Witanowski and Z. Biedrzycka, Magn. Reson. Chem., 1994, 32, 62. 148. S. Gronowitz, R. Servin and Y. Yang, Magn. Reson. Chem., 1989, 27, 1099. 149. S. Gronowitz, A,-B. Hoernfeldt, Y. Yang, U. Edlund, B. Eliasson and D . Johnels, Magn. Reson. Chem., 1990, 28, 33. 150. M. Dandarova, A. Krutosikova, J. Alfoeldi and J. Kovac, Chem. P a p . , 1988, 42, 659.
226
K. KAMIENSKA-TRELA
151. E . M. M. van den Berg, A. U. Baldew, A. T. J. W. de Goede, J. Raap and J . Lugtenburg, Rec. Trav. Chim. Pays-Bas, 1988, 107, 73. 152. S . R. Maple and A . Allerhand, J . A m . Chem. Soc., 1987, 109, 56. 153. K. Kamienska-Trela. L. Kania and E . Bednarek, Magn. Reson. Chem., 1993, 31, 268. 154. B. Kamienski, W. Schilf, J. Sitkowski and L. Stefaniak, J . Cryst. Spectrosc. Res., 1989, 19. 1003. 155. D . Seebach, R . Hassig and J. Gabriel, Helv. Chim. Acta, 1983, 66, 308. 156. L. B. Krivdin and I. N. Domnin, Zh. Org. Khim., 1990, 26, 2229. 157. M. Eckert-Maksic and Z . B. Maksic, J . Mol. Struct. (THEOCHEM), 1982, 86, 325. 158. M. Stocker, Org. Magn. Reson., 1982, 20, 175. 159. R. Faure, A . R. P. Ramanoelina, 0. Rakotonirainy, J.-P. Bianchini and E. M. Gaydou, Magn. Reson. Chem.. 1991, 29, 969. 160. L. B. Krivdin, L. I. Kasjan, S . V. Zinchenko, M. F. Seferova and L. V. Porubliova, Zh. Org. Khim., 1990, 26, 2482. 161. M. Stocker, Monats. Chem., 1982, 113, 1415. 162. B. Trupp, H . Fritz, H. Prinzbach, H . Irngartinger and U. Reifenstahl, Chem. Ber., 1991, 124. 1777. 163. J . Buddrus, H . Bauer and H . Herzog, Chem. Ber., 1988, 121, 295. 164. R . Koster, G . Seidel, J. Suss and B. Wrackmeyer, Chem. Ber., 1993, 126, 1107. 165. B. Wrackmeyer, G. Kehr and R. Boese, Chem. Ber., 1992, 125, 643. 166. R. Koster, G . Seidel, I. Klopp, C. Kruger, G . Kehr, J. Suss and B. Wrackmeyer, Chem. Ber.. 1993, 126, 1385. 167. B. Wrackmeyer, G . Kehr, A. Sebald and J. Kummerlen, Chem. Ber., 1992, 125, 1597. 168. H. Booth and J. R . Everett, Can. J . Chem., 1980, 58, 2709. 169. V. A. Chertkov and N. M. Sergeyev, J . A m . Chem. SOC., 1977, 99, 6750. 170. J. C . J. Barna and M. J. T. Robinson, Tetrahedron Lett., 1979, 1459. 171. A. E . Aliev, Zh. Org. Khim., 1990, 26, 1393. 172. A. E . Aliev and A. A. Fomiczev, Khim. Geterotsikl. Soedin., 1989, 512. 173. L. Ma and P. Bigler, Magn. Reson. Chem., 1992, 30, 1247. 174. V. M. S. Gil and W. von Philipsborn, Magn. Reson. Chem., 1989, 27, 409. 175. (a) R . H. Contreras, C. G. Giribet, M. C. Ruiz de Azua, C. N. Cavasotto, A. Aucar and L. B. Krivdin, J . Mol. Struct. (THEOCHEM), 1990, 210, 175; (b) R . H . Contreras and J. C . Facelli, in Annual Reports on NMR Spectroscopy, Vol. 27, 255. Academic Press, London, 1993. 176. C. V. Zinchenko, R. Yu. Kiselev and L. B. Krivdin, Zh. Org. Khim., 1991, 27, 1233. 177. J. Jirman, A . Lycka and M. Ludwig, Collect. Czech. Chem. Commun., 1990, 55, 136. 178. I. K. Moiseev, M. I. Kalinina, Yu. A. Strelenko and L. I. Kmel’nitskii, Zh. Obsch. Khim., 1988, 58. 203. 179. A. Ariza-Castolo, M. A. Paz-Sandoval and R. Contreras, Magn. Reson. Chem.. 1992, 30, 520. 180. J. Schraml, H.-M. Boldhaus, F. Erdt, E. W. Krahe and C. Bliefert, J . Organomet. Chem.. 406, 1991, 299. 181. J. R. Snyder, Carbohydr. Res., 1990, 198, 1. 182. L. B. Krivdin, S. V. Zinchenko, V. V. Shcherbakov, G. A. Kalabin, R. H. Contreras, M. F. Tufro, M. C. Ruiz de Azua and C. G . Giribet, J . Magn. Reson., 1989, 84, 1. 183. A. E . Aliev, V. V. Kuznietsov, L. A. Gayvoronskaya and N. S. Prostakov, Khim. Geterotsikl. Soedin., 1989, 1405. 184. A. V. Afonin, L. B. Krivdin, D. K. Danovicz, V. K. Voronov, L. A. Es’kova. B. V. Trzhtsinskaya, L. V. Bajkakalova, S. R. Buzilova and G . A. Gareeva, Khim. Geterotsikl. Soedin., 1989, 197. 185. L. B. Krivdin, S. V. Zinchenko, G . A. Kalabin, J . C. Facelli, M. F. Tufro, R . H . Contreras, A. Yu. Denisov, 0. A. Gavrilyuk and V. I. Mamatyuk, J . Chem. SOC. Faraday Trans., 1992, 88, 2459.
ONE-BOND '3C-'3C SPIN-SPIN COUPLING CONSTANTS
227
186. S. V. Zinchenko, L. B. Krivdin and G. A. Kalabin, Zh. Org. K h i m . 1990, 26, 2474. 187. L. B. Krivdin, S . V. Zinchenko and A. B. Trofimov, Zh. Org. K h m . , 1991, 27, 1226. 188. M. H. Chisholm, K. Folting, D . M. Hoffman and J. C . Huffman, J . A m . Chem. Soc., 1984, 106, 6794. 189. M. H . Chisholm, B. K. Conroy, D . L. Clark and J. C . Huffman, Polyhedron, 1988, 7, 903. 190. S. Aime, D . Osella, E. Giamello and G. Granozzi, J . Organomet. Chem., 1984, 262, C1. 191. S . Zobl-Ruh and W. von Philipsborn, Helv. Chim. Acta, 1981, 64, 2378. 192. S. Zobl-Ruh and W. von Philipsborn, Helv. Chim. Acta, 1980, 63, 773. 193. C. M. Adams, G. Cerioni, A. Hafner, H. Kalchhauser, W. von Philipsborn, R . Prewo and A . Schwenk, Helv. Chim. Acta, 1988, 71. 1116. 194. R. Benn and A. Rufinska, J . Organornet. Chem., 1982, 238, C27. 195. R. Benn and A. Rufinska, J . Organomet. Chem., 1987, 323, 305. 196. R . Benn and A. Rufinska, Organometallics, 1985, 4, 209. 197. H . Yamamoto, H. Yasuda, K. Tatsumi, K. Lee, A. Nakamura, J. Chen, Y. Kai and N. Kasai. Organometallics, 1989, 8, 105. 198. E. G. Lundquist, J. C. Huffman, K. Folting and K. G. Caulton, Angew. Chem. Znt. Ed. Engl.. 1988, 27, 1165. 199. M. H. Chisholm, J. C. Huffman and M. J . Hampden-Smith, J . A m . Chem. SOC.,1989, 111, 5284. 200. B. R. Bender, J. R. Norton, M. M. Miller, 0. P. Anderson and A. K. Rappe', Organometallics, 1992, 11, 3427. 201. M. Brookhart, A . F. Volpe, Jr, D . M. Lincoln, I. T. Horvath and J. M. Millar, J . A m . Chem. Soc., 1990, 112, 5634. 202. H. C. Clark, M. J . Hampden-Smith, G. Furgeson, B. Kaitner and H . Ruegger. Polyhedron, 1988, 7, 1349. 203. R. Koster, G. Seidel, B. Wrackmeyer and D. Schlosser, Chem. Ber., 1989, 122, 2055. 204. L. Mole, J. L. Spencer. N. Carr and A. G . Orpen, Organometallics, 1991, 10, 49. 205. Y. W. Alelyunas, Z . Guo, R. E. LaPointe and R . F. Jordan, Organometallics, 1993. 12. 544. 206. P. Clarke, A. M. Hounslow, R. A . Keough. S . F. Lincoln and K. P. Wainwright, Inorg. Chem., 1990, 29, 1793. 207. K. G . Caulton, R. H. Cayton, M. H. Chisholm, J. C. Huffman, E. B. Lobkovsky and Z . Xue. Organometallics, 1992, 11, 321. 208. K . Mashima, H . Haraguchi, A. Ohyoshi, N. Sakai and H. Takaya, Organometallics, 1991, 10, 2731. 209. K. Mashima, K. Jyodoi. A. Ohyoshi and H . Takaya, Bull. Chem. Soc., Japan, 1991, 64, 2065. 210. J . D. Meinhart. B. D . Santarsiero and R. H . Grubbs, J . Am. Chem. Soc., 1986, 108, 3318. 211. S. Cai, D . M. Hoffman, D . Lappas, H.-G. Woo and J . C. Huffman, Organometallics, 1987, 6. 2273. 212. C. P. Casey and L. M. Baltusis, J . Am. Chem. SOC., 1982, 104, 6347. 213. V. L. Coffin, W. Brennen and B. B. Wayland, J . A m . Chem. Soc., 1988, 110, 6063. 214. J . Bluemel and F. H . Koehler, J . Organomet. Chem., 1988, 340. 303. 215. J . Bluemel, N. Hertkorn, B. Kanellakopulos, F. H . Koehler, J . Lachmann, G. Mueller and F. E. Wagner, Organometallics, 1993, 12, 3896. 216. M. Saunders and H . A. Jimenez-Vazquez, Chem. Rev., 1991,91, 375. 217. H . Bircher and M. Neuenschwander, Helv. Chim. Acta, 1989, 72, 1697. 218. P. Boenzli and M. Neuenschwander, Helv. Chim. Acta, 1991, 74. 255. 219. T. R. Forbus, Jr, and J. C. Martin, Hereroat. Chem., 1993, 4, 129. 220. H.-D. Franken, H. Riiterjans and F. Muller, Tetrahedron, 1991, 36, 7593.
228
K. KAMIENSKA-TRELA
221. T. J. Simpson, Isotopes in the Physical and Biomedical Sciences, Vol. 2 (eds E. Buncel and J. R. Jones), p. 431. Elsevier, 1991. 222. R. M. Horak, P. S. Steyn and R . Vleggaar, Magn. Reson. Chem., 1985, 23, 995. 223. M. J. King-Morris and A. S. Serianni, J . Am. Chem. SOC., 1987, 109, 3501. 224. J . Wu, P. B. Bondo, T. Vuorinen and A. Serianni, J . Am. Chem. SOC., 1992, 114, 3499. 225. J. R. Snyder and A. S. Serianni, J . Org. Chern., 1986, 51, 2694. 226. J . M. Duker and A. S. Serianni, Carbohydr. Res., 1993, 249, 281. 227. P. C. Kline, A . S. Serianni, S.-G. Huang, M. Hayes and R . Barker, Can. J . Chem., 1990, 68, 2171. 228. E. C. Garrett and A. S. Serianni, Carbohydr. Res., 1990, 208, 23. 229. T. Vuorinen and A. S. Serianni, Carbohydr. Res., 1990, 209, 13. 230. T. Vuorinen and A. S. Serianni, Carbohydr. Res., 1990, 207, 185. 231. J. R . Snyder and A. S. Serianni, Carbohydr. Res., 1991, 210, 21. 232. J. Wu and A . S. Serianni, Carbohydr. Res., 1991, 210, 51. 233. P. C. Kline and A. S. Serianni, J . Org. Chem., 1992, 57, 1772. 234. P. C. Kline and A . S. Serianni, J . Am. Chern. Soc., 1990, 112, 7373. 235. V. Bossennec, P. Firmin, B. Perly and P. Berthault, Magn. Reson. Chem., 1990, 28, 149. 236. S. N. Dhawan and W. J. Goux, Carbohydr. Res., 1988, 183, 47. 237. L. Grehn, U. Bondesson, T. Pehk and U. Ragnarsson, J . Chem. SOC., Chem. Commun., 1992, 1332. 238. J . Vervoort, F. Mueller, S. G . Mayhew, W. A . M. van der Berg, C. T. W. Moonen and A. Bacher, Biochemistry, 1986, 25, 6789. 239. J. Vervoort, F. Mueller, J. LeGall, A. Bacher and H. Sedlmaier, Eur. J. Bzochem., 185, 151, 49. 240. B. J. Stockman, A. M. Krezel, J. L. Markley, K. G. Leonhardt and N. A. Straus, Biochemistry, 1990, 29, 9600. 241. B. J. Stockman, W. M. Westler, P. Darba and J. L. Markley, J . Am. Chern. SOC., 1988, 110,4095. 242. W. M. Westler, M. Kainosho, H. Nagao, N. Tomonaga and J. L. Markley, J . Am. Chem. SOC., 1988. 110. 4093. 243. J. L. Markley, Proteins, 1991, p. 29. Renugoplakrishan, Venkatesan, ESCOM, Leiden. 244. K. Wiithrich, Proteins, 1991, p. 3. Renugoplakrishan, Venkatesan, ESCOM, Leiden. 245. D. Neri, T. Szyperski, G. Otting, H . Senn and K. Wuethrich, Biochemistry, 1989, 28, 7510. 246. D. Neri, G . Otting and K . Wuethrich, Terrahedron, 1990, 46, 3287. 247. H. Senn, B. Werner, B . Messerle, C. Weber, R. Traber and K. Wuetrich, FEBS Lett., 1989, 249, 113. 248. T. Szyperski, D. Neri, B. Leiting, G. Otting and K. Wuethrich, J . Biomol. NMR, 1992, 2, 323. 249. M. Sailer, G . L. Helms, T. Henkel, W. P. Niemczura, M. E. Stiles and J. C. Vederas, Biochemistry, 1993, 32, 310. 250. J. S. Rajagopalan, L . X . Chen and E . K. Jaffe, Bioorg. Chem., 1992, 20, 115. 251. S. Cerdan, B. Kuennecke and J. Seelig, J . Biol. Chem., 1990, 265, 12916. 252. T. J . Fennell, G . L. Kedderis and S. C. J. Sumner, Chem. Res. Toxicol., 1991, 4, 678. 253. S. C . J. Sumner, J. P. MacNeela and T. R. Fennell, Chem. Res. Toxicol., 1992, 5 , 81. 254. C. R. Malloy, A . D . Sherry and F. M. H . Jeffrey, Am. J . Physiol., 1990, 259, H987. 255. S. M. Winter, G. L. Weber, P. R. Gooley, N. E. MacKenzie and I. G. Sipes, Drug Metab. Dispos., 1992, 20, 665. 256. C. T. Evans, B. Sumegi, P. A. Srere, A. D. Sherry and C. R. Malloy, Biochem. J . , 1993, 291, 927. 257. T. Hemscheidt and I . D . Spenser, J . Am. Chem. SOC., 1992, 114, 5472. 258. W. A . Ayer and P. A. Craw, Can. 1. Chem., 1992, 70, 1348.
ONE-BOND I3C-l3C SPIN-SPIN COUPLING CONSTANTS
229
259. P. Bhandari, L. Crombie, P. Daniels, I. Holden, N. Van Bruggen and D . A. Whiting, J . Chem. SOC. Perkin Trans. 1 1992, 839. 260. W. Offermann, E. Fiedler, C. Helmle-Kolb, W. Hofer, H. Kugel, T. Reese, W. Werk and D. Leibfritz, Magn. Reson. Chem., 1992, 30,347. 261. B. Kuennecke and J. Seelig, Biochim. Biophys. Acta, 1991, 1095, 103. 262. A . Nishimura, S. Okamoto, F. Yoshizako, I. Morishima and T. Ueno, J . Ferment. Bioenerg., 1991, 72, 461. 263. A . D . Sherry, C. R . Malloy, P. Zhao and J. R. Thompson, Biochemistry, 1992, 31, 4833. 264. A. Bax, R. Freeman and S. P. Kempsell, J . Am. Chem. SOC., 1980, 102, 4849. 265. A . Bax, R. Freeman, T. A. Frenkiel and M. H. Lewitt, J . Magn. Reson., 1981, 43, 478. 266. J. Buddrus and H. Bauer, Angew. Chem., lnt. Ed. Engl., 1987, 99, 625. 267. H. Kessler, M. Gehrke and C. Griesinger, Angew. Chem., Int. Ed. Engl., 1988, 27, 490. 268. Atta-ur-Rahman, One and Two Dimensional NMR Spectroscopy, Elsevier, 1989. 269. J. K. M. Sanders and B. K. Hunter, Modern NMR Spectroscopy, A Guide for Chemists, Oxford University Press, 1987. 270. 0. Sorensen, R. Freeman, T. Frenkiel, T. H. Mareci and R . Schuck, J . Magn. Reson., 1982, 46, 180. 271. S. W. Sparks and P. D. Ellis, J . Magn. Reson., 1985, 62, 1. 272. I. S. Podkorytov, J . Magn. Reson., 1990, 89, 129. 273. P. J. Keller and K. E . Vogele, J . Magn. Reson., 1986, 68, 389. 274. S. Berger. Angew. Chem., lnt. Ed. Engl., 1988, 27, 1196. 275. D. Canet, J. Brondeau, J. C. Boubel and A. Retournard, Magn. Reson. Chem., 1987, 25, 798. 276. K. E. Kover, D . Uhrin, T. Liptaj and G . Batta, Magn. Reson. Chem., 1992, 30, 68. 277. I. S. Podkorytov and A. V. Lubnin, Magn. Reson. Chem., 1991, 29, 561. 278. M. H . Lewitt and R. R. Ernst, Mol. Phys., 1983, 50, 1109. 279. M. H . Lewitt, Prog. Nucl. Magn. Reson., 1986, 18, 61. 280. J. Lambert, H . J . Kuhn and J. Buddrus, Angew. Chem., Int. Ed. Engl., 1989, 28, 738. 281. J. Lambert and J. Buddrus, J . Magn. Reson., 1993, 101A, 307. 282. L. E. Kay and R . E . D . McClung, J . Magn. Reson., 1988, 77,258. 283. T. Nakai and C. A . McDowell, J . Magn. Reson., 1993, 104A, 146. 284. V. Blechta and R . Freeman, J . Magn. Reson., 1993, 102A, 253. 285. R. Benn, H. Grondey, C. Brevard and A. Pagelot, J . Chem. SOC., Chem. Commun., 1988, 102. 286. T. Nakai and C. A. McDowell, J . Chem. Phys., 1992, 96, 3452. 287. T. Nakai and C. A. McDowell, Mol. Phys., 1992, 77, 569. 288. S. W. Fesik, H. L. Eaton, E . T. Olejniczak and E . R. P. Zuiderweg, J . A m . Chem. Soc., 1990, 112, 886. 289. L. E. Kay, M. Ikura and A . Bax, J . A m . Chem. SOC., 1990, 112, 888. 290. B. D. Christie and M. E. Munk, Anal. Chim. Acta, 1987, 200, 347. 291. B. D. Christie and M. N. Munk, J . A m . Chem. SOC., 1991, 113, 3750. 292. K. Funatsu, Y. Susuta and S.-I. Sasaki, J . Chem. Inf. Comput., 1989, 29, 6. 293. G. Massiot and J. M. Nuzillard, Phytochem. Anal., 1992, 3, 153. 294. B. H . Oh. W. M. Westler, P. Darba and J . L. Markley, Science, 1988, 240, 908. 295. R. Dunkel, S. L. Mayne, J. Curtis, R. J. Pugmire and D . M. Grant, J . Magn. Reson., 1990, 90,290. 296. R. Dunkel, Ph.D. Thesis, University of Utah, December 1990. 297. R. Dunkel, C. L. Mayne, M. P. Foster, C. M. Ireland, D. Li, N. L. Owen, R. L. Pugmire and D . M. Grant, Anal. Chem. 1992, 64, 3150. 298. M. P. Foster, C. L. Mayne, R. Dunkel, R. J. Pugmire, D . M. Grant, J. M. Kornprobst. J. F. Verbist, J . F. Biard and C. M. Ireland, J . A m . Chem. SOC., 1992, 114, 1110. 299. R. Dunkel, C. L. Mayne, R. J. Pugmire and D. M. Grant, Anal. Chem., 1992, 64, 3133. ~
230 300. 301. 302. 303. 304. 305. 306.
K. KAMIENSKA-TRELA S.-G. Lee, Bull. Korean Chem. Soc., 1993, 14, 416. J . Barber, Magn. Reson. Chem., 1991, 29, 740. I. H. Sadler and T. J. Simpson, Magn. Reson. Chem.. 1992, 30, S18. H . Kogler and H.-W. Wolfram, Magn. Reson. Chem., 1991, 29, 993. V. Amico, M. Piatelli, P. Neri and M. Recupero, Gaz. Chim. Ifal., 1991, 121, 335. T. Yasuzawa, M. Yoshida and H . Sano, J . Chem. SOC. Perkin Trans., 1990, 3145. A. Miiller, G. Nonnenmacher, B. Kutscher and J. Engel, Magn. Reson. Chem., 1991, 29,
in. 307. A . Nakagawa, Y. Kondo, A. Hatano, Y. Harigaya and M. Onda, J . Org. Chem., 1988, 53, 2661. 308. A. V. 8 . Sankaram, M. M. Murthi, K. Bhaskaraiah, G. L. N. Rao, M. Subrahmanyam and J. N. Shoolery, Tetrahedron Lett., 1988, 29, 245. 309. D . Laurent, N. Goasdoue, F. Kohler, F. Pellegrin and N. Platzer, Magn. Reson. Chem., 1990, 28, 662. 310. A . Pabst, D . Barron, J. Adda and P. Schreier, Phytochemistry, 1990, 29, 3853. 311. J. Wu and A . S. Serianni, Carbohydr. Res., 1992, 226, 209. 312. R . E . Moore, V. Bornemann, W. P. Niemczura, J. M. Gregson, J.-L. Chen, T. R . Norton, G. M. L. Patterson and G . L. Helms, J . A m . Chem. Soc., 1989, 111, 6128. 313. T. Asakura, N. Nakayama, M. Demura and A. Asano, Macromolecules, 1992, 25, 4876. 314. K . Hikichi, T. Hirai, M. Ikura, K. Higuchi, K. Eguchi and M. Obuchi, Polym. J . , 1987, 19, 1317. 315. T. Hayashi, Y. Inoue, R. Chujo and T. Asakura, Polym. J . , 1988, 20, 895. 316. A. Aoki, T. Hayashi aild T. Asakura, Macromolecules, 1992, 25, 155. 317. T. Asakura, K. Hirano, M. Demura and K. Kato, Macromol. Chem., Rapid Commun., 1991, 12, 215. 318. T. Asakura and N. Nakayama, Polym. Commun.. 1992, 33, 650. 319. K. Hikichi and M. Yasuda, Polym. J . , 1987, 19, 1003. 320. N. Nakayama, A. Aoki and T. Hayashi, Macromolecules, 1994, 27, 63. 321. L. E . Bogan, Jr and S. K. Wolk, Macromolecules, 1992, 25, 161. 322. A . V. Lubnin, I. S. Podkorytov and L. S. Bresler, Magn. Reson. Chem., 1992, 30, 847. 323. B. Brycki and M. Szafran, M a p . Reson. Chem., 1992, 30, 535. 323. R . D. Thompson, W. L. Jarrett and L. J. Mathias, Macromolecules, 1992, 25. 6455. 325. H. Hoberg, D. Baerhausen, R . Mynott and G . Schroth, J . Organomet. Chem., 1991, 410, 117. 376. S. Braun, V. Sturm and K. 0. Runzheimer, Chem. Ber., 1988, 121, 1917. 327. C. Kruk, N. K. de Vries and G. van der Velden, Mugn. Reson. Chem., 1990, 28, 443. 328. E. Kolehmainen, K. Rissanen, K. Laihia, P. Malkavaara, J. Korvola and R. Kauppinen, J . Chem. Soc. Perkin Trans., 2, 1993, 437. 329. R. D. Johnson, G. Meijer, J. R. Salem and D. S . Bethune, J . A m . Chem. Soc., 1991, 113, 3619. 330. J. M. Hawkins, S. Loren, A. Meyer and R. Nunlist, J . Am. Chem. Soc., 1991, 113, 7770.
Carbon-13 NMR Spectra of Sesquiterpene Lactones M. BUDESINSKY and D. SAMAN Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, 166 10 Prague 6, Czech Republic 1. Introduction 2. Structure classification 2.1. Skeletal types 2.2. Nomenclature 3. Methods of structure determination 3.1. Chemical correlation 3.2. Spectral methods 3.2.1. Mass spectra 3.2.2. IR, UV and CD spectra 3.2.3. NMR spectra 3.2.4. X-ray structure analysis 4. Carbon-13 NMR spectra 4.1. Structural assignment of signals 4.1.1. Chemical shifts 4.1.2. Signal multiplicities 4.1.3. Coupling constants J(C,H) and J(C,C) 4.1.4. Relaxation times 4.1.5. Nuclear Overhauser effect 4.1.6. Carbon-proton correlations 4.1.7. Carbon-carbon correlations 4.1.8. Solvent effect 4.1.9. Shift reagents 4.1.10. Isotope labeling 4. I . 11. Derivatization 4.1.12. Molecular dynamics 4.2. Identification acyl groups 4.3. Carbon-13 chemical shift data 4.3.1. Germacranolides 4.3.2. Eudesmanolides 4.3.3. Guainolides 4.3.4. Pseudoguaianolides 4.3.5. Elemanolides
A N N U A L REPORTS O N NMR SPECTROSCOPY VOLUME 30 ISBN 0-12-505330-4
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4.3.6. Eremophilanolides 4.3.7. Lactones of other structure types 4.3.8. Lactone dimers References
426 436 436 456
1. INTRODUCTION
The major goal of this review is to present carbon-13 N M R data of sesquiterpene lactones. From the chemical point of view there are two main reasons for the interest in this group of natural products: (1) sesquiterpene lactones have been successfully used in chemotaxonomical studies (mainly in the Compositae - e.g. ref. 581); (2) various biological activities of sesquiterpene lactones form a basis for the structure-activity relation s t ~ d i e s . Large ~ ~ ~ numbers ~ ~ ~ "of~ sesquiterpene ~ ~ ~ lactones were isolated from plant material (about 4000 compounds were described in the literature up to 1992; for review see refs 146, 177). Additionally, hundreds of sesquiterpene lactones were synthesized. 'H and 13C N M R spectroscopy has, in the past 30 years, played a very important role in the structure determination (constitution, configuration and conformation) of these compounds. Although the number of sesquiterpene lactone skeletons is limited, a variety of substituents, and their position and configuration isomerism, leads to an enormous number of possible structures. Complete structure determination often represents a difficult task as it is documented in the literature by a number of structures which were revised later. The extensive collection of 13C N M R data of sesquiterpene lactones can be used: (1) for identification of already described compounds, (2) for structure elucidation of new compounds, ( 3 ) as a valuable source of data for correlation between the structure features and N M R parameters. Although 13C N M R data for some series of sesquiterpene lactones were published, 130,151,166,175,375,398,408,409,459,469,672so far no review covering this class of compounds has appeared in literature.
2. STRUCTURE CLASSIFICATION
The sesquiterpenoids are C15-compounds formed of three isoprenoid units. Based on biogenetic assumptions, it is now generally accepted that all sesquiterpene lactones arise from a common precursor - farnesyl pyrophosphate - by various modes of cyclizations followed in many cases by skeletal rearrangements. 146
233
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES 14
I
14
qq ql2 13
GERMACRANE
EUDESMANE
GUAIANE
14
11
12
4
6
11
6
4
15
11
14
15
13
15
13
13
PSEUDOGUAIANE
ELEMANE
EREMOPHILANE
Fig. 1. Main types of sesquiterpenes with numbering of carbocyclic skeletons.
2.1. Skeletal types
In contrast to the large number of skeletal types of sesquiterpenoids there is a relatively small group of different ring systems among the sesquiterpene lactones. Their classification in general is based on the carbocyclic skeleton. Most of the naturally occurring sesquiterpene lactones can be derived from one of six following sesquiterpene skeleton types: germacrane, eudesmane, guaiane, pseudoguaiane, elemane and eremophilane (Fig. 1). Numbering of the carbocyclic ring systems shown in Fig. 1 is generally used in the literature and through this review. A lactone function is mostly represented by a-exomethylene y-lactone moiety (A), and/or some of its modified versions (B-D) - see Fig. 2. This usual lactone type arises by oxidation of C(12)-methyl group to COOH and following lactone ring closure into position 6 (12,6-olides) and/or 8 (12,s-olides). Other lactone types - formed by oxidation of C(14)- or C( 15)-methyl group and following cyclization into position 2 (14,2-olides) or 6( 15,6-olides) - occur much more rarely. The examples of individual lactone types are shown in Fig. 2.
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M. BUDESINSKY AND D. SAMAN
B
A
C
D
12 EUDESMAN-12,6-OLIDE
EUDESMAN-12,8-OLIDE
14
GUAIAN-14,2-OLIDE
GERMACRAN-15.6-OLIDE
Fig. 2. Types of lactonic function and examples of its position in naturally occurring sesquiterpene lactones.
2.2. Nomenclature
The systems used for the nomenclature of terpenoids have evolved over a long period. There are four main types of naming of sesquiterpene lactones in the literature: (1) Various trivial names chosen by authors (sometimes before the complete structure determination). Such names are frequently derived from the botanical names of plants from which the corresponding compound was isolated for the first time. In some cases more than one trivial name was introduced for the same compound.
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
235
(2) Semisystematic names derived from parent sesquiterpene skeleton with indications on type, position and configuration of substituents. These names are usually longer than the trivial ones, but they allow one to derive corresponding structure formulae easily.
(3) Names based on the systematic nomenclature system used in Chemical Abstracts from the 9th Collective Index. Because of their length, frequently different names for structurally similar compounds and rather complex “structure-name coding and decoding procedure”, they were not generally accepted by terpenoid chemists in original papers.
(4) Some authors do not use the names but structure formulae only for description of sesquiterpene lactones in original papers. Comparison of three above types of naming is shown in the following example.
HO
,,to-
( I ) Janerin (2) la. l ~ - E p o ~ ~ - 3 ~ - h ~ d r o ~ ~ - 8 a - ( l - h ~ d r o ~ ~ i i i e t h a c ~ l o ~ l o ~ ~14). ) - 1l aI ( HI .;)-dien. ~ a H - lG2 u. i~~i ~~ -- l ~ ~ ( olide (.3) 2-Propenoic acid, 2 - ( h ~ d r o ~ ~ n i e t h ~ l ) - d e c a h ~ d r o - 8 - h ~ d r o ~ ~ - ~ . 6 - b 1 s ( n i e t h ~ l e n e ) - 2 - o ~ o s p 1 r o - [ a ~ ~ 1 [4,~-b~furan-(2H),2’-osiran]-4-~1 ester
The configuration at ring systems is indicated with a dashed bond for substituents and hydrogen atoms below the plane of the ring (aconfiguration), and with a wedge bond for substituents and hydrogen atoms above the ring (p-configuration). For acyclic carbon atoms the CahnIngold-Prelog descriptors (R or S) are used. Some authors use the R,S-descriptors also for absolute configuration on ring system carbons, while R*$*-descriptors designate relative configuration.
3. METHODS OF STRUCTURE DETERMINATION Although there is no generally applicable best strategy for structure elucidation of natural compounds, a typical algorithm showing individual steps and possible methods can be represented by the following scheme.
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M. BUDESINSKY AND D. SAMAN
APT, DEPT (CH multiplicities) C,H-COSY, C,H-COLOC, C,H-HMQC (J(C,H)-connectivities) structure fragments 2D-RELAYED COSY assembling of fragments -+ 2D-INADEQUATE (J(C,C)-connectivities) molecular structure
selective proton decoupling (J(H,H)) H,H-COSY (J(H,H)-connectivities)
vicinal J(H,H) (H,H-torsion angles) 'J(C,H) (C,H-torsion angles) H,H-NOE (rel. interproton distances) "C chemical shifts (y-effects) relative configuration and conformation X-ray structure analysis -+ t CD spectra
3.1. Chemical correlation
Chemical transformation of studied compounds in one reaction step or in a series of well-defined reaction steps to a derivative with already known structure was a classical method of structure analysis of natural products (including sesquiterpene lactones) in the past. Hydrolysis of ester groups, relactonization (12,6- to 12,8-olides), esterification of hydroxyls, reductive transformation of epoxides to alkenes, epoxidation of double bonds, cyclization reactions and Cope rearrangement of germacranolides were reactions frequently applied in the course of structure elucidation (for review see e.g. ref. 205). Fast development of spectral methods in the last 30 years has changed this situation dramatically. Nowadays most new structures are derived completely from spectral data. This has allowed extension of the study of natural compounds to minor components isolated in very small amounts (milligrams or even lower). The application of chemical reactions is therefore - if necessary - limited to some simple derivatization. Another approach represents the total synthesis of given sesquiterpene lactone from an appropriate precursor.
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
237
3.2. Spectral methods The combination of various spectral methods is the most common way to determine the structure of sesquiterpene lactones. The most important methods - MS, IR, UV, CD, NMR and X-ray - are briefly discussed in the following sections. 3.2.1. Mass spectra
The main goal of routine application of mass spectroscopy (using electron impact ionization) is to determine the elemental composition of the compound under study. Unfortunately, a parent peak of the molecular ion is frequently missing in compounds containing hydroxyls and/or ester functions due to the loss of water and/or the side chain by McLafferty rearrangement.664In such cases the acylium ion of the ester group is usually observed as an intense peak, and very often represents the base peak of mass spectrum. The problem of a missing molecular ion peak can usually be solved using FAB (fast atom bombardment) ionization. The FAB-mass spectrum typically contains a peak corresponding to the [ M + H]+ ion. Preparation of trialkylsilyl derivatives, sometimes combined with the isotope labelling, was used for the detailed establishment of a cleavage pattern (e.g. ref. 513). 3.2.2. IR, UV and C D spectra IR spectra are commonly used to determine the presence of some characteristic function groups (carbonyl, double bond, hydroxyl, etc.). In some cases the detection of intramolecular hydrogen bonding can give helpful information on the relative position and orientation of substituents involved. The use of UV spectra is limited to compounds containing a proper chromophore. For example a strong low wavelength absorption in the 210-220 nm region was assigned to transannular interaction of the rr-orbitals of double bonds in ten-membered rings of germacranolides which adopt a crossed c o n f o r m a t i ~ n . ~ ~ CD spectra have been used for the determination of the stereochemistry of many sesquiterpene lactones. A large number of compounds contain a specific chromophore - a-methylene-y-lactone group (A) - with a Cotton effect (due to n-rr* transition) in the range 245-260nm. The StocklinWaddell-Geissman correlates the sign of the corresponding Cotton effect with the position (12,6-resp. 12,8-olide) and stereochemistry of the lactone ring (cis or trans). The exceptions to the rule have been explained by Beecham’s suggestion that the sign of the Cotton effect is determined by chirality of the lactone ring.69
238
M. BUDGSINSKY A N D D. SAMAN
3.2.3. N M R spectra NMR spectroscopy has played a very important role in the structure analysis of sesquiterpene lactones. Due to a typically limited amount of sample and the lower sensitivity of the 13C NMR method, it was 'H NMR spectroscopy that was still used extensively for obtaining the detailed structure information in the era of low-field continuous-wave NMR spectrometers. The introduction of high field magnets, pulse Fourier-transform methods and two-dimensional NMR techniques extended the potential of NMR spectroscopy enormously. The complexity of proton NMR spectra of sesquiterpene lactones strongly depends on the number and character of substituents. Poorly substituted compounds can contain structure fragments giving strongly coupled spectral patterns which are difficult to analyse even at 500MHz. The relative intensity of signals, their multiplicities and chemical shift values provide initial structure information from the routine proton 1D NMR spectrum. Identification of mutually coupled protons (through a series of 1D decoupling experiments and/or more efficiently from a 2D-COSY spectrum) can define the structure of molecular fragments or even the topology of a whole molecule. Stereochemical information is obtainable from:
(1) vicinal and long-range coupling constant values, related to the torsion angles between coupled protons; (2) Nuclear Overhauser Effect (NOE) enhancement (measured either in difference 1D-NOE or 2D-NOESY spectra), dependent on the distance between corresponding protons; (3) induced chemical shifts in the presence of lanthanide shift reagents which are dependent on the distance between the lanthanide ion and a given proton and the angle of this perimeter with the main magnetic axis of the complex. It should be noted that all NMR experiments in achiral solvent can result only in information on relative configuration (enantiomers give identical spectra under such conditions). A rule for determining the stereochemistry of a-methylene-y-lactones which is based on the size of the allylic coupling constants between exomethylene protons (H-13a and H-13b) and proton H-7 was proposed by Samek.ss6~ss7Trichloroacetyl isocyanate (TAI) has been extensively applied for in situ reactions to characterize hydroxylcontaining sesquiterpene Iactones.ss8 A collection of 'H NMR spectra of about 250 naturally occurring sesquiterpene Iactones was in 1973. A short discussion on the application of method in this field can be found in ref. 205 from 1978, but no recent review containing 'H NMR data of sesquiterpene lactones has appeared.
CARBON-I3 NMR SPECTRA OF SESQUITERPENE LACTONES
239
One- and two-dimensional NMR methods for structure determination of natural products have been reviewed. 174,553 Experimental methods and structure interpretation of 13C NMR spectra will be discussed in Section 4.
3.2.4. X-ray structure analysis The X-ray spectroscopy is one of the most powerful methods of structure analysis in a solid phase. Under proper conditions it can give the complete three-dimensional structure of a compound under study, including the absolute configuration. The accurate geometry parameters (atomic coordinates, bond lengths and angles) can be used as the input data for quantum chemical calculations. Packing of molecules in a crystal lattice provides information on intermolecular interactions, namely hydrogen bonding. The requirement of a good-quality crystal places a certain limit on the application of this method. Nevertheless an increasing number of papers with X-ray data on sesquiterpene lactones appear in the literature (a few hundred compounds have been analysed so far; a complete list of compounds and their data can be found in the Cambridge X-Ray Data Base'29). Some sesquiterpene lactones have been studied in more than one crystalline form. The comparison of a crystal structure (from X-ray) and a solution structure (from NMR) for a given sesquiterpene lactone shows usually a close similarity. Sometimes certain differences can be found not only in the sense of higher mobility of substituents, but even in the carbocyclic skeleton, namely for medium rings (seven- to ten-membered). The common problem of comparison of the X-ray and NMR data arising from different physical states of material under study (crystal vs. solution) can be solved if solid-state NMR spectroscopy is used. High-resolution solid-state 13C NMR spectra recorded by CP-MAS (cross-polarization magic angle spinning) technique212 can be obtained for samples accessible in only tenths of milligrams. Recently we have studied sesquiterpene lactone helenalin in two crystalline forms - monoclinic and orthorhombic - by X-ray and solid-state 13C NMR.548 Although the X-ray analysis showed that helenalin conformation is nearly identical in both forms which differ in their intermolecular hydrogen bonding networks (see Fig. 3), solid-state I3C NMR spectra are significantly different and the chemical shifts differ also from those observed in CDC13 solution (see Table 1). Assuming the absence of intermolecular association of a substrate in dilute solution in a non-polar solvent, then the observed differences ASc = &-(solid) - Gc(solution) can be interpreted as the shielding effects resulting from intermolecular interactions in crystal. For the monoclinic form the largest A& are observed for C-6 (-5.84 ppm), C-4 (5.61 ppm) and C-2 (5.16 ppm) in agreement with H-bonding between C(6)-OH (proton donor; negative A&-) and C ( 4 ) = 0 (proton acceptor; positive A&). On the other hand the orthorhombic form shows a similar large effect on C-6
240
M. BUDESINSKY AND D . SAMAN 14
13
HELENALIN
Fig. 3. Perspective view of the molecule of helenalin in crystal (A) and hydrogen bonding network in two crystalline forms: (B) monoclinic and (C) orthorhombic.
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
241
242
M. BUDESINSKY AND D. SAMAN
Table 1. Carbon-13 chemical shifts of helenalin in solid-state and in solution: (A) monoclinic form; (B) orthorhombic form; (C) chloroform solution.
Sample
C-1
C-2
C-3
C-4
C-5
C-6
C-7
C-8
55.60 57.58 57.98
68.26 67.62 74.10
52.18 48.65 50.76
78.59 79.40 78.15
C-13
C-14
C-15
19.24 21.24 20.15
18.62 18.14 18.69
~~
A B C
A B C
53.84 54.34 51.34
169.04 128.78 217.82 164.96 131.66 211.52 163.88 129.99 212.21
C-9
C-10
36.98 37.75 39.40
26.50 27.80 26.17
C-11
C-12
136.84 169.75 120.99 137.32 172.11 122.18 137.86 169.74 123.05
(-6.48 ppm) but a significant positive effect on C-12 (2.37 ppm) while C-4 stays nearly unaffected. Analogously it can be interpreted as the result of the intermolecular H-bonding between C(6)-OH (proton donor; negative A&-) and lactone carbonyl C(12)=0 (acceptor; positive hac). 4. CARBON-13 NMR SPECTRA Although the first 13C NMR spectra of sesquiterpene lactones were described in the early 1970s, the routine application of the method started in the 1980s with commercial high-field multinuclear FT-NMR spectrometers. In general, the 13C NMR spectra of sesquiterpene lactones were recorded with proton broad-band d e ~ o u p l i n g 'which ~~ eliminates the splitting from I3C-lH spin interactions and hence the 13C signals appear as singlets. Figure 4 shows a proton-decoupled 13C NMR spectrum of helenalin. With such a spectrum it is possible to determine the number of carbons in the molecule (coincident lines are very rare), but it does not provide any information about the number of attached hydrogen atoms. Structural assignment of signals therefore requires some additional information.
4.1. Structural assignment of signals Some NMR parameters (chemical shifts, signal multiplicities, carbon-proton coupling constants, and relaxation times), correlation NMR experiments (selective proton decouplings in 13C NMR, heteronuclear NOE, carbon-proton or carbon-carbon connectivity 2D NMR methods) and NMR methods using a chemical modification of the sample (lanthanide shift reagents, isotope labelling, derivatization) can be used for the structural assignment of carbon signals. They will be briefly discussed in the following paragraphs.
14
7 \
2 12
5
9
OH
10
6
13
HELENALIN
3
1
13 8 11
I 5
4
I
12
L 1 I ) I I I I
/ / I I , I I I I
1 1 1 , , 1 1 1 1
1 1 1 1 1 1 1 [ /
L
, 1 1 1 , 1 1 ~ 1
, I I iI i , r i l l , I
1 1 1 1
L
m
1 1 1 1
1 1 1 1 1 1 1 1 1 1 1 1 1 ' 1 1 1
200
180
160
140
120
100
80
60
Fig. 4. Broad-band proton decoupled I3C NMR spectrum of helenalin in CDCl3
40
PPm
244
M . BUDESINSKY AND D. SAMAN
Table 2. Empirical effects upon replacement of H by substituent (according to ref. 673).
a-effect
Substituent
CH3 CH=O COOH COOR COR OH OR OCOR ~~
~
y-effect'
p-effect
CH2
CH
CH2
CH
9 31 21 20 30 48 58 51
6
10 0 3 3
8
16 17 24 41 51 45
1
10 8 6
2 2 1 8 5 5
-2 -2 -2 -2 -2 -5 -4 -3
~
"Averaged value.
4.1.1. Chemical shifts Some information about carbon type can be obtained from the chemical shifts. Carbon chemical shifts are influenced namely by hybridization and s u b s t i t ~ t i o n . 'Carbonyl ~ ~ ~ ~ ~ ~ carbons ~ ~ ~ ~ resonate at the lowest field range, 6 = 210-160, olefinic carbons at 6 = 160-110, aliphatic carbons with electronegative substituents at 6 = 110-55 and other aliphatic carbons at the highest field, 6 = 55-5. Substituent effects, reported for aliphatic compounds,h73can be used for predicting approximate chemical shift values. The effects of substituents, commonly occurring in sesquiterpene lactones, on carbons at a - , 0- and y-positions are given in Table 2. While the effects on the a- and @-position depend mainly on the electronegativity of substituent, the effect on the y-position is strongly influenced by spatial relationship of substituent and given carbon atom. This dependence originates from a sterically induced polarization of the C-H bond and the y-effect has largest negative values (up to -1Oppm) in rigid molecules with a synperiplanar and synclinal arrangement of substituent and given carbon. The 13C chemical shifts thus reveal the relative configuration of substituents in molecules with a single preferred conformation. If there is free rotation, then the effect is averaged over gauche and trans conformations to ca. -2 to -3.5 ppm in substituted alkanes. Substituent effects over four bonds (&effects) are negligible in flexible systems. In rigid molecules a significant downfield shift (up to +4 ppm) can be observed for a synaxial arrangement of substituent and observed carbon. Application of substituent effects requires the shift data of unsubstituted parent compounds. The isomerism connected with the annelation of
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
245
carbocyclic rings and lactone ring closure and variable number, position and configuration of double bonds leads to a large number of possible parent compounds not all being known and characterized by 13C NMR data. Carbon-13 chemical shifts of some representative unsubstituted lactones are shown in Table 3. Theoretical quantum chemical calculations have not been so far successfully used for prediction of carbon chemical shifts in sesquiterpene lactones. Some authors have investigated the possibilities of automation of structure analysis on the basis of computer-assisted analysis of 13C NMR spectral data (for review see ref. 254). As far as we know there is no example of the successful use of this approach in the field of sesquiterpene lactones, probably also due to insufficient collection of reference data. We have applied a similar approach to verify the possibility of automatic identification of ester groups present in sesquiterpene lactones. Our results are briefly discussed in Section 4.2.
4.1.2. Signal multiplicities Various experimental NMR techniques have been employed to determine the multiplicities of carbon signals. In the so-called off-resonance protondecoupled 13C NMR spectrum'95 all C-H couplings are reduced to such an extent that only the largest one-bond coupling constants give rise to observable residual splitting. As a result, quaternary, methine, methylene and methyl carbons appear as singlets, doublets, triplets and quartets respectively (see Fig. 5 ) . The disadvantage of this method is lower sensitivity (due to distribution of total signal intensity into more lines) and possible signal overlap in crowded areas of the spectrum. To overcome these difficulties various pulse sequences have been proposed. Among these, APT (attached proton test504), DEPT (distortionless enhancement by polarization transfer"') and INEPT (insensitive nuclei enhanced by polarization transfer45') have been employed most frequently. In APT spectrum the carbon signals are phase-modulated according to 'J(C,H) and signal multiplicity in such a way that quaternary and methylene carbon signals have a positive amplitude, while methine and methyl carbon signals are negative (see Fig. 6). Pulse sequences for non-selective polarization transfer - INEPT and DEPT - are useful not only for signal enhancement but also for multiplicity selection. Dependence of signal intensity on polarization angle (@) allows one to generate DEPT spectra for: (a) CH carbon atoms, (b) all protonated carbons with negative CH2 signals and positive CH, CH3 signals. Three DEPT experiments with different polarization angles = 45", Q2 = 90" and Q3 = 135") can be used to generate edited subspectra (Fig. 7) for CH (@' = 45"), CH2 (@, - Q 3 ) and CH3 (Q1 + Q3 - 0.707 Q2).
246
M. BUDESINSKY AND D. SAMAN
Table 3. Carbon-13 chemical shifts of some parent unsubstituted sesquiterpene lactones. 21.9 127.0
39.6
A
124.9 2
5 136.7 .
26.7
28.2
4
25.1 124.4
41 1 112.4
I
0-co
17.5
0-co
I
17.2
170.4
170 3
Germacranolides 25.8
26.8
18.2
/
331 138 5
CG 128.5 75.9
41.2
142,3
- 120.1
- co
19.3
1214
19 2
170.9
Eudesmanolides 24.2
109.4
1
123.1
30.9
30 2
152.9
132.5
150 9 78.1
0,
co
112 4
15.2
co
170.0
180 0
Guaianolides 15.8
35 6
36 1 54.9
50 0 44.4
219 2 120.9
co
0
17 3
139.3
!23 3
170.3
Pseudoguaianolides
p2
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
% 3
111.2
’’*.’ \ 146.0
19.2
247
L’
co
39.3
170.5
26.6 27”
i4’”
30.1
40.2
24.4
40.3
41.4
[email protected]
163.0
141.1
31.0 16.0
120.8
Elemanolide
24.0
80
Eremophilanolide
4.1.3. Coupling constants J(C,H) and J(C,C)
Carbon-proton coupling constants provide a useful aid for both spectral assignment and structural e l u ~ i d a t i o n . ~According ~ ’ ~ ~ ~ ~ to the number of bonds separating coupled nuclei they are classified as direct couplings (over one bond) and long-range couplings (over two or more bonds). In principle they are observable either in 1 D proton-coupled 13C NMR spectra or in 2D-J-resolved I3C NMR spectra.833460 The examples of both types of spectra of sesquiterpene lactone helenalin and arctolide are shown in Figs 8 and 9. The cross-peaks in a 2D-J-resolved spectrum (Fig. 9) clearly indicate basic splitting of the carbon signal (doublet, triplet, quartet) and allow one to estimate large one-bond J(C,H)-values (in the range 120-250 Hz). However the resolution on the J(C,H) axis is usually not sufficient to see the fine structure of individual cross-peaks. Adequate digital resolution can be achieved more easily in 1D proton-coupled 13C NMR spectrum (Fig. 8) but the polycyclic character of sesquiterpene lactones leads to a large number of long-range couplings (in the range 0-20 Hz) at skeleton carbons, resulting frequently in complex and poorly resolved fine splitting of the basic multiplet. This is the main limiting factor for the attractive application of vicinal couplings 3J(C,H) as a function of the carbon-proton dihedral angle for configuration and conformation analysis. Well-resolved fine structure is usually observed only for carbons belonging to small substituents (like acyl groups) and for skeletal carbons with a limited number of long-range couplings. A typical situation is illustrated for helenalin in Fig. 8. Resolved multiplets are observed for acyclic carbon atoms C-13, C-15 and sp*-carbons C-2, C-3, C-12 with a number of long-range J(C,H)s less or equal to four. The signals of other carbons with 4-11 long-range couplings are not sufficiently resolved. The ‘J(C,H) values strongly depend on the hybridization and substitution of given carbon atom. 1183368,673Typical ‘J(C,H) values obtained by us from the measurement of small series of sesquiterpene lactones are summarized in Table 4.
d
rL1
t
dd
rc1
1 A S
58
n T - r i - r r r r 1 1I
200
~
I
I
I
I II I I
180
1 1
1 1 l 1
1 1 1 1 1 1 1 1 1
160
1 1 1 1 1 1 1 1 1
140
56
54
1 , 1 1 1 1 1 1 1
120
Fig. 5. Single frequency off-resonance proton-decoupled
50
52
1 1 1 1 1 1 1 , 1
100
48
46
1 1 1 1 , 1 1 1 1
80
1
60
1
44
1
1
1
42
1
1
1
1
40
NMR spectrum of helenalin in CDC13.
9ppm
1
1
~ ~ ~ ‘T
PPm
9
I 11
13
5
4
1
13
HELENALIN
7
Fig. 6. Attached proton test I3C NMR spectrum of helenalin in CDC13.
14
I
CHZ
I
2
3
7
6
a
1
CH A
Fig. 7. Edited DEPT I3C NMR spectra of helenalin in CDCI?
10
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
12
13
HELENALIN 2
12
4
13
8
6
Fig. 8. Proton-coupled 13C NMR spectrum of helenalin in CDC13.
251
252
M. BUDESINSKY AND D . SAMAN a
-
I
-
1
7
-
I
I
I
I
3H
3
-
I
'6
I-, ,3 -0 300 5
ARCTOLICE
I I
I 1 I'
I
I
I
I
I
I
I
I
I
I
160
120
80
40
%
Fig. 9. Heteronuclear 2DJ(C,H)-resolved NMR spectrum of arctolide in CDCI?.
The multiplet pattern of C=O carbons of acetate groups in proton-coupled 13C NMR spectra can be used for determination of their position in sesquiterpene lactones. Geminal couplings from methyl protons (J = 7 Hz) split the C=O carbon signal into a quartet which appears in the spectrum if an acetate group is bonded to a quaternary carbon. The quartet is further split into a doublet of quartets and/or triplet of quartets (with J = 3.5 Hz) if acetate is located on a CH and/or CH2 carbon atom.32' Low natural abundance of 13C (1.1%)drastically limits the experimental accessibility of carbon-carbon coupling constants to either extremely highly concentrated solutions of small molecules or to 13C-enriched compounds. Within 13C natural abundant samples only one-bond carbon-carbon coupling constants are sufficiently large (30-100 Hz) to be separated from strong
253
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 4. Typical 'J(C,H) in some structure fragments of sesquiterpene lactones.
Methyl
carbons
'J(C,H)
C-CH3
127-131
Methylene carbons
'J(C,H)
Methine carbons
'J(C,H)
C O-CH3
140
C-CH2-C C-CH2-0
127-131 140
C-CH2
CH-C C /
c\
0
/\
\
CH-0
175
0-CH2-0
158-166
C=CH2
159-164
/
129-135
149-155
C 0 /\
C-CH-C
147-155
0
\
/CH-C
165-175
C=CH-C
152-156
C-CH=O
172
0
centre band. An experimental method for measuring 'J(C,C) is 1DINADEQUATE.64 The isotopic enrichment above 90% is desirable for observation of much smaller long-range couplings. Avent et ~ 1 have . ~ measured 1D-INADEQUATE spectrum of alliacolide (structure 1930 in Table 31) biosynthesized from [1,2-13C2]-acetate and obtained some IJ(C,C) coupling constants (values J(1,lO) = 34.7Hz and J(14,7) = J(15,7) = 36.7 Hz are given). 4.1.4. Relaxation times
Spin-lattice relaxation is responsible for restoring equilibrium magnetization after pulse excitation, and it is characterized by a rate constant - relaxation time TI - which has a specific value for each carbon atom in the molecule. The relaxation times T I of carbon atoms lie in a broad range between a few milliseconds (macromolecules) and several minutes (quaternary carbons in very small molecules). The inversion-recovery method206,661is most frequently used to determine the T I values of individual carbon atoms. The dominating mechanism of spin-lattice relaxation of carbons is their dipoledipole interaction (dipolar relaxation) with protons. If all parts of a molecule were to move at the same rate we should expect the relaxation times T1 for
~
254
M. BUDESINSKY AND D . SAMAN
CH, CH2 and CH3 carbons to be in the ratio Tl(CH):T1(CH2): T,(CH3) = 6:3:2. While for CH and CH2 a 2:l ratio is commonly observed, the T1-values of CH3 carbons are longer due to free internal rotation. Quaternary carbons have typically the highest T I values. These trends can be illustrated for TI values in Fig. 10 determined for some sesquiterpene lactones in our laboratory. Routine 13C NMR spectra are usually acquired with short pulse repetition times (ca. 1-3 s), not allowing full relaxation of slow nuclei and employing a sensitivity gain from NOE. The resulting signal intensities Z are therefore different - typically I(CH) == Z(CH,) > Z(CH,) >> Z(C) - and these intensity differences can be usually used for tentatively distinguishing between carbon-type signals. The higher mobility of some molecular segments (like linear substituents on a polycyclic backbone) leads to longer T1 values of their carbons. This can be documented by comparing T,s of CH and CH2 carbons of the methylbutanoate side chain with corresponding skeletal carbons in trilobolide (see Fig. 10).
ci, . co-0 3.7
17.8
0.4
0.4
99
ARCTOLIDE
TRILOBOLIDE 0.8
12.8
CHjCO .O
4.0
LASEROLIDE
24.2
ISOSILEROLIDE
Fig. 10. Carbon-13 relaxation times TI (in seconds) in some sesquiterpene lactones: arctolide, trilobolide, laserolide and isosilerolide. Data were measured at 50.3 MHz by inversion recovery technique in CDCl3.
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
255
4. I .5. Nuclear Overhauser effect
When dipole-dipole relaxation is a dominating relaxation mechanism of nuclei A and X, then the saturation of X-transitions (X-decoupling) will induce intensity changes in the NMR signal of nucleus A. The intensity ratio of A-signals measured with and without X-irradiation is called the nuclear Overhauser effect (NOE) .471 The maximum observable value is NOE(max) = 1 + yx/2yA, where yx and yA are magnetogyric ratios of nuclei A and X. It means that the homonuclear NOE observable in 'H NMR spectra can achieve a value 1.5 (50% intensity enhancement), while for heteronuclear NOE in a I3C NMR spectrum at proton irradiation it is 2.99 (199% enhancement). The NOE from irradiated protons thus significantly increases the sensitivity in 13C NMR spectra. The contributions of individual protons to full observable NOE at given carbon are inversely proportional to the sixth power of proton-carbon distance. The NOE at protonated carbons (CH, CH,, CH3) is therefore dominated by directly bonded protons. Practical application of selective heteronuclear 13C{'H} NOE is thus limited to quaternary carbons.558a Figure 11 shows the application of the method for the assignment of two quaternary carbons in sesquiterpene lactone archangelolide. The difference NOE spectra using selective saturation of previously assigned methyl protons H-14 and H-13 give unambiguous assignment of neighbouring quaternary carbons C-10 and C-11. 4.1.6. Carbon-proton correlations
Once the unambiguous assignment of protons in 'H NMR spectrum is achieved it can be correlated via J(C,H) to assign carbon signals. Individual carbons can be in principle assigned by selective proton decoupling in 13C NMR spectra. Proton decoupling requires the irradiation of 13C-satellite lines in the 'H NMR spectrum, which are more than 100 Hz distant in the case of lJ(C,H). This can be realized selectively only for some well-separated signals in the 'H NMR spectrum. In practice a series of experiments with the decoupler frequency placed in different positions of the proton spectrum is run and the chemical shifts of coupled protons are derived by extrapolation from partially decoupled 13C NMR spectra. Selective decoupling can be successfully applied on smaller long-range J(C,H)s. Figure 12 shows selective decoupling of individual acetate protons allowing an unambiguous assignment of corresponding carbonyl signals in the molecule of archangelolide. Nowadays heteronuclear decoupling experiments are successively being replaced by more efficient two-dimensional NMR methods. 2D-C,H-COSY techniques65 provide connectivities between 13C and 'H signals and therefore substitute the complete series of selective decoupling experiments,
ARCHANGELOLIDE H-13 H-14
i
r
~
~
160
i
~
~
r
(
140
~
t
~
tV ~ T - t l -t - T i l t? -( I
120
100
~
~
A0
~
~
I
~ I I ~ I I~ 1 I tI
60
'
I
1~ I I ~
I It I
40
I
'
I
I
I
20
I I
IT
ppm
Fig. 11. Selective heteronuclear NOE in 13C NMR spectrum of archangelolide in CDC13: (A) Proton-coupled I3C NMR spectrum; (B) Detail of C-0 signals in the area 6 = 75-82; (C) and (D) Difference NOE spectra at irradiation of H-14 and H-13 methyl protons at 6 = 1.43 and 1.58, resp.; (E) partial proton NMR spectrum showing irradiated methyl signals.
OAc(1)
14
OAc(2)
ARCHANGELOLIDE
175
1
1
1
174
(
1
1
1
173
1
~
160
1
1
172
1
1
~
1
171
1
1
140
1
~
I
170 169
1
1
1
1
~
1
120
1
1
1
~
1
1
1
11
I~
100
1
1
1
1
1 I
80
rI I
I 1 I
I
I
1 1 1
60
'
1 ' 1
1 1
I
f
40
I
f
t i )
1
1 1 1
I
20
ppm
Fig. 12. Selective proton decoupling in NMR spectrum of archangelolide in CDCI,: (A) Proton-coupled 13C NMR spectrum; (B) Detail of carbonyl signals region; (C) and (D) The same region at selective irradiation of acetate protons at 6 = 2.08 and 2.02 resp.; (E) partial proton NMR spectrum showing irradiated acetate signals.
I
258
M. BUDESINSKY A N D D . SAMAN
some of which would be difficult to realize. The common C,H-COSY experiment is optimized for large IJ(C,H) couplings, allowing one to detect proton-bearing carbons only, as shown in the example of sesquiterpene lactone archangelolide in Fig. 13. The C,H-COSY experiment can be modified for detection of small long-range couplings 2J(C,H) and 3J(C,H) (5-10 Hz). The corresponding prolonged time delays (a few milliseconds) lead unfortunately to a loss of sensitivity due to proton relaxation. An improved sequence, denoted COLOC, is inserted into the evolution period in order to reduce relaxation attenuation of signal intensity. The C,H-COSY sequence can be combined with H,H-COSY in the so-called RELAYED experiment. The H-RELAYED H,C-COSY (H-H-C COSY) pulse sequence first involves a coherence transfer between mutually coupled H(A) and H(X) protons (H(A)-H(X) correlation) and then mixed magnetization is transferred from H(X) to C(X). In such a way fragment H(A)-C(A)-C(X)-H(X) can be directly identified. Recently the inverse modifications of two-dimensional C,H-COSY experiments - HMQC (heteronuclear multiple quantum coherence) - has become popular. It utilizes highly sensitive 'H nuclei for indirect detection of insensitive 13C nuclei through multiquantum coherences. The method requires a special inverse probe and high phase and amplitude stabilities in the observation and decoupler channels but the gain in sensitivity is remarkable (theoretical value given by (.yHly-)5'2is 31.6 times). The HMQC experiment623 is optimized for large 'J(C,H) and therefore only protonated carbons are detected. Figure 14(a) shows HMQC spectrum of sesquiterpene lactone helenalin. Cross-peaks correspond to eleven proton bearing carbons in the molecule while quaternary carbons C-4, C-5 and C-11 are not detected. The modification of HMQC, called the HMBC experiment (heteronuclear multiple bond coherence) ,623 is optimized for detection of small long-range couplings and it allows one also to detect quaternary carbons if they are coupled to protons through 2J(C,H) or 3J(C,H). The HMBC experiment is again illustrated with helenalin (Fig. 14(b)). The spectrum contains crosspeaks of all 15 carbon atoms, and detailed analysis showed that nearly all 21(C,H) and 'J(C,H) were detected. The experiment was optimized for J(C,H) = 7 Hz and a few missing cross-peaks obviously correspond to very small J(C,H) values.
4.1.7. Carbon-carbon correlations
The methods for directly establishing the connectivity of carbon atoms in the carbon skeleton are based on one-bond 13C,13Ccouplings. Since only every ninetieth carbon is 13C, only one of 8000 molecules contains two I3C nuclei in vicinal positions. Thus, the sensitivity of such a measurement is very low
2' '
8
2
3'
2' 3
7 9 15
lo.\
I
140
130
120
110
100
90
80
F1
70
60
(ppm)
Fig. 13. 2D-C,H-COSY spectrum of archangelolide in CDC13.
50
40
30
20
10
.-
0
#
0-0.
I
! t
t
.i
'$
7
.
*
.
..
. -..
I
7 1
Fig. 14. The proton-carbon HMQC (A) and HMBC (C) spectrum of helenalin in CDC13. The upper part of the HMBC spectrum containing intensive methyl cross-peaks is shown with a lower vertical scale (B) eliminating T,-noise from spectrum.
262
M. BUDESINSKY AND D . SAMAN
and, moreover, weak signals of coupled carbons can easily be overlapped by the main signal arising from the molecules containing only a single 13C. These problems can be partly overcome by the 1D-INADEQUATE technique,64 which suppresses the main signals and also removes spinning sidebands and signals from trace impurities. The spectrum contains one or more doublets for each carbon atom (according to the number of C-C bonds) from which 13C,13Ccoupling constants can be derived and therefore directly coupled carbons determined. Unfortunately, the similarity of coupling constant values (J = 30 to 40 Hz in the absence of electronegative substituents) , isotope shifts and second-order effects often make complete C-C connectivity establishment difficult or even impossible. The two-dimensional modification of this method - 2D-INADEQUATE (C,C-COSY)63 - still suffers from a low sensitivity but eliminates the other above-mentioned problems. It resembles the H,H-COSY spectra, the only difference being the absence of diagonal peaks corresponding to the single 13C labelled molecules and which are filtered out by the INADEQUATE technique. Figure 15 shows the 2D-INADEQUATE spectrum of sesquiterpene lactone acetylisomontanolide, allowing one to derive completely the carbon skeleton and to assign carbon signals of three acyl groups. Using CH multiplicities as obtained from the APT spectrum and the chemical shift arguments indicating the sp2 character of some carbon atoms and substitution with oxygen, the structure formula can be derived (except for alternative positions of acyl groups). The position of the two acetates at quaternary carbons C-10 and C-11 and angelate ester at methine carbon C-8 can be established from fine splitting of carbonyl signals in the protoncoupled I3C NMR spectrum (see Section 4.1.3) on J(C,H)) and/or from the CH-COLOC spectrum (see Section 4.1 S). 4.1.8. Solvent effects
Carbon-13 chemical shifts are relatively insensitive to solvent changes. Larger shift variations (more than 1ppm) appear in cases of specific solute-solvent interactions on carbon atoms close to the active site of the solute (e.g. C = O , C-OH, COOH). Although as many as 10 different solvents appear in Tables 11-32 with 13C NMR data of sesquiterpene Iactones a large majority were obtained CDCl,. The application of other solvents like d6-dimethyl-sulphoxide, d5-pyridine, d4-methanol, etc. had been dictated either by low solubility of sample, overlap with solvent signal or the need to use solvent for low and/or high temperature measurement. Carbon-13 shift variations of helenalin in the series of solvents is illustrated in Table 5 . Shifts induced in benzene are mostly negative (upfield), and relatively small, with the largest values at carbonyl and vicinal carbon. Solvent shift values and their positive (deshielding) character increase in the order pyridine, acetone, methanol. Detailed interpretation of
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
263
II
I /
20
CH CH,
I /
/
2I ;1.--
1
-Ill7 24
/
/
i
12
1
/
120 159 80 EC 40 Porn Fig. 15. 2D-INADEQUATE spectrum of acetylisomontanolide in CDC13. 160
Id?
Table 5. Solvent dependence of carbon-13 chemical shifts of helenalin (solvent effects related to chloroform are given in parentheses). Solvent" C
C-1
C-2
C-3
C-4
51.34 163.88 129.99 212.21
B P A
M
51.18 (-0.16) 52.44 (1.10) 52.34 (1.00) 53.04 (1.70)
162.88 (-1.00) 164.00 (0.12) 163.85 (-0.03) 165.88 (2.00)
129.68 (-0.31) 129.72 (-0.27) 130.03 (0.04) 130.29 (0.30)
211.09 (-1.12) 211.47 (0.26) 210.77 (-1.44) 213.80 (1.59)
C-5
C-6
C-7
C-8
C-9
c-10
57.98
74.10
50.76
78.15
39.40
26.17 137.86 169.74 123.05
57.62 (-0.36) 57.85 (-0.13) 57.69 (-0.29) 58.48 (0.50)
74.10 (0.00) 74.14 (0.04) 75.02 (0.92) 75.44 (1.34)
51.18 (0.42) 51.87 (1.11) 52.13 (1.37) 52.74 (1.98)
77.56 (-0.59) 79.22 (1.07) 79.12 (0.97) 80.55 (2.40)
39.51 (0.11) 40.35 (0.95) 40.76 (1.36) 41.07 (1.67)
26.04 (-0.13) 26.51 (0.34) 27.02 (0.85) 27.45 (1.28)
C-11
138.73 (0.87) 139.69 (1.83) 140.24 (2.38) 140.42 (2.56)
C-12
169.13 (-0.61) 170.42 (0.68) 170.20 (0.46) 172.18 (2.44)
C-13
121.90 (-1.15) 121.94 (-1.11) 122.07 (-0.98) 123.34 (0.29)
C-14
C-15
20.15
18.69
19.74 (-0.41) 20.16 (0.01) 20.40 (0.25) 20.46 (0.31)
18.67 (-0.02) 18.81 (0.12) 18.94 (0.25) 19.27 (0.58)
"C: chloroform; B: benzene; P: pyridine; A: acetone; M: methanol.
Table 6. Dilution effect on carbon-13 chemical shifts of archangelolide in CDC13: (A) 0.2 M solution; (B) 0.01 M solution; (C) shift differences upon 20-fold dilution. Solvent
C-1
C-2
C-3
C-4
C-5
C-6
C-7
C-8
C-9
C-10
C-11
C-12
C-13
C-14
C-15
20.35 20.43 0.08
26.20 26.28 0.08
17.63 17.71 0.08
~~
A
B C
52.70 52.71 0.01
78.97 127.10 148.90 79.07 127.18 148.94 0.10 0.08 0.04
50.06 50.13 0.07
76.81 76.84 0.03
48.10 48.16 0.06
c
170.02 169.68 170.08 169.78 0.06 0.10
22.28 22.36 0.08
44.11 44.23 0.12
80.86 80.88 0.02
78.11 173.54 78.17 173.61 0.06 0.07
Ang
2xAc A B
65.37 65.44 0.07
20.87 167.38 127.74 137.76 20.97 167.47 127.80 137.84 0.10 0.09 0.06 0.08
15.65 15.74 0.09
Mebu 20.35 174.78 20.43 174.86 0.08 0.08
41.28 41.35 0.07
26.35 26.42 0.07
11.60 11.68 0.08
16.30 16.37 0.07
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
265
observed solvent-induced shielding differences is difficult. Practical use for the structural signal assignment is rather limited. Carbon-13 chemical shifts obtained in a certain solvent are still more or less dependent on the concentration of solution. Constant shift values independent of further dilution may be reached at low concentrations. No systematic study of dilution 13C shifts has been described for sesquiterpene lactones. Our measurement of archangelolide at high concentration (0.2 M) and low concentration (0.01 M; no further changes upon dilution) in CDC13 showed lowfield dilution shifts in the range 0-0.12 ppm (see Table 6). 4. I.9. Shift reagents Effects of paramagnetic lanthanide ions binding to polar groups of the substrate (e.g. NH2, O H , C=O) resulting in increased chemical shift dispersion from pseudocontact shielding contributions have been widely used for: (1) simplification of spectral analysis; (2) structural assignment of signals;
( 3 ) conformation analysis of complex The perfluorinated tris-p-diketonates of europium (111) and praseodym (111) have found widest use among lanthanide shift reagents (LSR). Although contact contributions are generally not negligible in 13C NMR spectra the pseudocontact shielding contribution usually dominates. Under such conditions a lanthanide-induced shift (LIS) depends on the LSW substrate molar ratio and upon geometry parameters of a given carbon with respect to the lanthanide ion. The interpretation of LIS values is straightforward when only one binding site is present in substrate. In polyfunction substrates the observed LIS values are averaged over equilibrium populations of individual LSWsubstrate complexes. Even in that case the relative LIS values can be used for structural assignment of some carbon signals as illustrated in Fig. 16 which shows the effect of stepwise addition of Eu[fodI3 on the carbon chemical shifts of helanalin. The large difference between LIS values of the two methyl carbons (54.1% vs. 7.8% related to 100% for C-4) allows unambiguous assignment of the more movable signal to C-15 which is much closer to the present binding sites (C(5)-OH and C(4)=0) than C-14. The effect on proton chemical shifts under the same conditions is shown for comparison. A series of binuclear complexes formed from ytterbium (111) tris-Pdiketonate and silver (I) diketonate have been introduced as NMR shift reagents for o ~ e f i n s . ~ ~ ~
n
14
C-4
12
10
c-2,c-3 c-15 C-6
c-1
8
A6H
HELENALIN
6
, H-6
4
I H-I, H-3 '
c-5
(2-7, c-12, c-13 C-8, C- I0 C-1l.C-9 2
-
H-I5
1 1
I{-7. 1 1 - 1 0 H-2, tl-8. II-%x, I IN\\. I I - I 3 1 H-12'. H - I 4
C-14
LSR
0 1I
13
0
LSR
-
Fig. 16. The effect of Eu[fodIi on I3C and 'H chemical shifts of helenalin in CDCI?. Four stepwise additions of Eu[fodI3 without weighting have been used. The induced shifts of C-4 signal (in I3C N MR ) and OH signal (in 'H NM R ) were assumed to be linear and they were used to define positions on the x-axis.
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
267
4.1.10. Isotope labelling
The change in natural abundance of two stable isotopes of hydrogen (99.98% 'H with spin 1/2; 0.02% 2H with spin 1) and/or carbon (98.89% '*C magnetically inactive; 1.1% 13C with spin 1/2) has a characteristic effect on 'H and '3C NMR spectra which can be employed for structure assignment. The deuterium exchange of protons which are bonded to heteroatoms (OH, NH, SH) by adding of a small amount of D 2 0 , CD30D or CD3COOD to the sample solution in the NMR tube is a classical method for their detection by 'H NMR (the signals XH-+XD disappear). Partially deuterated hydroxyl protons (H:D ca. 5050%) in polyhydroxyderivatives measured in DMSO were used for the structure assignment of carbon signals.144.518 The deuterium isotope effect on C-13 chemical shifts (upfield p-effect 0.1-0.15 pprn and smaller y-effect 0.03-0.06 ppm) lead to spectra which are superpositions of spectra of the individual isotopomers. The signal pattern of each carbon reflects the number of directly bonded and vicinal OH groups. The potential value of this method in the field of sesquiterpene lactones is limited to polyhydroxy derivatives (e.g. glycosides). The compounds selectively labelled with deuterium bonded to certain carbon atoms can be prepared synthetically. The presence of deuterium is then manifested in proton-decoupled 13C NMR spectra by characteristic splitting of the corresponding carbon signal into a triplet, pentet and/or heptet for CD, CD2 and CD3 (coupling 'J(C,D) is 6.5 times smaller than 'J(C,H)) and the upfield isotope shift ( 0 . 3 4 6 ppm). Signal intensity is further reduced by less efficient relaxation (longer Tls) and the decrease of NOE due to the absence of directly bonded protons. Synthetic 13C enrichment results in signal enhancement of the labelled carbon and the observation of one-bond coupling 'J(C,C) on neighbouring carbon atoms in the proton-decoupled 13CNMR spectrum. Such 13C isotope labelling is efficiently used in biosynthetic studies (biosynthetic metabolites produced by organisms feeding a 13C-labelled precursor) and in NMR experiments based on the detection of J(C,C) (see Section 4.1.7). 4. I . 11. Derivatization The defined simple structure modification - derivatization - induces chemical shift changes usable for structure assignment of signals. Acetylation, which has been used extensively, results in low-field shift of hydroxyl-bearing carbons (a-effect) along with an upfield shift of neighbouring carbons (p-effect), while the other more distant carbons remain essentially unaffected. More complex acetylation shift patterns can be observed for 1,2- and/or 1,3-diols. The presence of acetoxy groups is manifested by its C=O and CH3 signals at 6 = 170 and 6 = 20 allowing one to determine the number of acetylated OH groups. Typical values of a-,p- and
Table 7. Acetylation shifts in carbon-13 NMR spectra of hydroxy compounds
A&
(ppm)
p-effects
a-effects
-CH2-OH >CH-OH >C-OH
= SC(R-OAc)-6,(R-OH))
1.0 to 2.5 1.5 to 3.5 ca 5.0
y-effects
CH?-C-OH
CHq- C- C-C- OH
- CH*”-C- OH
>CH-C-OH >C-C-OH =CH-C- OH =C-C-OH
<1.0
>C-C-C-OH -
2.0 to 5.0
Table 8. TAI-induced acylation shifts in carbon-13 NMR spectra of hydroxy compounds.
A8, = G,(R-OTAC) - 6,(R-OH)) (ppm)
a-effects
-CHZ-OH >CH-OH >C-OH
p-effects 3.5 to 5.5 5.5 to 8.0 8.0 to 17.0
CH3-C-OH -CH,-C-OH >CH-C-OH >C-C-OH =CH-C-OH =C-C-OH
y-effects -1.0 -4.0 -2.0 -1.0 -5.0 -2.5
to -8.0
to to to to to
-8.0 -4.0 -2.0 -7.0 -5.0
CH3-C-C-OH -CH,-C-C-OH >CH-C-C-OH >C-C-C-OH -CH=C-C-OH >C=C-C-OH
<1.0 2.5 to 5.5
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
269
y-acetylation shifts collected in the series of sesquiterpene lactones are given in Table 7. Similar chemical shift changes are induced with other acyl groups occurring in natural products. An elegant method for characterization of alcohols is in situ reaction with trichloroacetyl isocyanate (TAI) in the NMR tube leading to trichloroacetyl carbamates. 1163241 TAI reacts instantaneously even with most of the tertiary alcohols, except in some cases of strong sterically hindered OH, where stepwise derivatization can be observed. The method originally suggested for 'H NMR characterization of alcohol^^^^,^^^ can also be successfully used in I3C NMR spectroscopy. 11' The TAI-induced shift value of hydroxylbearing carbon is characteristic for primary alcohols (3.5-5.5 ppm), secondary alcohols (5.5-8 ppm) and tertiary alcohols (8-17 ppm). The @-carbons are shifted upfield (-1 to -8 ppm) while the effect on y-carbons is usually small (< 1 ppm; larger positive y-effects are typical for ally1 alcohols). Typical TAI acylation shifts are summarized in Table 8. Acylation with bulky TAC-groups results in significantly shorter relaxation times T1 of product (by factor of two to four times) and allows faster accumulation of I3C NMR spectra. Trichloroacetyl carbamate carbons give low intensity signals at characteristic positions (6 = 92 (C13C), 6 = 158 (C-CO-NH) and S = 150 (NH-CO-0)). The signals of unreacted TAI are not observed due to extremely long relaxation times. The reagent reacts with some solvents such as methanol, pyridine and dimethylsulphoxide which cannot be used for in situ TAI acylation. Chloroform and/or acetone are used most frequently. If small amount of water is present in solution it reacts with TAI to give trichloroacetamide (signals are usually not detected). In special cases the reaction with TAI can lead to the formation of elimination or substitution products.558 The interesting special application of TAI method represents in situ modification of the benzoate rule for the configuration assignment of secondary alcohols. It has been shown that R-OTAC derivatives give the same sign of molecular rotation difference
A[@] = [@](R-OTAC) - [@](R-OH) as b e n ~ o a t e sdistinguishing ~~~ thus between R and S configuration on the CH-OH carbon atom (see Table 9). In principle some other derivatization reactions can be exploited under proper conditions. The methylation and silylation of hydroxy group and hydrogenation or epoxidation of double bonds represent the most common cases.
4.I,12. Molecular dynamics Intra- or intermolecular dynamic processes (rotation around single bonds, conformation ring inversion, valence tautomerism, exchange of labile
270
M. BUDESINSKY AND D . SAMAN
Table 9. Comparison of the benzoate rule and its in situ modification using TAI.
A[@] = [@](R-OX) - [@](R-OH) C-OH configuration X = Benzoyl X = TAC
Compound
Menthol
Eupatolide
b, A W
R
-101 .la
-22.1
R
-90. I b
-70.9
0-w
4cyH-Slovanolide, lOP,l l-diacetoxy-
n !
Q&
oQ kr
S
t-119.7
+484.2"
3-OXO O'CU ~
~~
OBenzoate. 'Dinitrobenzoate.
protons) can influence NMR spectra. The effect depends on the rate of a given process and its NMR time scale, which is defined by frequency difference of signals corresponding to individual states. Slow processes can lead to the observation of separate signals for those states, while fast processes result in one set of signals which can be more or less broadened at medium rates. As the rate of a dynamic process depends on temperature, the NMR spectra are also in general temperature dependent. Nearly all I3C NMR spectra of sesquiterpene lactones run at room temperature show a single set of signals either due to the existence of one preferred conformation of cyclic carbon skeleton or fast conformation equilibrium. The only exception is formed by some germacranolides which give either significant line-broadening of certain carbon signals or even two to four sets of signals for individual conformers. The excellent example is l a ~ r e n o b i o l i d which e~~~ shows extremely broad I3C signals at 30°C, while four sets of sharp signals in the ratio 5:4:3:1 can be observed at -15°C. Detailed analysis (using 'H NMR spectra, lanthanide shift reagents, J(H,H) values and interproton NOE data) has proven the existence of four conformers A, B, C, D of a ten-membered carbon ring (see Fig. 17). The differences in chemical shift values reflect the sensitivity to conformation changes.
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
271
Me
Me
(C)
(D)
Fig. 17. Laurenobiolide: four conformers (A.B,C,D) observed at - 15°C.
4.2. Identification of acyl groups
In natural hydroxyl-containing sesquiterpene lactones, some of the hydroxyl groups are esterified with carboxylic acids. Besides the lactone grouping, acyl residues of various carboxylic acids are the most frequently occurring functional groups in these molecules. Therefore, determination of structure of native sesquiterpene lactones very often requires identification of acyl groups. The chemical approach consists of hydrolysis and subsequent identification of free acid and implies destruction of the relatively large amount of material. Identification of acyls by mass spectrometry does not afford detailed information on acyl structure. The study of extensive series of sesquiterpene lactones showed a possibility to identify acyl groups using a collection of proton and/or I3C NMR data.127 The wide range of chemical shifts, the line character of spectra and rather low sensitivity of the acyl signals to the character of substrate and solvent make the application of I3C spectroscopy preferable. Carbon-13 chemical shifts of about 80 different acyl groups found in sesquiterpene lactones are given in Table 10. Generally, data obtained in deuterochloroform were preferred; if not available, data obtained in another solvent were used. For frequently occurring esters the given values represent arithmetic means. Standard deviations of the obtained values do not exceed 0.8ppm. As follows from Table 10, the 13C NMR data for esters are highly characteristic, and if all acyl carbon signals are considered, an error in the structural assignment is very unlikely. This was verified with a simple program for automatic identification of the acyl
272
M. BUDESINSKY AND D. SAMAN
Table 10. Carbon-13 chemical shifts of acyl groups occurring in sesquiterpene
lactones. Abbrc\ liltion C-l Ac
C-2
C-3
C-4
Name / Chemical slidis Other carbons
C-5
~
-~
acehl
169 9 21.0 2-(l-l1ydro~yetliyl)ac~loyl 165.0 345.3 123.3 64.5 23.3 Acr-2-CH,CHIOH 2-(2-liydro~yethyl)aclylo).l 166.9 136.6 128.0 35 0 61.1 Acr-Z-CH(OH)CH,OH 2 4 I ,2dihydro~yethyl)actyloyl 70.3 65.5 165.1 132.1 127 8 Acr-Z-CH(OAng)CH,OH 2-( I -angeloylow~-2-hydro~~ethyl)acrylovl 1643 138.6 1275 69.8 6 7 0 1682 127 I l ? 9 6 1 5 0 1'17 Aiig angeloyl 1664 126.9 1100 I58 2 0 3 Ang-4-OAc I-acelo\yangeloyl I65 5 127.8 140.2 63.0 19.3 171.1 20.') Ang-5-OH = Sar 4-hydroyangeloyl = sarracionyl 165.6 131.4 142.5 15.7 63.8 Airg-5-OAc = Sarac S-aceto\yangeloyI = acelylsarraclonyl I64 7 127.0 147.0 15.9 65 6 Aiig-4-OAc-5-OH 4-accto~~-5-liydro~yangeloyl a a 141.5 62.5 63.2 a 2(1 X Ang-Z.i-cp-.3-OH Z.j-epo.i~-3-li?dro~yan~~lo~ 1 171 5 81 -3 59.6 I95 653 AII~--I-OH-~-OAC~-~'-CH(OH)CH~OH 5-(2'-(1'.2'-dihydro cth! I);icn lo! lo\! ~ - - I - l ~ ~ ~ rI o ~ ~ ~ ~ ~ ~ g c l ~ ~ 1 6 5 7 126.3 1 4 8 9 582 6 6 I647 1.30(1 7 0 6 5 9 2 1 2 7 X
Acr-2-CH(OH)CH,
Blll DL
RA'-OH
B/-.I'-OMe Clllll
CIIIII-;'.-I'-OH
butniio! I 174.4 37.7 19.2 be11royl 165.9 1302 1297 p-li?drokybenzoyl 165.9 120.6 131 3
14.7 128.7
133 3
128.7 1297
115.6 161.3 p-methowyknzoyl 164.7 122.3 131.4 114.0 1637 ci iina mo! l I65 I 1163 142.6 I32 5 126.1 3 ',l'-diliydro\~ciiiiiaiiiayl
115 6 131 3
I140
1.714
556
1269 1 2 x 2 1 2 6 9 I26 I
166.4 115.5 145.8 126.6 115.0 148 7 147 4 I I6 5 2,3dihydro-2,4'-dihydroxycinnamoyl 174.4 72.8 40.8 128.7 131 4 1162 I578 1 1 6 2 131 4 Cinii-diH-l'-OH-2-OiVal-2''-OH 2,3-dihydro-4'-liydro~yw-2-(2"-hydro~yiso\~aleroylo~~)ciiinamoyl 169.7 74.1 37.1 126.7 131.3 116.4 158.1 1164 1 3 1 3 1 7 4 7 7 5 r ) 19.4 17 ?. Epmg 2,3-epokyangeloyl 168.6 59.5 59.9 13 7 19 0 Ep;iiig-5-OH 2.3-epo~~-5-hydroxyangel0~l 167.2 64.1 5 4 9 I3 5 61 9 Fur furoyl 161.9 119.2 109 6 1442 147.8 Fur-diH-5-OMe 2.3-dihydro-5-rnetho.\yfuroyl 72.8 54.4 161.1 137.5 136.0 109.4 Hep-&Me 6-methylheptanoyl 174.3 35.2 27.2 27.9 39.8 290 23 0 2 1 0 tk\ hexanoyl 173.8 34.5 25.2 31.9 22 9 14 2
Ciiiii-diH-2.4'-OH
>2'J
273
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table lo.--continued
* 0
AC
CH,OH 0
Acr-2-CH(OH)CH3
Acr-2-CH(OAng)CH20H
CH20H
OH
Ang
Acr-2-CH,CH20H
Ang-4-OAc
OH
Acr--2-CH(OH)CH20H
Ang-5-OH
Ang-5-OAc
( Sar )
( Sarac )
CH20H 0
Ang-4-OAc-5-OH
0
Ang-4-OH-5-OAcr-2'-CH(OH)CH20H
Ang-2.5-ep-SOH
,,p
OH
0
0
G
O
C
H
But
K"0 \
3
\
4
0
0
0
0
0
0
Br
BZ-~'-OH
Bz-4'-OMe
Cinn
Cinn-3'.4'-OH
Cm-diH-Z.d'-DH
Cinn-d~H-4'-DH-Z-OiVd-2'-OH
0
Fur
Fur-dbH-S-OMe
Epong
Heo-6-Me
Epang-5-OH
Hex
OH H
274
M. BUDESINSKY AND D. SAMAN
Table 10.+ontinued N:iiiic
c-l
c-2
c-;
C-1
C-5
~
dro\! isobuta~~o)l I4 0 174X 434 643 ?.1-diIi!dro\?isobulano~I I60 1 76 3 6X 0 21 '1 i-nceto\~-2-Ii~dros~isobul;ino! I 1740 735 688 205 2-~ceto\~-3-liydrosyisobiitano~ I 1746 78X 467 216 2..3-di:icc1o\! isohulnno! I I600 77 8 65 2 1'1 7
3-cliloro-?-li~dro\~isobulnno! I 171 7 747 51 I 271 I so\ ii l c ro! I 1.3 3 253 222 1711 dro\-yiso\-alcroyl 1711 754 322 2-aceco\! tsowleroyl I697 764 366 melll;lcn li'\ I I 6 5 7 I . < i O 1270 4-11! dro\! inctli:icn lo! I 1666 l ? ' J ? 1260 l-accIo\! Illcrhacl)lo! I 1 6 1 3 135.0 121 5
/ Clrciiiic:tl \IIIflS Orlicr c;lrboiic
170 6 22 0 1 7 1 1 2110 lh')2
2iI:
I O < J 3 2110
222
2-11!
I65
103
I53
I14
17ll52lli
1x0
616 622
170 ?
20 6
2.3-epo\! nicrhacryloyl 1695 53.8 528 2-nielh! Ibutanoyl 1754 41.3 266
17 3
11 5 165 .?-hydro\? -2-metIi~Ibiitano~ I 1752 477 720 I4 I 2117 ? . 3 - d i I i ~ d r o ~ ~ - 2 - 1 Ihitintio! iiclli~ I 1751 774 714 167 217 2.3-d~acc10~~-2-1i1elliylbulaiio~ I 1685 816 721 164 1-15 3 -acetoxy-2-hydroq -2-nicth!lbutano).I 174.0 760 73.5 I3 7 22 0
1695 2 0 9
1'114
2ii9
171 3
21 9
1 7 0 0 20 9
2.5dih: drosy-2-niethyl-3-nierk~plobutanoyl 1713 813 595 I99 625 ?.5-diacetosy-3-hydro~>-2-nielh) Ibutano:d 203 61 7 1 7 0 7 21') 83 5 564 166.3
2-1iierl1)I-2.3.5-lrihydro~~butaiio~ I 1729 oclallo! I 17.1')
818
686
354 261 6-nieth! loctnnoyl 174 I 356 263 p-h!dros?.phenylacet) I 40.9 124.9 171 4 p-nietlio\~phenyIacetvl 1707 409 I 2 7 0
177
647
.30I
301
3 2 9 23 7
I4 '1
277
352
37.5
II 8
131 0
116.4
158.1 1164 131 0
1309
1145
1 5 9 4 114.5
306
196
1 3 0 9 55 3
~
__
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
275
Table lO.
aJ-
CH,OH
,But
iBut-P-OH
But-3-OH
-k""
CH,OAc
But-2-OH-3-OAc
+OH
But-2.3-OH
+OH
iBut-Z-OAc-3-OH
CH,OH
CH,CI
iBut-Z,3-0Ac
OAc
iV0l
Nal-2-OH
;Val-2-OAc
Mac
Mac-4-OH
Mac-4-OAc
& 0
0
OH
Mebu-3-OH
Mebu
Mac-ep
OH
Mebu-2.3-OH
*
Mebo-2 3-OAc
0
0
OAc
Mebu-Z-OH-3-OAc
0
SH
Mebu-2.5-OH-3-SH
0
OH
Mebu-2.5-OAc-3-OH
OH
Mebu-2.3.5-OH
CCH,
oc t
Oct-6-Me
Phac-4-OH
Phoc-4 -0Me
276
M. BUDESINSKY AND D. SAMAN
Table 10.-continued Name /Chemical shifts C-5 Other carbons c-l c-2 c-3 c-4 propionyl Prop 174.1 27.7 9.0 senecioyl Sen 27 5 161.9 115.1 159.3 2 0 1 lE-hydroxysenecioyl Sen-l-OH(E) 15.7 165.8 111.8 160.8 66.6 4-acelosysenecioyl Sen-4-OAc 21.5 1705 2 0 6 161.1 116.3 157.7 63 5 tigloyl Tlg 12.1 166.8 127.9 138.5 14.5 4-hydroxytigloyl Tig-4-OH 12 6 166.1 126.9 1428 59.4 4-oxotigloyl Tig-4-ozo 166.0 12G.8 144.4 191 1 11 9 5-hydrox7.tigloyl Tig-S-OH 56 2 1662 131.6 1126 I4 5 5 -acetoqligloyl Tig-5-OAc 57.3 170 6 20 7 1652 127.5 I159 147 1,Sdihydroxytigloyl Tig-4.5-OH 56 8 165.9 131.5 145.1 58.8 5-acetox~-4-hydrox~igloyl Tig-4-OH-S-OAc 58.2 171 3 2 0 9 165.6 127.1 147.7 5 9 4 Tig-4.5-OiPr 4.54-isopropylidenetigloyl 5 9 6 1023 2 3 6 1638 1323 142.2 6 0 7 Tig-i-oT~g-S‘-oH j-(j’-h?drox~iigloS.loxy)tiglo~ I 5 7 5 1667 1.31 7 141 ‘) I 4 3 5 6 2 I647 1276 145.7 146 Tig-j-OTig-J’-OH 5-(4’-li~dros)tigloylox~)~iglo! I 57.5 167-1 127 -3 1-11I 5 9 6 I! (r 1653 127.4 1462 1-17 Tig-l-OH-.i-OTig-5’-0H 5-(5’-h~drox~igloylox~)-4-hydroz~l1glo~l 165 I 127.0 147.9 5 9 3 57.0 1670 1.31 4 I42 2 1-15 5 x 6 Tlg-l-OH-.i-OTig-4’,5’-0H5-(4’,5’-dihydrox~11gloyloxy)-4-liydrox~~1glo~l 165.3 125.2 147.8 58 9 58.4 166.6 1260 14-1 6 59 I 5 X X Tlg-l-OH-S-OTig-l’-OAc 5-(4’-acetoxyt1gloylox~)-4-hydro~~igloyl 167.2 126.9 148.2 59.5 58.6 1 6 5 3 1303 I 3 7 4 61.1 1 2 8 1 7 1 1 s ? I I Tig--1-OH-J-OTig-4’-0so 5-(4’-osotigloyloxy)-4-hydrox~ligloyl 165.0 126.2 158.3 59.6 59 3 167 I 136 o 1-18 2 1‘96 I I: I Tig-4-OH-j-OAng 5-(angeloyloxy)-4-hydrox~11gloyl 164.7 126.7 1179 5 9 1 57 5 167 7 I 2 6 9 l 3 Y 5 I5 S X I ? Tlg-5-OH-.l-OTig--l’-oso l-(4’-osotigloyloxy)-5-hydro.~~~1glo~l 6 1 3 1656 I360 1 4 x 3 1 9 1 7 I 7 1 1648 138.3 145.0 572 T1g+OStear-3’-OH 4-(3’-hydroxystearoylox~)tigloyl 3 2 0 2‘1 X ( i \ ) 2‘14 2 4 6 a 370 32 I 168.5 141.6 a 602 a 228 142 Val-2-OH-3-Me 2-hydroxy-3-methylvaleroyl 1 1 6 157 174.1 75.5 39.1 24.5 2-aoetoxy-3-niethylvaleroyl Val-2-OAc-3-Me II 5 I54 170.2 76.8 36 6 24 9 Val -2 -en-3 -Me 2.3dehydro-3-methyl\’illeroyl 120 a 165.5 113.5 164 5 340 Abbre! iation
-
~~
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
277
Table lO.+ontinued
0 Sen
Prop
Sen-4-OH(E)
T ig-4-OH
Ti3
CH,OH
Tig-4-0x0
Sen-4-OAc(Z)
Tig-5-OH
Tiq-5-OAc
CH20H
yfHZ0% &oJH20" 0
CH20Ac
H2@+
,J;x
Tiq-4.5-OH
Tig-4-OH-5-OAc
&o&cH20H
0
CH,O
Tig-4.5-0iPr
0
Tig-5-0Ttg-4
0
J y H " H
-OH
0
g-4-OH-5-OTig-S-OH
0
Tig-5-011g-S-OH
J y H 2 O A c
CH20H
0
CH20Ac
CH20H
0
0
0
0
T ~ ~ - ~ - O H - ~ - O T I ~ - ~ ' . S - O Tiq-4-OH-5-OTtq-4'-0Ac H
Tiq-4-OH-5-OTiq-4'-oxo
Tig-4-OH-5-OAng
Tig-5-OH-4-OTiq-4'-oxo
Val-Z-OH-3-Me
Val-2-OAc-3-Me
Val-Z-en-3-Me
Tig-4-0Steor-5-OH
278
M. BUDESINSKY AND D. SAMAN
groups.’27 Sets of 13C NMR data of 70 randomly chosen sesquiterpene lactones containing acyl groups (signals taken as structurally not assigned) were analysed. It was shown that the reliability of acyl structure determination does not depend much on the accuracy of the experimental shift data and for values from k0.7 to k2.0ppm reliability ranged between 97% and 90%. In some cases, acetyl was erroneously identified, because its I3C data are least characteristic. However, since its identification can easily be made from the ‘H NMR spectrum, this drawback does not devaluate the automatic procedure. There is a characteristic difference between acyl C = O signals of saturated (6 = 176-169) and unsaturated carboxylic acids (6 = 167-161). The C =O signals of a,&epoxyacyls appear in the region 6 = 171-167. The structural identification of acyls derived from hydroxy acids can be supported by in situ acylation with trichloroacetyl isocyanate.
4.3. Carbon-13 chemical shift data
This section presents 13C NMR data of more than 2000 sesquiterpene lactones (native and synthetic) published in the literature up to the end of 1992 and some unpublished data from our laboratory. The compounds are divided into eight main groups. First six groups contain lactones with most frequently occurring carbocyclic skeletons in the order: germacranolides, eudesmanolides, guaianolides, pseudoguaianolides, elemanolides and eremohphilanolides. Last two groups present lactones with less common skeletons and finally dimeric sesquiterpene lactones. Each group is briefly discussed in Sections 4.3.1 to 4.3.8. Compounds in most extensive groups are further subdivided into separate tables according to lactone closure (12,6- and 12,8-olides, resp.), substitution at C-11 (ll-exomethylene vs. the others, called for simplicity 11-methyl type) and the extent of structure modification. The sequence of compounds within the tables should respect cis- and truns-configuration of lactones and bring structurally similar compounds together. NMR data are presented in two-page blocks together with structure formulae to make both structure and data search easier. For each compound the table contains a number (referring to structure formula), elemental composition, compound name, carbon chemical shifts, solvent used and literature reference. For easier recognition of structurally similar compounds, prefixes and substituents indicating the structure modifications follow the parent name. If the compound name is missing in the original paper then we either use the semisystematic name (whenever its construction from parent sesquiterpene is straightforward) or we indicate the compound as having “no name”. Chemical shifts presented in the tables are rounded off to tenths of ppm (this accuracy is believed to reflect the reproducibility of data).
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
279
Symbols for ester acyl groups, their full names, structures and typical shift values are given in Table 10. Acyl carbons chemical shifts for individual compounds are presented in each two-page block in table footnotes. Additional abbreviations and symbols used throughout all tables are:
* after the literature reference number means that assignment (not given in original paper) was done by the authors of this review;
* after some chemical shift values means changes in assignment of indicated carbons done by the authors of this review; a
value of parameter is not given in corresponding paper;
b,c,d,e,f assignment of signals with same symbols may be mutually interchanged; ?
evidently incorrect value given in original paper.
Solvents: A acetone B benzene chloroform C D dioxane E ethyl acetate L dichloromethane M methanol N acetonitrile P pyridine S dimethyl sulphoxide
Substituents: Et Glc Ph Pro Rha SePh TAC TBDMS iPr SiEt, SePh(2-N02)
ethyl p-D-glUCOSyl phenyl pro1in e rhamnoside phenylseleno trichloroacetyl carbamoyl tert-butyldimethylsilyl isopropylidene triethylsilyl ortho-nitrophenylseleno
4.3.1. Germucrunolides
Carbon-13 NMR data of more than 600 germacranolides are collected in Tables 11-15. Tables 11 and 12 contain the compounds lactonized into position 6, and Tables 13 and 14 those lactonized into position 8. Both groups are further divided according to the presence of either exomethylene (Tables 11, 13) or a methyl group (Tables 12, 14) in position 11. Finally Table 15 contains modified germacranolides, namely 14,6-olides and secoderivatives. The division into Tables 11-15 is schematically shown in Fig., 18 together with numbering of the germacrane skeleton. The germacranolides represent the largest group of sesquiterpene lactones. The cyclodecadiene skeleton with double bonds in positions l(10) and 4(5) leads to four possible isomeric forms which differ in their double bond configurations and are sometimes denoted germacrolides, melampolides, heliangolides and cis,&-germacranolide (see Fig. 19). The reactivity of the cyclodecadiene skeleton further contributes to the great structure variety of
280
M. BUDESINSKY AND D.
SAMAN
Table 13
Table 12
Table 11
m? co
W
-
Table 14
R
2 CH~R'
0-co Table 15
Fig. 18. Schematic representation of germacranolide structure types in Tables 11-15 and numbering of gerrnacrane skeleton.
this group. The double bond configurations seem to have a strong influence on the conformation of ten-membered rings. Typical conformations of germacrolide, melampolide heliangolide and cis ,cis-germacranolide with the trans-lactone group closed at C-6 are also shown in Fig. 19. The ten-membered ring can adopt more than one conformation, as reflected in 13C NMR spectra of some germacranolides. The observation of four conformers of laurenobiolide [525]635 at - 15°C was discussed in Section 4.1.12. Similar conformation equilibria were described for some other germacran-12,8-olides. Two conformers of germacra-1(10)E, 4E,1 l(13)trien-l2,8@-olide [523]with a cis-7,s-annelled lactone ring were observed through the examined temperature range -30" to +60°C.6y8 Two conformers were also detected for compounds with a tr~ns-7~8-annelled lactone ring: chamisselin [524],532/3,15-dihydroxygermacra-l( 10)E,4Z,7(11)-trien12,8a-olide [527],642dilactone isabelin [5N],280 dihydrolaurenobiolide [596] and dihydrodesacetyllaurenobiolide [597].635Three conformers in the ratio 10:9:6 were observed at -40°C in the 13C NMR spectrum of 14acetoxydesacetyllaurenobiolide [526].93 The observation of slow conformational equilibrium is less common in 12,6-olides. Two conformers were observed in caudatol [IS],366 8/3-acetoxy-lP-peroxycostunolide[ 15315'* and tetragonolide isobutyrate [388].351 Some germacranolides with exocyclic lO(14)-double bonds (tanachin [554],tatridin B [555]and their acetates [556] and [557]) give broad unresolved I3C NMR spectra at room temperature while at +57"C sharp well-defined signals are observed.571High temperature 13C NMR spectra were needed to observe all carbon signals of artemorin
GERMACROLIDE
MELAMPOLIDE
HELIANGOLIDE
cis.cis-GERM ACR ANOL IDE
Fig. 19. Configurational types of germacranolides and their typical conformational forms. The tuans-12,6-olides only are shown.
282
M. BUDESINSKY AND D . SAMAN
[ 1451, its derivatives 436, 442563 and achillolide B [451].5x4 Somewhat broadened signals of the ten-membered ring (especially C-9) as the result of conformational interconversion were observed in the series of melampolides 542-548.263 The variable temperature 13C NMR spectra of linderalactone [630] showed no significant change between -90" and + 100°C indicating just one conformer of the ten-membered ring636 in agreement with earlier conclusions from 'H NMR. Lange et u1.389,389ahave suggested a simple method for I3C NMR determination of the configuration of methyl-substituted double bonds in medium- and large-ring terpenoids. A number of examples in the germacranolide field show that C-14 and C-15 methyl resonances appearing at 6 > 20 ppm is indicative of Z-configuration, whereas 6 < 20 ppm indicates E-configuration. The rule should be applied with care - e.g. in 8P-OH or 8P-OCOR derivatives with 1(10)E-double bond configuration the C-14 methyl group is deshielded and its chemical shift is close to or even slightly greater than 20 ppm.389a It seems that also substitution in some other positions can influence the validity of rule - compare e.g. C-15 chemical shifts in the series of 3a and 3P-substituted compounds in Table 11 (6 = 17.1-18.4 in 80-86 w. 6 = 22.S23.1 in 87-95, all with 4(5)Z-double bond). The rule allowing one to derive the configuration of the 11-CH3 group in e u d e ~ m a n o l i d e s-~6(a-CH3) ~~ = 12-15 ppm and 6(P-CH3) < 10 ppm - was shown to be applicable also in g e r m a ~ r a n o l i d e s .Intermediate ~~ cases in which 11-CH3 resonates in the range 6 = 10-12ppm are known30x where this relationship cannot be applied. In compound [393] the chemical shifts of Me-14 and Me-15 (6 = 16.3 and 11.7) revealed E-configuration on double bonds, and the absence of y-gauche effect between C-13 and C-8 (6 = 13.2 and 28.5) was used as evidence for a-orientation of M ~ - 1 3 . ' ~ Unequivocal information on the alternative positions 8 and 11 of two ester groups - acetate and angelate - was obtained from J(C,H) couplings observed in the proton-coupled I3C NMR spectrum of laserolide (392].321 Various 1D-NMR methods have been used for the structure assignment of germacranolide carbon signals: INEPT,2.479,"88 ~~pT54,236,237,238,294,397,398,479,483,484,S42,584,SY6,652,686 and APT, 126,216,225,SO8,511.537-539,549,599 usually in combination with some known chemical shift rules. Selective proton decoupling was used for structure assignment of quaternary carbons in 13C NMR spectrum of melampodin A.74 TAI acylation was helpful in structure characterization and the assignment of '3C-signals in hydroxyderivatives ursiniolide B [4], eupatolide [171, eupatoriopicrin [21], alloschkuhriolide [ 1101, urospermal A [ 1291, eulanthaefolide [167],126 budlein A [268],'6x and 11~,13-dihydrourospermalA [426].'49
The comparison of lactuside B [432] and its aglycone 433 obtained by
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
283
enzymatic hydrolysis showed glycosidation shifts at the a-position (5.3 ppm at C-3) and P-position (-2.8 ppm at C-2, -2.9 ppm at C-4).473 The shifts accompanying the glycosidation into positions 3 and 8 were derived from I3C NMK data of cichorioside C [406] and hypochoreoside A [405] respectively and their aglycone 404.591,490 Application of the Eu(fod)S induced shifts had been found powerful for differentiating between the C-2 and C-3 and between the C-7 and C-11 signals in linderalactone [630] and linderane [631].636 Recently heteronuclear 2D NMR experiments - namely HETCOR and COL,OC - have been used in the assignment of carbon signals in tamaulipin A angelate [ll],652 onopordopicrin [54],397 costunolide derivative 72,695 lecocarpinolides A and B [126, 117],398 melampolide [119],441 lphydroperoxyisonobilin [1571,431 sintenin [407],272 heliangolidin [420],119 shonachalin A 8-acetate [446],415 achillolide A and B [453, 451],5s4 micranthin [468],272,440 reduction products of glaucolide A 505, 506 and hirsutinolide derivate [519],420 divaricins A , B and C [589-591] ,421 linderanine A , B [616, 6121 and linderane [631],682acutotrine [620], acutotrinone [621], zeylanane I6331 and zeylanine [634].393 HMQC experiment was successfully applied on 1la,13- and ll~,l3-dihydro-salonitenolidediacetates [410, 411].414 Energy and electronic density MNDO calculations were done on glaucolide .4 [503] and its reduction products 505, 506.420 13C NMR spectra of verlotorin [145] and peroxyparthenolide [293] were compared with spectra of their 3 ,4-epoxy derivatives, and differences were discussed in the sense of a , P and y-effects of the oxirane ring.’” The configuration assignment on C-1, C-4, C-7, C-8 and C-11 in tetrahydro arucanolide [322] was supported by y - e f f e ~ t s . ~ ’ ~ X-ray structure analysis together with I3C NMR data is described for some germacran-12,6-olides: 9~-acetoxy-8a-epoxyangeloyloxygermacra1( 10),4,11(13)-trien-12,6P-olide [6] and 9~-acetoxy-8a-epoxyangeloyloxy7a-hydroxygermacra-l( 10),4,11( 13)-trien-12,6P-olide [9],283 tamaulipin A angelate[ll],652 7a-hydroxycostunolide [ 131,163 glucohaageanolide [27],465 2a-hydroxy-SP-(2’ ,5 ‘-dihydroxy-3’-mercapto-2’-methyl-butanoyloxy)germacra-1(10),4,11( 13)-trien-12,6a-olide [40],298idomain [61],208euserotin [63],.’77 santhemoidin B [94],510 3P-acetoxy-8P-hydroxy-9P-(2’methyl)butanoyloxy-germacra-l(lO)E,4Z,11(13)-trien-12,6a-olide [98],276 acantholide [ 1111,554 longicornin A [I401,399 epitansanin [1581,596 eupahyssopin diacetate [171],392 9,lO-dihydro-8-tigloyloxy-(6R,7S,8S,9S710R)germacr-4E-en-12,6a-olide [189],656melnerin A [199],670leptocarpin acetate [2lO],478 lacinolide A [214],223niveusin 2’,3‘-epoxide [236],231 15-acetoxy8~-acetylsarracionyloxy-lOa-hydroxy-germacra-4E,l1( 13)-dien-12,6a-olide [2911 ,3l 9 3P-acetoxy-la-hydroxy-8@-(2’-methyl)butanoyloxygermacra4Z,9Z,11( 13)-trien-12,6a-olide [272],276isocentratherin [304],402neurolenin A [3191 ,401 neurolenin B [320],401laserolide [392],321heliangolidin [420], l I 9
284
M. BUDESINSKY A N D D. SAMAN
Table 11. Carbon-13 chemical shifts of germacr-11(13)-en-12,6-olides. Mol formula C-l C-2 C-3
No
1 CZOH2806
124.9 26.8
40.0
2 C22H2807
124.3 31.6 75.3 3 C24H3209 1240 31.4 75.1 4 C27H.72011NC13
Name I Chemical shifts C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-I1 Ursiniolide D 143.7 128.9 76.5 46.0 81.9 43.5 136.6 139.8 Ursiniolide A 139.5 124.3 77.0 45.7 80.9 43.4 137.5 135.4 Ursiniolide B 139.2 124.0 77.0 45.1 81.6 42.8 137.4 135.3 Ursiniolide B + T A I 139.4 123.8 77.0 45.1 82.2 42.4 137.2 135.6
C-12 C-I3 C-14 C-I5
%I
I(c.1
170.4 124.5 16.6 21.6
I20
169.6b 124.3 15.7 20.6
I26
168.8 124.0
126
15.6 20.5
124.4 31.4 75.1 169.1 124.6 15.6 20.4 I C2OH2606 Germacra-1(10),4,11(13)-trien-12,6~-olide,9~-epoxyangeloyloxy-8a-hydroxy 130.2 25.1 38.7 135.6 123.4 68.4 47.8 82.8 76.1 138.1 134.7 170.5 126.7 19.2 17.0 6 C22H2807 Germacra-1(10),4,11(13)-trien-l2,6~-olide, 9~-acetoxy-&r-epoxyangeIoyloxy 131.3 25.1 38.7 135.2 122.9 70.2 46.6 78.7 75.0 138.5 133.9 168.Zb126.7 19.2 170 7 C19H2606 Leucanthanolide 129.6 25.4 39.0 136.8 122.1 83.5 81.6 74.7 79.2 139.9 140.4 169.1 128.6 18.0 17 2
R CZIH2807
2x3 2x3 500
Leucanthanolide monoacetate
131.6 25.3 39.1 135.7 122.5 83.6 82.6 76.5 Y
I26
C22H2807
74.5 140.0 142.2 167.7 127.2
a
51x1
;I
Germacra-1(10),4,11(13)-trien-12,6~-olide, 9~-acetoxy-Xa-epoxyangcln~l11x)-7a-ll~clr~1x~
16.9
c
2x3
120.1 119.1 119.4 119.4 119.6 119.4
16.3 174 16.3 17.4 16.0 17.0 16.0 17 2
hl
,z
?6(, 1 hl
C
I‘JO
c
s
16 7 16.1
17 5
c
141
17 3
;I
041)
50.8 27.9 40.9 141.0 139.6 201.0 119.9
17.2 18.4
C
6i2
83.3 140.9 127.0 81.2 50.1 28.4 41.2 137.7 141.8 170.1 119.4 16.2 12 3 83.3 140.8b 126.9 81.2 50.1 28.4 41.1 137.7 141.Sb170.1 119.5 1 6 3 I2 7 c 125.3 33.6 83.3 140.9 127.1 81.3 50.1 28.4 41.2 137.8 142.0 170.3 119.5 16.3 I 2 5
I’
471 7
131 9
24.9
39.0 135.5 122.2 83.4 82.8 77.1 75.0 140.Sb 14O.Zb167.9 127.7
10 ClSH2002 Costunolide a 128.6 27.6b 40.3Cl41.Yd127.9 83.7 h 128.7 26.7 41.6 137.9 127.5 82.2
51.1 51.0 c 127.0 26.Ib 39.4‘ 141.1 127.3 81.8 50.4 cl 126.9 26.1 39.4 140.1 127.2 81 8 50.4 c 127.0 28.2 41.1 140.0 127.2 82.0 50.5 I 127.5 26.2 41.1 136.9 127.1 81.9 50.5
11 CZOM2604
29.1b 28.5 28.0b 28.0 26.3 28.2
42.0’142.5‘138.2 39.9 141.5 141.9 40.9’ 137.0 140.1 40.9 141.3 136.8 39.6 136.9 141.4 39.5 140.3 141.3
172.5 170.5 170.3 170.3 170.4 170.3
180
Tamaulipin A, angelate
126.8 71.0 45.2 193.0 130.0 81.5 12 C2IH3008
Picriside C
a 125.3 33.6 h 125.2 33.5
13 C I 5 H 2 0 0 ~
128.7 27.2 40.6 138.0 122.5 86.2 83.6 32.4 35.2 142.8 146.0 170.8 120.3 I 6 0
17 7
i\
17 7
C’
i1
17.6 19.0 17.6 19 I1
“
c
366 366
163
Chamissanthin
39.0
a
127.4 77.1 54.7 71 3 52.8
a
a
169 3 1266
17 2
Caudatol (2 conformers)
39.4 143.2 130.9 76.2 52.5 72.5 44.0 134.0 136.4 170.3 121.8 39.4 143.3 130.9 76.1 52.4 72.5 44.0 134.0 136.4 170.3 121.8
16 C15H2003
Eupatolide
1240 26.5 39.6 h 129.3 26.2 39.4 17 C18H2OO5NC13 131.2 26.2 39.4
141.8 123.8 75.7 54.3 71.4 48.4 140.3 136.8 170.9 120.0 142.5 127.6 75.1 53.7 71.8 47.2 138.4 135.8 170.1 120.3
18 C2OH2.606
Germacra-1(10),4,11(13)-trien-12,6a-olide, 8~-(5’-hydroxytigloyluxy)
il
127.3 26.2
447
Costunolide, 7a-hydroxy
1 1 CI5H2003
129.5 25.R I5 (’2SH3209 il 126.8 26.2 h 126.8 26.2
I’ I’
Eupatolide
17 3 17.1
I’
668
19.5
c
126
18.6
17 5
c
126
42.9 134.1 136.7 169.6 121.0 19.0 17 3
C
277
17 5
C
277
121.4 I9 I 121.3 17 4 121.3 17.4 120.2 19.0
17.5 I9 4 I!, (I 17 I
c
126
c‘
367
i
36h
I’
331
121.7
l9.U
17 6
C
1x1
121 5
l9.ll
17 1
+TAI
143.1 127.0 75.8b 52.3 75.Yb 43.7 136.6 133.6 169.4 121.1
39.4 142.2 130.6 75.7
52.7 72.0
I9 C22H2806
Germacra-1(10),4,1l(l3)-trien-12,6a-olide,
127.3 26.2 39.4 20 ~ 2 0 ~ 2 6 0 6 a 127.1 2 6 2 39.4 h 127.0 26.1 39.3 c 127.0 26.1 39.3 d 130.4 26.2 39.3
142.4 130.7 75.6
19.9
X~-(5’-acetoxytigloyloxy)
52.8 72.2 44.0 134.2 136.6 169.3 121.0 18.9
Eupatoriopicrin
142.7 130.8 131.4 130.7 142.7 130.7 141.6b 127.7
75.8 75.8 75.8 75.8
52.7 72.4 44.0 134.0 136.5 169.8 52.6 72.2 43.8 133.9 136.4 169.9 52.6 72.2 43.8 133.9 136.4 169.9 52.7 72.2 43.9 134.Ib137.6 169.3 21 C26H2601ON2Cl6 Eupatoriopicrin + TAI 126.9 26.2 39.3 142.3 131.2 75.7 52.3 74.1 43.9 133.6 136.7 170.0 Costunolide, 8~-(5’-(4”-hydroxytigloyluxy)tigloyloxy) 22 C25H-<207 127.2 26.3 39.5 142.9 130.8 76.2 52.8 71.9 44.0 134.2 136.7 170.4
C 1‘17 __
285
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Mol formula
\ < )
C - I C-2 23 C25H7207 127.6 26.4 2 1 CZSHj208 a 127 2 26.2 11 127.5 26.3
C-3
Name / Chemical shifts C-4 C-5 C-6 C-7
C-8 Liacylindrnlide 39.8 142.3 131.0 75.8 52.9 72 4 Liacylindrnlide, 4'-hydroxy 39.4 142.6 130.9 75.7 52.7 72.5 39.5 142.8 131.1 75.7 52.8 72.6
C-9
C-10 C-11 C-12 C-13 C-14 C-15
Sol
I
44.2 134.4 137.1 169.6 120.8
19.1
17.6
C
197
43.9 133.9 136.5 169.7 121.2 44.1 134.2 136.8 169.8 121.2
19.0 1'9.1
17.4 17.6
C C
110 519
OIIICI carbons: 1 Mebu-2,3-OH: 175.2 77.3 71.4 16.9 21 6; 2 Ac: 169.3b 21.1 Epang: 168.6 59.4 59 9 I R 9 I 3 I: 3 Mebir-2-OH-3-OAc: 174.0 76.0 73.4 13.7 22.0 170.0 20.9 Ac: 169.6 21.0; 4 Mebir-2-0TAC-1-0Ai~ 167 7 R4 3 71.5 14.6 16.4 169.8 20.8 Ac: 169.7 20.9; 5 Epang: 169.1 60.1 60.2 13.9 19.2: 6 / < / I L I I I , ~ IhS 8* 59 6 59.8 14.1 19.2 Ac: 169.5 21.0; 7 iBiif: 176.4 33.9 18.6 18.7: 8 !Bur: 176.0 34.1 I 9 0 I X 7 Ar 169.7 21.1. Y Epmig: 168.3 59.6 60.1 13.9 19.1 Ac: 169.9 21.3; 11 Ang: 162.2 128.0 138.0 15 S 10 6. IZa Glc: 102 7 75 1 78.4 71.8 78.2 62.9; 12b Glc: 102.5 75.0 78.2'71.7 78.1' 62.8: 12c (;/< 101 S 7'. 3 78 5' 71 8 78.6b 63.0; 15a A ~ ~ - ~ - O H - ~ - O A C ~ - ~ ' - C H O C165.8 H , O H126.3 : 149.0 58.3 65.4 I64 7 I I'JI1 70.7 59.2 127.8: 15b A~I~-~-OH-~-OAC~-~'-CH(OH)CH,OH: 165.6 126.3 148.8 58.1 65.7 164.7 13') I
7 0 6 V 2 127 8. IR ~ I P C - O H :166.1 131.9 141.5 14.4 56.5; 19 Tig-5-OAc: 165.2 127.5 145.9 14.7 57 3 1706 207. ZOa 7i.v d < J / 1 165 8 131.7 144.7 59.1 57.2: 20b Tig-4.S-OH: 165.7 142.7 144.5 5X X 56X. Zllc 7 1 . 9 5 4 1 1 . I65 i I i l 4 144.5 58.8 56.8; 2Od Tig-4.5-OH: 165.8 131.8 146.5 58.8 56.4: 21 Yi,q-4,50TAC: 163.8 128 3 143.4 62.8 60.2; 22 Tig-S-OTig-4-OH: 165.3 127.4 146.2 14.7 57.5 167.4 127 3 142.1 59.6 12.4; 23 Ttg-5-0Tig-5-OH: 165.4 127.8 146.0 14.8 56.8 167.1 132.0 341.7 I 4 4 57'). 2 4 1 ?is-4-OH-5-OTig-5'-OH:164.9 127.0 147.7 64.5 57.7 166.5 131.1 142.0 15.6 59.3: 24h 71,~-4-l)l/-5-OTig-S'-OH. 165.2 127.1 148.1 59.5 58.3 167.4 131.6 142.6 14.4 56.6
OR'
2
R = Epang
3 R = Mzbu-2-OH-3-OAc 4
R = Mebu-Z-OTAC-3-OAc
OR'
R'
R'
R'
R'
5
H
Epang
J
H
l8"t
6
Epang
AC
a
AC
#gut
qq=Ango"'qq=p+ 9
Epanq
0-co
0-co
0-co
0-co
13
12
11
10
&c
Ac
p= 0-co
0-co
14
K = H
15
R = .Ang-4-Ch-
5--OAcr-2
C.i(OP)CH20H
16
R = H
21
R = Tig-4.5-OTAC
17
F' = .iAC
22
R = Tig--5--OTig-4'--014
18
R = Tig-5-OH
23
R = Tig-5-OT1g-S-OH
19
R = Tig-5-OAc
24
R = Tig-4-OH-5-OTig-S-OH
20
R = Tig-4.5-OH
286
M.BUDESiNSKY AND D. SAMAN
Table 11.--continued ~~
hlol formula C -l C-2 C-3 25 CIS112003
Nil
127 I 25.4 26 C17H220 127 0 25.4 27 C21f1.7008 127.6 26.0
Name I Chemical shifts C-4 C-5 C-6 C-7
C-8
C-9
C-I0 C - l I C-12 C-13 C-I4 C-15
35.6 140.9 128.9 81.2 47.3 39.3 79.4 139.2 139.0 169.8 119.8
10.6 17 A
Haageanolide, acetate
81.0 138.9 134.7 169.4 120.0 1 1 4
17 3
394
83.4 140.5 136.6 170.2 119.4 11.2
17 3
149.7 26.6b 39.1‘ 139.7d125.9 81.8 50.2 36.4‘ 30.0b 130.1 142.9’ 173 0 119.9 170.3
I6 X
29 C16H2004
146.3 26.7b 30 C2IH2809 a 149.7 27.6b h 149.6 27.6b 31 C29H36013 150.4 26.7b
33.6 141.2 131.1 80.7 47.1 Glucohaageanolide
34.5 141.3 131.8 81.4 47.6 Taraxinic acid
Taraxinic acid, methyl ester
39.3’140.16 126.4 82.0 51.4 30.2’ 36.8‘131.2 143.6 1706 1200 I706
I60
Taraxinic acid, B-D-glucopyranosyl ester
39.9’ 141.8‘127.2 83.8 51.1 40.0’141.84 127.1 83.8 51.1
31.3b 37.2’ 131.9 144.Y 169.8 120.4 172.7 31.3’ 37.2’ 131.9 144.4’ 172.6 120.4 167.8
17 3 17.3
Taraxinic acid, f3-D-glucopyranosyl ester tetraacctate
39.3’ 140.04 126.1 Picriside B 32 C2IH3008 P 126.9 27.8 35.9 141.0 130.1 h 126.8 27.1b 35.9 141.06130.1 c 126.9 27.1b 36.0 141.0’130.1 33 CISH2004 Costunolide, il 132 9 67.8 48.7 141.5 129.3 h 130 8 69.4 49.8 142.7 134.2
.U C2OH2805
Ki.I
0
39.1
2X CISHI804
Sol
Haaeeanolide
81.9 50.3 30.1b 36.5’ 129.9 143.4‘ 170.3 120.1 I65 6
16 X
80.3 50.8 27.1 41.1 137.5 141.1 170.2 1190 16.2 677 80.3 50.8 27.P 41.1 137.5 141.1‘ 170.2 119.0 162 67 7 80.3 50.8 27.7* 41.1 137.6 1412’170.3 1 1 9 1 16.3 67X Za,lp-dihydroxy
74.7 53 1 70.4 47.1 134.8 138.8 169.8 119.9 20 3 I X 2 75.6 5 4 7 72.1 48.4 136.4 140 3 1706 119.9 20 Sh I X 7
Costunolide, Za-hydroxy-8b-isovaleroyloxy
134.2 69.3
48.8 142.8 129.5 75.4 53.1 71.0 44.2 135.3 136.7 169.6 121.4 20.0 I X 7 35 C2OH260S Eupatolide, Za-hydroxy, 8-angelate = Costunolide, R ~ - a n g c l n y l o x y - 2 a - h ~ 1 l I 1 1 ~ ~ a 134.0 69.1 48.8142.7129.3 75.7 53.1 71.2 44.0134.8136.6169.5 121.2 19.7 1x6 c‘ 302 h 134.2 69.3 48.9 142.8 129.5 75.7 53.3 71.1 44.1 135.3 136.7 169.6 121.4 19.8 187 c‘ 4 7 i c 133.9 69.2 48.2 142.6b129.4 75.5 53.2 71.0 44.0 134.3b125.6 169.5 121.2 20 5 1X.6 C 178 36 C20H2606 Eupatolide, Za-hydroxy, 8-(2’S,3’S-epoxyangelate) 1346 68.2 48.7 143.1 128.8 75.5 52.6 72.8 43.8 133.9 136.5 169 0 121.2 1 9 9 I X 15 C‘ %I? 37 C2OH2606 Eupatolide, 2a-hydroxy, 8-(2’43’R-epoxyangelate) = Mollisorin IS i’ 102 a 134.4 68.0 48.7 143.1 129.0 75.4 52.6 72.8 44.1 133.9 136.3 169.8 121.3 20 5 I X 7 C’ 2’)s h 134 5 69.3 48.7 143.0 129.3 75.2 52.8 72.8 44.2 134.2 136.3 169 3 121.4 20 3 I X K’ C 4’13 c I29 3 69.3 48.8 134.6 134.6 75.3 52.9 72.6 44.8 136.6 143.2 169.3 121.5 2OOh 1‘9 Jh 3X C2OH2607 Germacra-1(10),4,11(13)-trien-1~,6a-olide,8~-(2’,3’-epoxy-5’-hydroxyangcl11yl11x~ )-2ii-I1jtlriix! 134.7 67.8 48.6 142.2 128.8 75.0 51.6 72.9 43.5 132.8 136.6 168.8 120.8 19.5 IX.3 S ?OX 39 C2OH2607
Costunolide, 8~(2’,5’-epoxy-3’-hydroxyangeloyloxy)-Za-hydroxy
51.7 73.3 43.7 133.5 136.5 169.4 121.4 19.5* IX.hb S 507 Germacra-1 10) 4 l l ( 1 3 trien-12 6a-olide Za-hydroxy-~B-12’,5’-dil;ydroxy-j’-merc~~to-Z~-m~thy,hutan”~,”~~) I34 5 68.1 48.7 142.2 128 2 75.0 51.7 73.2 42.6 133.4 136.2 169.2 121.3 I9 5 I X h S20X.iO7 41 C2OH2808 Costunolide, Za-hydroxy-8~-(Z’,3’,5’-trihydroxyangeloyIoxy~ 134.5 67.Yb 48.7 141.7 129.4 75.2 51.9 72.3 43.9 133.3 136.7 169.4 121.2 19.6 I X 3 S 507 42 C2OH2606 Germacra-1(10),4,11(13)-trien-12,6a-olide, Za-hydroxy-8B-(Z’-hydroxyeth) l a w ) 10) lox) ) 134.5 68.1
48.8 142.3 129.4 75.1
41) C2OH2807S
133.3 67.9 43 CZOH2606 il 135 0 67.8 h I34 0 69.1 c 129.4 69.3 U C22112808
129.6 69.4 45 C2OH2605
129.6 69.3 46 C261134011 a 131 Xb 76 1 h 131 9* 76 I
48.9 142.3 128.8 75.4 52.0 72.1 43.2 132.4 137.3 169.0 120.2 19.7 IX 4
S
20s
S C
2‘iX 29X
c‘
4‘11
IX X
c‘
4Ij3
IX 7
C’
I’i7
c‘
507
Eupasserin, deacetyl
48.7 142.3 128.7 75.5 51.9 71.5 43.2 132.7 137.2 169.0 120.3 19.4 18.2 48.8 143.1 129.2 76.0 53.0 71.8 44.0 134.8 136.5 169.8 121.5 19.9 18.8 48.8 135.1 134.2 75.9 53.1 71.8 44.0 136.6 141.1 169.9 121.6 19.8 18.8 Eupaserrin
48.8 155.1 134.3 75.5 53.2 71.5 44.2 136.6 143.1 170.7 121.3 19.9 Mollisorin A 48.8 135.4 134.1 75.7 53.3 71.4 44 I 136.6 142.7 169.5 121.5 207 Germacra-1 10) 4,11(13) trwn 12,6a-olide
2a-acetoxy-$P-~2’,5’-dtacetoxy-J‘-hydroxthy~~~tan11?~~~~?) 46.2 142.6 131.4b 75.2 53.7 72.6 45 4 137.5 138.1 170 3 123.4 21.3’ 1‘1 8‘ 45.9 142.0 131.6b 76.1 52.5 72.6 44.8 137.6 138.0 170.2 123 2 21.2 I9 6‘
S j0-i
287
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 11.-continued Mol. formula Name I Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-ll 47 C20112606 Costunolide, 3~-hydroxy-8~-sarmcinoyloxy 129.0 35.4 76.7 144.4 123.2 75.3 51.0 71.7 43.1 132.4 137.3 48 C24112806 Sonchuside B, aglycone 1300 35.7 77.7 145.0 130.0 81.2' 47.1 34.0 81.5'136.2 140.2 49 CZOf118011 Sonchuside B 126.5 32 7 82.gb 139.8 128.8 81.4b 46.9 34.0 80.7b 135.8 142.2
No
C-12 C-13 C-14 C-15
SIII
169.2 120.8 18.6 11.9
S
232
170.06 119.8 11.6b 12.5b
I'
447
169.7 119.9 11.4' 12.4
I'
447
I<el
Other carbons: 26 Ac: 169.6 21.2; 27 Glc: 99.9 75.0 78.5' 72.0 78.7b 63.1: 29 #Me: 51.4; 30a GIc 95.3 73.9 78.3' 71.0 78.7' 62.3; 30b Glc: 95.3 73.9 78.3' 71.0 78.7' 62.4: 31 Glc70.3 73.0 61.6 169.3 20.6 169.6 20.6 170.3 20.6 170.7 20.6 32a Glc: 105.1 75.1 78.6 71.8 78 5 63 0. 32hGlr: 105.2 75.1 78.5' 71.8 78.64 63.0; 32c Glc: 105.3 75.2 78.6 71.8 78.6 62.9; 34 iVak 171 9 43.4 25.6 22.4 22.4: 351 Ang: 166.4 126.7 140.0 15.8 20.5; 35b Ang: 166.6 126.8 140.3 15.9 20.6; 35c A!!$ 166.3 1364* a 15.9 19.7; 36 Epang: 168.5 59.5 59.7 13.8 19.3; 37a Epang: 168.5 59.4 60.0 13 6 19.1, 37h Epaiig: 168.5 59.4 60.1 13.7 19.2b; 37c Epang: 169.3 59.6 60.0 13.9 18.7: 38 Epang-SOH: 167 2 64 I S4.9 13.5 61.9; 39 Ang-3-OH-2.5-ep: 171.5 81.3 59.6 19.0b 65.3; 40 Mebu-2S-OH-3-SH: 171.3 X I 3 50.5 19.9 65.2; 41 Mebii-2,3,5-OH: 172.9 81.8 68.6b 17.7 64.1: 42 Acr-2-CH(#H)CH,: 165.0 145 3 64 5 23 2 123.3: 43a Sar: 165.2 132.3 137.6 15.1 61.9; 43b S a c 165.9 131.5 140.7 15.9 64.0: 43c S w I660 131.6 143 I 15.9 64.3; 44 Sarac: 164.5 126.9 1478 16.1 65.5 169.5 20.8; 45 Tig: 166.7 128.1 1 3 x 9 I4 6 I 2 2; 46d Meba-2.S-OAc-3-OH: 166.3 83.0 56.1 20.2' 61.9 170.5 21.9 171.2 21.9 Ac: 171 6 22 3 , I6h ~te611-2.5-OAc-3-OM:1664 82.9 56.8 20.4' 61.4 170.8 21.9 171.4 21.9 Ac: 171.4 22 3: 47 5111 165.3 133 X 137.3 15.0 61.7:48 Phac-4'-#Me: 170.8' 41.0 127.1 131.0(2) 1 1 4 3 2 ) 159.5 55.3; 4Y G h . I02 6 75 1 7X.Jd 71.8 78.3' 62.8 Pkoc-4'-#Me: 170.7 40.8 126.9 l30.8(2) 114.5(2) 159.2 55.2
OR
0-co
0-co
GlcOH,C
25
R = H
28
R = COOH
33
R = H
26
R = Ac
29
R = COOCH,
34
R = iVal
27
R = Glc
30
R = CO-Glc
35
R = Ang
31
R = CO-Glc-2.3.4.6-Ac
36
R = Epang(Z'S.3'S)
37
R = Epang(Z'R.3'R)
38
R = Epang-5-OH
39
R
40
R = Mebu-2.5-OH-3-SH
41
R = Mebu-Z.3.5-CH
42
R = AC~-Z-CH(OH)CH,
43
R = Sar
32
OPhoc-4'-OMe
A
46
c
o
' 0 - c' o '
R = Mebu-2.5-OAc-3-OH
~
H
O
47
0-co
R
R
o
6-co
e
=
Ang-3-0h-2.5-ep
48
R = H
44
R = Sarac
49
R = Gk
45
R
= Tig
288
M. BUDESINSKY AND D. SAMAN
Table ll.-continued No 50
51 52
53
a h 54 a
h 55
56 57
sx 59 60 61
62 63 (5.1
65 66 67 6x 69
70
71 72
73
71 75 76
Mol. formula Name I Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C - l l C-12 C-13 C-14 C-15 CISH2004 Ovatifolin, desacetyl c 300 134.1 26.0 39.7 142.3 126.9 75.3 53.7 70.2 44.5 138.4 135.4 170.7 120.8 60.3 17.2 C19H2405 Costunolide, 8p-hydroxy-1Qiibutanoyloxy c 670 134.6 25.1 38.3 141.3 127.1 74.7 52.9 70.4 41.9 137.9 133.4 170.0 119.9 62.5 16 I C17H2006 Grazielia acid, desacyl, acetate 152.6 26.2 38.1 144.3 124.9 75.3 52.4 69.5 38.8 125.1 136.6 169.4b 120.9 172.9 16.8 c 2ix C2OH2406 Taraxic acid, Sa-angeloyloxy c ')X 150.4 26.0 37.7 142.5 127.2 78.4 52.7 73.8 43.0 126.8 135.3 166.9 124.1 172.3 17.1 149.3 26.4 40.0 141.8 127.5 78.2 53.1 74.4 42.9 127.5 136.6 166.9 123.0 169.4 17.0 13 ')X C19HZ406 Onopordopicrin 129.7 26.0 34.5 144.5 127.9 77.3 52.8 72.8 48.8 139.6 132.1 170.5 125.6 16.6 60.5 c 3'17 129.9 26.4 34.5 144.7 128.6 76.9 53.0 73.2 48.7 132.6 137.0 169.7 124.3 16.5 60.4b A 5fi C19H2606 Arctiopierin 130.1 26.8 34.9 145.0 128.6 77.1 52.9 73.1 49.2 133.3 137.0 170.2 128.8 16.8 6 0 6 A $6 CZOH2607 Cnicin s I?(> 130.4 25.9 34.0 141.8 129.4 76.4 51.8 72.8 48.0 144.5 136.4 169.7 123.R 16.6 5 0 2 C2OH2605 Costunolide, 15-hydroxy-8~-tigloyloxy 128.8 26.9 35.6 144.2 130.2 74.5 53.1 71.5 44.0 135.2b 136.6b 169.9 121.5 18.8 hl 2 " 443 ~15~2004 Germacra-1(10),4,11(13)-trien-l2,6a-olide, 9!3,15-dihydroxy I) 226 128.3 26.5* 35.8 144.5 127.0 80.4 48.0 36.8* 79.3 141.6 140.9 170.3 119.0 11.2 60.6 C22H2806 Germacra-1(10),4,11(13)-trien-12,6a-olide, 9~-acetoxy-15-senecioloxy 1308 26.1* 33.4 138.7 130.5 80.7 47.5 35.5' 79.6 138.6 139.0 169.3 120.3 11.5 606 C 2x1 ~22~3006 Germacra-1(10),4,11(13)-trien-12,6a-olide, 9~-acetoxy-15-isovaleroyloxy 130.8 26.1* 33.4 138.7 130.5 80.7 47.5 35.5* 79.6 138.6 139.0 169.3 120.3 I I 5 61 2 c' ?2f, C19H2406 Idomain 130.7 26.1 35.4138.1 130.7 77.6 47.4 33.3 7 9 . 4 1 3 8 . 4 1 3 5 . 2 1 6 9 2 120.6 116 6 1 4 c' 20s' CZOH2406 Cronquistic acid 129.1 27.4 35.7 131.7 145.1 74.3 52.9 70.5 44.0 138.1 135.6 169.2 121.9 18.7 171.4 c' 443 C21H2606 Euserotin c' 277 128.9 27.4 35.9 131.2 144.5 69.3 52.7 75.0 44.0 138.2 135.5 169.2 121.8 I X 9 170 ? C29H36011 lxerin I 133.2 28.1 35.7 141.0 130.5 80.2 50.8 27.1 36.9 135.6 1407 170.1 119.2 62.1 67 7 I' 40 C22H2808 Eupaserrin, 3p-hydroxy (' 2x6 126.2 74.8 83.6 144.2 132.2 75.0 52.6 71.8 44.1 136.6 135.7 1705 121 6 13.5 19') CZOH2606 Costunolide, 8~-angeloyloxy-2a,l4-dihydroxy i' i 0 7 136.4 68.1 48.5 142.6 129.5 75.6 53.3 70.8 38.8 136.5* 138.3'169.6 121.6 61 3 I X 3 CZOH2607 Costunolide, 2a,l4-dihydroxy-8~-(2'R,3'R-epoxyangeloylnxy) i' 317 136.4 68.0b 48.4 142.9 129.5 75.2b 52.9 72.6b 38.4 136.4' 138.4' 169.5 121.4 60.4 I X 4 ~20~2806 Germacra-l(10),4,11(13)-trien-l2,6a-olide, 3 ~,9 - d ih y d ro x y - 8 P - ( 2 ' - me t h y lh u t ~1 1 ~~~I~1 ~? ) 123.6b 34.6 74.9 144.0 129.4b 74.9 50.5 80.6 77.7 137.3 135.6 169.4 122.4 12 2 l i h i' 300 CZOH2606 Germacra-1(10),4,11(13)-trien-12,6a-olide, J P , Y P - ~ ~ ~ ~ ~ ~ I , ~ ) . - ~ P - ~ ~ C ~ I I I ? I ~ I X ? 122.9 34.5 74.8 143.6 127.8 75.0 49.2 78.5 76.5 137.0 136.3 168.7 121.4 13 I I 1 X S ?S'J C22H2807 (3S,61/7~8R)-Germacra-1(10),4,11(13)-trien-12,6-o1ide, 3-hydroxy-8-(5'-acctr,x?tifflll?lllxg) 129.0 35.3 77.6 144.4 123.4 75.0 52.2 70.2 43.8 134.3 136.4 169.3 121.0 18.8 12 0 c' 276 Jurineolide CZOH2607 131.3 24.6 32.9 142.3 127.0 75.8 51.3 72.2 43.9 142.8 134.4 168.2 122.4 57.9 57 2 CIS 1 2 6 C22H3008 Costunolide, 8a-acetoxy-15-hydroxy-14-(2'-methyl-3'-hydroxyhutan~yl1~xy) 1364 26.1 34.3 135.3 128.3 77.2 52.6 70.0 45.4 129.3 144.1 169.8 125.5 62.0 61 3 c' 6'15 Germacra-1(10),4,11(13)-trien-l2,6a;l4,2a-diolide,8u-acetoxy C17H1806 C ?<)4 149.7 79.3 39.8 135.7 124.7 78.6 49.5 73.4 29.7 131.0 1344 169.2 122.5 174 3 21 2 C2OH2406 Elephantopin, desacylisodeoxy, Z'methylhutyrate <' ??S 149.2 79.0 30.2 131.5b 125.4 78.8 49.8 73.3 40.1 133.Sb135.3 169.3 123.6 174.2 ? I i C20H2206 (2S,6R,7~8S)-Germacra-1(10),4,11(13)-trien-12,~14,2-dio1ide, 8-seneciiiyliix? 148.9 79.4 40.3 135.2 125.6 78.8 49.9 72.8 30.3 131.9 134.2 169.5 123.3 174.2 21 6 c' h X h C2OH2206 (2S,61/71/8S)-Germacra-1(10),4,l1(13)-trien-12,6;14,2-diolide, 8-tigloyloxy c' 6Xh 149.1 79.4 40.2 135.3 125.7 78.8 49.9 73.9 30.3 131.8 134.2 169.4 122.9 174.2 21 6
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
289
Table ll.--continued Mol. formula C-1 C-2 C20H2406 153.0 81.3 153.1 81.3 C20H2206 152.8 81.2 C20H2206 153.0 81.3
No.
77 a
h 78
79
Name / Chemical shifts C-3
C-4
C-5
C-6
C-7
C-8
C-9 C-10 C-ll C-12 C-13 C-14 C-15
Sol. llel
Elepbantopin, desacyldeoxy, 2'metbylbutyrate
41.4 135.9 134.0 78.0 52.5 70.3 33.8 129.0 134.2 169.5 123.8 172.3 20.0 c 33.6 128.6b133.7 77.9 52.1 71.0 41.3 128Xb135.9 169.3 123.9 172.2 20 1 C ~2%6~7~8S~-Germacra-l(lO),4,11(13)-trien-14~;12,6-diolide, 8-senecioyloxy 41.4 135.8 133.8 78.0 52.3 70.1 33.7 128.7 134.0 169.2 123.8 172.2 20.0 C
6x6 22K 6x6
(2~~~~8S~-Germacra-l(lO),4,l1(13)-trien-14~;12,6-diolide, 8-tigloyloxy
41.5 135.8 134.0 78.0 52.6 71.3 33.8 128.9 134.2 169.4 123.4 172.3 20.1
c'
6x0
Othercarbons:51 ;Bur: 176.7 33.3 18.2 18.2; 52 Ac: 169.3b 20.3; 5311 Ang: 170.0 126.1 139.6 20 4 15 8 . 53h Ang: a ; S4a Mac-4-OH: 165.0 135.2 125.7 60.9; S4b Mac-4-OH: 165.2 141.5 123.7 60.gb; 55 iEirr-3-OH: 174.8 43.4 64.3 14.0 56 Acr-2-CH(OH)CH20H: 165.1 132.1 127.8 70.3 65.6; 57 Tig: 1669 128.1 138.9 a 12.2; 59 Sen: 166.1 115.4 158.0 20.4 27.4 Ac: 169.8 21.2; 60 iVal: 172.6 43.4 25 7 22 4 22.4 Ac: 169.8 21.2; 61 2xOAc: 169.8 20.9 170.5 21.3: 62 Tig: 166.7 127.9 139.4 a 12.0; 63 Val-2-en-3-Me: 165.5 113.5 164.5 34.0 12.0 a ; 64 Glc: 104.6 74.9 78.3 71.6 78.3 62.8 Phac-4'-011 172.1 41.0 125.0 116.3(2) 130.9(2) 157.9; 65 Sarac: 164.4 127.1 146.9 15.9 65.4 169.5 20.7; 66 Arip 166.5 126.9 140.3 15.8 20.5: 67 Epang: 168.5 60.0 60.5 13.8 18.7; 68 Mebu: 176.9 41.5 26.6 11.6 17 I 69 Ang: 165.9 127.2 137.2 15.3 20.1; 70 Tig-5-OAc: 164.9 127.4 145.7 14.4 57.1 170.3 204; 71 Tig-4-OH: 164.9 125.0 141.9 58.9 11.1; 72 Mebu-3-OH: 175.7 47.7 72.9 14.1 20.7 Ac: 169 9 21 0. 73 Ac: 170.0 20.6; 74 Mebu: 175.9 41.0 26.0 11.7 16.8 75 Sen: 165.6 114.8 159.8 20.4 27.5; 76 7i.q. I67 2 128.1 139.0 14.5 11.4: 77. Mebu: 175.5 41.0 26.0 11.7 16.7; 77b Mebu: 175.6 41.0 25.9 11.6 I6 7. 7X Serf: 165.3 114.9 159.6 20.4 27.4: 79 Tig: 167.0 128.2 138.7 14.5 11.9
=($+ 0-co
HOH,C
0-co
0-co
R20H,C
0-co
HOOC
R'
R'
54
R = a-OMac-4-OH
R'
R'
62
R = Tis
50
@-OH
CH20H
55
R = a-OiEut-3-0H
58
H
H
63
R = Val-2-en-3-Me
51
@-OH
CH,OiBut
56
R = a-OAcr-2-CH(OH)CH20H
59
Ac
Sen
52
@-OAc
COOH
57
R = P-OTug
60
Ac
iVal
53
a-OAng
COOH
61
Ac
Ac
R2
HO GlcOH,C
64
0-co
R = CH20Phac-4'-OH
HOH&
R'
R'
R'
R'
66
Ang
CH,OH
68
Mebu
OH
67
Epang
CH,OH
69
Ang
@-OH
70
Tig-5-OAc
H
65
0-CO
71
Ttg-4-OH
72
AC
CH20H CH20Mebu-3-OH
13
R = Ac
77
K = Mebu
74
R
70
R = Sen
75
R = Sen
79
R = Tig
76
R = Tig
= Mebu
290
M. BUDESINSKY AND D. SAMAN
Table ll.--continued hlol fmnula
Nu
XI) XI x2
X3 a h
U4 85 86 X7 XX
XY YO 91
92
93 94
95 Yf,
97 YX
YY
100 101
102 103 104
1115 1116
C-I C-2 L2FH1208 I240 33.9 C20H2606 123.4* 33.4 C17fI2205 122 9 30.6 C22H2808 1243 3 0 6 124.1 30.4 C29H3601 I 125.5 30.6 C27H.32010 124.2 29.8 C27H.?2010 124 3b 29.6 C17H220.5 126.9 29.3 C2SH3208 123 X 31.8 C19H2406 125.0 29.4 C22H2407 125 3 29.6 C22H2807 125.3b 29.5 C22H2607 125 Sb 29.6 C22112808 125.1‘ 29.4 C2.3H2808 125.6 29.6 C25H3408 125.2’ 29.6 C20H2407 IS08 25.7 CISHI804 126.9 27.0 C22H.1007 124.7 28.7 C2OH2406 128.5 29.4 C25H.3209 127.6 29.3 CISHI804 153.7 27.3 C21H2809 153.4 27.1 C29H340II 153.3 27.3 C 2 9 H 4 0 1I 153 4 27.4 CISH2004 I23 6 25.3 C16H2005 141 0 25.3
C-3
Name / Chemical shifts C-4 C-5 C-6 C-7
C-8
C-9
C-10 c - I I C-12 C-13 C-14
c-Ii
\III
k t
Provincialin. 4’-desoxv-3-desacetoxv-3a-hvdroxv . . .
68.5 140.4 124.3 77.2 49.0 74.1 43.4 133.9 137.6 169.3 125.7 IX.5 17 I C’ ?OO (3~6~7R,8R)-Helianga-1oP,11(13)-trien-~2,6-nlidc, 3-hydroxy-X-(5’-h~dr11x~li~l11~ I
70.9 139.3 125.7 73.8 50.2 78.2 46.9 138.1 135.4 1700 123 4
1‘) 1
I X li
Euccanabinolide, 3-epi = Eupaformosanin
70.7 137.2 125.0 74.4 70.6b 135.9 125.0 79.5
48.8 79.7 43.3 136.1 135.9 1702 125.2 18.6 1 x 0 48.5 74.4b 43.1 135.8 137.0 169.7 125.0 18.5 17 9 Eupaformosanin, 5’-(4”-acetoxytigloyloxy) 80.0 137.4 124.5 74.3 48.7 70.8 43.2 a 135.9 170.2 124 X 18.6 1 x 0 Eupaformosanin, 4’-(4”-oxotigloxy)
74.1 137.2 125.2 80.1 48.9 70.3 43.2 135.3 134.0 170.2 124.2
IX Ob I X 4‘
Provincialin, j-epi, 4”-oxo-S”-desnxy
74.1 137.2 125.2 80.1 48.9 70.4 43.2 135.3 133 8 170.1 I24 Zh 17 9‘ I X 4‘ Euccanabinolide, desacyl
7 5 . 9 139.3 1282 76.7b 50.0 76.7 47.0 137.1 135.4 1700 123.3 19 X
23
(1
Provincialin, 4’-dcsoxy-3-desacetoxy-3~-hydroxy
78.6 140.1 126.4 75.7 48.4
75.3 43.3 134.7 137.9 169 5 125 1
I9 5
??
75 3 43.4 136.0 135.2 169.5 I24 0
19.4
21 0
75.7 43.5 136.5 135.5 169 6 124.3
I!, 4
23 I
76.9’ 43.4 136.6 135 b 170 I 1 2 4 7
19 4
23 0
I!, 6
23 I
76.8‘ I137.3 I26.Ob 76.0’ 48.3 79.1‘ 43.2 136.6‘‘ 135.4d 170 2 125.1 19 4 SanthemoidinB 76.9 I137.3 126.6 79.0 48.5 75.5 43.4 169.7 135.1 169 3 I24 5 19 5
23 0
Hiyndorilactone C, acetate
78.0 137.4 126.6 75.3 48.4 SanthemoidinA
77.0 137.8 126.7 78.7 48.7 Chromolaenide
76.9’ 137.7 126.Sb 78.7’ 48.5
Chromolaenide, 4’-dehydro
76.8‘ 137.3 126.4b 78.8’ 48.4
75.6 43.3 134.9 134.3 169.7 124.9
Euccanabinolide
21 I
Euccannabinolide, 3-desacetyl, 3-isovaleroyl
77.7‘ 137.4 126.2b 79.2’ 48.5
76.0‘ 43.2 136.6‘ 135.dd 170.2 125 0
19 5
23 I
Douglasine
3 9 0 135.7 124.7 81.6 54.1 75.4‘ 73.3b 144.7 127.4 I69 4 1 2 2 0 16X 9 17 4 Germacra-l(10)E,4E,11(13)-trien-12,6a-olide-15-oic acid 36.0 141.8 134.2 83.2 47.1 27.4 41.5 135.6 139.4 172.4 124.6 15 7 175 3 Germacra-I(lO)E 4 2 11(13)-trien-12 6a-olidc 3~-acetoxy-8~-hy~rdy-9~-(~~-meth;lbutaon~lnxy~
74.2‘ 138.5 126.9 76.4b 47.8 80.9b 78.Xb136.2 135.6 169.7 123.6 14 2 27 I Germacra-1(1O)Z,4Z,11(~3)-tricn-l2,6a~olide,8 ~ - a n g e l o y l o x y - 3 , 1 4 - ~ p ~ 1 x ~ - 1 5 - h ~ c l r 1 1 \ ~ 71.1 137.8 125.1 73.8 46.5 78.4 40.7 144.2 136.8 169 3 124.4 63.6 63 I S ?i SchkuhripinnatolideC
47.1 74.8 44.7 135.7 134.1 170 3 124.7 4 6 0 22 9 Urnspermal A, 8-desnxy 33.2 142.1 127.7 79.6 46.1 22.Ib 24 3b 144.9 140.8 170 3 118 I I 9 h l 6 0 4 Ixerin B 33 5 138.4 129.7 79.4 46.1 22.1‘ 24.1b 145.0, 140.5 170 1 118.2 I96 I 67 X Ixerin G 33 3 138.1 129.7 79.5 46.2 222 24.3 145.0 140.6 170.1 118 2 195‘) 67 4 Ixerin C 33.9 138.3 130.0 79.6 46.1 22.1’ 24.2’ 145.0 140.6 1702 IIX.2 196 I 6X I
79.8 137.6 130.2 76.0
c‘
214
I’
42
I’
42
I’
41
I’
12
Germacra-1(1O)E,4Z,11,(13)-trien-12,6a-olide-14,15-dihydrnxy 34.5 142.3 126.8 79.4 45.9 26.0 24.1 141.4 142.5 170.3 117.6 65 6 6 0 6 I’ Germacra-1f1O~E.4Z.1I~l3~-trien-12.6a-olide-~S-hydroxy-~4-~~ic acid mcth! I cslcr . , , . 25.8 140.0 125.5 78.2 43.8 23.8 32.7 132.6 139.2 167.7 123 0 170.1 66 2
40
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES 'Table I 1
291
- continued
Mol. formula C-l C-2 C-3 in7 ~ 1 8 ~ 2 2 0 6 139.8 25.0 26.3
No.
Name / Chemical shifts C-4 C-5 C-6 C-7 C-8
C-9
C-10 C-I1 C-12 C-13 C-14 C-15
Sol Rct.
Germ~cra-1(1O)E,4Z,11(13)-trien-12,6a-olide-lS-acetoxy-14-oic acid methyl ester 134.1 130.9 79.4 45.8 23.0
33.0 139.0 135.4 167.8 119.0 170.1 61.6
C
620
80 Tig-S-OTig-S'-#H: 165.3 127.7 146.1 14.7 56.8 167.0 131.8 141.4 14.1 57.9: X I 131.5 142.5 14.2 55.8; 82 Ac: 170.7 21.1: 838 Tig-4.5-OH: 165.9 131.6 145.0 59.2 57 0 Ac: 1720 21.1: 83b Tig-4,5-OH: 165.8 131.2 145.1 56.2 58.9 At: 178.3 21.0; 84 Tlg-4-OH-5-077s-4'-- 0 A f . 167.2 126.9 148.2 59.5 58.6 165.3 130.3 137.4 61.1 12.8 170.8 21.1 Ac: 169.4 20.7; 85 -S-OH-4-OTig-4'-oxo:164.8 138.3 145.0 57.2 61.3 165.6 136.0 148.3 191.7 13.1 Ac: 169.4 21.0: S6 -4-O(I-S-OTig-4'-oxo: 165.0 126.2 158.3 59.6 59.3 167.1 136.0 148.2 196.1 13.1 Ac: 169.2 21 0 : X7 Ac: 170.8 21.1: 88 Tig-S-OTig-S'-OH: 165.4 127.6 145.8 14.5 56.3 166.8 131.6 141.2 14.0 57.6: 8Y ? ! A ( . . 169.5 21.0 169.1 20.7; 90 Fur: 161.9 119.2 109.6 144.2 147.8 Ac: 169.3 21.2; 91 Tig-+OH: 166 3 127 4 142.7 59.6 12.5 Ac: 169.9 21.2; 92 Tig-4-010: 166.0 126.8 144.4 191.1 11.9 A c , 169.5 21.2: Y3 7ig-4.5-OH: 165.5 131.1 145.5 58.8 56.5 Ac: 169.9 21.1: 94 Fur-diH-5-OMe: 161.1 137.5 1360 109.4 72.8 5 4 4 Ac: 169.2 21.1; 95 Tig-4.5-OH: 165.7 131.4 145.1 58.9 56.6; iVa/: 171.9 43.2 25.4 22.4 22 4: Y6 TI^: 167.5 126.4 139.9 14.5 11.9; 98 Mebu: 175.5 41.1 26.8 11.6 16.5 Ac: 1702 21.2: 99 h i s : I65 7 126.7 139.3 15.4 20.0; 100 C16-C20 175.8 87.2 32.6 18.0 15.7 Tig-4.5-OH: 166.2 132.0 145 5 5'1.1 3 0 4 : Ill2 G k : 105.0 75.0 78.5 71.6 78.5 62.8; 103 G/c-2'-OPhac-4"-#H: 101.7 76.1 75.3 71.9 78.7 62 6 171 2 40.9 125.2 116.3(2) 131.0(2) 157.9; 104 G/cd'-OPhac4"-OH: 104.6 75.4 78.3 71.2 74.7 64.7 172 I 40.5 125.2 116.2(2) 130.9(2) 157.8; 106 #Me: 51.8; 107 OMe: 51.8 Ac: 170.0 20.9 Olher carbons
/ I v - 4 - 0 / / . 166.1
OH
R'O
co R'
- R'
R2
96
R2
~. 80 H
Tig-5-OTig-5
87
AC
H
81
H
Tig-5-OH
a8
n
lig-5-OTig-5'-OH
82
4c
H
a9
AC
AC
83
Ac
Tiq-4.5-OH
90
AC
Fur
a4
4~
TI~-~-OH-~-OT,~-~'-OA~
AC
Tiq-4-OH
85
AC
Tiq-5-OH-4-OTig-4
--ox0
91 92
AC
Tig-4-0x0
86
Ac
T#q-4-0H-5-071g-4
-ox0
93
Ac
Tiq-4.5-OH
94
AC
Fur-diH-5-OMe
95
#Val
Tig-4.5-OH
-OH
HOOC
qR
O'CO-
99
"'OH
'-CO-
97
GJ+
4cO
HOH2C
R = COOH
0-co
R?OH,C
O'Co-
R'
R2
101
CHO
H
102
CHO
Glc
103
CHO
GIc-Z'-O-Phac-4'-0H
104
CHO
Glc-6-O-Phoc-l"-OH
105
CHIOH
H
106
COOCH,
ti
107
COOCH,
AC
100
292
M. BUDESINSKY AND D.
SAMAN
Table lI.-continued No
Mol formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7
C-8 C-9 10X C2IH2408 Orientalide 1589 27.6 32.4 140.7 128.4 72.4 50.9 69.8 68.8 1OY C15111804 Schkuhriolide, allo a 154.3 26.3 37.1 136.5 126.5 74.8 50.7 64.1 31.5 h 154.2 26.4 37.3 143.2 126.8 74.7 50.9 64.4 31.5 110 C18Hl806NCI3
154.8 26.2 111 C19H2406
Schkuhriolide, allo
+ TAI
C-10 C-ll C-12 C-13 C-I4 C-15
Sol I
141.4 133.6 170.0 122.5 193.9 60.6 143.4 138.0 169.9 120.2 196.0 17.2 136.8 138.0 170.0 120.0 195.5 17.2
37.0 134.8 125.9 75.4 49.1 70.1 28.8 142.2 138.5 169.3 121.0 195.5 17.0 Acantholide
68.6 78.3 140.8 134.1 a 122.1 183.8 16.9 112 C23H3008 Acanthospermal A 159.2 26.8 36.9 138.3 126.8 74.9 51.0 72.0 67.8 140.8 134.2 169.0 121.8 193.5 I 6 8 1563 26.3 36.8 136.9 127.3 75.0 50.8
113 CI7H2007
LecocarpinolideE
158.8 27.8
32.8 140.2 129.3 72.8 51.8 68.3 72.8 140.0 134.3 169.3 120.6 194.3 61 2 I14 C2Ot12407 LecocarpinolideF 155.5 26.8 32.5 140.2 129.3 73.6 51.4 71.1 70.4 139.2 134.3 169.1 121.6 195.4 60.7 1 15 CZOH2607
155.7 27.4 116 C2OH2607
Acanthospermolide, !h,lS-dihydroxy-8p-methylbutyrylnxy-l4-oxo
32.1 140.0 129.0 73.8 51.5 71.2
70.4 140.0 134.3 169.3 121.9 195.4 6 0 7
LecocarpinolideG
155.0 27.4 32.5 140.3 129.0 73.8 51.5 70.4 71.2 Lecocarpinolide B 158 7 26.4 32.1 140.7 128.2 73.6 50.9 70.0 67.8 I18 C22112808 Acanthospermal B ISX.4 26.6 32.4 141.0 128.5 73.6 51.2 70.3 68.1 11Y C l i H 2 0 0 2 Melampolide 124.9 26.7 38.9 138.1 124.4 80.7 45.0 25.4 25.1
139.5 134.0 169.0 123.1 195.4 60 7
117 C22H2608
120 CISH2003
125.1b 24.V I21 c17112204 129.9 25.3b 122 CISHIX03 153.3 26.2' 123 CZIH2809 143 0 26.2b I24 C l C l l l X 0 5 15.5 1 27.3 125 C2OH2406 153.8 26.5 I26 C20112406 153.6 27.1 127 C20112606 153.8 26.5 128 C20H2606 153.6 27.0
153.8 27.7
141.5 134 1 168.4 122.0 193'1 60 4 136.7 140.1 1703 1184 21.9
172
25.W 23.5' 138.5 140.1' 170.8 118.9 65.9
17 I
Soulangianolide A
38 4 140.8' 125.7b 81.0 45 4 Soulangianolide A, acetate
38.2 138.3 125.5 80.6 45.4 24.2b 25.0 136.0 140.0 170.6' IIX.8
67.6
17 I
22.2' 24.4' 137.5 139.5 170 3 1 I9 3 195.6
17 I
24.2b 26.4b135.1 1390 1724 1194 I076
172
60.8 26.8 140.4 134.0 168 X 122.9 195 4
60 X
Germacra-1(1O)E,4E,11(13)-trien-l2,6a-olide,14-ox0 37.3 144.9 126.4 80.8 45.7 Ainsliaside B 38.0 141.3 127 I 82.8 46.7 LecocarpinolideH 32.4 140.5 128.6 73.6 51.4 LecocarpinolideD 28.7 142.0 126.8 73.8 47.0
72.6 25.3 139 4 135.4 169.5 124.5 194.5 66 2
LecocarpinolideA
32.6 142.8 127.1 74.0 49.6 65.6 28.9 140.3 134.8 169.3 121.1 195.4 60 7 LecocarpinolideC 28.6 141.9 126.8 73.6 47.0 72.1 25.9 139.0 135.2 169.5 124.5 194.9 66.2 Acanthospermolide, 15-hydroxy-8~-methyIbutyryloxy-14-0x0 32.6 142.8 128.4 73.8 49.5 65.5 28.7 140.4 135.0 169.3 1209 195.4 6 0 6
129 CI5I11805 Urospermal A 160 3 27.8 32.8 141.6 126.7 75.8 51 5 130 C2IH1809N2C16 Urospermal A + T A I 131 C17H2006
141.4 133.9 169.1 122.1 1940 60 I
70.0 33.1 144.2 1369 175.2 125 1 I W h 61 0
74.6 28.2 142.9 137.5 a 124.2 194.3 h 4 6 Germacra-l(10)E,4E,11(13)-trien-l2,6a-olide,& - a c e t o x y - 2 a - h y d r o x ~ - I ~ - 1 1 ~ 1 1
32.4 135.4 129.9 75.4 48.4
155.4 67.8 46.3 140.6 126.3 72.8 132 C21H2409 Melampodin A 133.0 59.Sb 55.3b 128.9 120.7 74.2 133 C17HI807 Melampodin B 68.6 23.9 28.7 136.6 122.9 73.9 134 C28H3601 I Repandin B 147.6 29.2 26.8 143.6 80.2 80.6 135 Reoandin D ~ .CZliH(40lO .~ . .... . ~ . 147.5 29.0 26.8 143.3 80.3 80.4
. -
48.0 76.4 29.3 138.2 136.3 169.9 123 7 193 5 49.7
IX 1
71.2 70.2 132.5 132.5 166.0 118.5 164.0 I 6 0
50.3 79.7 154.2 148.7 131.1 169.9 123.0 173 0 6.S 3 41.1
74.6 69.1 127.8 133.9 168.9 126.6 I6hO I ? I 7
40.9 76.2 69.1 127.7 134.1 168 5 126.3 I05 9 121 5
C
iil
293
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table ll.+ontinued hlol. formula
No ~
136
I37 13% 13Y 140
I41
142
C-l C-2 C2OH2606 150 I 35.8 C16I12OOS 141 0 25.3 C21112407 142.X 25.0 C241132010 147 3 25.9b C241122O10 IS2.9 69.2 C2OH2606 62.9 35.8 C22fI2XO7 65 2 32.4
Name I Chemical shifts C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-ll C-I2 C-13 C-I4 C-15 EuDachifolin A 72.7 14I.Yb 127.8 73.0 47.0 73.0 28.2 137.Xb135.2b175.1 123.9 194.4 24.5
C-3
Sol I
C
332
Germacra-1(1O)E,4E,11(13)-trien-12,6a-olide,15-hydroxy-14-oicacid methyl ester 25.8 140.0 125.6 78.2 43.8 23.8 Melcanthin F, 9-desacetoxy 25.8 130.3 125.7 73.6 47.1 74.0
32.7 139.2 139.2 167.7 123.0 J70.1 66.4
C
620
30.1 139.4 135.7 175.5 124.0 169.6 66.2
C
400
25.7b 128.0 123.4 73.8 48.1 71.5' 69.9' 143.3 134.0 169.0 127.1 165.6 65 4 Longicornin A 39.2 124.9 124.6 73.8 48.8 70.7b 70.4b 141.9 133.2 168.8 125.9 165.1 6 5 3
C
300
c'
W'j
S
2x6
C
2x6
Longicornin B
Eupacunin, desacetyl
71.4 141.6 125.1 74.2 46.9 67.2 121.3 142.4 135.9 168.7 120.0 23.0 17 6 Eupacunin
73.2 139.2 126.1 74.3 47.5 67.8 123.3 141.6 134.6 168.9 121.9 23.5 17.5
Othci carbons: 108 Mac: 165.7 135.2 126.8 18.3 Ac: 170.4 20.7: 111 iBuf: 175.5 34.1 18.9 19 I: 112 l / h l f . 176.2 34.1 18.9 18.9 rBic1-2-OH: 175.4 72.2 26.8 26.8; 113 Ac: 170.2 21.0; 114 Ang: 165.7 126.6 I 4 0 0 lS.9 20.5: 115 Mebu: 176.0 41.2 26.8 11.4 16.8; 116 Mebu: 176.0 41.2 26.8 11.5 16.8; 117 A q : I660 126 7 141.5 15.6 20.3 Ac: 170.2 20.5; 118 Mebu: 176.0 41.4 27.6 11.5 16.8 Act 170.3 20.7: 121 k . 170.3' 21 0: 123 Glc: 95.7 73.9 78.6' 71.0 77.9' 62.4; 125 Ang: 167.3 126.8 141.9 15.8 204: 126 Airy I664 127 I 139 2 15.8 20.5: 127 Mebu: 175.4 41.2 26.5 11.6 16.8; 128 Mebu: 175.2 41.2 26.7 I I 5 16.7. 131 A , : 170.7 21.3: 132 Epotig: 167.0 58.7 59.0 13.4 18.3 OMe: 51.9; 133 Ac: 170.4 21 7. 134 OM? 5 2 2 Ang-5-OAc: 164.9 130.6 143.2 15.7 64.1 a Mebu: 176.0 41.1 26.2 16.2 11.3. 135 O M r 52 Z F~$OIIV 16x0 59.1 60.3 12.7 18.9 Mebu: 175.6 41.1 26.0 16.6 11.5; 136 Mebu: 169.4 41.0 2 6 4 I I i 166: 137 OMe' 51.8; 138 Mebu: 167.3 41.1 26.4 16.7 11.5 OMe: 52.0; 139 iBnr: 176.0 33.6 19.1 IN') 174.7 3 3 6 19.1 18.1 OMe. 51.7: 140 2xiBuf: 176.9 33.8 19.1 18.4 174.5 33.8 19.1 18 4 OAfe. 5 1 X. 141 Arip. 165.6 127.3 137.7 20.1 15.4; 142 Ang: 166.0 126.4 141.2 16.0 20.4 Ac: 169.2 21.1
*+ CHO
0-co
6-co
HOH2C
R'
R'
R'
R'
0-co 119
HOH,C
R = CH,
124
0-co R = P-OH
108
Mac
OAc
113
H
Ac
120
R = CH20H
125
R = a-OAng
109
H
H
114
Anq
H
121
R = CH,OAc
126
R = U-OAng
110
TAC
H
115
Mebu
H
122
R = CHO
127
R = 0-OMebu
111
H
OiBut
116
H
Mebu
123
R = COOGlc
128
R = 6-OMebu
112
,But
OiBut-2-OH
117
Anq
Ac
118
Mebu
Ac
129
R
130
R = TAC
=
H
131
132
COOCH,
133
COOCH,
COOCH,
HOH,C
'Zo
~
'b co
co
~
OH 134
R = Aiq-5-OAc
135
R = Epcng
136
137
R = H
139
R = H
141
R = H
138
R = OMebu
140
R = OH
142
R
= Ac
294
M. BUDESINSKY AND D . SAMAN
Table ll.-continued No
Mol. formula Name I Chemical shifts C-1 C-2 C-3 C-4 C-5 C-6 C-7
C-8
C-9
C-10 C-11 C-12 C-13 C-14 C-15
Sol. Ref.
143 C17H22OS G e r m a c r ~ - 1 ( 1 0 ) ~ 4 ( 1 5 ) , 1 1 ( 1 3 ~ ~ n - 1 2 , 6Ep-wtoxy-Sp-hydroxy a~lld~ 131.7 27.7 28.0 130.3 76.8 80.5 44.2 79.8 43.8 148.0 138.0 169.1 122.5 17.0 117.1 B 583 144 C22H2807 C e r m . e r a - l ( l O ) E , ~ l S ) , l l ( l 3 ~ ~ & nSp-wto~2a-hydroxy-8~-tigloyloxy -l~~~~ c 579 131.2 67.4 37.4 139.1 79.3 79.0 45.6 16.7 44.0 136.9 134.5 169.1 124.6 19.0 121.9 145 CISH2003 Artemorin C 190 a 78.2 32.6’ 25.9b 145.5 123.0 79.3 47.9 30.0 36.1’ 151.1 140.3 170.4 118.3 110.8 17.9 C 563 h 78.2 32.3’ 30.0’ 145.0 122.9 80.5 49.0 25.6 36.1’ 150.9 140.1 170.4 118.8 110.8 17.9 c 77.7 33.3b 30.0b 144.6 124.0 80.2 48.0 25.8 35.9’ 151.7 141.5 169.7 116.9 109.9 18.0 B 563 146 C16H2204 coStunolkk, methylperoxy c I90 89.1 33.1b 263’146.6 122.6 80.7 49.6 28.5’ 37.0b 146.3 140.1 170.2 118.4 112.9 17.7 147 CISH1804 Verlotorin P 190 91.4 34.0b 27.0’ 148.0 123.1 80.9 49.8 28.3b 37.2b 146.5 141.0 170.4 117.9 112.6 17.5 148 C17H2204 Costunolide, acetyl, dewxyperoxy c I90 78.8 31.4b 25.9’ 145.4 123.0 80.5 48.6 30.9b 36.3’ 147.2 140.1 170.1 118.3 112.8 18.0 149 ClSH2004 Ridentin S 396 73.6 41.4 74.0 140.3 120.8 79.7 47.5 31.1 25.9 147.8 150.0 170.0 118.4 11.6 110.0 150 CISH~OO~ Sachalin P 331 76.9 33.4’ 34.8’149.4‘125.5 75.2 49.1 65.1 35.4b142.3’138.1 170.4 119.2 112.9 18.1 151 C20H2607 Sachalinin 76.6 31.6b 33.3’ 149.3’ 124.5 75.5 47.3 68.0 34Sb 143.6‘ 136.6 169.4 119.2 113.4 17.9 I’ 331 152 C2OH2608 Sachalinin, peroxy I’ 331 89.9 28.4b 33.2’149.2’124.5 75.4 48.2 67.9 35.0 143.9‘136.8 169.4 119.5 117.2 17.7 153 C17H2205 Costunolide, Ep-acetoxy-1s-peroxy (2 conformers) a 91.2 26.0 29.8 134.9 124.7 75.2 $2.5 66.7 34.2 142.0 142.7 169.9 119.6 20.4 17.6 C 578 h 90.5 26.2 37.3 135.8 121.7 75.0 45.9 66.9 67.8 147.4 138.3 169.9 121.1 118.0 17.7 C 578 154 CISHI803 Costundide, snhydroperoxy = Verlotwin, anhydro a 204.4 35.6’ 29.0b 142.9 125.0 81.0 49.4 28.2’ 38.3’150.9 139.7 170.1 119.0 123.5 17.1 C I90 b 204.4 35.6 28.1b142.9 124.9 80.9 49.5 29.0 38.3b150.8 139.5 170.1 119.1 123.4 17.1 c 563 155 C20H2807 Germncra-4~10(14~,11(~3)-trien-l~6a~Ilde, 1-oxo-8~-(4’,5’-0-ipropylidenetigloyl~1xy~ 203.1 30.2’ 34.4b 144.2’124.8 74.3 50.9 68.1 38.1 142.5’135.6 168.6 120.6 126.8 17.2 C 331 156 C20H2606 Calhertolide C 72.7b 38.7’ 72.5b 139.9 126.4 74.8‘ 47.5 76.g4 36.4‘143.2 144.4 171.0 125.4 118.7 23 7 C 4x2 157 CZOH2607 Isonobiline, le-hydroperoxy 85.6 41.0 72.4 143.4 125.2 74.1 49.6 73.9 32.8 138.9 135.4 170.1 126.5 122.2 23.1 C 431 158 ClSH2003 Tamanin, 4-epi 117.2 42.6 207.8 39.8 39.8 81.6 43.9 34.8 40.0 141.4b 140.4b 169.7 122.8 15.8 18.3 C 596 (4R,6R,7S,8R)-Ger1nacra-l(lO),ll(l3)dien-l2,f&oli~3-oxo-8-(5’-hydroxytigloyloxy) 159 C20H2606 120.0 42.5 207.1 40.0 40.2 76.7 46.1 80.2 44.3 139.3 137.7 169.2 124.7 18.2’ 18.Ib C 236 160 CISH2003 Parthenolide a 125.3 24.2b 36.5b 61.5 66.4 82.5 47.7 30.2b 41.2b 134.7 139.5 169.3 121.0 17.3 17.0 C 190 h 125.3 24.2 36.2 61.5 66.4 82.5 47.7 41.7 30.2 134.7 139.5 169.3 121.0 17.3 170 C 539 161 ClSH2004 Stizolin 128.0 24.7 35.7 61.5 66.4 78.3 52.2 71.3 52.0 130.0 134.0 169.8 128.5 18.1 17 4 C 121 162 C17H2205 Lanuginolide, 11,13-dehydro a 127.4 24.3 35.9 61.0 66.5 72.5 49.6 80.1 47.3 129.6 133.9 169.0 125.2 18.3 17.3 A 1x1 h 127.5 24.3 36.0 60.9 66.7 80.0 49.8 72.4 47.6 129.7 133.9 170.1’ 125.3 18.2 17.3 C 121 163 CI7H2205 Lipiferolide P 179 a 129.1 44.0 36.4 61.8 66.8 76.4 49.4 74.5 24.5 132.0 137.9 169.1 121.9 19.7 17.2 P 6x0 h 129.1 24.5 36.4 61.8 66.8 76.4 49.4 74.5 44.0 132.0 137.9 169.1 121.9 19.7 17.2 c 126 c 128.9 43.8 358 61.8 66.5 75.4 49.3 73.5 24.2131.4136.1 168.5122.5 19.6 17.1 1M C2OH2605 Germacra-1(10),11(13)-dien-12,6a-olide, 4a,5gspoxy-8~-tigloyloxy 128.8 24.3 35.9 61.9 66.6 75.7 49.7 74.0 44.0 131.7 136.3 168.6 122.6 19.6 17.2 C 277 165 C2OH2606 Eupassopilin P 128 5 23.9 35.6 61.8 66.2 75.6 49.1 74.0 43.5 131.2 136.0 168.5 122.3 19.4 16.9 C 313 h 128.5 23.9 35.6 61.8 66.2 75.6 49.1 74.0 43.5 131.2 136.0 168.5 122.3 19.4 16.9 C 277
295
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table ll.-continued Mol formula
No
C-1
C-2
Name / Chemical shifts C-3
C-4 C-5 C-6 C-7 C-8 C-9 C-I0 C-ll C-I2 C-13 C-14 C-15 I66 C25H.1208 Eulantanaefolide 129 1 24.2 35.8 62.0 66.6 75.7 49.5 74.3 43.8 131.3 136.0 168.4 122.5 19 6 17 I 167 C28H32010Cl3N Eulanthaefolide + TAI 129.2 24.2 35.8 61.9 66.5 75.4 49.4 74.8 43.7 131.1 136.0 168.2 122.5 lY.7 17.0 168 C251f3208 Parthenoiide, 8~-(3'-angeloyloxy-4'-hydroxyethylacryloyloxy) a 129 3 24.3 35.9 61.8 66.6 75.3 49.6 74.4 44.0 131.2 136.0 168.4 122.7 20.5 17 2 h 129.3 24.3 35.9 61.8 66.6 75.3 49.6 74.4 44.0 131.2 136.0 168.4 122.7 20.5 17 2 169 C1S112004 Germacra-l(lO),l1(13)-dien-12,6a-olide, 4a,SP-epoxy-9a-hydroxy 121 9 23.5 36.3 61.3 66.6 82.4 37.6 37.6 71.4 137.5 139.8 169.4 121.1 16.4 17 3 170 C17H220S Germacra-1(10),11(13)-dien-l2,6a-olide, 9a-acetoxy4~,5P-epoxy 1227 23.5 35.6 61.2 66.5 82.2 38.7 36.2 73.2 133.5 139.3 169.Sb121.3 16.4 17 3
\,!I
l(iI
C'
126
c'
120
C C
I02
C'
121
C
I?!.
1'12
Odiercarbons: 143 Ac: 169.5 20.2; 144 Tig: 166.7 127.9 139.0 14.6 12.0 Ac: 169.8 21.0: 146 Uhfc (12 4. 151 Tr.9-4,S-OH: 166.2 132.1 146.2 58.8 56.5; 152 TIg-4,S-OH: 166.0 131.9 146.4 58.8 56.4: 1531 .A< 170.8 21.0; 153b Ac: 170.2 21.0; 154 Tig45-0iProp: 163.8 132.3 142.2 60.7 59.6 102.3 23.6 23 6: 156 ?is. 167.9 138.2 139.7 15.4' 12.6': 157 Ang: 166.8 127.2 139.5 15.9 20.5; I59 Atrg-5-OH: 166.1 131 7 142 6 14.3 56.4; 162a Ac: 170.2 21.0; 162b Ac: 168.9b 21.0; 163a Ac: a ; 163b Ac: 169.9 20 6. l63c A1 169.5 20.9: 164 Tig: 166.4 127.9 138.7 14.5 12.2; 16% Tig-4-OH: 165.9 126.7 142.6 59.1 12.4. 1651) 71g-4-0H: 165.9 126.7 142.6 59.1 12.4; 166 Tig-4-OH-5-OAng: 164.7 126.7 147.9 59.4 57.5 167.7 l26<) 139.5 15.8 20.4; 167 Tig-4-OTAC-S-OAng: 163.9 129.7 140.6 62.9 57.2 167.0 1266 139.9 15.X ?01. 16th Acr--2-CN(OA,rgICH,OH: 164.4 138.6 69.8 67.0 127.5 168.2 127.1 139.5 15.9 19.7: 16Xh A(.r--Z-C~~(I(OAtig)CH~OH: 164.2 138.6 69.8 67.0 127.5 168.2 127.1 139.6 15.9 19 7; 170 A < ' IhS S" 21 I
*
HO
0-co
144
143
145
R = H
146
R = GCH,
147
R = OH
148
R = AC
149
0-co R'
R2
150
H
H
151
H
Tig-4.5-OH
152
OH
Tig-4.5-OH
154
R = H
156
H
8-OTig
158
R = ti
153
OH
Ac
155
R = OTig-4.5-0iProp
157
OH
a-OAng
159
R
0
OTig-5-0t
*
m 0
=
0 %- c o
0-co
160
R = H
163
R = AC
166
R = Tig-4-W-5-OAng
169
R = H
161
R = OH
164
R = Tig
167
R = Tig-4-OTAC-5-OAng
170
R = Ac
162
R
165
R = Tig-4-OH
168
R = Acr-Z-CH(OAng)CH,OH
= OAc
296
M. BUDESINSKY AND D. SAMAN
Table 11.--continued No 171 a
h
172 173
Mot formula Name I Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-I0 C-lI C-12 C-I3 C-14 C-15 C20H2607 EuDaWDin = EuDahyssopin 128.8 31.8 23.9 64.5 66.8 75.0- 49.8 -74.0 44.0 132.2 136.4 169.0 122.8 19.6 60.8 a a a 64.366.8 a a a a a a166.0 a a a C38H6009 Eupassofilin 128 8 32.0 23.9 64.4 67.0 74.8 49.8 74.2 44.1 132.1 136.3 168.5 122.7 19.6 60.8 C17H2205 Germacra;1(10),11(13)-dien-126a-olide,8$-acetnxy-5-oxn 131.8 24.8 36.1 43.1209.2 75.8 46.9 73.7 43.4135.0135.5168.6124.3 19.1 15.4
%I1
KCl
c
313 302
c
313
c
OSII
c'
174 CI7112305F Germacra-1(10),11(13)-dien-l2,6a~lide, 8P-acetoxy-4-fluoro-5P-hydr11xy c' 6x0 1300 21.0 36.1 99.5 77.4 75.0 49.2 79.7 43.9 136.1 135.5 170.0 123.9 19.3 I Y 9 175 C17H230SCI Gerrnacra-l(10),11(13)-dien-12,6a-olide, 8~-acetnxy-4-chlorn-S~-hydroxy " f,SO 129 7 22.7 40.3 79.3 79.7 74.6 49.4 79.5 43.8 136.1 135.5 170.0 123.6 19.3 25 5 176 C17ff2205 Germacra-1(10),3,11(13)-trien-12,6a-olide,8$-acetoxy-SP-hydroxy 130.5 27.7 122.0 140.5 74.3 82.5 49.0 79.3 43.6 138.5 134.4 169.9 122.2 I X 2 18 5 ,\ ( A X Melfusin 177 C23H26011 125.8 119.3 124.4 53.8 44.5 76.4 38.5 72.3 70.7 135.3 133.7 171.0 119.7 170.6 66 I c' 5 2 2 17X C20H2407 Orthopappolide, methacrylate (' 3i2 133.3 74.5 42.9 57.8 59.2 81.8 47.3 80.3 31.5 133.1 134.3 166.9 126.9 111.2 2 2 2 17Y C20H2407 Tomenphantopin A C' 273 a 72.2 a 56.8 55.6 79.6 a 78.0 a a a a a 109.0 a Germacra-l(lO),ll(13)-dien-12,6a;14,2P-diolide,4a,5~-epoxy-8a-(2'-metli?ll~ul~ii~i~ lox! I 1x0 C20112407 151 5 79.1 41.4 59.0 65.7 79.7 48.1 70.7 32.6 128.8 132.9 168.7 124.6 172.6 21 I c' h S h 1 x 1 CZOH2207 Germacra-1(10),11(13)-dien-12,6a;14,2$-dinlide, 4a,5~-epuxy-8a-seneci~i~I11x~ 151.4 79.1 41.4 58.9 65.6 79.7 47.8 70.2 32.6 128.6 132.6 168.7 124.6 172 5 21 I C' 6 S h 1x2 C17HIXO7 Germacra- 1(10),11(13)-dien-l2,6a;14,2a-diolide, 4a,5P-epoxy-Ba-aretc,x) 152 6 80.2 40.8 56.6 58.7 78.4 45.2 73.1 29.8 129.6 133.2 168.6 124.1 174.3 21 7h c' 31-1 Trichosalviolide, 9~-acetoxy-8~-epoxyangeloyloxy-5hydrnxy(5a- and Sp. cliiiiicr) 1x3 C22H2X09 a 129.6 30.9 38.5 47.9 105.4 84.2 87.7 76.4 76.5 130.7 138.9 168.4 128.0 19.1 1 3 6 h 129.3 30.9 38.5 50.7108.7 86.1 83.6 77.3 76.1 130.7140.2168.4127.6 19.1 1 3 2 1x4 C20H2606 Cmtunolide, 1~,lOa-epoxide-8~-epoxyangeloyloxy-3~-hydr1~xy 64 5 33.8 69.4 149.2 120.9 74.5 51.7 73.5 42.5 60.3 136.7 169 X I21 6 20.1 I 2 S Tithifnlin, 8~-epoxyangeloyloxy-14-hydrnxy I x5 C201f2607 6 7 2 2 5 0 37.8 145.2 125.3 74.5 53.3 68.9 35.9 59.2 137.2 169.6 I21 I 63 2 IS 'I 186 CZZllZXO7 Sphaerocephalin, (Z)-lS-methyl 66 3 24.6 35.8 136.3 124.7 74.4 53.6 67.0 37 2 59.9 145.1 169.0 1209 65 9 20 J J h 66.6 24.8 35.7 137.4 125.3 74.1 53.4 66.6 37.3 59.8 144.1 169.0 119 7 66.3 2 0 I Tithifolin, 14-acetoxy-8~-epoxyangeloylnxy 1X7 c22112xox 66X 24.5 35.8 145.1 124.5 74.0 53.2 68.7 37.4 58.7 136.4 168 8 120.6 65.1 17 1 Costunolide, I0a-hydroxy-8a-rnethacryloylnxy-l-nxo 1 xx Cl9H2406 217.9 32.7 34.2 143.9 124.4 77.3 48.3 70.2 40.8 78.0 136.2 169.5 120.7 29 2 2 0 0 (6I/7S,8S,9S,10R)-Gerrnacr~E-en-12,6-nlide, 9,10-dihydro-8-tigloyloxy 189 C20112607 215.7 38.2 36.1 144.6 129.2 79.7 49.4 70.5 75.3 80.5 135.4 169.7 121.6 26.2 I X 9 Germacra-4,Il(13)-dien-12,6a-olide, 8P-angelnyloxy-2P,3a-dihydroxy IYO C20H2806 31.7 74.7 82.6 141.2 126.5 79.0 45.7 28.7 80.3 28.9 138 5 169.X 120.0 12 2 20 '1 Melampomagnolide A IYI C1SH2004 62.6 27.3 24.2 142.4 124.4 79.5 46.4 27.3 34.6 63.3 139.9 170 I 119 I 64 X 17 1 Germacra-1(10)E,11(13)-dien-12,6a-olide, 4a,5P-epoxy-14-ox11 IY2 CISHI804 153.5 22.5 36.1 59.5 63.1 81.3 42.3 25.0 25.0 144.0 138.4 169 3 120.6 195.0 17 Y Melampomagnolide B, acetate 1Y3 CI m z a 5 130.6 25.7 36.6 59.9 63.3 81.1 42.6 24.5b 23Ab 130.0 139.0 169.4 120.0 66.8 17.9 Melampornagnolide B 194 ClSH2004 126.8 24.2b 36.9b 60.3 63.3 81.4 42.8 25.7b 23.7b 139.8' 139.0' 169.8 120 2 65 4 I X 0 195 C19112G07 Miller-l(lO)E,8E-dienolide, 4$,15-epoxy 157.4 28.9 28.8 58.0 79.2 82.4 40.5 147.9 113.3 132.9 137.2 168 5 127 I1 193 0 54 I 196 C16H2205 Germacra-1(1O)E,11(13)-dien-l2,6a-olide, 15-hydroxy- 14-ciic acid mriti) I c\icr 139 7 2 6 3 29.4 45.8 38.5 83.5 41.3 24.0 33.3 139.7 139 7 167.7 122 4 17llll 61 7 C' (90 1Y7 C2IH2X07 Repandanolide, 8p-angeloyloxy-4$,15-dihydro-IS-hydroxy 145.0 29.2 27.3 35.7 38.6 76.4 43.2 73.7 30.2 127.8 136.0 169.5 124.5 166.3 6X I C 151
297
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 11.4ontinued Other carbons: 171a TIg-4-OH: 166.2 127.0 142.9 59.6 12.8; 171b Tig-4-OH: 168.8 a ; 172 Tig-4-OStear-3-OH: 172.5 141.6 a 60.2 a 37.0 32.1 32.0 29.8(8) 29.4 25.6 22.8 14.2; 173 Ac: 169.9 21.2; 174 Ac: 170.0 21.0; 175 Ac: 170.0 21.1; 176 Ac: 169.9 20.6 177 Epang: 169.0 59.4 60.2 18.8 13.4 OMe: 52.5 Ac: 168.8 20.9; 178 OMe: 54.2 Mac: 168.7 135.4 124.1 18.1; 179 OMe: a Mac: a ; 180 Mebu: 1759 40.9 26.0 11.6 16.6 181 Sen: 164.8 114.6 160.2 27.5 20.4; 182 Ac: 170.3 20Xb; 183a L/iarig. a Ac: a: 183b Epang: a Ac: a; 184 Epang: 168.9 59.9 59.7 13.9 19.1: 185 Epang: 173.5 60.1 63 4 17.2 23.2. 186a Ang: 165.6 126.4 142.0 17.4 16.1 Ac: 170.5 20.4; 186b Ang: 165.7 126.9 141.6 16.8 16.1 Ac: 170.0 20.4: 187 Epang: 170.5 59.8 60.8 13.2 18.5 Ac: 168.3 20.7; 188 Mac: 166.0 135.6 126.6 17.9: 189 Tig: 1663 127.8 139.0 14.5 12.2; 190 Ang: 167.5 127.9 138.4 15.9 20.6; 193 Ac: 170.6 20.9: 195 Mar: 166.1 134.7 128.4 18.2; 196 OMe: 51.9: 197 Ang: 167.2 127.5 139.8 15.8 20.3 OMe: 52.2
*
HOti,C
0-CO
171
R = Tig-4-OH
172
R = OTig-4-0-Stear-3-OH
RR 0-co
0-co 173
-*1
174
R = F
175
R = C;
176
OMac
0 ' -
0-co
AcOH,C 177
R = COOCH,
a
178
R
179
R = 8-OCH,
- g
= a-OCH,
/
ti0
R'
R2
180
a-H
Mebu
181
&-ti
Sen
& p
182
6-H
Ac
0-co
0-co
6-co
184
y+= 0-co
190
R'
RZ
185
CH,OH
Epang
186
CYOAc
Ang
188
a-OMoc
H
187
CH20Ac
Epang
189
8-OTig
OH
q
c--'-;c R
191
183
0
% 0-co
192
R = CHO
193
R = CH,OAc
194
R = CH20H
HOH~C 195
0-co
196
R = H
197
R = OAng
298
M. BUDESINSKY A N D D. SAMAN
Table ll.--continued Name / Chemical shifts C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-lI C-I2 C-13 C-I4 C-15 ((11 Kcl C2IH2608 Longipilin c iX? 145 3 35.4 24.7 59.2 62.8 72.2 46.1 76.3 71.0 133.9 133.3 166.5 122.5 168.3 17 7 C2OH2807 Melnerin A c 670 145.2 29.1b 30.2b 35.8 27.3b 76.5 43.2 73.8 38.7 127.6 136.1 169.7 124.5 68.3 167.2 C25H32011 Repandanolide, 4~,15-epoxy-8~-(5’-hydroxyangeloyloxy)-9a-isobutanoyl~xy n 351 147.8 28.8 26.5 57.3 78.4 80.7 40.9 75.6 69.9 127.2 135.0 169.5 125.8 166.0 53.7 Cl9H2406 Erioflorin c 456 60.5 32.6 71.9 141.6 125.9 74.1 48.2 76.5 43.4 58.6 137.1 169.3 124.6 19.6 22.8 C19H2606 Viguiestin, desacetyl = Tagitinin E C‘ 167 60.7 30.7 72.4 141.7 126.6 74.2 48.6 75.7 44.1 58.7 137.5 169.6 124.7 20.0 23.0 c‘ 456 60.5 32.6 72.0 141.5 126.1 74.0 48.2 75.5 43.8 58.6 137.2 169.3 124.5 19.9 22‘1 CZOH2606 Leptoearpin c 167 60.7 32.7 72.5 141.7 126.7 74.2 48.7 75.9 43.8 58.7 137.7 169.5 124 5 15.7 22.9 c 47x 60.7 32.5 72.2 141.7 126.4 74.2 48.4 75.8 43.6 58.7 126.9 169.6 124.7 22.9 20.3 C20H2606 Heliangine c 456 60.6 32.6 72.0 141.5 126.1 74.1 48.4 76.1 43.5 58.6 137.2 169.4 124.5 19.7 22.9 c 374 60.5 32.5 72.0 141.4 126.0 74.1 48.4 76.1 43.5 58.6 137.1 169.1 124.4 19.7 229 C2OH2607 Heliangolide, l~,l0a-epoxy-8~-(2’Q3’R4poxyangeloyloxy)-3~-hydr~xy c‘ 223 60.6 32.4 71.8 141.8 125.8 74.0 47.8 77.3 43.5 58.4 137.0 168.8 125.2 18 7 22.X CZOH2607 Heliangolide, 1~,l~-epoxy-8~-(2’S,3’S-epoxyangeloyloxy)-3~-hydrl~xy 60.4 32.6 71.8 141.8 125.8 74.1 47.8 76.9 44.0 58.5 137.0 168.8 125.0 18.9 22.X c‘ 2 2 3 . C2OH2806 Heliangine, 8-desacyl-8-isovaleryl 60.7 32.5 74.1 137.3 126.2 75.5 48.2 72.0 43.8b 58.6 141.7 169.5 124.7 22.9’ 22 2‘ c 4x4 C2JH3409 Heliangine, 8desacyl-8-(5’-~5”-hydroxytigloyloxy)ti~oyl) 125.4 32.1 74.6 139.6 127.7 78.8 52.2 71.8 43.9 136.1 135.9 169.2 121.3 12.5 20.8 C 2(H) C2IH2807 Viguiestin 60.2 30.7 73.0 138.3 126.3 74.5 48.6 75.7 44.0 58.3 137.2 169.1 124.8 19.7 23.0 C 167 ~22~2807 Leptoearpin, acetate c I67 60.4 30.6 73.0 138.3 126.3 74.6 48.7 75.7 43.7 58.3 137.2 169.2 124.7 19.4 23 0 60.1 30.2 72.8 138.1 125.9 74.4 48.2 75.5 43.3 58.2 126.2 169.2 124.9 22 8 20.2 c‘ 47x C22H2808 Leptoearpin, acetyl, 2’,3’-epoxy C 167 60.2 30.7 73.0138.6126.1 74.1 48.5 75.5 44.3 58.1137.0169.0125.0 21.1 23.0 C22H2808 EupalininB c‘ 334 60.0 30.4 72.7 138.3 125.4 74.5 48.3 76.3 43.3 58.1 136.5 168.9’ 1249 19.4 229 C22H2808 EupalininA c 334 60.0 30.5 72.8 138.4 125.7 74.5 48.3 76.7 43.3 58.1 136.7 169.0*125.1 19.4 22.9 C27H3008 LacinolideA c 223 60.2 30.6 73.7 136.7 126.8 74.6 48.2 77.1 43.7 58.0 137.4 168.9 125.5 18.9 23.2 C22H2808 EupalininD C 334 59.0 31.7 68.6 137.6 125.3 72.9 48.6 76.3 43.3 56.9 136.4 168.4b124.9 18.4 17 6 C22H2808 EupalininC C‘ 331 58.9 31.6 68.6 137.6 125.3 72.9 48.5 76.4 43.3 57.0 136.6 168 7b 125.1 18.3 17 5 C22H2809 Eupaformosanin, epoxy c 334 59.0 31.7 68.7 137.8 125.2 73.1 48.5 76.7 43.3 58.6 136.5 169.1b125.5 18.4 17 6
91) h40l lormula
C-1
198 I99 200 201 202 a
h
203 a b
204 a h
201 206 207 208 209 210
a h
211 212 213 214 215 216 217
218 CISHI805 Eleganin, 15-deoxy s 2%) 60.8 56.1 53.5 131.3 126.6 .74.5 50.0 73.3 45.3 57.6 139.6 169.6 122.5 20.1 21.0 Liscunditrin, I5-deoxy-S’desaeetyl 219 C20H2407 c 290 61.7 56.3 53.8 133.7 125.8 75.0 49.7 76.1 42.5 56.5 136.5 169.0 125.5 20.0 21.6 Punctaliatrin, 15deoxy 220 ~ 2 0 ~ 2 4 0 6 c 2qo 60.4 132.3 128.4 137.2 126.0 75.9 50.4 78.0 42.8 61.3 136.2 169.3 124.9 19.7 23 7 Punetaliatrin 221 C2OH2407 C 290 60.4 131.3 128.6 139.5 124.5 75.6 50.2 77.7 42.8 61.6 137.0 169.7 125.2 19.6 65.2 Germacra-t,4E,11(13)-trien-12,6a-olide,1~.I0spoxy-l~hydroxy-8~-(4’-acctoxyangrl11) Ioxy) 222 C22H2608 60.4 131.2 128.6 139.3 124.7 75.3 50.1 77.7 42.8 61.5 136.9 169.2 125.3 19.7 65.3 C 290 223 C2OH2408 Liscunditrin, 5’-desaeetyl 61.5 55.2 51.7 136.3 124.7 74.9 49.4 75.7 42.4 56.7 136.3 169.5 126.0 19.8 63.9 c‘ 2%)
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
299
Table ll.--continued Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-I0 C-11 C-I2 C-13 C-I4 C-I5 224 C22H2609 Lixunditrin 61.4 55.0 51.7 136.0 124.8 74.5 49.3 75.4 42.5 56.5 136.2 168.8 125.X 19.9 6 3 8 225 CZOH2407 Liseundin 61.5 55.1 51.7 136.0 125.0 74.6 49.4 74.9 42.5 56.7 136.4 169.1 125.6 l'J.9 63.9
Nu
hlol formula
Sill I
c'
200
c'
200
Other carbons: 198 Ang: 167.3 133.3 140.2 20.5 15.9 OMe: 52.4; 199 B u r : 178.9 34 1 18.9 1R.7 0121~ 52.2; 200 I B w 176.5 34.0 18.5 18.4 Ang-SOH: 164.8 131.3 141.9 15.3 63.7 OMe, 51.4. 201 h / m 16i 7 135.1 126.6 18.0; 202a iBur: 175.9 34.3 18.6 18.9; 202b iBuf: 175.6 34.1 18.9 18.5; 2031 A I I ~ : I66 127.7 140.0 15.7 20.3; 203b Ang: 166.4 137.4 a 15.7 19.7: 204a Tig: 166.4 127.6 138.7 I I X I4 204b TIQ: 166.3 127.5 138.6 11.9 14.5; 205 Epang: 169.4 59.4 59.7 13.4 19.9; 206 Epa~rg- I6X 5 5 0 0 60.4 13.0 20.1: 207 iVal: 172.0 43.3b 25.4 20.0 19.8: 208 Tig-5-OH-Tig-S'-OH: I650 127.4 146.1 14 h 56.4 166.9 131.5 141.8 14.1 57.5; 209 iBut: 175.4 34.5 18.7 18.9 Ac: 169.1 21.1; 210aAtrg: 166.1 I26 7 140.9 15.8 20.2 Ac: 169.2 21.0; ZlOb Ang: 165.8 a 136.8 15.7 19.2 Ac: 169.1 20.9; 211 Eyu~rg. I6X 1 59.3 0 . 1 13.2 19.0 Ac: 169.1 19.8; 212 Tig-l'-OH: 165.4 126.8 142.4 59.5 12.5 Ac: 169.0b a; 213 Tis-S'-OH: 165.8 131.7 142.1 14.4 56.3 Ac: 169.2b a ; 214 Epang: 168.9 59.4 59.7 13.6 19.6 0:. 165 7 129.7(2) 128.7(2) 133.3 129.7; 215 Tig-&OH: 165.8 127.1 142.1 59.5 12.7 Ac: 169.4b a ; 216 Ti.y-LO// 165.9 131.3 142.5 14.5 56.5 Ac: 169.4b a ; 217 Tig-4.5-OH: 165.6 131.2 145.3 58 9 57 I A( IhOO* .I , 219 TIg-SOH: 166.0 131.4 142.9 14.6 56.6; 220 Tig-SOH: 166.1 131.4 142.7 146 56.6: 221 S t i r I 6 5 4 130.9 142.5 15.6 64.0;222 Ang-4-OAc: 165.2 127.4 141.4 62.9 194 170.7 20.9; 223 So) I65 4 l l ( J ' ) 147.8 15.8 63.8: 224 Sarac: 164.4 126.5 142.6 15.6 65.0 170.7 20.9: 225 Ally: 166.1 126.4 1 1 1 2 I 5 S 20 2
198
199
200
214
201
R = Mac
209
R = iBut
202
R = iBut
2lO
R = Ang
203
R = Ang
211
R = Epmg
204
R = Tig
212
R
205
R = Epang (ZR.3'R)
213
R = Tig-5-OH
206
R = Epang
207
R
208
R = Tig-5-OTig-S-OH
-
-
215
R = Tig-4-OH
216
R = Tig-5-OH
217
R = Tig-4.5-OH
Tig-4-OH
(P'S.35)
iVd
o"" co 218
R = ti
219
R = Ttg-5-OH
220
221
R = Sar
223
R = Sor
222
R = Ang-4-0Ac
224
R = Sotac
225
R = Ang
300
M. BUDESfNSKY AND D. SAMAN
Table ll.--continued No.
Mol. formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-ll C-12 C-13 C-14 C22H2806 Leptocarpin, 3-acetyl-15-hydroxy 60.1 31.5 74.2 141.2 125.8 75.5 47.9 70.2 43.6 58.4 136.6 129.8 125.6 I 9 I 65 I C22H3008 Leptocarpin, 3-acetyl-15-hydroxy-2',3'-dihydro 60.1 31.5 74.1141.1125.8 75.4 47.8 70.2 43.3 58.3136.6129.8125.6 19.1 65.1 C20H2807 Rotundin, 14-desaeetyl-l'l,l8-dihydro 63.8 32.2 75.0b 141.0 126.8 75.4' 48.4 13.1 39.1 60.5 137.2 169.5 124.8 72.4 23.0 C22H2808 Rotundin 59.9 32.7 74.0 141.4 126.4 75.7 48.4 71.9 37.7 58.7 137.5 169.6 124.8 66.9 22.9 C20H2406 Leptocarpin, 3-dehydroxy-3-0x0 57.7 43.1203.8142.3125.4 75.2 49.2 75.3 43.1 57.7136.7168.5125.0 202 1 x 5 CJ9H2407 Tagitinin C, lfS,2a-epoxy 58.1 65.5 193.5 137.1 141.5 75.1 49.6 73.0 42.3 70.0 135 5 168.8 125.0 26.0 2 0 2 C20H2408 Tifruticin, 3-dehydro-15-hydroxy 58.0 65.7 194.1 139.1 142.3 75.3 49.6 72.8 42.4 70.0 135.3 169.2 125.4 25.5 62 5 C20H2607 Tifruticin 60.0 56.9 69.9 143.8 126.8 74.4 51.2 67.1 41.3 67.4 134.9 169.3 122.9 27.8 25.4 C20H2606 Germacra4Z,11(13)-dien-12,6a-olide, 8~-angeloyloxy-3~,10~-epoxy-la-hydr1~xy 76.0 37.3 76.6 143.9 123.3 74.5 45.4 73.1 38.0 73.6 137.1 170.3 123.5 31.1 21 5 C 301 C20H2806 Germacra-4Z,11(13)-dien-12,6a-olide, 3~,l0~-epoxy-3u-hydrox~8~-(2'-methylhutano~lf~x~ ) 37.2 40.7 106.3 136.5 127.9 75.3 49.6 71.4 37.9 83.1- 141.3 169.7 122.5 28.1 22.3 C20H2607 Niveusin C, 2',3'-epoxide 77.5 44.9 106.7 140.7 128.3 75.4 49.9 73.2 39.6 86.2 136.0 170.0 123.5 22.1 22.3 C20H2607 Niveusin C 77.3 44.8 106.3 140.5 128.0 75.6 49.8 71.7 39.5 86.3 136.2 170.1 123.0 22.3 21.9 77.7 44.9 106.6 140.3 128.7 75.6 50.0 71.7 39.7 86.6 136.4 170.3 123.2 20.4 22.0 C20H2607 Annuithrin 77.3 37.4 106.3 143.1 132.6 74.9 50.0 72.0 41.0 83.4 136.4 169.8 123.4 20.4 20.3 C19H2407 Zexbrevin B 77.8 44.8106.7140.1128.9 75.2 50.1 72.4 39.5 86.6136.1 170.0123.1 22.0 222 C19H2607 Orizabin 77.8 44.9 106.7 140.1b128.9 75.1 50.0 71.3 39.5 86.5 136.2b170.1 123.1 220 2 2 2 C20H2807 Tagitinin B, desoxy, la-methoxy 86.5 41.3 103.6 140.5 129.2 70.8 57.9 75.2 35.7 81.7 137 3 16Y 5 121 9 22 4 27 I C21H2808 Woodhousin 42.7 76.7 108.7 136.5 132.4 80.4 50.2 71.6 41.9 83.5 137.7 169 I 122 9 21 Xb 21 C22H2808 Germacra-4Z 11(13)-dien-12,6a-olide, 2~-acetoxy-3~,1Oj3-epoxy-3o.-hydroxy-8~-tigloyloxy 42.6b 80.4' 108.5 138.0 131.9 76.9' 50.2 72.6 41.9b 83.3 136.5 170.3 123.0 28.9 21.8 C20H2607 Niveusin B 37.4 40.9 106.2 143.6 131.2 75.4 49.9 72.1 39.3 83.3 136.6 170.3 123.4 28.2 65.9 C20H2807 Niveusin B, 2',3'-dihydro 37.0 40.6 105.9 136.1 131.2 74.9 49.5 71.5 39.0 82.9 143.2 169.7 122.9 28.0 65.7 37.3 41.0 106.2 136.5 131.1 75.4b 49.9 71.9b 39.3 83.2 143.7 170.3 123.4 28 2 65 X C2IH2808 Niveusin A, 3-0-methyl 86.2 35.4 103.2 135.9 133.8 74.6 50.0 70.8 42.6 81.8 142.0 169.5 123 2 27 2 h6.X C20H2807 Niveusin A, 2',3'-dihydro 77.3 45.6 106.2 135.8 131.1 75.3b 50.0 71.3b 39.1 86.5 142.2 170.2 123.4 21.9 65 3 77.6 46.6 106.7 137.7 128.8 76.0' 50.6 72.7b 39.8 86.9 144.4 170.2 122.8 22.2 64 I C22H3007 Gerrnacra4Z,11(13)-dien-12,6a-olide, 8 ~ - a n g e l o y l o x y - 3 ~ , 1 0 ~ - e p o x y - 3 u ~ t h a x y - l 5 - h ~ t l r ~ ~ x g 37.5 40.8 108.6 143.4 130.5 75.9 49.6 71.4 40.0 83.7 136.6 169.5 122.5 268 65 4 C hOX C20H2608 Niveusin A 77.9 46.9 107.0 144.8 129.3 76.0 50.9 73.2 40.2 87.1 138.3 169.8 122.5 22.3 64.5 A 404 C22H2808 Niveusin B, acetate 37.5 40.9 105.7 139.9 133.0 75.1 49.8 71.9 39.0 83.7 136.4 169.9b123.3 28.2 6 6 0 c' 4'94 C22H2809 Niveusin A, monoacetate 77.4 45.8 105.6 135.9 132.4 15.2 49.8 71.6 39.5 86.7 138.5 170.0b123.5 21 9 65 5 C' 1
('2-
226 221 228 229 230 231 232 233 234 235 236 237 a b
238 239 240 241 242 243 244 245 a h 246
247 a h 248 249 250 251
301
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES Table 11 .continued
Mol. formula Name / Chemical shifts c-1 c-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14 C-15 252 C26H32011 Niveusin A, triacetate 76.8 45.6 108.5 136.2 132.3 75.4 49.0 71.4 40.1 87.5 137.2 170.2b123.5 21.9 66.1 253 C20H2408 GermacradZ 11(13 dien-12 6a-olide
No.
Sol. Rcl C
49l
C
40.4
8~-angeloylo~;-l~~~&-dibyd;oxy-JB,jOB-e~5-0~0
77.5
47.1 104.7 142.0 156.1
74.9 49.4
71.4 39.8 87.9 134.9 169.0 124.3 20.4 195.2
Other carbons: 226 Ang: 166.0 126.2 141.6 15.8 19.5 Ac: 169.8 21.0 227 Mebu: 166.0 41.2 26.4 1 I 3 16.0 Ac: 169.8 20.2; 228 Mebu: 175.5 41.5 26.3 11.6 16.6; 229 Ang: 166.2 126.8 141.2 15.9 20.3 A ( 170.7 20.5; 230 Ang: 166.2 126.8 140.7 15.7 19.5;231 ;Bur: 176.1 34.1 18.6 18.6: 232 Any: 166.5 1266 141.1 15.8 20.1; 233 Ang: 167.3 127.1 140.1 15.9 20.5; 234 Ang: 166.7 127.2 139.6 15.7 20.3: 235 Mebrr: 175.5 41.0 26.3 11.4 16.5; 2% Epang: 169.0 59.6 60.2 13.7 19.1; 237a Ang: 166.5 127.0 13'1.3 15.7 20.2; 237b Ang: 166.8 127.3 139.8 15.7 22.3; 238 Ang: 166.6 127.1 139.6 15.7 20.3; 239 M o o 166.4 135.6 126.6 18.1: 240 iBut: 176.2 34.1 19.1 18.7; 241 iBut: 175.6 34.3 18.7 19.2 OMe: a ; 242 ;Bat: 176.1 34.1 19.1' 18.8' Ac: a ; 243 Tig: 166.9 127.9 138.3 14.4 11.9 Ac: 169.1 21.2: 244 Afrg: 166.7 127.3 139.6 15.7 20.4 24% Mebu: 175.3 40.9 26.2 11.3 16.4; 2451, Mebu: 175.8 41.2 26.5 16.7 11.6; 246 Ang: 166.0 127.2 139.5 15.8 20.4 OMe: 58.7; 2471 Mebu: 175.7 41.2 26.5 16.7 11.6: 24711 Mebrr: 175.5 41.8 27.0 17.0 11.8: 248 Ang: 166.7 127.3 139.1 15.7 20.3 OEt: 58.4 15.2: 24Y A I I , ~ : I O h X 128.6 138.8 15.7 20.5; 250 Ang: 166.8 127.3 139.6 15.7 20.4' Ac: 170.8' 21.1'; 251 Afig: 166.7 117.1 139.9 15.7 20.3'Ac: 170.gb 21.1';252 Ang: 166.6 127.1 140.0 15.0 20.4' 3xAc: 169.2b 169.3b I70 3* 20'J 20.9'21.2'; 253 ANg: 166.5 126.9 140.3 15.8 21.6
-t
0
HO
4co
O'CO
226
R = Ang
227
R = Mebu
R'
R'
228
Mebu
CHIW
229
Ang
CHzOAc
231
230
R'
OH
HO 'CO
HOH2C
232
;But
242
R
243
R = Tig
=
R'
R2
235
H
Mebu
236
a-OH
Epang
237
a-OH
Aoq
238
OH
Ang
239
a-OH
Mac
240
a-OH
)But
241
8-OCH,
iBut
233
244
R = Ang
245
R = Mebu
R'
OH
AcOH,C
R'
R'
248
H
Et
249
OH
H
247
O'CO
R'
R'
250
H
H
251
OH
H
252
OAc Ac
253
302
M. BUDESINSKY AND D. SAMAN
Table ll.--continued No.
254 255 256 257 258 259 260 261 262
a b 263
264 265 a h 266 267 a b C
d 268 269 270 27 1 272 273 274 275 a b
276 277 278
Mol. formula Name I Chemical shifts C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14 C-15 Sol R t l C20H2807 Tithonin C 24 37.5b 39.1b106.9 141.6 128.6 73.2 49.7 75.5 31.5 85.8 137.2 169.8 123.2 68.1 21 1 C2 I H3007 Tithonin, 3-0-methyl c 24 37.7b 37.9b110.4 139.9 130.9 72.2 49.7 76.1 29.7 86.5 136.9 169.6 122.6 68.7 32.2 Zexbrevin B, 1,Z-dehydro CI9H2206 130.5 139.2 108.3 140.4 127.7 74.9 47.9 77.5 43.6 86.9 139.1 170.1 124.5 31.0 20.7 c 395 Niveusin C, l,Zdehydro-2’,3’-epodde C20H2406 130.8 139.4 108.5 139.9 128.1 74.6 47.7 77.8 43.9 87.0 138.8 169.5 124.5 31.5 20.6 c 231 C20H2407 Niveusin A, 12-anhydro c 60‘) 141.3 140.0 108.6 134.6 126.7 76.5‘ 47.8 73.9‘ 43.6 87.7 138.6 169.5 124.5 31.1 66.2 G o y w m l i d e , 1S-deoxy CI9H2006 c hi‘) 204.6 104.6 186.8 130.4’ 135.1 81.5 51.2 73.4 43.8 89.6 133.6‘ 168.7 124.3 20.6 20.2 Lycbnopbolide C20H2206 204.7 104.7 186.8 130.c 135.1 81.6 51.2 73.0 44.0 89.6 133Xb168.0 124.1 20.6 20.2 c 651) C20H2206 Budlein A, deoxy 205.0 103.0 184.9 131.8’ 134.1 75.4 48.5 74.1 42.0 87.5 138.7b168.7 123.5 21.2 20.0‘ c 654 Vlguiepinin, 17,18-debydro C19H2007 205.1 105.0 182.6 138.9 134.4 75.1 48.5 75.3 42.6 87.9 136.1 168.7 123.4 21.4 62.6 c 172 C 207 205.1 104.9 182.8 138.9 133.9 75.3 48.3 75.6 42.6 88.0 136.0 169.0 123.4 21.3 62 3 Viguiepinin CI9H2207 205.7 104.7 183.1 138.5 133.5 74.3 48.3 75.3 42.0 87.7 136.3 169.0 124.0 21.1 62.1 C 172 C20H2207 Germacrn-2Z,4Z,ll(lJ)-trien-l~6aloIide, 3,10~-epoxy-1S-hydroxy-l-oxo-8~-tigl11~loxy 205.4 104.9 182.8 138.9 133.9 75.3 48.2 74.9 42.6 88.0 136.0 169.0 123.4 21.4 62.3 C 2‘17 C20H2407 Budlein A, 2’,3’-dihydro (2 epimers) 205.1 104.6 182.4 138.1 134.4 75.1 48.5 73.8 41.9 87.6 135.8 168.7 123.9 21.0 625 C 293 205.3 104.7 182.9 138.4 133.7 75.3 48.4 74.0 42.0 87.6 136.4 168.7 123.8 21.1 62.1 C 17?.?93 C20H2407 Germacra-ZZ,4Z,11(13)-trien-12,~lolldeJ,1OB-epoxy-lS-hydrox~l-oxo-8~~is11v~l~r11~ lox y 205.8 104.7 183.0 138.5 133.4 75.4 48.0 74.2 42.0 87.7 136.2 168.8 124.0 21.0 61.9 C 300 CZOH2207 Budlein A 205.0 104.3 183.0 136.7 132.6 75.0b 47.8 74.8b 41.4 87.4 139.7 168.3 122.7 19.1 61 2 A 101 209.1 108.3 187.1 141.1 136.2 78.9’ 51.6 78.6b 45.3 91.3 142.9 172.5 127.8 23.5 64.7 S 4‘JI 205.6 105.0 182.9 136.2 134.2 75.6’ 48.5 74.3b 42.2 88.0 138.8 169.2 124.0 20.1 62.4 C 4‘11 205.2 104.9 182.8 138.6 134.2 74.2 48.6 75.5 42.1 87.9 136.2 168.9 123.8 21.2 62.4 C 172 C23H2009C13N Budlein A + TAI 204.9 105.3 180.7 138.4 139.1 74.3’ 48.1 75.1’ 42.2 88.0 149.6 168.6 124.0 21.2 654 C I6S CISH1804 Ainsliolide 3 3 S b 26.1‘ 3OSb138.7’ 121.5 78.9 44.6 29.5’ 145.2 133.1 139.8‘ 172.7 120.4 169.7 24.1 C 3hi CI6H2004 Aimliolide, methyl ester 34.0b 26.0’ 31.6 139.2d122.7 79.2 44.9 29.7’ 142.3 134.3 140.1*170.1 120.6 168 0 24 I C 365 C2 IH2809 Ainslioside, l’-~-D-glucopyranoside 34.6b 27.2’ 31.8’ 141.r 122.9 81.3 51.7 31.W 145.4 134.1 141.7* 172.6 121.3 167.6 24.6 M 365 CZZH3007 Germacra4Z,9Z,11(13)-trien-12,6alolide, 3~-acetoxy-la-hydroxy-8B-(2’-methylhuI~n1~~l1~x~~ 65.1 32.4 73.1b 143.9 126.0 74.1b 47.5 67.0 123.2 139.0 134.4 169.2 121.9 11.6 23.3 C 276 C22H3008 Germacra4Z 9Z 11(13 -trien-lZ,h-oIide 3~-acetoxy-l&,1~-dibydroxy-8~-(2’-meth~lbu~noyloxy~ 65.8 35.4 72.4b 141.5 125.9 75.8b 49.8 69.1 124.0 142.5 136.3 170.9 122.9 19.9 65 3 h4 216 C22H2808 Eupacunolin 65.1 33.1 70.8 142.3 126.6 74.3 47.6 67.8 123.3 141.6 134.4 169.0 122.3 17.4 65.1 C 2x15 C20H2407 Germacra-1E,4Z,11(13)-trien-lZ,6a-olide,8~-angeloyloxy-l0a,l5~dihydroxy-3-l,xo 162.0 129.7 196.4 141.6 137.1 75.8 46.9 73.9 48.4 71.9 135.8 169.8 125.0 28.6 62.6 C 5OX 161.3 129.8 196.; 141.7 140.5 75.7 48.7 ?3.9 47.1 12.1 135.9 169.6 124.9 28.9 63.0 i‘ (>OK CI 9H2406 Tagitinin C 160.5 129.6196.9 138.8137.1 76.1 47.1 74.1 48.4 71.9 136.1 169.8 124.4 28.9 19.7 C 50 C22H2607 Germ~cra-1E,4Z,11(13)-trien-lZ,6a-olide,l0a-acetoxy-8fl-cpoxyangeloyloxy-3-~1~11 157.7 128.8 195.9 139.2 135.8 75.6 47.5 73.9 47.5 79.6 135.8 170.0 124.9 24.6 200 C 231 C24H2809 Niveusin A. diacetate 159.6 128.6 193.8 137.4 141.1 75.0 47.6 72.5 47.3 79.5 135.4 170.0’ 125.2 24.4 64.1 C 404
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
303
Table ll.--continued Mol. formula C-1 C-2 C20H2606 131.9 130.5 C20H2806 35.6 29.8 C20H2807 79.2 39.1 C22H3008 76.2 35.5 C24H3209 73.8 34.8 75.1 33.5
No. 279 280 281 282 283
a b
Name I Chemical shifts C-3
C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-ll C-12 C-13 C-14 C-15 Sol. I k l ' Tifruticin, deoxy 72.9 146.8 125.9 73.9 51.3 68.9 43.8 70.8 135.5 169.4 122.6 29.5 25.1 C 2x9 Germacr~4~11(13)-dien-l2,~-olide, 8p-angeloyloxy-3p,10-dihydraxy 75.0 138.4 127.5 74.2 48.1 74.4 38.9 71.7 136.7 170.6 123.5 31.5 23.9 C 27') Germacra4Z,11(13)-dien-l2,~-olide,8~-angeloyloxy-l~,3~,l~-trihydroxy 72.2 139.8 127.3 74.2 48.7 73.1 39.5 73.1 137.8 170.0 122.5 24.2 24.0 I' 219 GermacradZ,ll(l3)-dien.12,6a-olide, 3-aeetoxy-8p-angeloyloxy-l~,lOa-dihydriix~ 68.6 144.1 125.6 74.6 49.3 70.2 38.4 72.3 135.8 169.7 123.1 27.7 23.5 C 279
Germ~er~4~11(13)-dien-l~6a~lide, lp,3p-diacetoxy-8p-angeloyloxy-lOa-hydri1x~ C C
72.4 135.2 128.5 74.0 48.0 73.2 39.1 72.7 135.8 170.6 124.0 24.8 24.5 69.8 140.8 125.8 75.1 47.1 70.9 38.5 72.6 136.3 169.7 123.6 29.3 22.5
279
279
Other carbons: 254 Mebu: 175.6 41.3 26.5 11.5 16.6; 255 Mebu: 175.7 41.2 26.5 11.6 16.7 #Me: 50.4: 256 Mac: 166.1 135.7 126.9 18.1; 257 Epang: 168.6 59.7 60.2 13.2 19.0; 258 Ang: 166.1 126.7 14O.'J 15.8 20.5; 259 Mac: 166.7 135.6 126.3 17.9; 260 Ang: 167.0 126.5 140.5 15.6 19.9; 261 Any: 165.7 126.5 141.0 15.7 19.4'; M 2 a M o c : 165.9 135.2 127.3 18.1; 262b Mac: 165.4 134.5 127.4 18.2. 263 i / t l f f , 175.4 21.1 18.8 18.4; 264 Tig: 166.4 127.3 139.8 14.6 11.8; 26% Mebu: 174.9 41.0 26.2 11.4 16.3. 265b Mebri: 175.0 41.0 26.5 11.4 16.0 266 iVal: 171.4 42.7 25.2 22.2 22.1; 267a Ang: 165.4 126.7 139.3 14.7 20.4; 267b Ang: 169.5 130.6 143.7 19.3 24.8; 267c Ang: 166.0 126.5 141.7 15.9 21.3: 267d Ang: 165.9 126.5 141.1 15.7 20.0; 268 Ang: 165.8 126.4 141.2 15.7 19.9: 270 OMe: a; 271 Glc: 95.7 74.2 78.9 71.2 78.5 62.4: 272 Mebu: 174.8 41.5 26.3 11.6 16.4 Ac: 169.2 21.0; 273 Mebu: 175.9 42.7 27.4 10.8 17.7 Ac: 170.9 21.7; 274 Ang: 166.1 126.6 140.9 15.5 20.4 Act 169.9 21.1: 27% Ang: I664 126.7 140.4 15.7 20.1; 275b Ang: 166.5 126.8 137.4 15.8 20.1; 276 Bur: 176.2 34.1 18.8 18.6: 277 Epang: 168.6 59.4 60.3 13.3 18.9 Ac: 169.2 21.7; 278 Ang: 166.2 126.6 137.7 15.8 21.6 Ac: 169 2b 20.1' 170.8' 20.8'; 279 Ang: 167.3 127.1 140.7 15.9 20.4; 280Ang: 167.1 127.3 139.3 15.7 20.3 2x1 A f f , ~ . 166.4 127.9 138.1 15.6 20.4; 281 Ang: 166.8 127.0 140.1 15.7 20.3 Ac: 171.4 21.2: 2x2 Aw: I66.j n OMebu HO"'
RO"
O'CO
254
R = H
255
R =
CH,
& 0
256
R = Mac
257
R = Epang
258
0
259
R = a-OMac
260
R = a-OAng
261
R = P-OAng
COOR
O'CO-
hOh&
H
262
R = Mac
267
R =
263
R = #But
268
R = TAC
264
R = Tig
265
R = Mebu
266
R = iVai
269
R = H
R'
R'
270
R = CH,
272
Mebu
H
271
R = Glc
273
Mebu
OH
274
Ang
OH
HO R'
R'
R'
R'
275
OH
Ang
276
H
!But
277
H
Epang Ac
278
R'
280
8-OH
H
H
281
@-OH
OH
H
282
OAc
Oh
283
OAC
OAc
279
304
M. BUDESINSKY AND D. SAMAN
Table ll.--corttinued No.
284 285
286 281
288 289 290 291 292 293 294
Mol. formula C-l C-2 C23H3207 75.8 32.6 C20H3006 35 3 29.5 C17H2006 73.2 23.2 C22H2808 39.5 32.5
Name I Chemical shifts C-4 C-5 C-6 C-7
C-10 C-ll C-12 C-13 C-14 C-15 %I I
C-8
C-9
Germacra-4Z,11(13)-dien-12,6a.olide,
91.2 24.4b 27.3b 60.7 63.9 80.2 44.4 26.2' 34.4b 145.2 140.5 169 8 118.8 117 7 I X 3 I' 1'11) 295 C17fi220S Parthenolide, acetyl, deoxy 79.1 23.Eb 27.7b 60.2 63.7 79.8 43.3 25.6b 33.7b 144.0 139.4 169 6 119.4 117.9 1 x 3 C' 1'10 296 C16H220S Parthenolide, methylperoxy 88.9 34.0b 26.0b 60.4 63.7 79.9 44.0 25.9b 24.2b 144.3 139.5 169.3 119.4 1170 I X 3 c' I90 297 C l S f f 1 8 0 4 Parthenolide, anhydro, peroxy 203.3 34.4* 30.8' 59.2 65.3 81.5 45.0 28.7b 35.7'149.8 139.2 169.1 120.1 127.0 17.5 C 1'10 298 C17H2206 Ferolide, desacetyl 7 8 2 33.3 30.3 6C.4 63.8 75.6 45.8 66.2 29.8 146.2 134.5 168.7 120.8 117.0 I X 3 C' 17'1 299 C17H2207 Fcrolide, peroxy 90.9 34.1 32.1 607 64.4 76.4 46.7 67.0 26.6 142.9 136.1 169 3 1204 I20 1 I X 5 I' 17'1 300 C19H2407 Ferolide 7 8 0 33.5 31 2 60.0 63.9 75.4 45.8 6 6 4 27.8 141.3 134 3 168 3 I19 4 1209 I X 3 C 17'1 301 C22H2608 Germacra-4(1S),11(13)-dien-12,6a-olide. 5 ~ - a c e t o x y - l ~ , l l ~ a - e p i i x y - 2 - i i x i i - X ~ l - l i ~ l 1 ~ ~ I i i r ~ 62.3 199.4 45.6 137.0 76.5 78.3 44.7 76 5 42.9 61.9 136.4 I67 6 12.4 6 17 0 125 X I< 57') 302 C20112407 Cordifene (two isomers) a 53.3 55.1 62.8 142.0 81.6 78.0 48.7 69.0 45.7 55.9 136.2 168 7 126 I 17 9 I17 4 C 70 h 52 4' 542' 62.4 139.5 8 0 6 77.8 47.9 67.9 45.4 55.2 134.0 167.8 127.1 17 X I I R 6 c' %> 303 ~ 2 0 ~ 2 2 0 6 Atripliciolide, iso, A',", tiglate 205.0 103.5 184.3 136.3b 41.9 77.5 51.3 73.9 43.3 88.6 139.4* 168.1 122 I' 22 2 I21 0' C' 2 3 3 304 C20H2207 Centratherin, is0 204.5 106.7 186.1 137.9 75.1 86.2 44.5 71.6 44.5 90.5 1342 169.6 126.X 21.3 1 2 4 1 c' 4(12 305 C22H2408 Centratherin, iso, acetate 204.2 107.0 185.3 133.6 74.9 83.8 46.0 71.7 44.6 90.4 133 8 169 6 124.0 21 3 130 7 c' JI)2 306 C20H2407 Germacra-2,4(15),11(13)-trien-12,6a-olide, 3 , 1 0 ~ - e ~ x y - 5 a - h y d r u x y - X ~ ~ - i s c l r . l e r c 1 ! I 1 1 x ~ - l - ~ 1 ~ 1 1 204 7 104.9 184.3 141.5 73.9 80.0 49.4 75.1 42.6 86.0 140.8 1686 122.2 22.1 I I 9 7 I' 300 307 C22H2408 Germacra-2,4(15),11(13)-trien-12,6a-olide, S~-acetexy-~~-sngcl11yl1~xy-3,1O~l-rp~~x~ - 1- I I A C I 204.4 105.3 182.9 139.5 78.5 74.5 43.4 75.1 42.5 89.3 135.1 169.5 122.5 21.X I ? X 5 c' IhS 3011 ~ 2 1 ~ 2 8 0 7 Lychnostatin 2 208.3 3O.lb 27.1 29.7 43.4 77.9 47.0 68.2 35.9' 84.3 134.7 169.6 124.9 2 4 0 1 x 2 c' 517 309 C2IH2808 Lychnostatin 1 207.6 41.Ib 24.1 32.1 77.5 82.4 44.3 70.8 35.3b 84.9 134.9 169 6 126 3 22 4 I X 2 <' 577 310 ~ 2 0 ~ 2 6 0 7 Ternifolin, SP-angeloyloxy 213 5 41.9* 69.1' 30.3 35.6b 75.9' 41.9 72.1' 40.6b 77.6 1368 169.0 123.5 27 X 20 5' ~2
305
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 11.-continued No
Name I Chemical shifts C-4 C-5 C-6 C-7
Mol. formula
C-2
C-l
C-3
311 CZlH.1007
C-8
C-9 C-I0 C-I1 C-12 C-13 C-14 C-15
Sol I < c l
Ternifolin, 8p-angeloyloxy-3-methoxy
70.0 40.2b 78.1 136.3 169.3 123.4 28.5 20.2'
C
234
312 C23H.1407 Ternifolin, 8p-angeloyloxy-3-isopropyloxy 215 2 40.0h 77.2' 30.5 35.7 76.2' 43.2 71.4' 40.7b 78.6 137.1 169.7 123.6 29.0 23.8'
214.8 37.7b 80.3' 30.2 35.1 76.5' 42.9
C
609
Other cnihons: 284 Ang: 166.3 127.2 139.1 15.6 20.2 OiPr: 105.3 28.3 27.9: 285 Mebu: 175.2 40.9 26.2 11.3 16.4: 286 OEr: 65.3 15.7: 287 Ang: 166.9 127.5 138.8 15.7 20Sb Ac: 170.4 20.6b; 288 Soroc: 163.8
127.4 145.4 15.9 65.4 170.8 20.8; 289 Suruc: 164.9 127.1 145.8 15.9 65.0 170.7 21.2 Ac: 170.2 20.9; 2YO A I I , ~167.0 : 127.4 1388 15.8 20.8 Ac: 170.7 20.5; 291 Surac: 164.8 127.5 145.0 15.8 65.3 170.6 20.7 Ac: 170.5 20.7; 292 Sarac: 164.7 127.0 145.7 15.8 65.0 170.9 21.0 2xAc: 170.8 20.4 169.6 204: 2Y5 Ac: 169.2 21.2: 296 OMe: 62.4: 298 Ac: a ; 299 Ac: a ; 300 Ac: a : 301 'fig: 166.1 127.0 139.5 14.2 11.9 A c . 168.8 20.2; 3021 Ang: 166.6 128.3 139.3 15.8 20.4: 302b Ang: 166.0 127.0 140.0 15.8 2 0 I: 303 lig: 166.2 127.4 139.0 14.4 11.7: 304 Ang: 167.3 126.5 140.6 15.7 20.1: 305 A J I ~ :167.3 126 3 140.9 15.7 20.0 Ac: 168.5 21.1; 306 iVol: 171.4 43.4 25.3 22.2 22.2; 307 Ang: 165.8 126.5 1409 IS 7 20.0 Ac: 1680 20.8: 308 Mac: 165.9 135.9 126.5 21.3 Ac: 169.0 21.5: Jo9 Moc: 165.8 135.9 126.3 20.2 Ac: 168.5 21 4; 310 Ang: 165 6 127.0 138.6 15.3 19.84:311 Ang: 166.3 127.2 139.8 15.7 20.Od OMr: X I : 312 Aiig: 166.6 127.8 139.8 16.2 22.5' OiPr: 70.7' 20.7 20.7
> OH
"
O O'CO
W
m 285
".*
0
2.38
H
289
OAc Sorac H
290
H
Ang
291
H
Sarac AC
292
OAc Soroc Ac
SO~OC
H
Ac
287
286
0 L
O
A
c
%
293
R = H
298
R = H
294
R = OH
299
R = OH
295
R = Ac
300
R = Ac
296
R = OCH,
308
R = H
309
R = OH
310
R = ti
311
R = CH,
312
R = CH(CH,),
297
o,y-g
m o
..,,o' co
0-CO 301
3020
R'
R'
303
H
P-OTig
304
a-OH
a-OAng
305
a--0 A c a-OAng
306
a-OH
p-OivaI
307
p-OAc
p-OAng
2a.Sp-epoxy
302b 2p.Sp-epoxy
RO
306
M. BUDESINSKY AND D. SAMAN
Table ll.-continued No 313 314 315 316 317 318 319 a b
320 a b 321 322 a b c
323 a b
c 324 325 326 327 328 329 330 331 332 333 a b
334 a
b
335 336
Mol formula Name / Chermcal shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 C-13 (2-14 C-15 ,501 l
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
307
Table ll.+ontinued No.
337 338 33Y -340
311
Mol. formula C-I C-2 C2IH2609 205 7 55.7 C23H2809 2060 55.9 C23H3009 2060 55.9 C24H2808 206.8 5 5 9 C24H3009 206.1 55.9
Name / Chemical shifls C-4 C-5 C-6 C-7 no name 62.9 26.0 38.7 74.7 40.8 no name 62.8 25.1 39.0 74.8 41.1 no name 62.8 25.1 39.0 74.8 41.2 no name 62.8 26.1 38.9 74.2 41.1 no name 62.8 26.1 38.9 74.8 41.1 C-3
C-8
C-9 C-10 C - l l C-12 C-13 C-14 C-15
74.1
71.7 79.7 134.3 170.3 126.7 24.4
18.5
C
207
74.1
72.0 80.0 134.8 168.3 126.4 24.5
18.6
C
207
74.1
71.2 80.0 134.8 168.3 126.5 24.5
I86
C
297
74.2
71.3 79.9 135.0 168.3 126.4 24.8
18.6
C
2'17
IXh
C'p:x7
74.2 70.8
79.9 135.0 168.3 126.4 2 4 X
SIII I(cI
Orhercxhons: 313 Ang: 166.8 127.2 139.2 15.8 20.1 0 M e : 58.6; 314 Ang: 166.2 127.1 1401 I5 7 20 I 315 Muc: il Ac: a ; 316 Tig: a Ac: a ; 317 Mac: a iBur: a ; 318 Ang: a Muc: a ;31Ya I V ~ I / 171.3 43.0 28.3 22.2 22.2; 3196 iVul: a ; 320a iVul: 170.8 42.5 24.9 22.3 22.3 Ac: 170.0 20.5. 32011 ~ V a l . a Ac: a ; 321 Ang: a Ac: a ; 322a Mac: a Ac: a ; 322h Mac: a Ac: a ; 322c Mac: 165.4 135.0 127 3 18.1 Ac: 170.4 20.4: 323a Mac: a ; 323b Mac: a : 323c 2xMoc: 166.6 134.8 127.2 l9.X 165.5 I27 6 126.4 18.1; 324 Tig: 165.8 127.3 138.8 14.5 11.8 Ac: 168.7 20.3; 325 Ang: 165.2 126.5 I4OX 15.7 20.1 Ac: 168.7 20.3; 326 Mac: 165.2 134.9 126.9 18.0 Ac: 168.7 20.3: 327 Mac: 165.2 134 6 127 2 I X 0 i & f r 176.5 34.0 18.7 19.0: 328 Atig: 166.6 126.5 141.1 15.9 20.1 Mac: 165.2 134.7 I 2 6 6 I X 11. 32Y 21hfoc: 165.3 134.6 127.6 18.1 166.5 134.7 126.7 18.0, 330 rig: 168.6 127.4 139.6 14 6 I ? 1) 170.2 21.5; 331 Ang: 166.4 126.7 140.6 15.7 20.3; 332 Ang: 166.3 1266 141.0 15.8 20.3. 333a All:. I h f A 127 0 140.2 15.7 20.2: 333h Ang: 166.4 127.0 140.2 15.7 20.2: 3Wa A q : 165 8 126 3 141 I 15 h ? I ) I 33th AII,~: 165.8 a 141.2 15.8 20.4; 335 Muc: 166.8 135 8 126.9 18.1; 336 Tiy: 166.4 127 X IVJ 2 12.2 3 ; 337 Mac: 165.2 134.8 127.8 18.0 Ac: 168.4 20.3; 338 2xMuc: 165.1 134.7 127.X I X 0 I M 1264 126 7 18.0: 339 Muc: 165.1 134.7 127.1 18.0 iBul: 176.5 34.1 16.6 19.0: 340 Mar: I65 2 13.1 6 127 0 17.9 r V d 173.0 42.5 24.6 15.2 10.1; 241 Muc: 165.2 134.6 126.6 17.9 Ang. 166 X 126 4 1-11 7 15 x x . 0 CH,O
,n*
.
-
=
0-co
-
HOH&
0-co
0-CO
R'
314
313
i
R'
R'
315
Mac
8-OAc
316
Tig
B-OAc
317
iBut a-OMac
318
Ang
a-OMac
ii/uI
b
iVal
a-OAc
321 322 323
Ang
a-OAc
Ac
a-OMac
Mac
a-OMac
AcO R'
R'
324
AC
Tiq
325 326 327
At
Anq
Mac
Ac
328 329
MOC
HO
0-co
;But
MOC
Anq
MOC
Mac
p& 0
330
R~,C
0 %- c o
R'
R'
337
AC
Mac
338
Mac
Mac
339
Mac
iBut
335
R = a-OMac
340
MOC
iVal
336
R = p-OTiq
341
Mac
Ang
R'
R2
331
H
H
332
OH
H
333
rl
OH
R'
319 320
334
308
M. BUDESiNSKY AND D. SAMAN
Table ll.-continued Name I Chemical shifts C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 '2-13 no name 62.8 26.1 38.9 74.8 41.1 74.2 70.9 79.9 135.0 168.3 123.4 no name 62.8 26.1 38.9 74.2 41.1 74.2 71.3 79.9 135.0 168.3 126.4 no name 62.8 25.2 39.0 74.8 41.2 74.1 71.2 80.0 134.8 168.3 126.5 no name 62.9 26.0 38.7 74.7 40.8 74.1 71.7 79.7 134.3 170.3 126.7 Calein D, 2,3-epoxy 62.9 26.1 38.9 74.8 41.0 74.1 71.7 79.8 135.0 168.4 127.2 no name 62.8 25.1 39.0 74.8 41.1 74.1 72.0 80.0 134.8 168.3 126.4 Juonislpmin, 2aJacrspoxy 62.9 26.1 38.9 74.9 41.0 74.1 71.9 80.0 135.0 168.5 126.9 62.8 26.1 38.9 74.9 41.0 74.1 71.9 80.0 135.0 168.5 128.0 Tirotundin 108.8 43.4 38.0 81.3 47.9 6 9 8 38.4 80.0 137.2 169.4 121.4 108.8 43.4 38.0 81.3 47.9 69.8 42.2 8 0 0 137.2 169.4 121 4 Tagitinin A 105.7 44.4 37.8 81.9 47.8 69.9 34.6 81.7 137.0 169.8 121.7 105.7 44.4 37.8 81.9 47.8 69.9 34.7 81.7 137.0 169.8 121.7 Viguilenin 105.6 44.3 37.8 81.7 47.7 69.9 34.6 81.7 137.0 169.5 121.6 no name 111.6 45.6 38.1 81.8 47.6 69.8 41.3 79.8 137.2 169.4 121.3 NiveusinA, l-methoxy4,5-dihydro 106.6 43.3 32.0b X6.7 46.7 ( 6 . 3 35.6b 81.7 136.9 169.5 119.2 NiveusinA, 4,Sdihydro 104 2 47.8' 33.R' 82.2 47.9b 69.9 34.5' 81.8 136.9 169.9 122 2 Tagitinin C, 4,s-dihydro 202.5 41.7 40.9b 77.5' 47.0 72.7' 43 Zb 70.X 135 I 168.8 123 I Tagitinin A, dehydro 104.0 45.0 37.8 80.5 47.8 68.3 36.4 X1.8 136.4 169.1 122.0 Viguilenin, dehydro 104 1 42.0 37.8 81.9 47.7 68.4 36.5 81.9 137.3 169.2 122.3 C?IIII?6OX Calyculatolide, 8p-angeloyloxy-9a-acetoxy 201 ' 1 103.8 192.5 31.2 40.8 74.7b 47.0 74.Ib 73.7b 89.4 139.7 168.4 122.9 CIY112206 4s 6R,7S,SS,IOR Germacra-2 11(13)-diene-l2,dolide,
Mol. formula
No. 342 343
341 345
346 347 348 a h 519 a h
350 3
h 351 352
353
3-q 355
356
C-1 C-2 C24H3009 206.1 55.9 C24H3209 206.8 55.9 C23H3009 206.0 55.9 CZIH2609 205.7 55.7 CZIH2609 206.1 55.8 C23H2809 206.0 55.9 C23H2809 206.1 55.9 206.1 55.9 C19112806 38.9 42.2 38.9 38.4 CIYt12807 7X.5 46.9 78.5 46.9 C2OH3007 7X 3 46.9 C20112006 39.6 31.9 "?//1(008 77 5 37.6 C211112808 78.4 47.5 C19H2606 151.7 129.2 C19H2607 213.5 47.0 ('2OH2807 213.4 47.1
C-3
'2-14 C-15
Sol Itcl
18.6
24.8
C
Ilj
18.6
24.8
c
115
18.6 24.6
C
11.5
18.5
24.4
c
lli
18.6
24 5
c
I l i
18.6
24.6
C
I l i
18.6 18.6
245 24.5
C
297 115
26.9 269
IY? I!, I
c'
i'l
C'
311
25 0 25 0
I!, 2' I9 2
c
434
c'
5')
25 0
IX4
c'
434
25.5
1X.7
c
5x0
25 8
65 6
c
60')
24.6
64 2
c'
434
2X 7
I60
C'
(776
c
ill
22.2' I!, Oh
['
22 3
1x4
c'
ii?
20.5'
I9 9'
c
4x3
IX5
('
OVl
1x4
L'
6i')
1X.2
c
659
204.6 105.7 192.3 33.3 42.3 82.1 53.9 73.3 45.2 89.7 132.9 168.4 124.9 21.1 18.4 363 C21H2609 4s 6 q 7 S 8s 10R)-Germacra-2 11(13)-diene-12 6-olide $-(l'-aeet~x~-3'-hydroxy~~u~noyloxy)~~,l~~~xy-l~~o 205.0105.8192.1 73.5 42.3 82.1 S38 72.7 45.2 89.6132.8168.6125.1 20.9 18.6 364 C19H2206 Zexbrevin 205.2 103.0 192.1 31.4 41.0 74.7 51 6 74.3 43.1 88.3 139.5 168.5 123 1 22.7 I 6 0 365 C2OH2406 no name 205.2 103.0 192.1 31.4 41.0 74.7 51.6 74.4 43.1 88.3 139.6 168.5 122.9 22.7 16.0 366 C19H2206 Zexbrevin B 2054 1032 1924 31 5 41 2 7 4 7 51 9 7 4 1 43 3 885 1396 1687 1234 2 2 9 16 I
c
65')
c
65')
c'
297
C'
2'97
L
WT
317 35x 359
S,l&poxy-s-metecryloyloxy-i-oxo
205.0 105.5 192.6 33.6 42.4 82.1 54.4 71.9 45.2 89.8 133.9 168.7 124.1 21.1 360 CI9112207 4s 6R,7S 8 s 10R Germacra-2,11(13)-diene-12,6-olide, !%,I&.pox;-S~(2',&- epoxypropanoy1oxy)-I-oxo 204.7 105.6 192.4 33.6 42.3 82.0 54.2 75.2 45.1 89.8 133.6 168 3 I24 2 2 1 I 361 C19H2408 4s 6 Y S 8s 10R):Germacra-2 11(13 diene 12 6 olide, &-(5',3 - d i h y 6 r o x y i s o b u t o n o y l o ~ y ~ ~ 3 , ~ ~ - ~ p o ~ y - l ~ ~ x o . 205.5 106.4 192.4 33.0 42.2 82.0 53.8 73.5 45.2 89.6 133.2 168.8 125.6 21.2 362 C21112609 4s 6q7S,8S,lOR)-Germacra-Z 11(13)diene-12 6-olide
&-(~-acetoxy-2'-hydroxyisobudnoyloxy)-3,lO-e~xy-l&xo
309
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table ll.--continued No
367 36X
369
370 371
Mol. formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-I1 C-12 C-13 C2OH2406 Ladibranolide 205.1 103.3 192.0 31.5 43.0 74.9 51.9 73.7 41.1 88.3 139.4 168.6 123.5 C30H4006 Atripliciolide, 4a.S-dihydro-Sp-myrteny1, 8-isovalerate 205.6 104.3 193.3 44.1 36.9 75.1 45.5 73.9 42.6 88.0 138.8 168.9 123.8 ClSH220S no name 40.9 22.6 30.0 35.7 74.8 77.7 41.7 68.8 64.1 61.0 136.6 170.5 125.7 C2OH2806 Blumealactone A 40.7 22.6 30.0 36.2 74.8 78.0 39.7 68.8 61.8 58.8 136.2 165.7 124.3 CI7H240S Blumealactone, deoxy 3 5 8 19.2 28.7 30.6 76.9 78.5 45.2 69.6 130.9 135.5b135.1b170.0 126.1
C-14 C-I5 22.9
Sol. Ilet.
16.1
C
21R
9.7 20.9
c
576
17.7
C
543
16.3 17.6
C
200
16.9 16.1
C
317
16.4
Olhercarbons: 342 Ang: a ; 343 iVal: a ; 344 ;Bur: a ; 345 Mac: a Ac: a ; 346 Mac: a Ac: a , 347 Al~ic: a : 348a 2xMac: 166.8 134.6 127.4 18.0 165.5 128.1 126.6 24.5; 348b Mac: a : 349a iBrrr: 176.1 34.1 18.6b 18.7b; 349b iBur: 176.1 34.1 18.7 18.6; 350. iBuf: 176.4 34.1 18.8' 18.4; 350b iBict: 176.5 34.1 18.8 18.4: 351 Mebu: 175.0 41.2 26.5 11.5 16.5; 352 iBur: 176.3 34.0 19.1 18.0 OMe: 48.6; 353 A q : 166.8 127.3 139.2 15.9 20.5 OMe: 58.6; 354 Ang: 167.1 127.3 139.1 15.7 20.4 355 ;But: 175.3 33.2 17.8 17.8: 356 rBur: 175.8 33.9 18.6b 18.3b; 357 Mebut 175.4 41.2 26.5 11.4 16.5; 358 Atig: I 6 4 K 125 6 146.6 15.Xd 16.3' Ac: 168.6 18.8; 359 Mac: 166.7 135.6 126.1 17.9: 360 Mac-ep: 170.3 53.5 52 5 17 2. 361 iIZi~1-2.3-0H:173.5 74.3 50.9 22.8; 362 iBur-2-OH-3-OAc: 174.0 73.4 68.8 20.5 170.6 22.0: 363 iftrit-2-0Ac-3-OH: 174.6 78.8 46.7 21.6 171.1 20.6; 364 Mac: 165.4 135.1 126.7 18.1; 365 Tig: 1 6 6 1 127.5 138 3 14.5 11.9: 366 Mac: 165.8 135.3 126.9 18.1; 367 iVal: 165.6 126.4 141 0 15.8 20 I . 36X I V U / 171.4 43.2 25.2 22.3 22.3 Mvnenyl: 52.9 145.2 118.4 31.3 40.8 38.1 31.6 34.8 26 2 ??'I. 370 Airp: 169.8 126.4 139.8 15.7 20.3; 371 Ac: 170.0 20.4
R'
R
RJO"''
0-co
=
HOH&
b-CO
342
R = Anq
R'
R2
R'
R'
R'
353
R = OCH,
343
R = Nal
345
8-OMoc
Ac
349
ti
a-OiEut
H
354
R = a-OH
344
R = #But
346
P-OAc
Mac
350
on
p-oiBut
n
347 348
a-Wac
Mac
351
OH
8-OMebu
H
p-OMoc
Moc
352
H
8-OiBut
CH,
355
356
R = @-;But
357
R = Mebu
358
0
364
R
365
R = Tig
=
Mac
369
R = H
370
R = OAng
359 360
R =
361
R = iBut-2.3-OH
362
R = But-2-OH-3-OAc
363
R = aBut-2-OAc-3-OH
MOC
R = Moc-ep
371
310
M. BUDESINSKY AND D. SAMAN
Table ll.-continued No. 372 373 374 375 376 377 318 319 380 381 382 383 384 385 386 387 388 a
h 389
Mol. formula Name I Chemical shifts C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 (2-10 C-11 C-12 C-13 C-14 C24H32010 Chapliatrin, Lso 31.4 27.0 71.4 52.1 78.1 77.8 47.2 67.4 45.5 79.4 135.3 169.4 121.6 30.6 C24H32010 Chnpliatrin 30.2 29.8 68.1 49.9 78.1 77.9 47.6 67.3 45.7 79.9 135.6 169.9 122.0 30.7 C26H34011 Chaplistrin, ncetyi 31.3 26.6 70.9 48.7 78.1 77.4 47.2 67.4 45.5 79.4 135.0 169.8 121.0 30.5 C22H3009 no name 30.0 28.9 67.5 49.8 78.6 77.5 47.2 67.3 45.2 79.6 134.9 168.9 121.6 30.5 no name C24H32010 30.0 29.2 67.6 49.8 78.7 77.6 47.3 67.3 45.3 79.5 134.9 168.9 121.5 30.5 no name C24H3009 24.7 36.5 131.3 137.8 82.5 76.8 46.4 66.9 45.4 79.7 134.5 168.7 122.0 29.2 C20H2407 Niveusin A, 1,2-nnhydridd,S-dibydro 143.9 126.7 195.6 37.4 33.9 7 S b 48.3 73.8’ 43.8 69.0 137.1 169.8 125.1 19.6 C2SH3209 no name 33.7 60.6 52.9 70.8 76.8 75.5 46.0 72.3 208.7 38.7 132.9 167.9 127.0 180 no name C25H3409 33.7 60.3 53.0 70.8 76.9 75.3 45.9 72.3 208.7 38.7 132.8 167.9 127.1 18.3 C20H2607 Cordlfolis PZ 66.7 66.1 47.8 60.3 64.4 79.6 50.5 69.3 43.5 57.3 132.6 168.6 125.3 18.3 C20H2408 Cordilene, 4pJSa-oxide 51.4 55.5 61.6 58.8 81.0 78.7 48.6 68.9 45.2 56.3 136.1 168.5 126.0 17.7 C19H2207 Miller3E-enolide, 4p,15-epoxy 22.3 17.0 32.4 55.2 78.6 80.0 44.0 72.3 142.3 133.5 137.1 169.2 125.5 190.5 C20H2608 no name 209.8 36.4 34.6 81.5 85.0 80.1 43.9 79.2 67.7 81.4 134.8 168.8 122.5 24.2 CISH2204 Germacr-11(13)-en-12,6a-olide, Sp-hydroxy-li3,9p-epoxy 35.1 30.9 38.5b 80.6 74.5 82.5’ 42.3 39.Ib 82.7’ 26.1 140.3 169.4 119.0 21.2 C25H28010 no name 83.8 28.8 34.3 72.1 116.4 149.6 82.2 70.5 35.4 77.9 130.7 161.0 130.3 14.4 C23H2609 16E -Brachycalyxolide, is0 83.6 27.5 33.4 70.6 116.6 149.9 82.2 69.2 37.0 77.8 131.5 164.5 128.2 14.5 C25H3301I CI Tetragonolide, isobutyrate (2 conformers) 75.9 29.6 29.2 88.5 77.9 80.3 42.6 74.2 70.6 54.7 136.4 169.1 126.4 171.8 74.4 29.4 28.9 86.2 77.2 79.2 41.7 72.9 70.2 50.3 134.2 169.1 125.8 170.6 CI9H2207 Miller-9Z-enolide, 48,15-epoxy 24.8 18.9 22.0 55.7 79.2 81.4 42.7 -72.8 149.9 144.2 134.3 169.0 m . 3 194.0
C-15
Sol. Rcf.
60.2
c
317
63.3
c
317
61.6
C
317
627
c
31x
62 7
c
31x
65 5
C
31X
65.3
c
609
23.8
c
251
240
c
251
19 2
C
70
503
c
70
48.4
c
344
24.4
c
577
218
c
h03
24 7
c
362
24 X
C
702
52.0 50.3
c
351
C
351
51.0
c
344
Othercarbons: 312 Sarac: 164.8 127.4 146.9 15.9 65.3 170.6 21.1 Ac: 171.4 20.9: 373 Samc: 165 3 127.3 147.6 16.0 66.2 171.8 21.0 Ac: 172.3 20.9; 374 Sarac: 164.4 127.4 145.6 15.8 64.9 170.2 20‘) 21Ar 169.9 20.7 168.4 20.6; 375 Sac 165.6 131.1 143.5 15.9 61.5 Ac: 172.2 20.9; 376 A~lg-l-OAc. 165 7 128.1 139.9 63.0 19.9 171.9 20.9 Ac: 170.8 20.9: 377 Sarac: 164.5 126.8 147.2 16.0 66.9 170.X 21.1 Ac: 170.7 20.7; 378 Ang: 166.8 126.9 140.5 15.8 20.4; 319 2xA1tg: 165.9 125.8 142.8 16.0 20.4 I65 9 125.8 142.8 16.0 20.4; 380 Mebu: 175.3 40.7 26.5 11.6 16.4 Ang: 167.1 126.7 140.3 15.9 20.4, 3x1 Arts: 167.0 126.4 141.2 15.9 20.2; 382 Ang: 166.6 128.2 139.4 15.8 20.3; 383 Mac: 166.3 135.1 126.1) 18.0; 384 rig: 167.0 127.7 139.3 14.5 12.0: 386 C16-CI9: 133.7 144.1 13.3 167.2 Mac-4-OAc: 163.7 136.1 125.5 61.9 170.2 20.8 387 CI6-CZ9: 136.4 142.1 24.8 169.0 Mac-4-OH: 164.1 136.4 126.1 61.5: 3889 OMe: 52.5 Sac 165.2 131.0 142.4 15.6 64.5 iBsr: 176.7 33.9 19.0 18.9; 388b OMe: 52.4 Sar. 164.7 130.9 142.4 15.5 64.3 <Bur: 175.7 33.9 18.6 18.5; 389 Mac: 166.0 135.0 127.5 18.1
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table ll.---continued -
ac
\
HO
6-co
AcOH,C P2
D'
372
AC
373
H
Ac
374
Ac
Ac
379
R = Ang
380
R = Mebu
375
R = Sar
376
R = Am-4-OAc
0
AcOH2C
381
6-CO 377
370
382
383
OH 385
384
H,COOC<
.
.p
u t
CHO
OMac
OH
389
386
R = Moc-4-OAc
387
R = Mac-4-OH
311
312
M. BUDESINSKY AND D. SAMAN
Table 12. Carbon-13 chemical shifts of germacran-12,6-olides(type 11-methyl). No 390 a h 3Y1 392 a h 3Y3 3Y4 3Y5 3Y6
397 3YX 39Y 400
401
402 a
h 403 404 a
h c
4ll? 406
Mol formula C-l C-2 C20H2804 1297 25.9 129 5 25.6 C20H2804 125.9 25.2 C22H3006 128.7 26.1 128.5 26.6 CISH2203 125 2 35.3 C I 7112404 125.9 32.0 C2IH3208 125.3 33 6 CISH2203 I29 2 25.5 Cl7H2404 129.9 25.4 CISH2204 127.2b 25.4 CISH2202 126.8 25.9 CIStI2204 124.8 38.2 ClSH2203 1293 2 5 5 CIin2404 131 3 25.4 131 3 25.3 C21H3208 132.0 26.1 C15H2204 127 5 34.6 1277 35.7 1252 35.7 (‘211/1209 127 X 35.6 C21H1209
1271 33.1 407 (‘19112606 1279 31.1 4OX C2IH3208 a 126.9 28.Zb h 1268 28 I JOY CIS112204 128.6 26.1 4111 C19H2606 129 4 26.1 411 C19H2606 12‘1 3 26.5 412 Clit12406 127.5 25.5 413 C19H2607 127.7 25.6 414 C25111409 1277
25.8
Name I Chemical shifts C-3
C-4 C-5 C-6 C-7 C-8 C-9 C-10 11PH-Germacra-1(lO)E,4Edien-12,6P-olide 39.5 138.4 124.1 75.3 51.6 73.2 43.8 133.3 39.5 138.4 123.2 75.5 51.4 72.2 43.7 133.0 Laserolide, 8-desacetoxy 39.9 140.8 122.7 76.2 44.9 27.4 35.8 138.5 Laserolide 39,7143.3123.5 74.1 47.5 74.1 42,2134.7 39.4 143.0 122.1 73.5 46.8 73.5 41.9 133.6 I 1 pH-Germacra-l(lO)E.4Edien-1Z,Q-olide, 78.2 141.6 124.3 81.0 54.5 28.5 41.2 137.5
C - l l C-12 c-13 C-14 c-15
Sol. Ref.
39.0 178.0 38.6 178.3
17.0 17.0
17.2 20.4 17.0 20.9
B 32 C 32.33
80.8 175.1
19.7
17.1 20.6
80.3174.4 20.1 17.5 21.0 79.4 174.3 19.7 17.4 20.9 3p-hydroxy 41.8 178.2 13.2 16.8 11.7 llpH-Germacra-l(lO)E,4Edien-12,6a-olide, 3p-acetoxy 79.1 138.7 123.9 80.4 54.3 28.4 41.0 137.5 42.0 178.2 13.2 16.3 12.3 Sonehuside A 83.5 140.8 127.4 80.7 54.4 28.6 41.3 137.8 42.3 178.5 13.5 16.3 12.3 Balchanolide 38.8 133.3 128.2 77.7 59.9 72.3 53.0 140.6 40.9 179.7 17.2 17.7 17 4 Balchanolide, acetate 38.7 132.4 127.7 77.7 58.0 73.3 49.3 141.1 40.5 178.2 17.0 16.8 17 3 Drostenophyllolide, dihydro 34.6‘ 141.8 127.7b 78.5‘ 51.0 35.9’ 78.8‘ 139.1 41.2 177.6 12.5 10.0 597 Costunolide, llaH,l3-dihydro 39.3b 139.4 127.6 80.7 49.3 25.2 40.9b 136.8 40.9 179.7 10.7 15.9 17.0 Shonacalin S 73.9 138.5 128.7 77.3 55.3 25.3 35.2 139.3 41.8 179.3 16.5 17.3 69.3 Herbolide A, desacetyl 39.4 140.1 127.2 80.9 51.5 36.5 79.6 138.9 42.0 178.2 13.3 107 17 3 Herbolide A 39.3 140.4 127.0 81.0 51.4 34.2 80.8 134.8 42.0 177.9 13.3 11 5 17.3 39.2 140.3 126.9 80.9 51.3 34.2 80.7 134.6 42.0 177.7 13.2 11.4 17.2 Plucheoside A 39.6 140.2 128.0 81.1 51.6 35.4 83.6 137.0 42.3 178.6 13.4 11.3 17.3 Balchanolide, 3p-hydroxy = Cichorioside C aglycone 77.7 142.2 124.9 77.2 59.7 72.2 53.0 134.0 40.6 179.5 17.7 17 4 120 77.Sb143.7 125.2 77.7b 60.3 71.6 53.4 136.8 41.2 179.7 18.3 17.2 122 77.7b 143.4 127.7 77.Sb 60.4 71 6 53.5 134.6 41.2 179.7 17.3’ 18.3‘ 12.4 Hypochwroside A 77.4 143.9 125.3 79.3 60.5 81.6 51.6 134.2 40.4 179.9 18.5 17.3 12.4 Cichorioside C X 3 I 141.0 128.3 77.6 60.5 71.7 53.6 135.2 41.2 1799 18.4b 17.Sb 12 7 Sintenin 78.5 137.3b 125.6 79.3 45.7 31.3 80.5 136.4b 40.4 178.7 10.9 11.6 12.4 Ixerin H 36.0 140.1 130.5 79.8 54.9 27.0b 41.3 137.5 42.2 178.4 13.4 16 3 67 7 359139.9130.3 79.6 54.8 269 41.1137.3 42.0178.1 13.3 16.1 67.6 Salonitenolide , 1lDJ3-dihydro 34.9 142.7 129.5 76.4 60.1 72.0 52.9 133.9 40.8 1799 17.6 17.1 61 I Sulonitenolide, diacetate, llf3,13-dihydro 35.0 138.0 131.6 76.1 58.2 72.9 49.1 132.9 40.3 177 7 17.0 168 61.6 Salonitenolide, diacetate, lla.13-dihydro 35.3 137.1 130.8 75.0 53.4 70.7 47.5 133.4 39.6 178.1 10.6 16.6 61.7 Tulipinolide, epi , llp,l3-dihydroxy 38.8 141.2 131.0 74.9 58.1 70.0 43.7 132.3 77.3 175.4 44.1 18.9 16.6 Tulipinolide, epi, llp-hydroxy-13-acetoxy 38.8 141.5 131.4 74.8 53.6 69.4 42.1 132.2 82.0 170.5 44.8 19.2 16.X Germacra-l(1O)E 4E-dien-12 6a-olide 8~-(4’,S’-dihydro~ytigloyloxy\-lla-h~droxy-l3-(S’-hydroxytigluyloxy~ 39.1 141.7 131.3 74.8 58.0 71.3 44.0 132.5 76.1 176.2 63.8 19.1 I69
c
599
A
126
c 321.599
c
54
c
54
P
441
C
415
C
415
c
132
c
564
C
SXX
c
5x7
c c
5x7 645
P
645
C+M 4 I I I’ J‘)O I’
iYl
I’
490
I’
501
c‘
272
I’ I’
590 40
C+M 414
c
414
C
414
C
216
C
216
C
2‘Xl
313
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 12.-continued OthCrcahns: 3Wa Ang: 166.5 127.8 138.9 16.0 20.9; 390b Ang: 166.4 127.3 138.8 15.7 20.4; 391 AQ: 166.4 126.8 140.2 15.8 20.2; 392s Ang: 166.6 139.8 127.8 15.9 20.4 Ac: 170.3 21.3; 3921, Alig: 166.4 126.6 140.7 15.9 20.2 Ac: 170.0 21.2: 394 Ac: 170.0 21.0; 395 Glc: 102.8 75.3 78.5 72 0 78.5 63.0; 397 AC: 169.9 21.2; 402a AC: 169.9 21.3; 4n2b AC: 169.8 21.2; 403 G/C: 100.0 75.1 78.8 72.1 78 5 63 I ; 411s Glc: 105.3 75.3 78.6 71.8 78.6 62.9; 406 Glc: 102.8 75.4 78.672.0 78.6 63.0; 407 2xAc: 169 9 21 2 169.8 21.0; 408a Glc: a ; 408b Glc: 105.0 75.0 78.3 71.6 78.2 62.8; 410 2xAc: 170.7 21.2 165, X 21 0. 411 2xAc: 170.7 21.2 169.8 20.9; 412 Ac: 169.7 21.1; 413 2xAc: 169.9 21.0 1690 21.2; 414 7ig-S-f/// 166.6 131 2 144.1 14.6 55.7 Tig-4.5-OH: 165.4 131.0 145.6 58.5 56.5
RRz R
%OR
0 - c oS
O
..,,,,
0-co
0-co
R'
R2
393
R = H
396
R = H
390
OAng
6-H
394
R = Ac
397
R = Ac
391
H
a-OAng
395
R = Glc
392
OAc
a-OAng
0-co
H
0-co
O
W
398
0 ..,,,,
R
1
0
R
o 0-c0 R 2
,
0-co
599
400
R = CH,OH
401
R = H
R'
R2
402
R = Ac
404
H
C
403
R = Glc
405
ti
Glc
406
Glc
t-
AcO
407
R'
R2
410
R = u-CH,
408
Glc
H
411
R
409
H
OH
= 8-CH,
R'
R'
412 a-CH,OH
AC
413 a-CH,OAc
AC
414
Tig-4,b-OH
@-CH,OTiq-5-OH
314
M. BUDESINSKY AND D. SAMAN
Table 12.--continued Mol formula Name I Chemical shifLs C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C - l l C-I? C-I3 c'-I4 C - l i 415 C17H2205 Tulipinolide, epi, llP,l3-epoxy 127 3 25.9 39.2 142.6 131.1 74.7 58.1 69.6 43.7 133.4 57.3 172.7 50.7 1 x 9 17 I 416 CI9H2407 Tulipinolide, epi, 3P-acetoxy-llp,l3-epoxy 125.7 32.1 78.9 140.1 128.3 73.7 49.2 69.5 43.6 135.3 57.1 172.3 5 0 9 1 9 2 1 2 5 417 CISHI803 Gerrnacra-l(10)E,4E,7(11)-trien-12,6~-olide, 8-oxo 133 9 23.8 37.5 140.9 123.4 77.8 161.1 197.9 54.8 124.4* 124.9b 172 7 9.2 16.2' 15 X' 41X C2OH2604 Torilolide 133.7 25 0 35.4 138.3 125.1 80.8 125.9 38.0 26.2 134.0 163.6 174.6 8.8 60 2 16 5 419 CISH2203 4-Z-Hanphyllin, IlaH,l3-dihydro 121.6 31.9 76.7 140.1 126.1 81.4 45.2 24.8 40.2 137.9 36.7 179 6 10'1 17 5 2 7 3 420 CI7H220.5 Heliangolidin 119.4 41.4 201.3 140.7 125.5 78.4 53.7 72.6 46.6 136.8 38.1 178 4 In') I 6 X I'J 7 421 CISH2204 Ixerin K 126.2 26.3 34.7 142.4 128.5 80.4 42.8 27.0 24.8 141.4 50.6 181 5 13 0 6 6 4 60 X 422 CISH2203 Soulangianolide A, 11J3-dihydro 125 4' 26.4' 38.5 141.1 125.7b 80.8 49.2 23.9' 24.7' 137.1 41 R 179 I 12.9 660 17 I 423 CISH2204 7aH,1I~H-Germacra-1(1O)E,4E-dien-l2,6a-olide, Ra,lQ-dihydroxy 128.6 35.1' 25.2' 138.6' 124.6 77.3 55.1 73.7 38.0b 139.0' 41.7 179 5 16.4 69.1 17 2 424 C2IH3009 Ixerin J 153.1 25.2 33.5 136.9 1303 79.2 41.4 270 22.4 145.3 49 8 178 5 12 7 I 9 5 0 67 7 425 C I j H 2 0 0 4 Ixerin A 153.0 27.0 32.7 138 8 129.2 7X.8 39.7 22 I * 22.4b 145.2 44 7 179 9 106 1960 60 A 426 CISH2005 Urospermal A, llp,l3-dihydro 159.5 27.7 32.7 140.6 127.5 75.9 55 9 71.3 33.1 144.5 41.2 179 4 I6 7 I99 5 60 X 427 C21H2009C16 Urosperrnal A, IlpJ3-dihydro + TAI 153 5 27.8 32.5 135.3 130.0 75.5 48.6 74.6 28.3 143.0 41.3 a 17.6 194.2 64 X 7aH,11pH-Gerrnacra-1(1O)E,4E-dien-l2,6a-nlide,Sa-hydroxy-14-oxti 428 CISH2004 159.3 33.3b 26.7b 137.1'125.9 77.1 56.0 71.8 36.Yb 144.9' 41.3 179.0 16.4 199.0 17 2 Lxerin L 429 CISH2204 126.0 26.3 34.7 142.6 128.9 80.7 41.1 23.5 24.9 141.0 45.4 1x26 1 0 9 6 6 2 6 0 7 430 ClSH2004 Lactulide A 151.1 36.0 74.8 139.8 123.7 80.6 49.6 22 4 25.6 145 5 41 5 17X 6 I ? X 195 7 I I I 431 C21H3009 Lactuside A a 150.2 33.0 79.9 137.0 127.1 80.3 49.5 22.5 25 5 145 7 41 4 178.6 12 9 195 X I I 3 h 150.1 32.9 79.8 136.8 127.0 80.2 49 5 22.4 25.5 145.6 41.3 17X 5 12.X 195 6 I I 2 432 CZIH3009 Lactuside B 127.4 32.8 83.3 140.6 126.7 80.8 54.5 29.0 36.8 142.1 42.3 178.4 13.3 58.6 I I 6 433 CISH2204 11~H-Gerrnacra-l(10)E,4E-dien-12,6a-olide, ZP,14-dihydroxy 127.5 35.7 78.0 143.4 124.6 81.2 54.6 29.0 36.8 141.8 42.4 178.6 13.4 58 6 1 I 7 434 CI7H2205 Il~H-GerrnacradE,10(14)-dien-12,6~-nlide, 8a-acetoxy-1-oxo 197.2 38.gb 38.4b 141.3 121.6 74.8 51.4 69.9 35.0b146.3 38.4 177.8 16 8 123.1 I h i 435 C20H2605 11~H-Gerrnacra-4E,10(14)-dien-12,6~-olide, Sa-angeloyloxy-1-(1x1) 197.2 38.8 38.4 141.3 121.6 74.8 51.4 69.9 35.0 146.3 38.4 177.X 1 6 8 123 I 16 i 436 CISH2203 Gallicin it 80.4 32.8 36.2 1446 1230 78.0 53.4 27 1 32.8 151.5 41 9 178 7 12 5 I10 3 17 S h 7X.2 33.0b 31.2b 144.5 123.1 80.4 52 5 27.3 36 3b 151 8 42 I 1784 12.8 110.3 I 7 '1 c 8 0 5 31.2b 36.3 144.7 122.9 78.2 52.3 27.2 32.@ 151.6 42.0 ,1787 12.8 110.4 17.41 437 CISH2004 Costunolide, peroxy, dihydro 91.5 35.0b 28.2' 148.2 123.3 80.6 54.0 29.0' 37.4b 145.3 42.0 178.7 12.9 112.4 17 4 438 C15H2204 Herbolide D, desacetyl 76.8 3 3 2 37.9 146.5 121.7 80.3 51.6 37.5 76.6 155.7 41.7 178.5 12.8 1 1 1 3 1x0 Herbnlide D 439 C17H2405 a 74.8 31.4 37.8 145.5 121.7 80.4 51.5 37.0 79.3 153.7 41.9 177.7 12 X 114 7 I7 X h 74.8 31.4 3 7 . 8 1 4 5 . 5 1 2 1 7 8 0 4 5 1 5 3 7 0 7 9 3 1 5 3 7 4 1 9 1 7 7 7 1 2 . 8 1 1 4 7 1 7 X 440 CIYf12606 Herbnlide D, acetate 77.2 31.0 37.0 146.1 122.1 80.0 51.6 35 2 76.5 147.6 41 6 178.0 12 7 1 1 7 0 I X I
Yo
I l'i
(
hl -lI).-l? c'
1x7
('
$72
I' I'
J73
I'
473
I'
473
c'
327
i?
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
315
Table 12.-continued No
441
442 a b 443
Mol formula
Name / Chermcal shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 CISH2203 Herbolide H 33.0 24.8 36.4 144.4 123.1 79.8 48.0 C17H2404 Gallicin, acetate 79.4 30.1b 35.5 143.6 122.1 78.0 52.1 79.0 3 U b 32.6b 144.4 123.3 80.4 53.2 C15H2204 Herbolide F a a 15.4b a 122.9 79.9 48.5
C-8 40.1
C-9 C-10 C-ll C-12 C-I3 C-I4 C-15
a
151.9 40.1 179.7
Ref
10.5 110.2 17.5
C
586
26.3 28.7b146.8 40.9 177.5 11.7 111.5 16.8 27.4 36Sb 148.0 42.0 178.3 12.8 112.5 17.8
C C
72 563
A
585
42.7 75.qb 152.0 40.7 179.9
11.8 110.6
10.6
Oihercarbons: 415 Ac: 169.9 21.1: 416 ZxAc: 169.6 21.1 170.2 21.2; 418 Ang: 167.8 127.5 138.6 15 X 20.6: 420 Ac: 169.9 21.1: 424 Glc: 105.1 75.0 78.5 71.6 78.5 62.7; 431a Glc: 102.2 75.1 78.6 71.8 78 6 62.9; 431b Glc: 101.9 74.9 78.2 71.6 78.2 62.7; 432 Glc: 102.5 75.0 78.2 71.7 78.1 62.8; 434 Ac: a ; 435 Ang: 1664 127.3 138.8 15.7 20.4; 43911 Ac: a ; 439b Ac: 171.9 21.4; 440 Ac: 170.1 21.1 169.9 21.1; 442a Ac: 169.1 20.2; 442b Ac: 170.0 21.2
HO
415 416
R
-
0-co 418
417
H
R = CH20Ang
419
R = OAc
cn20n
Q-
HW2C
R'
420
R'O
R'
0-CO
429 424 425 426 427
OGIC
n
OH
H
on
on
428
n
OTAC OTAC
on
@
430 431 432 433
6 - c o...*,,,
R'
R'
n
CHO
Glc
CHO
GIC
cn,oti cn,on
n
434 431
R = Ac
R'
R'
OH
n n on
~~
R = Ang
436
437 OOH 438 on 439 OH 440 OAc 441 n 442 OAc
OAc OAc OH
H
443
316
M. BUDESINSKY AND D. SAMAN
Table 12.-continued No. ~~~~
444 445 446 447 448
449 450 451 452 453 454 455 456 457 a b
458 459 460 461 462 463 464
465 466 467 468 a
h 469 470
Mol. formula C-l C-2 CISH2004 203.8 37.1 C15H2204 78.2 32.8 C17H2405 78.0 33.1 C19H2606 78.7 31.4 C15H2205 91.5 28.4 C17H2206 75.2 36.6 CI7H2206 75.2 37.0 C19H2407 75.1 37.0 C17H2006 198.4 44.2 C17H2006 198.4 44.1 C19H2207 198.2 44.2 CISH2204 73.3 39.3 CISH2205 86 1 34.5 CI5H2203 125.0 24.0 125.1 24.0b CISH2204 126.3 23.8 CI 7H2406 131.0 66.6 C20H2806 125.1 33.0 C20H2807 130.6 72.6 C17H2504N 125.1 24.1 CI 7H2505N 127.3 24.4 C23H2809 129.2 71.7 C21H2608 129.0 68.6 CI 5H2204 65.0 33.6 C17H2405 65.3 23.0 C19H2607 62.4 28.6 62.6 28.8 ClSH2204 67.0 27.8 C19H2606 69.0b 25.0
C-3
Name / Chemical shifts C-4 C-5 C-6 C-7
C-8
C-9
C-10 C-11 C-12 C-13 C-14 C-I5
sol. kl.
Shonachalin A, I-dehydro
57.7 72.0 41.2 146.8 40.3 178.7 16.4 123.9 17.1
C
569
57.7 73.7 42.7148.1
17.8
c
565,
39.9 147.8 41.1 177.8 15.6 112.1 17.9
C
415
c
415
17.5
c
415
77.2 141.3 125.2 79.7 164.2 23.8 33.9 147.9 127.1 173.8 55.1 113.1 1 1 7 Afraglaucolide, 13-0-desacetyl-1~-hydroxy 77.2 137.5 123.7 79.5 163.7 24.2 26.2 149.4 127.1 173.6 54.7 114.9 11.4 Achillolide B 74.8 137.9 123.1 79.2 167.7 27.0 24.5 149.5 123.2 172.2 54.8 114.1 11.2
C
376
c
376
C'
5x1
35.9 141.6 126.1 77.0 Shonachalin A
36.1145.6122.4
76.6
41.8178.9
16.2111.7
Shonachalin A, 8-acetate
36.1 146.1 121.9 76.6
55.7 75.0
Shonachalin A, diacetate
36.6 146.0 122.1 76.6 56.6 75.0 42.2 144.2 41.1 177.6 15.6 114.3
17.7
IlpH-GermacradE,lW14)-dien-12,6a-olide, 1p-hydroperoxy-8a-hydroxy 37.0 143.5 122.3 76.3
58.8 74.2 41.8 146.1 41.8 178.7
16.4 113.9
Afraglaucolide, 13-0-desacetyl-la-hydroxy
Afraglaucolide, 13-0-desacetyl-I-0x0
75.5 136.3 127.0 79.5 164.9 23.4 33.6 148.2 I27 5 169.9 55.0 125.2 10.8 Achillolide A 75.5 136.2 126.9 79.3 165.4 33.4 23.4 148.2 127.5 173.8 54.5 125.3 10.6
c
I
C
sx4
c
sx4
c
413
<'
413
Achillolide A, acetate
75.5 136.7 126.6 19.3 167.9 33.4 23.7 148.3 124.0 172.3 55.5 125.1 10.8 7aH,llaH-Germacra-4Z,lO(l4)-dien-l2,6a-olide, Ip,3p-dihydroxy 71.0 142.3 124.8 78.5 42.1 27.3 29.2 149.7 37.5 179.4 10 3 115.2 22 7 7aH,11aH-Germacra-4Z,10(14)-dien-12,6a-olide, 3j3-hydroxy-lP-hydroper~ixy 71.4 142.2 125.4 78.4 43.2 27.7 31.3 144.8. 37.6 179.5 10.6 118.8 22.8 Parthenolide, 11,13-dihydro
36.6 61.3 66.3 82.0 51.8 29.7 41.0 134.4 42.3 177.2 13.1 16.7 17.0 36.6b 61.4 66.3 82.1 51.9 29.7b 41.1 134.4 42.4 179.9 13.2 17.1 I6 8 Parthenolide, 11,13-dihydro-Ya-hydroxy 36.9 61.3 66.1 81.3 48.5 37.8 79.6 136.5 42.1 176.9 13.2 10.9 17.3
c' C
506 5 3'1
C
5 38
C
53X
Paramicholide
45.1
60.6
66.6 78.6
55.4 72.1 49.3 131.0 39.6 176.8 18.3b 18.Zb 17.0
Euperfolin
64.9 65.1 77.0 76.2 47.4
19.7
12.2
I)
2xx
72.8 44.1 133.3 40.9 178.5 12.0 20.5
12.8
1)
2xx
40.9 134.6 48.6 176.6 36.6k 17.2' 16.9'
C
537
C
i17
C
3iO
C
350
C'
54
c'
5x1
c' c'
440
C
415
72.0 43.5 133.2 40.3 178.3 1 1 . 1
Euperfolitin
65.6 64.2
83.0 77.5 47.9
Parthenolidine, N-acetyl
36.3b 61.7
66.2 82.9 46.6 29.8
Parthenolidine, N-acetyl, 8a-hydroxy
35.8 61.9 66.0 78.9
51.5 72.3 52.4 130.3 46.8 177.0 39.6 17.5* 17.3'
Glaucolide E, 2-epi
42.7
59.1
63.2
Rolandrolide,
82.3 163.8 68.5 40.5 131.0 128.2 170.7 55.2
19.5 21 I
is0
51.2
72.8 133.3 143.7 150.3 69.8 44.3 135.4 125.6 169 0 54.7 21.2 28.X IlpH-Germacr-4E-en-lZ,6a-olide, lp,lOa-epoxy-3p-hydroxy 74.4 145.7 121.7 80.1 55.0 26.0 39.6 61.2 41.2 178.1 13.0 17.1 12 2 Herbolide B 36.1 142.7 124.1 80.7 51.1 33.0 80.0 61.3 42.4 177.5 12.8 12.8 17.4 Micranthin
75.2 140.9 123.0 78.5 45.4 75.3 141.0 123.2 78.6 45.5
30.3 80.1 61.1 40.2 178.2 10.5 12.6 12.5 30.4 80.2 61.2 40.3 178.3 10.6 12.7 12 6
,-,. _
7aH,11pH-Gerrnacra-4E,YZ-dien-l2,6a-olide, la,&-dihydroxy 35.2 142.6 124.3 78.6 58.0 67.0 133.2 136.3 40.6 179.2 15.8 16.9 16.5 7aH,11~H-GermacmdE,9Z-dien-12,6a-olide, la,8a-diacetoxy 35.0 143.2 124.0 78.1 56.9 68.9b 130.3 134.3 40.3 178.0 15.3 17.9 16.7
C
415 .__
317
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 12.-continued NII.
Name / Chemical shifts
Mol. formula
C - l C-2 471 CI9H2206 218.5 39.4 472 C2IH2809 217.9 37.7 473 C2OH2605 66.5 21.9
C-3
C-4
C-5
C-6
C-7
C-8
C-9
C-10 C-11 C-12 C-13 C-14 C-15
sol. Ref.
Vernopappdide, 8-methylacrylate 32.9 142.7 122.0
79.3 162.7 72.3
76.6 48.5 126.4 166.7
56.1
20.2
13.9
C
362
29.7 142.8 128.5 112.2 168.4 74.3 76.2 47.0 126.1 160.0 55.4
17.1
14.7
C
362
63.3
16.9
C 336'
Verwpapplide, 6f3-hydroxy-8-nethylacrylate Toriolide, oxy 32.9 139.6 122.8
80.0 125.4 36.2
23.5
60.9 162.7 174.4
8.6
Other carbons: 446 Ac: 169.6 20.9; 447 2xAc: 169.9 20.9 169.6 20.9; 449 Ac: 169.9 21.1; 450 Ac: 169.X 21.1: 451 Ac: 170.5 20.9 169.7 20.5; 452 Ac: 173.9 21.0 453 Ac: 169.8 2J3.8; 454 2xAc: 170.5 21.0 169.7 20.8: 459 Ac: a ; 460 Tig: 166.3 128.3 138.8 14.5 11.8; 461 Tig: 166.8 129.1 139.3 14.5 12.3; 462 Ac: 170.7 23.2; 463 Ac: 173.2 22.9; 464 Mac: 166.2 135.0 127.4 18.0 2xAc: 170.2 20.9 170.0 20.7; 465 Mac: 166.4 135.3 127.4 18.4 Ac: 170.3 20.1; 467 Ac: 170.1 21.1; 468p 2xAc: 169.9 21.1 169.6 20.8; 468b 2xAc: 170.0 20.9 169.7 21.5; 470 2xAc: 170.0 21.2 169.8 21.0; 471 Mac: 169.9 126.0 136.2 18.0 Ac: a : 472 Mac: 168.7 135.2 128.4 17.9 Ac: 169.9 20.6: 473 Ang: 167.5 127.1 139.6 15.9 20.5
0-co R'
R'
449
R = a-OH:
8-H
453
R = H
445
H
H
4x)
R = P-OH:
a-H
454
R = AC
446
ti
Ac
451
R = a-OAc;
447
Ac
Ac
452
R = 0
448
OH
H
R'
R2
R'
462
R = H
459
OH
H
a-OAc
463
R = OH
460
H
OH
OTig
461
OH
OH
OTig
444
HO
P-H
Jr"'%o co ~
455
R = H
457
R = H
456
R = OH
458
R = OH
OAc
....,,
0-co 464
468
465
466
469
R = H
471
R = H
470
R = Ac
472
R = OH
467
473
R = CH20Aq
318
M.BUDESINSKY AND D. SAMAN
Vernncistifolide, 9-desacetoxy-14-0-(4'-hydroxyseneci1~yl~ 54.1 59.3 63.3 79.6 159.3 69.9 31.6 136.4 125.6 171.2 54.9 66.8 166 Vernncistifolide, 14-0-acetyl-8-0-methacryloyl 53.7 58.9 62.2 79.6 160.1 70.0 66.2 135.4 125.3 170.6 54 6 62 7 I 6 6 Vernncistifolide, 8-O-methacryloyl-14-~-sencci~~yl 53.8 59.0 62.0 79.7 160.4 70.1 66.3 135.9 125 3 170 7 54.X 62 4 I6 7 Vernncistifolide, 8-O-angeloyl-14-O-senecioyl 53.8 59.0 62.1 79.7 160.8 69.6 66.4 135.9 125.5 17119 54.8 62.4 1 6 7 Vernncistifolide, 8-O-epoxymethacryloyl-l4-~-~ne~inyI 53.8 59.0 62.3 79.6 159.6 70.5 65.9 135.5 126.1 170.5 5 4 9 62 I1 I6 7 Vernocistifolide, 8-O-angeloyl-14-O-(4'-hydroxysenecinyl) 53.8 59.0 62.1 79.7 159.7 69.6 66.2 135.5 125.7 170.9 54.6 62.1 16.6 Vernncistifolide, 8-O-epoxymethacryloyl-l4-O-(4'-hydroxysenecioyl~ 53.7 59.0 62.2 79.6 158.8 70.5 65.9 135.0 125.9 170.5 54.8 62.6 16.7 Rolandrolide, acetoxy 46 4 70 8 128 7 150.6 147.5 68.6 37.1 133.9 127.4 167 2 55.2 27 I 2') i Vcrnonallenolide, 5,6-dehydr~1-4,5-dihydro-4a-hydriix) 407 73.7 131.0 146.4 152 4 6X.I 37 7 94.5 12X 2 169 7 55 6 I9 i 27 7 Vernonallennlide, 4,5-dihydra-4a,5B-epoxy 35 2 61 6 61.2 82.8 163.5 67.5 36.5 95.3 127.5 171 I 5 3 0 18.2 21 7 4x4 C I S H Z O O ~ Punctaliatrin, 15-deoxy-11~H,13-dihydro 60 5 131.7 128.5 135.4 127.4 77.0 54.2 73.8 46.4 62.1 42.7 I804 I X 7 20 3 7 4 0 485 CZOH2307CI Germacra-2Z,4Z-dien-l2,6a-nlide 1~,lOa-cpoxy-lla-hydroxy-13-eh~oro-8~-(5'-hydrox~.tigl~~yloxy) 5 9 9 131.5 128.6 135.1 126.6 76.9 52.8 70.6 40.9 60.6 75.3 1740 4 5 4 2 3 6 2 3 6 486 CISHI805 11~H-Germacr-4Z-en-12,6aa-olide, I~,lOa;2a,3a-diepoxy-~~oxo 61 5 55.9 50.3 134.3 126.6 75.5 59.8 203.2 55.2 56.3 3 6 0 1779 17.5 17 3 ? I 7 487 CISH2005 Eleganin, 15-deoxy-11,13-dihydro 60.9 55.9 53.6 131.1 127.6 75.6 51.8 7 0 5 44X 57.5 4 1 0 1795 17X 2 0 1 21 I 488 Cl9H2206 Eremantholide A 205.5 104.7 187.4 130.6 135.1 81.8 64.1 7X 2 44.2 90.2 61 1 175 6 20 i 21 7 2 0 2 489 CZOH2406 Eremantholide IS 205.5 104.4 186.8 130.0 134.7 81.3 63 7 77.6 43 9 90.0 6 0 4 174 2 20.5 21 2 2 0 3 490 C2OH2207 Atripliciolide, 8P-O-angelate-ll,13-dihydro-lla,l3-epexy 205 4 104.0 1847 132.7 134.1 78.8 47.5 71.1 41.7 87.4 59.6 172 0 50.0 21.9 20 5 491 C2OH2208 Atripliciolide, 8P-O-angelate-l1,13-dihydro-lla,lJ-epox~-15-hydroxy 205 2 104.7 182.4 138.4 133.5 75.3 46.9 70.4 41.8 87.8 135.9 172.3 49.9 20.7 62 I 492 CISHZOOS Parthenolide , peroxy, dihydro 91.2 25.7b 27.9b 60.6 640 80.2 47.8 26.3' 34.6b 145.5 42.0 178 4 12.9 117.7 18 2 493 CISH2003 Il~H-Germacrd-3Z,1l1(14)-dien-lZ,~-olide, Ip.5P-epoxy 72.0 34.4 122.2 131.2 73.4 85.0 42.6b 25.7' 26.7' 150.4 42.9b 177 9 I 7 9 114.2 ? I 2 494 C 2 l f R 4 0 9 Vernncinerolide, R-(4'-hydroxymethacrylate) 57 2 56.0 4 4 4 58.1 65.0 80.5 162.7 67.4 35.8 138.4 127.6 165 2 55 I 118 0 I X 5 495 C2lHIOOX Arucanolide, lISHJ3-tetrahydro 79 4 123.2 136.0 28.7 38.9 78.2 34.5 69.9 74.6 76.0 37.8 179.0 8.8 26.7 21 X
474 C27H12011 I22 7 6 0 6 475 CZSHZXOl2 126 7 60.7 476 C261132012 126.4 60.8 477 C2YH.14012 126.5 60.8 478 C2Xlf32013 126.9 60.8 479 C2YH34013 126.1 60.6 480 C2XH32014 127.9 60.7 4x1 C23i126OY I ? X X 68 3 482 C19112207 ?(XI 2 87.8 4x3 CIYH2207 204.0 88.5
496 C15H2204
4~H,ll~H-Germacran-lZ,6a-nlide, 3a,SP-dihydroxy-3~,1UP-epuxy
38.5 33.3 110.2 35.5 37.8 80.0 60.0 69.4 47.1 78.5 42.9 178.7 13.6 28.5 1 5 6 497 C19H2406 (4S,6R,7S,8S,10R,llS,l6R)-Eremantholide C, 4.5-dihydro 205.8 105.1 192.6 33.4 44.0 81.5 66.4 76.9 42.3 90.4 60.2 175.8 22.6 21.0 18.9' (4S,6R,7S,8S,10R,11S,16R,17R)-Eremantholide C, 4,5-dih?.dr~1-17,1 X-epoxy 498 C19H2407 205 X 105.1 192.5 33.2 43.6 81.6 67 1 76.5 42 2 90.2 60.0h 175.0 21 3 20.9 I X 5.
c' c'
I'
I00
c'
241
c
340
c'
203
c
5x0
c
659
C'
659
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
319
Table 12.--continued Other carbons: 474Ang: 166.2 123.2 143.1 16.0 20.2 Ac: 170.2 20.7 Sen-l-OH(EJ: 165.8 112.4 163.5 66.X 15.6: 475 Mac: 165.5 134.8 128.0 17.9 3xAc: 169.0 20.4 170.1 20.4 170.2 20.5: 476 Moc: 165.6 134.9 127.7 17.9 Sen: 165.7 114.8 160.4 27.4 20.5 2xAc: 170.2 20.6 169.0 20.6: 477 Ang: 165.6 125.0 143.0 16.0 20.4 Sen: 165.7 114.7 158.9 27.5 20.6 2xAc: 170.2 20.3 169.0 20.2; 478 Mac-ep: 170.5 53 3 54.9 17.0 S e x 165.7 114.6 158.8 27.6 20.6 2xAc: 170.2 20.5 169.8 20.3; 479 Ang. 165.8 124.8 143.0 15 6 20.3 Se!r-l-OH(EJ: 165.7 111.9 160.8 66.5 15.9 2xAc: 170.1 20.5 169.3 20.2: 480 Mac-ep: 169.8 53.4 53.5 16.5 Sen-l-OH(EJ: 165.8 111.7 160.8 66.7 15.6 2xAc: 170.2 20.5 169.0 20.5; 481 Mac: 165.7 135.0 127.2 18.1 2xAc: 170.2 21.1 169.9 20.7; 482 2xAc: 169.3 20.3 170.1 20.6 483 2xAc: 169.9 20.3 170 I 20.6; 485 Tlg-S-OH: 165.1 132.2 142.0 14.3 54.0; 488 C16-Cl9: 108.3 32.7 17.1 16.8; 489 C16-CZO. 108.1 39.3 22.7 12.4 11.8: 490 Ang: 166.2 126.0 143.2 17.1 20.0; 491 Ang, 166.1 125.8 a 199 15 7: 494 Mac-4-OH: 170.4 135.8 127.7 61.8 Ac: 170.2 20.7; 495 Mac: 166.5 135.2 128.0 17.9 Ac: 169 7 20.4: 497 C16-Cl9: 106.4 142.2 115.8 18.5b 498 C16-C19 104.9 58.4b 53.6 17.3
R'
R'
R'
474
Ang
H
Sen-4-OH(E)
475
Mac
OAc Ac
476
Mac
OAc Sen
477
Ang
OAc Sen
478
Mac-ep
OAc
479
Ang
OAc Sen-4-OH(E)
480
Mac-ep
482
Sen
483
'CO
485
484
OAc Sen-l-OH(E)
R = 0
487
R = 0-H. @-OH
0-c0 "'
a
488
R = CH(CH,),
490
R =
489
R = CH(CH,)CH,CH,
491
R =
c-4-on
486
p)
OH
0~
CH,CI
n on
493
CH,OAc
0-co 494
0-co 495
496
497
R = C(CH,)=Cti,
320
M. BUDESINSKY AND D. SAMAN
Table 12.+ontinued No. 499 500
501 502
503 504
Mol. formula C-1 C-2 C25H28011 167.8 23.2 C25H30011 88.5 25.5 C25H3201I 90.5 25.8 C21H26010 206.9 33.0 C23H28010 207.1 33.3 C24H30010
C-3 38.5 33.0 33.0 32.9 32.5
Name I Chemical shifts C-4 C-5 C-6 C-7 C-8 Bothriolide 59.6 60.2 80.5 161.7 65.7 Brachycalyxolide 59.5 61.8 81.2 162.9 66.3 Brachycalyxolide, 16,l’l-dihydro 59.3 62.2 81.2 162.9 66.5 Glaucolide B 61.2 59.0 81.0 162.5 64.0 Glaucolide A 61.0 59.5 81.1 162.8 64.5
C-9 C-10 C-I1 C-12 C-13 C-14 C-15 42.7
85.5 124.8 170.4 61.6
20.8
18.8
c
IX
35.9
77.3 124.8 171.7
18.2
21.4
C
362
36.8
78.7 124.5 171.7 61.4
18.1 21.3
C
362
40.4
84.9 125.4 169.6
55.2
18.9
18.9
c
50
41.9
84.5 126.0 169.4 55.3
19 1
19 1
c
50
19.0
19.0
c
50
24.7
16.X
c
J?O
247
I6X
C
420
61.4
(4~5R,6S,8S,10R)-Germacr-7(1l)sn-12,6a-nlide, 10,13-diacetoxy4,5-epoxy-l-nxn-8-senecinylnxy
207.2 33.4 505 C2IH3008
32.5
80.5 29.6 506 C21H3008
38.3
80.5 29.6 507 C22H2808
38.3
Sol. Ref.
61.0 59.5 81.2 163.6 63.2 7pH-Germacran-12 6a-nliie,
41.9
64.5 59.1 61.5 47.0 65.2 7 H Germacran-12 6a-nlide
39.1
84.5 125.7 169.5
55.3
la-acetnxy-ll~H,13-dihydro-lOa-hydroxy-8a-methacrylnxy 72.6
37.5 176.9
9.6
l~-~etoxy-llpH,l~-dihydro)-l0a-hydroxy-8-methacrylnxy
508 509 510
511
512 513 514 515
516
517 518 519
520 521
522
64.5
59.1
61.5
47.0
65.2
39.1
72.6
37.5176.9
9.6
(lR,4R,5R,6S,8S,lOR)-Germacr-7(11)-en-lZ,6-nlide,
13-acetoxy-1(10),4(5)-die~xy-8-senecioyloxy 62.4 22.4 36.0 59.6 65.2 82.1 164.2 65.4 45.7 58.0 128.0 170.1 55.9 16.6h 17.2* c 50 C24H28011 no name 206.5b 55.5 197.0b a 62.4 80.2 162.ff 66.4 36.5 43.1 129.0 170.5 55.5 18.9 15.0 c 647 C24H30011 Glaucolide 211.9 48.6 72.9 55.8 61.0 81.2 164.8 67.6 37.9 41.9 127.9 167.8 62.6 12.0 21.3 A 100 C26H32012 Glaucolide, acetate 209.2 45.2 73.9 55.3 64.0 81.2 163.5 66.4 36.9 42.1 127.7 169.7 59.4 13.1 21 5 c 100 C24H28011 IOaH-Stilpnntnmentnlide, 8-(5’-acetnxysenecioate)-3-nxn c. 3-10 206.4 55.1197.1 63.3 62.2 79.9162.3 66.1 36.2 42.9128.3170.2 55.3 I4.X 189 C20H2607 Marginatin, 13-deacetyl-9,1~Z)-dehydrn-l,l0-dihydrn-la-hydrnxy c 316 66.8 28.7 32.6 55.4 59.5 80.1 156.4 65.7 122.6 145.3 128.7 172.8 66.4 17.7 I 6 7 C24H28010 Prevernncastifnlide, 14-0-acetyl-8-angelate c 362 59.9 124.7 134.9 57.2 64.1 80.0 162.1 66.2 34.6 60.7 124.2 170.7 54.8 67.3 I 9 0 C21H2608 Vernnpatcwlide, 8-methacrylatc C‘ 7-10 211 I 42.8 38.4 72.9 118.0 152.7 148.2 69.3 37.8 46.2 122.1 166.9 5 4 9 1 9 1 266 C21H3007 Hinutinolide, 1-desoxy-8a-hexannylnxy-10phydrnxy C 10-1 87.9 31.1 39.6 81.5 125.9 150.3 146.0 66.2 34.3 76.3 132.9 168 3 54.4 25 3 2 x 6 C25H3409 Gcrmacra-SZ,7(11)-dicn-12,6-nlide, 10~,13-diacctnxy-la,4a-epnxy-Xn-llrxano~I~1x~ a 251.5 C 104 87.5 29.5 38.4 82.4l24.2153.8148.3 65.9 43.2 83.71264167.0 C2IH2608 Hirsutinnlide, 13-O-acetate-8~-methacrylnyloxy 108.3 38.7b 38.0b 81.2 126.4 150.1 146.5 68.8 36.1 41.5 130.1 167.1 55.7 17 1 28 3 C X7 C21H2609 Piptncarphin A 108.5 32.0 37.4b 82.1 126.5 149.5 143.9 66.1 37.Yb 77.9 130.9 166.8 55.5 25.2 29 I C 117 C21H2808 Germacra-W,7(1 l)-dien-l2,,6olide l~lJaimethoxy-l~,4~spoxy-lOa~hydrox~8a-methacrylnyln~y 111.1 33.7 38.2 83.4 125.1 150.6 144.5 66.0 40.3 79.3 132.5 167.5 63.6 25.8 282 c‘ 420 C24H26010 1OaH-Germacra-1Z.SE 7(11)-trien-12,6-nlide 1,4~spoxy-13-acetoxy-~-oxo-8-(4’-Pcetoxy~e~ccinyloxy) 194.7 99.0 201.8 88.8 117.1 151.2 146.2 65.6 40.1 31.2 131.8 165.9 55.7 15.2 2 0 9 c‘ 3 1 X C20H2208 Hirsutnlide, 1,2-dehydrn-l -desuxy4a-(4’-hydroxy)methac 1qloyloxy-3-ox0, 13-mcthyl cthcr 194.5 97.9 202.1 87.0 116.9 145.5 150.1 65.9 40.3 31.1 135.3 166.6 63.7 15.6 1 9 X c‘ 6.11 C21H2209 Hinutolide, 1,2-dehydrn-l-desoxy-&r-(4’-hydrnxymethacrylnylnxy)~3-o~~1, I3-acctatt 194.5 98.2 201.9 87.0 118.0 145.5 149.9 65.7 40.1 31.2 132.9 166.0 55.5 15.5 2 0 0 C 611
321
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 12.-continued ~~
~
~
~~
Othercarbons: 499 CI6-C/9: 182.7 126.0 194.6 30.5 Muc-4-OH: 165.5 138.1 128.5 54.9 Ac: 170.6 20.7; 500 C / 6 - C / 9 : 134.0 142.0 167.7 14.2 Ac: 170.5 20.8 Moc-4-OH: 165.6 138.3 128.0 55.1; 501 CI6-CI9: 59.7 23.3 13.6 177.2 Act 170.5 20.8 Mac-4-OH: 165.6 138.3 128.0 55.1; 502 3xAc: 170.7 20.9 170.1 20.8 170.1 20.3; 503 Muc: 166.3 135.2 127.2 17.8 2xAc: 169.9 20.8 170.6 20.5; 504 Sen: 165.2 114.0 161.0 20.5 27.4 2xAc: 170.8 20.8 170.0 20.5; 505 Mac: 166.3 135.2 126.3 18.5 Ac: 170.6 21.0; 506 Mac. 166.3 135.2 126.3 18.5 Ac: 170.6 21.0; 507 Sen: 165.1 161.0 161.0 20.5 27.6 Ac: 170.6 20.7; 508 Srn-4-OAc: 164.0' 116.3 157.0 63.5 21.5 a 20.6 Ac: a 20.5; 509 Sen-4-OAc: 167.8 116.9 157.8 63.8 20.4 170.4 20.3 Ac: 170.7 20.4; 510 Sen-4-OAc: a ; Ac: a ;511 Sen-4-OAc: 164.3 115.6 157.7 21.5 63.4 170.5 20.6 Ac: 170.4 20.6; 512 Tig: 167.0 127.7 139.9 12.1 14.8; 513 Ang: 166.0 125.1 143.5 15.0 20.1 2 ~ 4 ~169.9 : 20.5 169.6 20.3; 514 Muc: 165.7 135.2 127.3 18.2 Ac: 170.3 20.7; 515 Hex: 1730 34.3 24.3 31.1 22.1 13.7; 516 Hex: 173.2 33.9 24.5 31.3 22.3 13.8 Ac: a ; 517 Muc: 167.0 136.3 126.5 1X.2 Ac: 170.1 20.7; 518 Mac: 165.7 135.6 127.2 17.9 Ac: 170.3 20.6; 519 Mac: 166.0 136.1 126.7 18.2 21OMe: 58.9 51.8; 520 Sen-4-OAc: 163.9 116.6 156.4 21.3 63.4 170.9 20.5 Ac: 169.8 20.4; 521 Mac-4-OH: 165.1 138.9 128.0 62.4 OMe: 59.0; 522 Mac-4-OH: 164.9 138.8 128.0 62.2 Ac: 170.3 20.6
cti,co$q
wo ,.I
OMoc-4-OH
'21
CH20AC
499
500
R = CHCH,
501
R = a-H,
508
507
(Z)
502
R = AC
505
R = a-Ac
j3-Et
503
R = Moc
506
R = 8-Ac
504
R = Sen
511
509 R 510
R = AC
. . OTtg CH,OH
514
513
512
,'-GO
517
R = ti
518
R = OH
OMOC
R'
R=
520
Sen-4-OAc
AC
521
Mac-4-OH
CH,
522
Mac-4-OH
Ac
519
515
R = H
516
R = Ac
322
M. BUDESINSKY AND D. SAMAN
Table 13. Carbon-13 chemical shifts of germacr-11(13)-en-12,8-olides. No
523 a h
524 a h
525 a b C
d e
526 a h c
527 d
h
Mol. formula Name I Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-I0 C-lI C-12 C-13 C-14 C-15 Sol Ikl C15H2002 Germacra-1(1O)E.4E.11(1J)-trien-12,8~-olide (2 conformers) 131.1b 26.7 43.6' 133.4' 125.6b 24.7 45.7 81.1 39.9' 130.6' 139.2 170.5 120.2 20.W 16.x' C h ' i X 128.4b 26.9 40.1' 132.3' 123.Sb 25.7 43.3 80.9 38.5' 130.6' 137.3 170.5 119 7 17.3' 15.6' c' hYX ClSH2003 Chamisellin (2 conformers) 126.8 23.0 35.9 135.8 129.6 70.2 51.2 79.8 42.3 130.4 135.8 170.1 126.8 16.6 17 5 C 53 126.8 24.2 38.5 135.8 131.9 70.2 53.9 83.3 47.2 130.4 135.8 170.1 126.8 20.7 17.5 c' 53 C17H2204 Laurennbiolide (a: average spectrum a[ 100°C; b e : spectra of 4 conformers at - I 5 C ) c 635 126.2 24.1 37.8 139.6 128.9 72.5 49.7 81.0 44.7 130.7 135.8 168.9 125.6 19.1 17.5 c' 615 126.6' 22.2 36.0 139.8 129.9 72.2' 48.1 83.3 46.6 131.7 135.0 169.4 126.6' 16.7 17.5 c 635 125.2 24.4 38.3 138.3 127.6 71.7' 51.1 80.0 42.1 130.3 134.6 169.4 126.2' 16.7 17.4 c 635 123.2 24.2 38.9 142.3 128.9 72.2' 47.2 80.1 40.9 130.7 135.0' 169.4 126.6* 20.7 17 5 c A35 a 23.6 a 140.9 a 71.7' 57.0 78.1 a a 134.6' 169.4 126.2' a 17.4 C17H2205 Laurenohiolide, lCacetoxy, desacetyl (spectra of 3 conformers at -40°C) c 'li 132.6 22.7 37.2 141.9 129.9 70.0 50.6 80.2 37.4 127.6 135.6 171.0 126 1 63 5 17 X c '13 136.8 23.8 36.2 136.6 130.9 69.6 49.1 83.2 38.7 127.8 135.5 171.3 126.7 63.1 1 7 2 C' 'I7 134.9 23.8 37.9 136.4 131.3 69.4 53.6 79.8 42.5 128.3 134.9 171.2 126 2 61 3 I 6 i CISH2004 Germacra-l(10)E,4Z,7(11)-trien-l2,Su-olide, 2PJS-dihydroxy (2 conformer\) c' 642 136.1 69.0 44.4 135.4 129.3 34.4 45.9 86.8 42.0 126.2 138.5 1699 122.8 21.7 690 c' 642 133.8 67.2 43.2 138.6 129.1 31.8 44.1 81.1 41.6 130.6 138 7 170 I 123 6 22 I 67 2
528 C17H2206 134.3 26.6 529 C19H2407 136.0 26.1 530 C21H2608 1349 26.0 531 C19H2207 136.0 25.6 532 CISH1804 141.5 29.1 533 C2IH2809 143.7 28.6
Artemisiifolin, 6a-0-acetyl-14-hydroxy
35.0 145.2 130.3 79.2 53.9 74.6 45.6 137.4 135 4 171.9 125 I
6 0 2 b h l [I'
hl
I50
('
IiO
61 '1
C'
li(l
131.1 133.6 168.6 126.0 hl 0 I X X J
c'
IS0
Artemisiifolin, 6a-O-acetyl-14-acetoxy
34.2 143.9 129.0 77.0 52.8 72.6 45.0 130.0 135.3 169.8 125.4 62.0 hl I Artemisiifolin, 6a,l5-di-O-acetyl-14-acetoxy
34.5 139.0 130.1 77.0 52.8 72.6 45.2 131.4 135.9 169 5 125 6
62 2
Germacra-1(1O)Z,4Z,11(13)-trien-12,8a-nlide, 6a,14-diacetiixy-15-iixii 29.9 142.2 145.9 74.6 51.9 72.0
a
Pertic acid
29.8 132.9 122.2 34.7 47.0
84.4 36.5 136.2 141.4 170.0 119.2 1700
IX 7
IJ 4hh'
29.3 131.3 122.2 33.8 46.5 83.7 36.1 135.6 140.7 169.3 119.0 166 I I X 3 534 CISH1604 lsabelin (2 conformers) a 130.5 25.2 23.6 136.9 148.1 81.5 50.5 75 7 41.2 133.Sb130.9 168.2 122.9 20 7 171 9 h 129.9 23.9 22.4 137.3 152.2 82.0 55.3 81.4 36.9 131.5 131.9b 168.2 124.1 17 9 172 7 535 ClSH1604 Pertilide, 3-epi 124.2 37.0 77.0 129.6 129.1 29.4 42.0 77.3 28.0 134.7 136.5 167.1 120.9 163.7 13 4 Schkuhriolide 536 CISHI804
I' Jhh*
Pertate, glucosyl
c' c'
?SO
C'
465
?Xi1
(' 126 155.2 25.8 36.8 134.9 126.3 65.2 49.5 77.0 27.2 140.7 138.0 169.6 I24 6 I95 6 16 7 537 C18H1806Cl3N Schkuhriollde + T A I c 126 155.3 25.9 37.1 136.9 121.5 72.7 46.5 76.4 27.4 140.6 140.0 168.9 126.1 195 7 17 2 Soulangianolide B 538 C17H2205 c 1x7 123.5 29.2b 35.0b 141.0 125.1 73.4 48.8 80.7 35.6b138.5' 137.0' 169.8' 125.1 66 I 21 T 539 C19H2406 Soulangiannlide B, acetate c' 1x7 128.6 29.3b 35.4b 141.0 123.6 73.3 49.1 80.2 35.7' 133.9' 136.9: 170.5*123.4 68 0 21 V 540 C17H2005 Germacr-1(1O)E,4E,7(Il)-trien-12,&r-olide, 6a-acetoxy-14-oxo c' 1x7 156.2 30.3' 35Sb 141.2 124.8 72.6 47.2 78.1 29.1b 138.4' 136.0' 169.1' I25 I I94 7 19 X Micrantholide 54 1 CISH2004 c' XJ 125.2 31.2 29.7 138.3 127.1 28.7 46.9 84.2 35.7 139.6 140.0 169.6 120.3 66.6 61 8 Germacr-l(10)E,4Z,7(11)-trien-12,8a-olide, 14-hydroxy-15-methacryloyloxy 542 C19H2405 c' 263 125.6 28.4' 29.Sb139.6 127.4 31.1b 46.5 84.1 34.7 138.4 136.1 1697 120.7 66.2 6 3 3 543 C19Hi406 Germacr-l(10)E,4Z,7(11)-lrien-l2,8a-olide, 14-hydroxy-15-(2',3'-epoxymethacr).111~I11~?.) 125.1 28.Jb 29.7b 139.0 128.1 30.9b 46.5 84.1 34.8 138.1 134.9 1696 120.8 66 1 64 2 C 263 Germacr-l(10)E,4Z,7(11)-trien-l2,8a-olide,14-hydroxy-15-(4'-hydroxymeth~cr~Ic1~l11xy) 544 C19H2406 125.0 29.2b 29.9* 139.4 128.0 30.9b 46.6 84.3 35.1 138.4 135.5 169.8 120.9 66.1 63.4 C 263 Germacr-1(1O)E.4Z.7(11)-trien-12.8a-olide, 14-hydroxy-15-isohutannyloxy 545 C19H2605 1256 284b 29 5b 1396 127 4 31 Ib 49 5 84 1 347 1384 135 8 1697 1207 6 6 2 h i I C 263
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
323
Table 13.+ontinued X l o l twmula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-I0 C-lI C-12 C-13 C-14 C-15 Sol I<el 546 C‘IY117606 Germacr-l(10)E,4Z,7(11)-trien-12,8a-olide, 14-hydroxy-15-(2’-hydr11xyis11hu~dn11~111x~~ 125 0 28 3b 29.6’ 139.1 128.1 30.6b 46.5 84.1 35.2 138.1 135.5 169.6 120.8 66.0 64.0 C 263 547 (’/Y/I?W6C/ Germacr-l(l0 E 4 2 7(11) trien-lZ,&r-oIide 14-hydroxy-l~-~~-chloro~2~-hydroxyisobut~noyloxy) 125 2 X 4 * 29.Xb 139.0 128.6 30.8b 46.5 84.2 35.0 138.1 134.9 169.6 120.8 66.1 64 7 C 263 541 CZIH2607 Cermacr-I(1O)E,4Z,7(ll)-trien-12,Sa-olide,14-acetoxy-15-(4’-acetoxymethacryl11~ IIIX~) I?S 1 2X.6’ 29.6h 139.1 128.3 31.0* 46.9 83.6 35.6 134.0 135.3 169.5 120.8 67.7 63.5 C 263
Nil
Other carbons, 52% Ac: 168.9 20.7 (at 100°C): 525b Act 169.4 21.1 (at -15 “C); S2Sc Ac: 169.4 21 I la1 -15 ‘ C ) , 525d Ac: 169.4 21.1 (at -15°C): 52% Ac: 169.4 21.1 fat -15 “C): 526a Ac: 170.2 21.1 (at -40°C). 526h A r . 170.2 21.1 (a1 -40°C): 526c Ac. 170.5 21.1 (a1 -40°C): 528 Ac: 172.0 21.2: 529 2xAc. 171.1 2 1 1 169.6 21.0; 530 31Ac: 170.9 21.1 170.5 20.3 169.4 20.8; 531 ZxAc: 170.2 20.8 169.4 20.6: 533 Glr 96 4 71.0 78.2* 71 3 7R.Xb 62.5: 538 Act 169.6’ 21.5’; 539 Ac. 169.4‘ 21.0’ 169.74 21.0. 540 Ac: 169.7’ 2 0 9 . 54.2 .Alnc: 165 9 135.8 125.8 18.2: 543 Mac-ep: a 61.9 63.2 17.3; 544 Mac-4-OH: 166.1 139.2 126.2 6 2 0 . 545 ,/tit!. 176 5 33.9 18.8 18.8: 546 ;But-2-OH: 176.9 72.1 27.1 26.9: 547 rBut-Z-OH-3-CI: 173 6 5 0 9 75 3 23.5. 548 Mac-4-UAr: 165.0 135.1 127.9 63.4 Ac: 170.3 20.9 170.6 20.7
523
524
R = H
525
R = Ac
R0 & -( R‘
526
R = CH,OAc
527
wo
pf0 co-0
OAc
R’
R2
532
R = COOH
528
CH,OH
CH,OH
533
R = COOGlc
529
CH,OH
CH,OAc
530
CH20Ac CH,OAc
531
CHO
534
535
CH,OAc
Go@ & + + R
CHO I
co
6R
OAc
CH20R
536
R = H
538
R = CH20H
541
R = H
537
R = TAC
539
R = CH,OAc
542
R = Mac
540
R = CHO
543
R = Moc-ep
544
R = Mac-4-On
545
R = But
546
R = iBut-2-OH
547
R = iBut-2-OH-3-CI
CH20Moc-4-OAc
548
324
M. BUDgSINSKY AND D. SAMAN
Table 13.4ontinued Mol. formula Name / Chemical shifts C - I C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-I1 C-12 C-13 C-I4 C-15 549 C19H2206 ~2R*JS*.7R*.8S*~-Melam~1~~0~.4.~~~13~-trien-~2.8-olide. ~ , 3 - e ~ x y - 1 5 - ~ b u t s n o y l o ~ y'- l ~ ' x'o 143.2 54.9 61.6 129.3 131.9 29.6 43.9 84.8 31.3 142.5 138.6 169.2 120.3 193.5 59.6 550 C2IH2607 * 7R* 8S*)-Melampo-l(lO) 4 11(13)-trien-12,8-olide,
No.
119.4 54.7 551 C21H2607 a h 552 a h 553
554 555
556 557 558
559 560 561 562 563 564
565 566 567 568 569
a h 570
571
572 573
~ ~ a ~ ~ ~ ~ y - ~ ~ ~ x y - l ~ - - t s n o ~ ~ x y 60.6 130.1 131.3 30.0 42.6 85.2 34.5 137.2 138.4 169.4 120.9 67.0 59.9 3R* 7R* 8S*)-Melampa-1(10),4,Il(l3)4rien-12,8-olide, ~ - achtox~-I S-l sobutnoy~xy 72.1 134.6 130.1 29.2 a 82.1 31.3 143.8 138.3 169.7 120.9 194.2 60.5 72.1 134.9 130.3 28.8 a 82.0 31.6 145.0 139.8 169.0 119.4 193.6 60.4 Chrysanolide, dihydro 31.7 148.1 127.8 73.2 49.5 79.3 42.2 138.9 138.2 169.4 123.8 114.2 17.4 31.1b 138.7 126.7 72.7 48.9 78.2 41.Xb 146.8 136.2 169.5' 124.9 114.7 17.4 Chrysanolide, dihydro, hydroperoxy 35.4b 139.2 127.5 73.2 48.8 78.6 a b 143.4 137.9 170.0' 124.2 118.3 17.6 Tanachin = Tatridin, I-epi 36.5' 138.2' 127.8 71.4b 58.1 83.5 41.9 152.9 137.3" 170.1 124.5 113 0 17 X Tatridin B 34.3 135Sb 130.8 70.6 52.0 79.2 41.4 147.1 137.0°170.2 125.1 114.4 17.3 Tanachin, acetate 36.7 140.6 124.7 73.0 50.4 82.3 42.7 148.5 137.2 170.0b 123.4 116.1 17.6 Tatridin B, acetate 34.6 13X.6b 1269 72.7 48.8 78.2 42.3 142.3 136.2b 170.3' 124.8 117.9 17.4 Tamirin 35.6 136.4b 131.5 70.2 50.5 76.8 40.2 146.6 136.3' 169.6 124.2 126.0 17 2 Chrysanolide 35.7b 146.7 127.7 72.3 47.7 76.7 40.4b 139.4 135.9 169.9' 124.1' 125.5' 17 4 Subcordatolide D 29.4 144.4 121.8 70.9 47.0 74.5 120.0 144.1 136.3 169.7 121.6 17.5 16.5 Germacra-4(15),10(14),11(13)-trien-12,~-olide, lp,SD-epoxy 26.9 139.1 75.3 73.0 53.5 72.2 42.7 149.7 139.1 169.4 121.5 107.2 117.7 Spiciformin 37 3 61.3 64.7 68.8 46.0 77.1 43.2 129.9 124.6 169.6 127 R 15.9 19 3 Quadrangolide 34.6b 59.8 61.7 36.4b 40.9 80.2 41.V 138.7 131.1 169.3 123.2 15 4 I X 5 Artemisiifolin, 6a-O-acetyl-14-acetoxy4a,5~-epoxy 33.1 63.2 64.4 78.8 47.6 72.8 44.8 128.2 134.1 170.0 124.8 60.Zh 60.0'
148.1 35.2 146.9 35.3 C17H2205 70.1 35.2 70.4 34.6b C17H2206 84.0 43.7b CI5H2004 76.6b 36.3' ClSH2004 70.6 31.2 C19H2406 77.8 33.4 C19H2406 71.5 28.0 C15H1804 203.1 36.4 C17H2005 202.8 36Sb C,j/>H,,O, 69.4 38.2 CISHI804 81.6 28.1 C15H2004 127.2 23.4 C15H2003 126.0 22.6b C19H2408 134.0 26.2 C19112407 Germacra-1(1O)E,11(13)-dien-IZ,Xa-olide, Za,6a-diacetoxy-4a,SP-epcix) 126.1 68.3 42.3 61.2 67.4 71.3 48.8 79.4 46.6 133.4 134.5 168.3 127.6 1X.Y 17 7 CISHI605 Pertilide, 3-epi-4P,Sa-epoxide 139.0 28.3 77.5 62.3 58.4 31.6 40.5 78.4 38.4 130.4 139.1 169.0 122.9 I65 4 17 0 CISHI804 Germacra-10(14),11(13)-dien-l2,8a-olide, h,SP-epoxy-l-oxo 202.1 36.1 35.2 59.6 66.2 32.1 42.7 80.9 39.9 143.9 138.4 168.9 122X 127.1 I 5 X C15H2004 Baileyin 132.0 66.6 46.6 60.5 66.3 31.1 46.3 83.7 46.9 130.6 139.0 168.9 122 0 I X 2 17 1 CI 7H2205 Baileyin, acetate 127.7 68.6 43.1 59.9 66.0 30.9 46.1 83.5 46.9 132.9 138.7 168.5 12I.X I X 2 17 2 127.9 68.7 46.9 59.9 66.1 43.2 46.2 83.6 31.0 138.9 133.0 168.6 121.8 IX.2 17 I CISH2004 Tatridin A 66.8 27.2 35.3 135.2b129.9 71.1 52.3 74.2 126.8 142.5 137.6b 169.9 123.7 16.8 15 7 C171f220.7 Tulirinol 66.3 21.2 35.4 138.2 126.0 73.2 49.2 74.5 125.9 143.2 137.2 169.7 122.5 16.8 15 6 C19H2406 Tatridin A, acetate 69.0 25.1 35.2 137.4b126.3 73.2 49.5 745 128.8 137.9b 138.1* 169.7' 122.3 17 4 15 7 CISHI405 Scandenolide, anhydro 59.3 151.4 123.8 131.0 135.1 82.4 49.5 77.0 43.8 58.6 137.4 167.7 124.5 22.4 I 7 0 i
Sol Ref. C
176
C
176
C B
176 176
A
IXI
C
1x9
A
1x9
M
571
C+M 571 C
571
C
571
C+hl 57 I
c
1x0
c
479
c
341
c'
53
c
323'
s
I50
c
225
I'
465*
c'
63')
C'
403
C' C
413
715
C+h1 571
c'
IS0
c'
i71
1 . ~ - 2
325
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 13.--continued No.
574 a b
575 576
Mol. formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 CISHI605 Mikanolide, deoxy 60.4 22.5 21.4 137.2 149.5 81.6 49.1 62.0 23.0 22.3 133.9 146.6 81.7 50.6 C17H1807 Scandenolide 58.7 29.6 67.2 134.0 145.7 82.2 50.6 57.6 28.8 66.3 137.0 149.0 82.2 48.9
C-8
C-9
C-10 C-11 C-I2 C-13 C-I4 C-15
Sol. Ref.
S
77.1 42.6 56.2 130.9 167.6 122.1 19.6 171.7 78.3 44.0 57.0 136.7 167.8 123.7 20.4 171.7
L
280 149
78.4 43.7 57.0 136.3 167.6 123.8 20.3 169.4' 77.4 42.2 56.6 131.1 167.6 122.1 19.7 169.7
L S
149 280
Oihercarbons: 549 iBur: 175.6 33.9 18.9 18.9; 550 ;But: 176.5 33.8 18.8 18.8 Ac: 170.2 20.8; 551a iBul: 176.5 34.0 18.9 18.9 Ac: 168.9 20.9; 551b iBuf: 176.1 34.2 19.0 19.0 Ac: 168.5 20.5; 552a Ac: 169.9 20.9: 552b Ac: 169.6' 20.9; 553 Ac: 169.5' 20.8; 556 2xAc: 169.6b 169.Ib 21.1 20.9: 557 2xAc: 169.4' 168.8' 21.0 20.8: 559 Ac: 169.3' 20.8; 560 iBut: 176.0 34.1 18.9 18.9; 564 2 . ~ 4 ~170.2 : 20.8 169.0 20.6; 565 7 ~ 4 ~170.1 : 21.0 169.3 20.8: 56% Ac: 170.0 21.1: 569b Ac: 170.2 21.0571 Ac: 170.1 21.0; 572 2xAc: 169.7' 21.0 168.9' 21.0; 575a Act 169Sb 21.1; 576 Ac: 169.1 20.6
.do,
o\%~.*co '+..
CH,OiBut 549
R = CHO
550
R = CH,OAc
RZ
558
R =
Ac
559
R = At
553
a-OOH
Ac
554
a-OH
H
555
@-OH
H
556
a-OAc
AC
557
B-OAc
Ac
552
co
560
H
R' a-OH
551
561
p
$
o
R
562
R = o-CH,
563
R = i3-W~
n
564
565
R = CHIOAc
568
R = H
569
R = Ac
566
567
R'
R1
574
R = H
570
H
H
575
R
571
H
Ac
576
R = B-OAc
572
AC
AC
573
=
a-OAc
326
M. BUDESINSKY AND D. SAMAN
Table 13.--continued Mol. formula
Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-I0 577 C I S H I 4 0 6 Mikanolide 58.4 55.9 50.6 131.5 147.3 83.2 51.0 77.0 43.7 57.4 578 C171f2205 Pyrethrosin 72.2' 22.6 46.6 139.4 125.6 65.7b 51.4 77 4h 36.5' 58.1 Goyazensolide 579 C19H2007 204.6 106.4 184.6 135.6 134.6 81.7 51.0 73.5 43.3 89.7 5x0 C16H2005 Hirsutolide (X-ray established the identity with
No
a 61.2 27.0 h 6 0 2 27.5 581 CI6H2005 61.0 26.9 582 CISH2OOS 82.8 39.1 583 C19H2207 198.7 106.6 584 a h 585
C21H2208
204.0 107.0 2040 107.0 CISH2004
63 4' 23.6 586 C22H3209
65.1h 70.1' 587 CZOH.3006 35.4 a 588 CZOH2806
a 35.4 589 CZSH.3609 43 9 74.1 590 C2SH3409 43.9 74.2 591 CZSH3409
44.0 74.0 592 C251U609 480 71.6 593 C25H34010
47.9
69.9
C - l l C-12 C-13 C-I4 C-15
137 2 167.5 124.4 21 7 170 3 136.3 169.4" 125.5
17.2' 17.h'
Sc>l I<
1
14li
C+A 131
c' 73.657 135.6 168.7 126.2 20.6 62.9 581) c' 120 22.8 131.8 138.8 30.5 46.0 79.5 45.6 56.3 140.5 167 3 120.6 17.1 168 5 I3 123 22.8 131.0 139.6 30.5 45.2 78.8 45.5 55.7 141.4 168.0 119.0 16.7 167.1 Germacra-4E,11(13)-dien-l2,8u-olide-l5-oic acid methyl ester, 113,lOa-cyrixy c' 1x4 22.6 131.5 140.3 30.4 45.3 79.4 45.8 56.3 1390 167.3 120.7 17.0 16x6 Radgerin c 260 24.9 70.6 78.5 77.4 33.9 72.5 42.8 147.9 141.6 169.4 119.5 126.7 21 5 Centratherin, is0 c 73 185.7 137.7 75.3 85.9 44.5 71.4 44.5 90.4 134.0 169.4 126.7 21.2 124.0 Goyazensolide, acetate c' 77 185.1 134.0 75.0 83.8 46.2 72.1 44.7 90.4 134.0 1669 1265 21.1 1306 C' 657 185.1 134.0 75.0 83.8 4 6 2 72 1 44.7 90.4 134.0 166.9 1265 21.1 130.6 Ivaxillin, IlJ3-dehydro c 423 35.9 W.7 64.4' 32.1 46.4 82.1 45.9 57.X 139 2 I h S 7 I Z I 9 I X 0 I 6 0 (;ermacran-12,8a-o!ide S~-acetoxy-Za,9~-d~hydroxy-l~,lOa-ep~ixy-6a-(2'-mcth~.lhuI) ryloxy) C' 163 31.2 27.1 75.3' 74.3' 41.0 78.9 69.Y 65.3b 132.1 167.6 123 I 22 4 I X 0 Ineupatorolide A C' 61 33.7 41.1 215.3 50.7 45.0 76Sb a 73.3 137 7 168.9 123.8 24.7 204 Ineupatorolide B c 61 33.8 41.1 215.3 50.7 45.0 76.6b 3' 73.3 137.6 169.0 123 8 24.5 I 0 X Divaricin A C' 121 37.3 36.7 105.9 75.6 44.8 77.4 78.0 7 2 2 133 3 I68 5 127.2 71.0 I 4 6 Divaricin B L' 421 37.4 36.8 106.3 75.7 45.1 77.4 77.8 72 I 113 I 16X 5 127 5 ? I I I 4 6 Divaricin C C' 121 37.2 36.9106.2 75.1 44.9 77.3 78.1 7 2 . 2 1 3 3 . 0 1 6 X R 1 2 7 3 7 1 0 1 4 6 lneupatolide c hl 40.8 44.5 105.9 73.9 45.5 77.3 80.3 73.1 134.1 169.4 125.6 25.2 I 4 0 Germacr-11(13)-en-12,8a-olide, 6a,8~-diangeloyloxy-2~,5~-epoxy-4~,5a,lU~-trihydrr~xy 46.6 79.2 105.6 74.9 46.0 77.2 80.3 73.0 134.1 169.3 125.9 25.3 21.6 C 251
Othercarbons: 578 Ac: 168.9' 20.9; 579 Mac: 166.8 133.6 124.5 17.8; 580a 0Me. 52.0; 5Wh UMr ( I 5 . 581 OMe: 52.1; 583 Ang: 167.1 126.3 140.5 15 6 19.9: 584a Mac: 168.2 a Ac: a ; 584h Mu( I6X 2 133.5 124.0 18.0 Ac: 169.5 21.4: 586 Mebir: 174.5 41 7 26.5 11.7 16.3 Ac: 169.1 21.0: 5x7 M r h r 1766 41.1 26.4 11.7 16.7: 588 At&': 167 6 126.8 139.8 204 15.8 589 Arlg: 167.1 127 2 139.4 1 5 . X ? I ) J IfJfif. 172.0 43.0 25.4 22.4 22.4: 590 2xArig: 167.0 127.2 139.5 15.9 20.4 166.6 126.2 I41 5 I 6 0 ?O 5 . 5Yl Ang' 167.1 127.5 139.2 15.8 20.5 Sen: 165.4 114.2 160.6 27.6 27.6: 592 Mebu: 1766 41 I 26.5 11.7 16.8 Ang: 166.1 126.7 141.2 15.9 20.4; 593 ZxArig: 167.6 127.1 139.0 15.8 2 0 6 166 5 1266 141 5 15.9 20.3
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 13.-continued -~
vqc0
co
C"0
OAc 577
580
579
578
n
581
582 583
,do, co OAc i OMebu
R'
ti
Anq
oco 584
HO,,,,
R'
AC
585
Mac
,,,% 0,
0
586
587
R = Mebu
588
R = Anq
R'
R=
589
But
O-OAng
590
Anq
p-OAnq
591
Sen
a-OAng
592
Ang
6-OMebu
593
327
328
M. BUDESINSKY AND D. SAMAN
Table 14. Carbon-13 chemical shifts of germacran-12,8-olides (type 11-methyl). Mol formula Name I Chemicalshifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-ll C-I2 C-13 C-14 C-15 Sol llrt 594 CI7H2404 ~ 3 S , 7 ~ 8 ~ l l R ) - G e ~ a c r a - l ( l O ) ~ 4 ~ i e n - 3-acetoxy l2,8-ol~~ c 231 123.9 29.1b 76.8' 133.44 127.4 30.7' 48.8 76.6' 43.3 133.1' 37.6 178.5 13.2 16.0 23.8 595 C17H2405 ( l S , 3 S , 7 q 8 ~ 1 O q l l R ) - G e m P e r - 4 Z ~ n - l 2 , 8 ~ lfacetoxy-1,lO-epoxy id~ c 237 62.9 28.3b 74.1 134.8 126.2 30.3b 48.5 78.3 40.8 57.8 37.3 177.8 13.1 17.5 23.8 5Y6 CISH2203 Laurenobidide, dihydro, desacetyl (a: average s uum at 115°C; b-c spectra oEconformers at 2 0 " ~ ) c 635 a 129.3 24.4 38.1 135.5 131.7 71.5 40.7 80.3 46.9 130.9 58.5 178.6 17.7 17.7 16.6 c 635 b 130.5 25.0 38.5 135.1 132.6 70.8 41.1 80.0 47.7 130.7 59.1 179.6 17.7 16.6 16.6 c 635 c 125.4 22.8 36.2 135.8 129.4 72.3 40.5 83.7 43.6 132.3 56.2 179.6 17.7 21.1 16.6 Laurenobiolide, dihydro (a: averages c m at 115°C; 597 C17H2404 tx:specma ope2 conformers at 2 0 " ~ ) a 129 7 24.8 38.4 138.7 127.7 73.9 40.7 80.2 47.2 130.9 56.8 177.1 17.1 17.1b 17Sb C 635 h 130.5 25.1 38.7 138.3 128.3 73.1 40.8 79.4 47.7 130.7 57.0 177.4 17.2 16.6 16.9 c 635 c 035 c 125.6b 23.1 36.3 139.3 125.1b 75.0 40.1 82.7 43.6 131.9 54.2 177.4 17.2 17.3' 16.9' ll~H-Cermacra-1(1O)E,4E-dien-lZ,8a-olide, 3a,6adihydroxy 598 C15H2204 c 302 126.6 32.8 74.0 137.6 129.2 70.7 59.4 80.0 48.0 132.0 41.1 179.5 17.9 16.2 15.8 599 C17H2405 ChamSonin, 3-ncetyl-ll~,l3-dihydro c 234 126.0 30.5 76.0 134.2 130.2 70.4 59.1 79.5 47.7 133.6 41.2 179.2 17.7b 15.7b 16.8 600 C17H2406 Artemisiifolin, Q-O-acetyl-14-hydroxy-llp,l3-dihydro 135.0 26.8 35.2 144.1 130.7 78.1 59.1 74.8 46.7 136.0 41.4 180.9 17.2 60.1b 61.0b M 1 5 0 601 C18H2405N2 Chamissonin, 3-acetyl, pyrazoiine C 215 126.4 30.8 76.2 135.1 130.1 65.5 60.4 80.1 47.3 134.0 100.7 172.7 25.8 15.8 16.X 602 C25H3208N4 no name c 263 129.0 28.1b a a 129.0 30.9b 52.4 83.6 a 133.4 99.4' 171.8 23.2' 67.7 64.3 603 C21H3209 (11R)-Tatridin B, 11,13-dihydro, 6-0-p-D-glucosyl hl 574 72.6 32.1 34.5 140.9 128.0 76.9 42.0 81.9 42.5 148.0 56.9 181.5 18.2 114.5 17.2 604 CISHIBOS Pertilie, j-epi, 11~,13-dihydro-4f%,Sa-epoxide c* 465 1370 27.4 77.1 61.8 58.9 28.4 38.6 79.5 39.3 131.5 37.1 178.7 12.9 1649 17.6 605 CISHI805 Pertilide, 3-epi, Il~,lJ-dihydro-4f%,5-epoxide c* 465 137.0 28.2 76.9 61.7 58.4 32.2 42.6 78.2 39.5 131.2 45.1 176.9 15.4 1647 17.3 606 ClSN2203 (4S,7~8~11R)-Germacr-1(1O)Esn-12,8-olidc, 3-OX0 c' 237 124.4 44.8 209.1 47.2 31.2 24.2 47.8 76.1 42.7 133.3 38.3 178.3 13.2 16.X I4 5 607 C17H2007 Scandenolide, dihydro I> I40 59.1 29.4 67.4 134.3 144.6 80.0 54.6 78.2 43.2 57.1 40.5 175.0 13.6 20.4 169.4* 608 CISli1606 Mikanolide, dihydro L I40 58.7 55.4 51.2 131.5 146.5 81.5 54.2 77.6 43.5 57.7 42.4 175.1 13.8 21.5 170.5 609 C151i2203 Nunolide, &pi, 11~,13dihydro-Q,5~-epoxy C'' 639 128.8 24.8 29.9 66.4 61.9 38.0 51.4 83.9 43.0 129.3 46.9 177 3 16.6 13.6 17 5 610 C15112204 Ivaxillin C' 308 65.1* 24.0 35.7 61.0 64.4b 26.3 45.6 82.0 45.1 57.7 40.6 177.9 11.5 18.2 163 611 ClSH1406 Liacine, neo s 476 87.8 a a a 60.2 71.1 148.P a 122.3 132.9 147.2b 11.9 1690 17.2 X5 612 CISHI405 ' LinderanineB c 6x2 131.2 22.2 24.5 61.4 65.2 72.9 146.5 140.8 119.5 134.6b 13I.Ob 167.9 9.8 16.6 168.8 613 CISHI605 Linderanine C c 682 129.2 22.5 24.8 60.9 64.4 75.1 155.5 79.6 48.2 130.7b130.6b 169.1 9.4 16.2 171 4 614 C21N2608 Rolandrolide, is0 c 2x5 51.2 68.8 133.1 135.3 129.3 150.5 143.7 69.9 44.3 72.6 125.6 169.1 54.4 2x7 20.1 615 C23H3008 Rolandrolide, iso, ethoxy c 2x5 51 2 68.9 133.0 135.5 129.4 152.0 143.9 70.1 44.2 72.6 123.6 168.8 61.8 28.7 2 0 2 616 ClSH1606 Linderanine A s (1x2 129.7 22.2 24.2 60.1 64.1 75.3 153.4 110.9 50.9 131Sb130.gb169.2 8.8 17.2 I704 617 CISHI806 Linderanine D c' 682 125.5 22.4 25.3 61.5 63.9 72.2 152.0 80.7 40.0 135.6b131.3b 169.0 9.5 19.9 171.6 61R C17H1806 Zeylaninone 68.7 21.9 20.8 129.9 149.8 74.3 152.7 75.8 128.7 137.4 130.8 171.6 9.2 17.3 172.4 C 3'13
No
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
329
Table M--continued (kher ciubons : 5% Ac: 169.7 20.8; 595 Ac: 169.4 20.7; 5971 Ac: 169.2 20.8; 597b Ac: 169.2 20.9; 597c Ac: 169.2 20.9. 599 Ar: 170.5 21.3; 600 Ac: 171.7 21.1; 601 C16: 79.8 Act 170.3 21.3; 602 C16-C21: 79.0 167.8 97.5' 23.5' 64.6 78.5 2xAc: 170.1 170.7 20.9 20.6; 603 Glc: 99.7 74.8 77.@ 71.7 78.3b 62.8; 607 A(. 1696b 21.1; 614 Muc: 166.3 135.3 127.4 18.4 Acr 170.4 21.2; 615 Muc: 166.1 135.3 127.0 18.4 Ac: 170.2 15.1 OEI: 66.7 21.2; 618 Ac: 169.4 20.4
AcO
AcO
594
p -
R'x''
595
R'
R'
H
OH
597
H
OAc
598
OH
OH
599
OAc OH
596
CH,OAc
600
R = CH,OH
604
R = o-CH,
605
R = P-CH,
HO
I
AcO""
601
606
603
607
608
609
9 q CO-6
610
611
612
OH
HO 614
R = H
615
R = Et
616
20-6
ec0 613
co--0 617
618
330
M. BUDESINSKY AND D. SAMAN
Table 14.--continued .-
No.
Mol. formula C-l C-2
619 C17H1807 70.2 23.3 620 CISH1606 64.1 22.3 621 ClSH1606 62.9 24.4 622 CI5H2005 62.2 25.5 623 CI6H2604 50.8 25.0 624 C16H2605 51.6 24.5
C-3
Name I Chemical shifts C-4 C-5 C-6 C-7
C-8
C-9 C-10 C-lI C-12 C-13 C-14 C-I5
Acutotrinol 21.0 130.3 149.3 74.7 148.9 105.7 129.3 138.9 133.4 169.7 Acutotrine 23.3 60.8 64.6 76.3 155.0 78.7 45.5 57.6 131.0 170.4 Acutotrinone a 58.9 63.4 71.9 151.7 76.5 124.2 145.8 132.1 170.9 Glechoman-12,8a-olide, Ip,l0a.4cr,Sp-diepoxy-8P-hydroxy 23.9 61.1 67.0 35.9 158.5 107.5 50.0 58.6 130.0 171.0 Glechomanolide, Ip,lOa-epoxy-4-methoxy 37.3 81.6 32.6 24.5 160.6 80.5 49.6 77.3 122.1 175.1 Glechomanolide, Ip,lOa-epoxy-8-hydroxy-4-methoxy 38.4 82.0 37.0 24.1160.1105.6 49.8 77.1122.9173.3
__
Sill 11c.1
9.1
17.8 172.5
C
303
9.3
17.0 171.7
A
393
8.9
17.1 173.2
A
393
8.8
17.1 18.9
A
2IX
8 0 25.4 2 5 3
<'
250
7.8
C 250
25.7 2 5 3
Other carbons : 619 Ac: 172.4 20.2; 623 OMe: a; 624 OMe: a
619
620
621
622
623
R = H
624
R = OH
Table 15. Carbon-13 chemical shifts of modified germacranolides. No. 625 626
627 628
629 630 631 632 633 634
635 636 a b 637
Mol. formula Name I Chemical shifts C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C - l l C-12 C-13 ClSH2002 Aristolactone 128.8 24.5 25.3 137.0 152.6 82.6 52.5 26.3 41.0 132.8 150.5 110.5 20.2 ClSH2003 Versicolactone B 79.0 28.1b 25.4b 135.7 149.5 83.3 45.9 24.2b 131.5 131.2 146.6 21 3 112.1 ClSH2002 no name 120.1 23.2 27.5 138.6 148.4 81.2 46.4 23.3 23.9 133.3 143.3 1 1 1 5 2 3 1 CISH2OO2 Aristolactone, is0 40.8 27.2 28.9 133.7 149.8 83.4 45.1 17.1 131.3 132.6 147.3 111.4 21.1 CISH2002 Aristolactone, pyro 26.9 25.0 24.4 138.4 150.8 82.7 47.7 23.8 121.1 130.7 148.0 111.7 20.7 CISHI603 Linderalactone 130.3 25.8 26.8 135.1 151.7 74.2 115.4 152.8 40.7 130.8 122.2 137.2 8.4 ClSH1604 Linderane 130.0 23.0 26.6 61.3 65.6 73.2 113.7 153.2 40.4 131.6 122.3 137.1 8.3 CISHI605 (+)-Linderadine 62.4 21.8 23.4 60.6 67.2 73.2 114.8 149.8 38.1 58.0 122.4 137.6 8.0 CI7HI806 Zeylanane 69.2 25.8 20.4 58.4 63.2 71.3 118.0 146.6 122.2 142.0 121.0 139.5 7.9 CI7HI805 Zeylanine 70.5 24.5 20.9 130.6 149.7 74.1 120.4 146.9 122.3 139.8 120.6 139.6 8.1 ClSH1803 (6R*)-Germacra-l(lO),3E,8E-trien-l2,6-olide,1,2-seco, 2-0x0 117.3 189.9 129.0 157.0 43.8 79.3 49.1 124.0 137.7 144.0 140.0 169.0 122.6 C23H34011 no name 69.6 29.1b 27.1b 45.6 212.4 48.6 39.3 78.9 45.4 205.6 138.3 171.3 122.9 68.4 28.6* 26.7b 44.7 212.2 47.8 38.5 78.1 44.1 205.4 139.0 170.1 121.1 no name C29H40014 69.6 29.7b 27.0b 45.6 211.7 48.7 39.3 78.8 45.6 204.9 138.2 170.5 122.8
(1-14 (2-15
Sol I
15.7 173 6
c
3x0
10 1 172.6
"
703
23.2 174.2
c
3x9
15.9 173.7
c
3x9
22.4 174.9
c
3x9
15.7 173 4
c'
636
15.X 171 5
c
630
16.1 1706
c
1'13
17.4 169 X
c
391
17.6 172 I
c'
391
17.0b 17.5'
c
433
30.5 30.1
16.1 15.7
c s
2x4 2x4
30.6
16.2
C
2x4
331
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 15.--continued ~~~
~ ~ _ _
~~~
N
639 6411
2101 1oi111uIa Name / Chemical \11111\ C-I C-? L;-3 C-4 C.5 C-6 C-7 CZ0//?,~06 P)cniilide 1 2 1 0 5 x 7 6 6 7 1 3 5 . 9 I 2 X . 9 7 4 6 477 I Z I 0 5 X 7 66 3 175.9 12X 9 7 4 6 47 7 “zo1174ox no name 3 6 1696 164.2 I31 5 145.5 772’ 51 6* C2 5 / / . ? 2 0 / 2 I’oskvdnolide ? I 0 7 ?X?174.3 7 2 9 1 I 6 . I 15291457
(141 C ’ / > / / : ( J O { 1708 1 % I M Z (‘I i//7204 746 762
c‘-x
C-I0 C - l I c‘-12 C-I3 C-I4 C-15
C-9
S ~ i l -~ I
711 4I914271323lh6X1233 71.1 41 (J 142.7 132 3 169 7 123.3
20.3 l 5 X 15.Xh 14 O*
c‘ (’
312 309
743b 41 I
8 2 0 136.0 1696 1242
225
179
C
2x4
661 366 4 3 . 6 1 2 4 3 I 6 6 7 547 no nume 3 x 7 7 0 6 3? 2 I 2 4 0 I33 7 i s I I9X.6 1 2 3 0 I 5 6 4 107 27 7 Antheindurolide A 44.9 137.6 1230 3 1 X 3 x 2 70 3 179 7 33.5 1340 170.6 122 I Germacrdne, s e w , anhydride
166
2f>3
c‘
340
169 I?? 3
“
(>X3
15.5
(’
1x3
164
i.aihon\ 633 Ac. 16X.7 20.7. 634 Ac: 168 8 20.9; 636a Glc-6-Ar: 102 6 73.7’ 76.4 70.3 73 5‘ 61 7 169 X 20 9. 636h Glc-6-Ar: 102.7 73.5’ 76.4 70.0 73 2‘ 63.6 169.1 20.6. 637 GJc-2,3.4.6-A<’ IW 7 71 X’ 72 X 6 x 5 71 3‘ h l 3 170.1 21.2 1698 207 169.3 20.6 169.3 207: 63Ra A J I , ~ . 3 , 63Rh Afly 16hX 1 2 7 2 1i x x I 5 ?0.3. 639 21 5 4c 170 3 20 7 Olllei
P
626
+
630
‘.c-J,.
H0 -
O-
635
O
m
wc 636
R
637
R = Glc-2.3.4.6-Ac
= Glc-6-Ac
09--&-oAc CHIOAC
H,COOC
0.
0 ‘
co
639
v
/
642
632
634
, ’
638
631
co--0
633
0-co
628
@q
CO-6 .
a
627
‘(7
co--0
629
HOH&
c0--0
co-0
co--0
625
HOH,C
c+p
$2 .,,,?
‘i(
co-0
643
6H
641 640
332
a
M. BUDESINSKY A N D D. SAMAN
11
15
- 13
R2
&CH2R1
0-co
RC
0-co
12
Table 16
Table 18
Table 17
Table 19
Table 20
Fig. 20. Schematic representation of eudesmanolide structure types in Tables 16-20 and numbering of eudesmano skeleton.
11,13-dihydrourospermal A [426],549 lactulide A [430],473 oxytoriolide [473],336 13-acetoxyrolandrolide [481],285 germacran-12,8-olides: dihydrochrysanolide [552] and hydroperoxy dihydrochrysanolide [553],lS9 subcordatolide D [560],479 baylein [568],403 tulirinol [571],lSo ineupatolide [592],61 ivaxillin [610],308 neoliacine [611],476 lP,lOa;4a,SP-diepoxy-8/3hydroxyglechoman-l2,8~-olide [622],248 and modiJied germacranolide: versicolactone B [626].'03 4.3.2. Eudesmanolides Carbon-13 NMR data on about 420 eudesmanolides (sometimes called selinanolides) collected from more than 100 literature references are summarized in Tables 16-20. Tables 16 and 17 contain eudesman-12,6-olides which differ in substitution at C(11) (exomethylene vs. methyl type substitution), similarly to Tables 18 and 19 containing eudesman-12,8-olides (see Fig. 20). Table 20 contains lactones with modified eudesmanolide skeleton. Two six-membered rings A,B are usually trans-annelled, giving a trans-decalin system. Many eudesmanolides contain double bonds in the 4 5 , 4(15)-, 1,2- or 2,3-position. Some compounds having a cis-decalin system of rings A,B have been isolated or synthesized. Various 1D-NMR methods have been used for structure assignment of eudesmanolide carbon signals - e.g. INEPT,"'
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
-
0-co
I
a-SANTONIN
0-co a-epi
SANTONIN
-
0-co
333
I
P-SANTONIN
0/3-epi
co SANTONIN
Fig. 21. Chemical shifts of C-6, C-7, C-11 and C-13 carbons in a-santonin and its
isomers.
DEPT~ 12,357,377,409,477,592,628,652 or ~p~,419,536,543,599 usually in combination with some known chemical shift rules. Recently, 2D heteronuclear C-H correlation experiments have been used in many papers (e.g. refs 12, 20, 27, 28, 54, 324, 349, 357, 409, 419, 436, 543, 567-570, 652, 692, 693). The C,H-COSY spectra were used for carbon and 4-epivulgarin [847].2 In the assignment for example in vulgarin [MI same pape8 vulgarin was shown to be identical with other compounds described earlier as barrelin, judaicin and tauremisin on the basis of proton NMR spectra of authentic samples isolated from different plant material. The assignment of carbon signals in peroxyvulgarin [&MA] was verified by 2D-INADEQUATE .20 Pregosin et ul.459,521 have measured carbon-13 NMR spectra of a-santonin [852], its p-, a-epi-, p-epi-isomers 910, 775, 777 and some other eudesmanolides. The data provide a simple method of determining the stereochemistry of the lactone ring fusion as well as configuration of the C(11)-methyl group, as illustrated in Fig. 21. Characteristic differences in chemical shifts of C-13 carbon for a- and p-oriented C(11)-methyl groups had later been used in
334
M. BUDESINSKY AND D.
SAMAN
Table 16. Carbon-13 chemical shifts of eudesrn-11(13)-en-12,6-olides. No
W
645 d
h
646 647 648 649 a h
650 a h 651
652 653 654 655 656 657 658 659 660 661 662 663 664 665 666 667 668 669 670
Mol. formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14 C-15 Sol I> 76.6 29.4 120.6 :33.1 50.8 81.0 50.8 21.0 34.0 39.6 138.6 170.5 117.0 23.2 1 2 3 C15H2003 Magnolialide 77.6 23.1b 27.Ib126.2 129.3 83.2 49.8 33.3’ 38.3’ 42.1 139.2 170.3 118.4 18.Y 19.hd t’ IS‘) C15H2003 , Cichoriolide A C’ 591 27.0b 33.2’ 77.6 128.9 126.2 83.0 49.6 23.0b 38.3’ 41.9 139.0 170.2 118.3 19.6d I R . 4 ‘ C2IH3008 Cichorioside A 23.Sb 33.5‘ 83.3‘ 130.6 125.6 83.7d 50.1 23.Ib 38.7’ 41.9 140.1 170 3 I I K I 19 8’ 19.6‘ I’ 5‘)l
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
335
Table 16.--continued Otlier carbons: 646 Ac: 170.4 21.1; 652 Ac: 170.7 21.0; 654 Ac: 170.9 21.3: 659 Ac: 170.4 20.9; 660 Elmis: 168 5 60.4 59.2 13.4 19.2 An$: 166.7 126.0 142.8 16.3 20.7: 661 Epang: 168.5 59.4 59.8 13.4 18.6 /\It.('. 166.5 125.8 142.6 16.1 20.6: 667 AC: a ; 670 Gic: 102.3 75.3 78.8' 7 2 2 78.5' 63.3
pF 0-co
644
645
646
647
R = Br
648
R = OH
0-c0 649
650
a
651
R = H
653
R = H
652
R = Ac
654
R = Ac
0-c0
655
656
657
q% q&
658
R = H
659
R = Ac
0-c0
0-co
-
-
Epanq(Z'R.3'R)
660
R
661
R = Epang(Z'S.3'S)
663
662
6-c0
665
H
666
R =
667
R = AC
668
664
RO
669
R = ti
670
R = Glc
336
M. BUDESINSKi' AND D. SAMAN
Table 16.--continued ~~
No
671 672 673 674 675 676 677 678 679 6x0 6x1
6x2
683 684
615 6x6
6x7 688 689 690 6Y1
692
693 694 695 696
697
Name I Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-I1 C-12 C-I3 C-14 C-15 Sol I k t CISH2003 Rothin A c 400 40.5 18.4 34.2 128.0b128.2b 79.9 55.4 68.7 52.2 36.3 137.5 170.2 121.3 27.2 19 8 CZIH3403S Eudesm4,11(13)-dien-12,6a-olide,8a-r-butyldimethylsilyloxy c' 400 4 0 6 18.5 34.2 127.5b128.5b 80.0 55.5 69.5 52.4 36.1 137.7 170.3 121 I 27 2 19 8 CISH2003 Reynosin c 1x9 78.2 35.Yb 33.7b 142.8 53.2 79.7 49.8 31.4b 21.6b 43.1 139.6 170.6 116.8 11.7 110.7 C2IH3008 Sonchuside D I' 447 83 8 28.3 36.4 144.2 53.5 79.8 49.8 21.5 33.8 42.9 140.5 170.8 116.3 12.8 110.0 CISH2003 Arbusculin C c 1x9 21.4b 21.9b 34.6b146.5 79.3 82.1 43.3 34.0b 31.6b 40.6 140.3 170.7 116.9 2 0 6 111.2 C15H2004 Arbusculin C, hydroperoxyde C' IX') 22.4b 22.6b 35.7b 145.7 86.7 82.6 42.8 34.6b 32Sb 42.6 141.3 170.6 116.0 21.9 113.3 C2IH2808 Ixerin W I' 5" 127.1 138.3' 76.2 141.1 49.0 77.3 51.7 20.4 39.5 35.7 139.1'169.4 115.1 19.6 107 5 C15H2204 Reynosin, 4~,15-dihydro-15-hydroxy I' 7(J4 77.9 30.8 28.9 39.1 50.8 83.7 50.0 21.8 37.3 42.6 140.4 170.5 116.1 12.6 6 5 4 CZlH3209 Sonchuside F I' 54J 84.4 28.6 26.8 39.0 50.8 83.7 50.1 21.6 37.2 41.8140.3170.81166 13.4 6 5 4 C30H40012 Ixerisoside G I' 665 79.3 23.6 25.8 34.6 50.7b 81.1 50.1b 21.5 38.6 40.8 140.6 1705 116.4 15.5 6 9 2 C35H48014 Ixerisoside H I) 6 6 i 79.2 23.5 25.8 34.5 50.8b 81.8 5O.lb 21.5 38.5 40.9 140.5 170.5 116.4 15.5 69 2 CISHZ004 Sonchucarplide I' 5YJ 76.9 29.2 24.9 48.7 48.9 83.2 50.0 23.2 37.3 41.9 140.0 170.9 116.8 12.2 203.3 CZIH3009 Sonchuside E I' 5" 83.2 25.5 24.7 48.7 50.1 81.9 49.2 21.5 36.8 40.9 140.1 169.9 117.1 12.9 203.2 CISH2004 Eudesm-11(13)-en-12,6aa-olide,4a,Sa-epoxy-Sa-hydroxy c 4119 34.2 15.5 29.5 66.4b 68.2b 75.5 51.6 68.1 48.0 36.0 136.7 169.7 121.1 23.0 21 7 C21H3404Si Eudesm-11(13)-en-12,6a-olde, 4a,Sa-epxy-Sa-t-butyldirnethylsilyloxy c 409 34.2 15.5 29.5 66.2b 68.2b 75.5 51.6 69.0 48.0 35.7 136.9 169.8 120.8 23.1 21 6 CISH2004 Eudesm-11(13)-en-12,6a-olide,4p,Sp-epoxy-Sa-hydroxy C 409 36.0 16.8 32.4 65Sb 67.9b 75.9 52.4 68.4 47.3 36.1 137.0 168.9 121.9 24.9 22.1 C21H3404St Eudesm-l1(13)-en-12,6a-olide,4p,5~-epoxy-Sa-f-butyldirnethylsilyloxy c 409 36.3 16.9 32.5 65Sb 67.8b 76.0 52.6 69.2 47.6 35.8 137.2 169.0 121.8 24.8 22 I CISHI804 Arglanin c 426 201.4 125.4 152.0 70.0 55.1 79.7 49.7 21.2 34.0 46.4 137.9 169.5 118.2 23.7 19.7 C2IH3009 IxerisosideE I1 Mi 74.5 33.6 124.9 134.0 51.Ib 81.3 49.8b 21.4 35.2 41.5 140.4 170.7 116.0 11.6 71 8 C15H2004 Tanacetin c IX') 71.7 30.5' 29.8b 144.8 77.1 81.9 43.3 29Ab 21.2b 44.8 140.0 170.6 116.4 13.3 1126 ClSH2005 Tanacetin, 5-proxy L) 1x9 71.0 31.8' 31.1b 144.8 87.8 82.9 42.8 31.1b 22.4b 47.5 141.3 170.6 116.4 14.4 114.4 C2IH32010 IxerisosideI I' 665 71.7 29.1 37.2' 78.2 50.6' 83.4 50.1' 21.6 36.7b 42.7 140.2 170.7 116.3 12.5 73.5 ClSH2004 Armefolin c 426 70.6 38.0b 71.8 132.9 127.4 82.7 49.4 22.9 36.3b 42.5 139.1 169.8 118.2 17.5' 17.3' C19H2406 Montathanolide, acetyl c 94 72.2 23.0 82.2 133.4 126.2 75.3 49.1 30.0 37.8 41.6 138.6 169.3 118.9 19.5 14.3 CISHI804 Armexifoiin c 426 74.4 42.6 196.7 129.6 152.2 82.0 48.8 23.2 38.0 43.9 137.9 169.0 119.6 17 6 11.0 C30H38012 Ixerisoside M I' 665 80.4b 23.5 27.2 113.3 50.9 78.9' 49.6 21.4 35.1 42.4 140.2 170.4 116.5 1 2 8 1407 CI 7H2205 Balchanin acetate, 'la-hydroxy n 29.7121.3133.1 43.0 82.1 75.5 26.9 29.8 39.3142.6170.7118.8 23.3 11.8 C I63 M o l formula
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
337
Table 16.-ontinued Oilier L.irhons. 672 TBDMS: 25.9(3) 18.0 -3.4 -4.2; 674 Glc: 102.3 75.2 78.7b 72.1 78Sb 63.3; 677 Glc. 104 2 74 4 77.5 70.8 77.5 61.8; 679 Glc: 102.2 75.2 78.3 72.1 78.6 63.3; 680 Glc: 106.2 75.4 78.6 7 1 h 7X 5 62.8 Cinn-diH-2.4'-OH: 174.4 72.9 40.8 128.7 131.5(2) 116.2(2) 157.8; 681 Glc: 106.2 75.4 7X h 71 6 7X 5 62.8 Cbin-diH4'-OH-2-OiVol-2'-OH: 169.7 74.1 37.1 126.7 131.3(2) 116.4(2) 158.1 1164 174 7 75 9 329 19.4 17.3; 683 Glc: 102.3 75.1 78.5 72.1 78.7 63.3; 685 TBDMS: 25.8(3) 17.9 -3.4 -I 2. 6x7 TBDMS: 25.9(3) 18.0 -3.5 -4.3; 689 Glc: 104.2 75.5 78.7 71.6 18.3 62.6; 692 Glc: 104.9 75 2 7 X 6 71 7 78.3 62.8; 694 2rAc: 170.3 20.9 170.0 20.9; 6% Glc: 105.2 75.1 78.7 71.0 78.4 62.1 ( ' I I I I I - , / ~ / ~ - ~ ,174.3 ~'-~H 72.8 : 40.8 128.7 131.5(2) 116.1(2) 157.8; 697 Ac: 169.9 21.1
671
R = H
673
R = H
675
R = H
672
R = TBC'MS
674
R = Gk
676
R = OH
677
R'
R'
682
R = ti
684
R = H
686
R = H
678
H
H
683
R = Glc
685
R = TBOMS
687
R = TEOMS
679
Glc
h
680
Cinn-diH-2.4'-OH
Glc
681
Cinn-diH-4'-OH-2-0iVa1-2-OH
Glc
688
689
0-co
=
0-CO
GlcOH,C
GkOH2C
690
R = H
691
R = OH
692
qq= oJp+
OCinn-diH-2.4-OH
6-co
0-co
R2
Glco
R'
R'
693
ti
o-OH
694
AC
8-OAc
695
696
697
338
M. BUDESINSKY AND D. SAMAN
Table 16.+ontinued No
Mol. formula Name / Chenucal shifts C-I C-2 C-3 C-4 C-5 C-6 C-7
6YX CI7H220S
C-8
C-9 C-10 C - l l C-12 C-13 C-14 C-15
Sol
llcl
Ludalbin
72.2 32.1 119.6 132.7 43.8 79.6 53.6 69.6 40.0 40.4 136.8 170.2 118.9 18.4 23.5 Balchanin, 8a-methacryloyloxy 69Y C I 9H240S 74.9 32.6 121.8 132.5 50.4 78.9 53.7 69.6 41.0 40.5 135 9 1697 119.3 12 I 23 I 700 C19H260S Balchanin, 8a-isobutyryloxy 74.9 32.6 121.8 132.5 50.4 78.9 53.7 69.6 41.0 40.5 135.9 169.7 119.3 12.1 23.1 701 C2OH2605 Balchanin, 8-tigloyloxy 75.6 32.8121.6133.1 51.4 77.5 53.6 66.1 39.3 40.7134.2170.0119.3 12.8 23.2 702 CZOH260S Eudesma-4,11(13)-dien-lZ,6a-olide,l~-hydroxy-8p-tigloyloxy 77.8 26.7 33.2 128.6 126.8 78.0 51.8 66.5 42.8 41.8 134.1 169.5 120.9 19.5 20.8 Armefolin, 8a-methacryloyloxy 703 C19H2406 70.7 35.7 72.5 131.7 128.4 79.1 51.8 71.4 44.2 41.8 136.1 169.5 121.6 18.2 17.6 704 CI 9H2606 Armefolin, 8a-isobutyryloxy 701 35.8 72.5 131.7 128.4 79.1 51.8 71.3 44.3 41.9 136.3 169.5 121.6 189 176 705 CISH2004 Rothin B 34.4 21.3 31.4 145.6 75.4 79.9 49.4 67.6 45.2 40.6 135.8 170.4 119.6 21.7 I l l 7 706 C2IHJ404Si Eudesma-4(15),11(13)-dien-lZ,6a-olide, Sa-hydroxy-8a-f-butyldimethylsilylox~ 344 21.3 31.4145.8 75.4 79.8 49.3 68.3 45.1 40.3138.2170.5 119.3 217 1 1 1 5 707 CZ!HJ40SSi Eudesma-4(15),11(13)-dien-I2,6a~lide, 5a-peroxy-8a-f-hutyldimethylsilyliix~ 34.8 21.5 31.7 1431 86.3 80.1 49.0 68.4 45.1 41.5 1376 169.8 120.5 23.2 1 1 4 6 70X C20H2606
Reynosin, 8-tigloyloxy
75 3 30.8 33.4 142.0 52.1 78.4 53.4 66.1 40.3 42.7 134.5 169.9 119.5 13 6 1106 70Y CI YH2406 Reynosin, 3a-hydroxy-8a-methacryloyloxy 73.3 37.5 73.6144.3 46.7 76.5 52.5 72.9 42.2 4 2 . 8 1 3 6 . 7 1 6 9 7 1 1 9 5 1 1 9 1 1 3 4 710 C19H2606 Reynosin, 3a-hydroxy-8a-isobutyryloxy 73.3 37 5 73.6 1443 46.7 76.5 52.5 7 2 9 42.2 42.8 1367 1697 119 5 I I 9 1 1 3 4 711 C I 7112006 Armexifolin, 8a-acetoxy 74 2 42.3b 196.6 130.2 150.2 78.5 50.8 69.9 44.1b 43.2 135.3 170.0 122 3 18 6 I I 0 712 C19H2406 Armexifolin, 8a-methacryloyloxy 741 42.3 196.5 130.4 150.1 78.5 51.0 70.0 44.1 43.3 135.4 168.2 122.5 1 x 7 I 1 I 713 C19H2606 Armexifolin, 8a-isobutyryloxy 74.4 42.3 196.5 130.4 150.2 78.4 51.0 70.2 44.1 43.5 135.4 I68 2 122.5 I X 7 I I I 714 C17H1805 Irazunolide 156.8 127.7 187.2 139.7 52.1 76.6 51.7 68.4 42.2 39.1 135.6 170.0 120 1 20.9 I?? 7 715 C17H1805
Gutenbergin
153.2 128.1 186.7 139.1 51.0 77.9 46.2 26.3 74.1 42.9 1369 170.2 I I 8 . I
15.2 1234 716 C19H2606 Artecalin, 8p-isobutyryloxy 76.4 50.2 205.8 52.5 44.1 77.4 46.3 65.2 40.6 42.8 1349 173.5 118.2 3 0 1 1 3 7 717 CI9H2406 Eudesma-2,11(13)-dien-12,6a-olide, l~,4a-dihydroxy-8a-methacryloyloxy 76.8 130.4 133.8 69.4 53.9 78.2 52.7 70.5 44.8 41.9 135.9 169.1 120.0 2 4 9 15 I 71 X CI YH2606
Eudesma-Z,ll(13)-dien-12,6a-olide,Ie,4a-dihydroxy-8a-isohutyryloxy
76.8 130.4 133.8 69.4 71Y CI7H2006 200.3 124.1 720 C19H2206 199.8 125.3 721 CI9H2406 199.8 125.3 722 C19H2206 201.2 125.0 723 C19H2406 201.2 125.0 721 C19H2207 201.1 37.9 725 C2OH2806 7 6 8 27.8 726 C22HJ206 76.1 27.8
53.9 78.2 52.7 70.5 44.8 41.9 135.9 169.1 120.0 24.9
15 I
Artemexifoh
153.4 69.4
53.9 76.9 52.2 68.7 40.4 45.6 135.9 169.8 120.0 23.0 2 0 4
(4S,5S,6S,7~8S,10R)-Eud~ma-Z,~~(~3)-dien-lZ,6-olide,4-hydroxy-8a-mcthacr).11,).11x~-l-11 151.8 70.0 54.4 77.2 52.6 68.8 40.5 45.4 135.2 168.5 121.1 2 0 4
23 6
c'
I12
(4S,5S,6S,7~8S,10R)-Eud~ma-Z,ll(l3)-dien-lZ,6-olide, 4-hydroxy-8a-isohu~yr~i~l1~x~ - I -IIXO
151.8 70.0 54.4 77.2 52.6 68.2 40.5 45.3 135.1 168.5 121.1 20.4 I 3 6 c' I12 (4R,5S,6S,7~8S,10R)-Eud~ma-Z,ll(l3)-dien-lZ,6-olide,4-hydroxy-~a~m~th~~r~l11~l11x~-l 150.4 68.1 52.4 77.2 51.0 69.3 39.0 45.2 135.9 169.2 120.6 21 4 31.5 C' I I ?
(4~5S,6S,7R,8S,10R)-Eudesma-Z,ll(l3)-dien-lZ,6-olide, 4-hydroxy-Xa-isi,hutyro) 150.4 68.1
52.4 76.7 50.9 68.7
39.0 44.1 135.8 169.2 120.1 21.4
lox? - 1 -iixo
31 5
c'
I I?
35.9 116.6 51.8 75.6 49.3 68.8 24.3 49.5 135.7 167.5 120.4 10.0 1325 Eudesm-11(13)-en-12,6a-olide, lp,4a-dihydroxy-8p-tigloyloxy 38.1 71.3 57.1 78.6 53.2 66.2 43.5 4 1 . 9 1 3 3 . 2 1 6 8 . 9 1 2 0 6 16.0 244
c'
302
c'
Z'JI
C
3
Costunolide, p-cyclo, (R)-8~,15-diacetoxy-l-?xo
Eudesm-ll(I3)-en-12,6a-olide,4a-ethoxy-l~-hydrox~8~-tiglnyloxy 35.4 74.9
54.7 78.6
53.2 66.3 43.8 42.3 134.4 170.3 119.1
16 5
I!, X
339
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 16.--continued No
727 72X 729
720
Mol formula Name I Chemlcal shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-I2 C-13 C-14 C-I5 Sol. I k f C17H2206 Ludalbin. a-ewxv 72.2 29.1 60.4 58.4. 45.6 i8.5 53.5 69.1 39.8 39.9 136.2 170.1 119.4 19.3 22.1 c' 426 Cratystyloide, cyclo C2VH2607 710* 31.2 70.6b140.7 39.5 73.2b 43.4 27.0 78.9' 39.1 139.1 170.4 116.9 15.8 115.4 C 696 ('22H.?6010 Eudesm-I I(l3)-en-l2,~;15,l~diolide, &-(4'-acetoxy-5'-hydroxyangeloyloxy)-4a-hydn~xy 76.0b 30.2'38.5' a 5 7 . 3 d 7 4 . 2 b 5 1 . 5 * 6 9 . 1 b 4 2 . 6 ' a 135.4 a 120.0 13.2 a C 132 CZOH2405 Badkhysinin 73 7 58.0 52.3 140.0 40.3' 76.3 39.3b 19.6 27.5 37.6 137.1 169.9 120.0 18.7 118.1 C 126
Oihercnrbons. 698 Ac: 169.9 20.9: 699 Mac: 166.4 136.3 126.3 18.2; 700 Bur: 176.4 34.5 19.2 19.2; 701 7i,q. 167.1 128.2 138.4 14.5 12.2: 702 rig: 167.1 128.2 138.3 14.5 12.2; 703 Mac: 169.2 136.0 126.5 I X 3. 704 fnur. 176.3 34.2 18.4 18.4; 706 TRDMS: 25.9(3) 18.0 -3.4 -4.2: 707 TBDMS: 25.8(3) 17.9 -3.3 -4 2: 708 Z i r 167.1 128.1 138.4 14.5 12.2: 709 MOC: 167.1 136.0 126.4 14.5: 710 iBuf: 1762 14 1 1X 2 I X 9: 711 ~ c 1682 . 20.9: 712 Mac: 166.2 135.3 126.7 18.1: 713~i B u i ~ l 7 6 . 134.2 18.3 19.0; 714 AC: 169.1 20.7. 715 Ac,: 169 2 21 0: 716 i B w 175.5 34.3 19.2 18.8; 717 Mac: 166.4 135.8 126.6 15.0; 718 iBirr: 176.1 34 2 I X 2 IR.2. 719 Ac: 169.0 20.9: 720 Mac: 166.2 135.7 126.7 18.2: 721 iBuc a 34.1 18.8 18.8: 722 Mac. 166.3 135.8 126.5 18.2: 723 iBur: 176.2 34.1 18.9 18.9: 724 2xOAc: 170.0 21.0 168.7 20.7; 725 Tfs: 167.1 ~~
~
~
128.0 138.5 14.5 12.2; 726 Tig: 167.2 128.1 138.3 14.5 12.2 Ef: 55.6 16.2: 727 Ac: 169.2 20.9 : 728 OMe: a : 729 Ang-4-OAc-5-OH: a a 141.5 62.5 63.2 n 20 X: 73(1 CIfi-CI7- 112.3 22 5 Ac: a I67 1 127.3 139.2 1.5.8 20.6
h g '
R,\~
R'
R1
R'
R'
a-OH
a-OAc
702
H
#-Olig
705
699
@-OH
a-OMac
703
OH
a-OMoc
706
700
@-OH
a-OBut
704
OH
a-OiBul
707
701
@-OH
@-Olig
698
711
R = Ac
R'
R'
712
R = Mac
714
OAc
H
713
R
715
H
OAc
719
R = Ac
722
R = Mac
720
R = Mac
723
R = iBut
721
R = iB~1
=
But
R'
R'
R'
H
H
708
H
@-Olq
H
TBOMS
709
OH
a-OMac
OH
TBOMS
710
OH
a-OBut
R'
716
724
717
R = Mac
718
R = 6%:
725
R = ti
726
R
= El
+
=
0-co
OCH, H
AcO"' O 727
728
729
R = Ang-4-OAc-5-OH
A
730
340
M. BUDESINSKY AND D. SAMAN
Table 17. Carbon-13 chemical shifts of eudesman-12,6-olides (type 11-methyl). No.
Mol. formula Name I Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7
~
~-
C-8 C-9 C-I0 C - l l C-12 C-I3 C-14 C-I5 Si)i.-%l731 CISH2403 4~H,5aH,llpH-Eudesman-l2,6~-0lide, la-hydroxy 75.5 28.9 30.3 28.6 43.8 77.9 42.3 23.6 32.9 37.0 44.6 180.7 14.6 19.4 I X X (. 27 732 CISH2003 4~H,5aH,llpH-Eudesm-2-en-l2,6~-olide, 2-0x0 203.8 126.2 154.4 30.8 48.6 76.5 41.7 23.0 30.1 43.3 44.4 179.8 14.5 17.6 17.5 c' 27 4pH,Sa~llpH-Eudesm-Z-en-l2,6$-olide, la-hydroxy 733 CISH2203 73.0 125.8 138.0 30.0 42.6 77.1 41.8 23.3 32.0 35.9 44.5 180.3 14.4 18.5 18 2 C 27 734 C17H2404 5aH,1 lpH-Eudesm-3-en-l2,6~-0lide, 1,l-ethylenedioxy 111.5 26.7120.8132.6 45.2 78.0 41.7 23.6 34.5 39.9 44.7180.4 14.5 15.6 20.7 C 27 6p-Tuberiferine, l l p , l 3 4 i b y d r o 735 CISH2003 159.3 126.2 201.4 40.5 48.4 76.4 41.5 23.5 35.7 35.3 44.4 179.8 14.6 19.2 1 1 3 C 27.2X 736 CISH1903Br 4~H,SuH,ll~H-Eudesm-l-en-l2,6~-0lide, 2-bromo-3-0x0 159.2 122.0 193.3 41.2 47.9 76.0 41.2 23.3 35.6 38.3 44.2 179.8 14.6 19.0 12 0 C 27 737 ClSH2203 4~H,5aH,ll~H-Eudesm-l-en-l2,6~-0Iide, 3a-hydroxy 143.0125.3 69.1 33.0 32.1 77.3 42.2 23.8 36.6 35.0 44.5180.6 14.7 20.1 13.2 C 27 4~H,SaH,llpH-Eudesm-l-en-l2,6~-0lide, 3p-hydroxy 738 CISH2203 141.0 127.3 76.2 36.0 47.2 76.7 42.0 23.8 36.6 34.5 44.6 180.4 14.8 21 6 I 5 0 C 27.2s ~H,ll~H-Eudesm-4(15)-en-l2,6~-0lide, 3p-acetoxy 739 CI7H2404 40.6 29.0 74.5 143.2 49.9 78.2 42.8 23.7 38.6 34.9 43.7 180.4 13 Y 1X.3 107 2 c' 2X 740 CISH2003 Tournekrtiolide, 11~,13-dihydrO-9-0~0 33.5 17.7 32.3 128.5 139.5 75.4 41.7 39.8 214.4 47.7 41.8 178 7 16.0 25 0 1') 7 c' 507 Tournefortiolide, lla,l3-dihydroJ-oxo 741 CISHZOO~ 34.0 17.7 32.6 128.3 140.1 75.7 41.4 31.8 213.4 48.4 40.7 178 3 9.7 26.2 2 0 0 (' 567 Santonin, deoxy, pseudo 742 CISH2003 213.9 30.8' 35.5 139.3 128.1 76.6 42.8 23.6 31.1b 46.1 44.4 180.0 15 2 1') 5 24 4 C' 4i'J Santonin, pseudo 743 CISH2004 214.3 29.6 35.0 139.4 127.0 77.5 51.0 67.3 39.2 46.7 41.5 180.4 15.6 1Y.X 25.1 C 4i'J 744 ClSH2203 6p-Artepaulin 41.8 38.0 211.8 43.0 50.4 77.0 41.8 23.6 38.6 32.6 44.5 179.9 14.6 I 8 I I 0 . X C 27.28 4aH,SaH,ll~H-Eudesman-l2,6~-olide, 3-OXO 745 CISH2203 41.6 34.9 214.2 50.0 47.8 81.4 43.0 24.1 41.2 32.6 43.5 180 1 16.0 20.4 14.0 c' 27 Frullanolide, tetrahydro, 3p-hydroxy 746 CISH2403 40.4 30.9 76.9 36.9 49.0 77.1 42.2 23.6 39.2 32.3 44.5 1X0.5 146 18.6 14.4 C 2X 747 ClSH2403 4aH,SaH,ll~H-Eudesman-l2,6~-olide, 3p-hydroxy 40.9 24.3 74.4 40.4 47.6 83.0 43.5 26.3 42.2 32.6 43.6 180 7 14 1 21.4 97 c' ZX 748 C17H2604 4~H,SaH,ll~H-Eudesrnan-l2,6~-olide, 3p-acetoxy 398 27.0 76.8 33.8 49.0 78.6 42.1 23.6 39.0 32.2 44.5 1804 14.6 IX.4 14 4 c' ?X 749 C17H2604 4aH,SaH,ll~H-Eudesman-l2,6~-0lide, 3p-acetoxy 40.6 24.3 76.4 37.4 47.3 82.6 43.4 24.2 42.1 32.7 43.6 180.6 14 I 21.4 106 C 2X 750 CISH2403 4~H,SaH,ll~H-Eudesman-l2,6~-0lide, 3a-hydroxy 36.2 29.1 72.1 33.2 43.0 77.8 42.4 23.8 39.3 32.7 44.6180.8 14.6 17.8 1 5 4 C' 27 751 ClSH2203 llaH-Eudesm-4-en-l2,6~-0lide, 9p-hydroxy 35.5 17.8 33.1 128.2b140.4b 76.0 39.6 26.8 77.0 38.8 41.0 179.3 9.4 18.1 2 0 0 c' 170 752 C17H2404 llaH-Eudesm-4-en-l2,6~-olide, 9p-acetoxy 35.1 17.6 33.0 127.4b 140.Lib 75.6 39.4 23.8 78.4 37.5 40.9 178.Y 9.3 19 5 2 0 0 C' 130 llaH-Eudesm4-en-12,6~-olide, 9p-triethylsilyloxy 753 C21H3603Si 36.1 18.1 33.3 128.8b140.1b 76.0 39.5 27.7 77.3 39.3 41.0 179.3 9 4 1 8 5 2110 C 1%) 5aH,ll~H-Eudesm-2-en-l2,6~-0lide, 4p-hydroxy-1-0x0 754 CISH2004 205.6 126.0 150.4 69.4 48.0 76.7 42.6 22.9 31.4 43.4 43.0 178.6 14.5 20.7 29 2 C 27 SaH,ll~H-Eudesm-2-en-l2,6~-0lide, 4a-hydroxy-1-oxo 755 CISH2004 202.5 128.4 151.4 82.8 44.3 75.9 42.4 23.2 33.0 44.0 43.8 180.0 13.9 20.5 20 3 c' 27 5aH,ll~H-Eudesn1an-l2,6~-0Iide, 3~,4~-epoxy-l,l.ethyrenediory 756 C17H2JOS 111.3 26.9 60.8 77.3 45.4 78.1 42.4 23.1 32.4 39.6 44.3 180.1 13.9 16.3 21K c' 27 757 C15H2004 4~H,SaH,ll~H-Eudesman-l2,6~-0lide, la,2a-epoxy-3-oxo 63.5 55.8 207.0 40.4 41.4 76.3 40.1 23.3 34.3 33.2 44.4 179.5 14.4 17.1 I4 3 C 27 758 C19H2806 4aH,SaH,ll~H-Eudesman-l2,6~-olide, lp,3p-diacetoxy 78.3 28.4 72.6 36.8 44.6 81.7 43.4 23.5 38.2 37.1 43.4 180.1 14.0 16.3 10 5 C 2
341
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 17.-continued Mol. formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14 C-15 Sol llef 759 CISH2004 4~H,SaH,ll~H-Eudesm-2-en-l2,6~-olide, S~-hydroxy-l-oxo 202.4 126.0 154.5 30.8 50.4 77.7 41.8 67.7 39.9 45.0 48.4 179.6 14.8 18.4 17.7 C: 27 760 C2OH28OS S~H,ll~H-Eudesm-4-en-l2,6~-olide, 10a-methyl, 8a-angeloyloxy-la-hydroxy 75.1 32.3 122.2 132.7 47.4b 77.3 47.0b 69.0 36.4 38.0 37.1 177.8 14.7 12.7 22.6 C 32 761 CISH2204 11!3H-Eudesm~n-12,6~-0lide, 2a-hydroxy-3-0x0 43.2 68.8 200.6 133.3 152.3 76.7 43.9 24.0 35.8 36.1 44.0 179.5 14.8 28.6 12.2 C 28
No.
Other carbons: 734 O-CH,-CH,-O: 65.7 65.1; 739 Ac: 170.3 21.2; 748 Ac: 171.0 21.4; 749 Ac: 170.6 21 4. 752 Ac: 170.6 21.1: 753 SiEI,: 7.0(3) 5.3(3); 756 0-CH,-CH,-O: 65.5 65.2; 758 2xAc: 170.5 21.1 170.2 21.1: 760 Ang: 166.4 127.3 138.8 15.7 20.4
n
,,,
0-co 731
734
733
732
0
0-co
=
: * . , I ,
0-coa
=
R
735
R = H
737
R
736
R = Br
738
R
5
AcO
0 - co a-OH
739
@-OH
742
R = H
744
R = a-CH,
743
R = OH
745
R = @-CH,
R'
R'
746
H
a-CH,
747
H
@-CH,
748
Ac
a-CH,
749
Ac
B-CH,
740
R =
3-cti,
741
R
B-Cti,
=
750
@+
,,,,
0-co
=
751
R = H
R'
R2
752
R = AC
754
OH
CH,
753
R = Si(CH,CH,),
755
CH,
OH
756
...,,,
AGO
758
759
760
0-c0
757
342
M. BUDESINSKY AND D. SAMAN
Table 17.--continued Mol. formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C - l l C-12 C-13 C-14 C-15 Sol I
No
343
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 17.-continued No
788 7x9 790
791 792
Mol formula Name I Chemcal shlfis C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-ll C-12 C-13 C-14 C-15 C21H3604Si llaH-Eudesman-12,6P-olide, 4a,Sa-epoxy-9B-triethylsilyloxy 3 0 0 1 5 1 27Yb 6 3 1 6 5 3 7 8 7 375 27Sb 741 3 8 3 4 0 2 1786 9 2 137 2 0 1 C20H2905Bv 5~H,llaR-Eudesman-lZ,6~-oli&, 8or-angeIoyloxy-la-bo~~~~ydroxy 64.4 30.6 41.8 67.7 48.1 77.1 53.1 71.0 36.0 41.8 39.9 175.9 16.6 13.7 24.1 CI5H2204 Frullanolide, lla,l3-dihydroJa,l3dihydroxy 39.3 18.1 33.4 140.7 126.3 80.7 76.9 25.1 33.4 33.0 54.7 175.4 57.6 19.3 25.4 C16H2404 Frullanolide, lla,l3-dihydro-7a-hydroxy.13-methoxy 39.3 18.1 33.2140.5126.5 79.8 77.9 25.2 34.1 33.1 52.7173.3 68.4 19.4 25.4 C2OH2604 Oopodin 74.0 134.4 122.9 141.9 41.6b 79.6 37.8b 19.0 30.9 35.1 37.6 179.4 11.4 22.2 117.4
Sol
I
C
130
C
33
C
592
C
592
C
I26
Olher carbons: 762 Arig: 166.2 126.8 140.2 15.8 20.2; 763 Arrg: 166.0 126.7 140.2 15.7 20 1: 766 Ail! 166.5 127 0 140.3 15.9 20.1: 767 Arig: 166.6 128.0 139.6 15.9 20.4 Ac: 170.4 21.0; 768 Bz 166.1 133.0 129.4(2) 128.5(2) 130.2; 769 Ang: 166.3 126.8 140.3 15.9 20.2: 770 Ang: 166.2 126.8 140.5 15 8 20.2: 7x0 21Ac: 170.6 21.3 170.5 21.3: 783 Ac: 170.6 21.0: 784 SiEf,: 6.9(3) 5.2(3); 787 Ac: 170.4 21 0: 788 SiEf,: 7 O(3) 5.2(3); 789 Arig 166.4 127.3 138.9 15.7 20.4: 791 OMe: 59.4: 792 Arig: 167 3 127 6 138 6
1 5 8 207
hOR2 woA"g R9 .
_
0-co
0-co
762
R = H
763
R = TAC
W
0 A- c o n
O
q
R'
Ra
769
R = H
771
R = H
764
H
H
770
R = TAC
772
R = 81
765
TAC
TAC
766
H
Ang
767
Ac
Ang
768
Bz
H
775
R = H
776
R = OH
774
773
0
777
R'
R'
778
OH
H
779
ti
OH 0
;;Jx -
a4-
781
780
r;r, '"0
0-co
0-co
0-co
786
R = H
AC
787
R = Ac
R = S>(CH,CH,),
788
R = Si(CH,CH,),
782
R = H
783
R =
784
785
0-co 790
R = H
791
R = CH,
0-co
792
789
344
M. BUDESINSKY AND D. SAMAN
Table 17.--continued No
Mol. formula Name / Chemical shifts C-1 C-2 C-3 C-4 C-5 C-6 C-7
41.8 21.6 791 CISH2402 42.0 21 4
36.9 '29.0
xno
C-9
C-I0 C-ll C-12 (:-I3
C-I4 C-15
50.3 83.3 41.9 24.9
30.8 36.1 44.3 178.9 12 5
c
28.9 22 0
370
4~H,SaH,ll~H-Eudesman-l2,6aslide 36.9 31.3 55.2 83.9 40.9
23.4 41.3
37.1
53.8 179.6
124
18.7 22 0
170
4crH,5aH,ll~H-Eudesman-lZ,Qr-olide
7% CISH2402
41.9 17.1 796 C15H2202 23.4b 36.1b 797 C17H2404 39.6b 39.8' 798 CISH2203 214.2 34.4 799 CISH2003 a 212.5 35.0 b 212.2 32.8
C-8
4aH,SBH,llBH-Eudesman-l2,6aslide
793 CISH2402
15.0
770
53.0 42.6 23.0b 38.6 40.7 179.3 12.3 18.1 108 X
I X'i
32.3 27.6 51.0 80.8 41.9 23.5 43.8
36.4 53.8 179.7
12.5 2 0 9
Cnstunolide, B-cyclo, dihydro
41.1b 144.9 54.7 79.8
11~H-Eudesm-4(15)-en-lZ,6a-olide, 3p-acetoxy 73.4 142.1 53.0' 79.0 52.6' 23.3 28.8 38.2 41.2 179.2 12.5 I X . 1 106X 4aH,SaH,ll~H-Eudesman-12,6a-oIide, 1-oxo 31.2 26.8 52.9 79.4 49.8 22.6 34.8 49.9 41.6 179.2 12 5 15.3 20 7
54
Taurin
35.9 130.2 126.6 81.5 53.0 23.8 34.9 129.9 126.2 81.3 52.9 23.7
33.0 48.8 40.8 177.8 12 3 19.7 23 7 35.8 48.7 40.6 177.6 12.3 19.7 23 2
~ 1 ~ ~ 2 0 0 4 Taurin, 8a-hydroxy
197
C'
42.1 33.9 198.5 128.5 152.9 82.1 53.4 23 7 '38.7b 38.5b 41.4 177 6 12.5 11.3 23 4 802 CISH2203 Balchanin, ll,l3-dihydro = Santamarin, dihydro 75.4 34.8b 121.2 133.8 50.7b 81.3 53.9b 22.9* 32.9b 40.7 4 0 9 179.5 125 11.2 2 7 7 803 ~ 1 ~ ~ 2 4 0 3 4~H,SaH,ll~H-Eudesman-l2,6a-olide, 3a-hydroxy 35 5 28.8 72.3 35.4 46.9 83.2 40.9 23.3 40.9 36.9 53.8 179 7 124 1 x 0 1 x 0
C'
212.4
35.6 33.1 128.0 128.0 78.5
801 C15H2003
XO4 CI7H2604
36.1 26.3 74.9
xns
58.8 69.6 44.4 47.7 40.8 178.3
1 4 3 24.9
a-Santonin, dihydro 45'1 I X'I
170
4pH,SaH,ll~H-Eudesman-l2,6a-olide, 3a-acetoxy 34.3 48.1 83.0 40.8 23.3 40.9 36.8 53.8 179.4 12.4
IR.0
17 6
3711
38.8 52.6 83.4 40.7 23.2 40.8 36.8 53.7 179.5 12.4 18.8 16 7 4pH,5aH,ll~H-Eudesmnn-12,6a-olide, 3P-acetoxy 35.9 52.6 83.0 40.6 23.2 40.6 36.6 53.6 179 2 12.4 1 x 7 I 6 5
170
~ 1 ~ ~ 2 4 0 3 4PH,SaH,llaH-Eudesman-lZ,6a-olide, 3P-hydroxy
40.0 30.4 75.9 X06 C17H2604 39.5 26.7 78.0 X07 C15H2403 40.3 25.2 73.4 808 C17H2604 39.9 22.2 75.7 no9 ~ 1 ~ ~ 2 4 0 3 347 24.2 71.2
770
4pH,SpH,ll~H-Eudesman-lZ,6a-nlide, 3a-hydroxy 35.0 46.1 82.4 42.0 23.7
34.6 34.4 44.1 1797
12.4' 30 3
I ? <"
302
134
i'
3711
1-10
c
170
4PH,SpH,ll~H-Eudesman-12,cia-nlide, 3a-acetoxy 32.3 46.0 81.9 41.9
23.6 34.6 34.4
43.7 179.2
126
4aH,SaH,ll~H-Eudesman-12,6a-olide, 3a-hydroxy
36.0 44.3 80.3 41.9 23.8 43.5 36.2 53.8 179 7 12.6 205 4aH,SaH,ll~H-Eudesman-l2,6a-olide, 3a-acetoxy 35.5 21.8 73.8 33.0 45.3 80.0 41.8 23.5 43.4 36.0 53.8 179.5 125 205 4aH,5aH,ll~H-Eudesman-lZ,6a-olide, 3P-hydroxy 811 CISH2403 40.2 25.8 72.8 34.4 49.7 80.1 41.8 23.4 43.3 35.9 53.6 179.7 1 2 5 21 I XI2 C17H2604 4aH,5aH,llBH-Eudesman-12,6a-nlide, 3p-acetoxy 39.8 22.5 75.0 31.6 49.5 79.6 41.7 23.4 43.2 35.8 53.6 179.2 1 2 5 2 1 0 813 C15H2403 4aH,SpH,ll~H-Eudesman-lZ.6a-olide, 3a-hydroxy 39.4 30.3 76.0 36.7 48.6 82.9 41.8 24.9 30.7 35.9 44.3 178.9 1 2 5 2 8 4 814 C17H2604 4aH,SpH,ll~H-Eudesman-l2,6a-olide, 3a-acetoxy 38.9 26.7 78.2 33.1 48.6 82.5 41.7 24.9 30.7 35.7 44.3 178.6 125 2 8 3 X I 5 C15H2403 4aH,SpH,11BH-Eudesman-12,6a-olide,JP-hydroxy 34.3 28.6 72.8 33.0 43.3 82.7 41.9 24.8 30.2 35.7 44.1 178.9 12.5 28.4 816 C17H2604 4aH,SBH,11BH-Eudesman-l2,6aslide,3p-acetoxy 35.0 25.8 75.4 31.9 43.9 82.4 41.8 24.7 30.2 35.6 44.2 178.7 12.5 28.4 xi7 ~ 1 . ~ ~ 2 2 0 7 4PH,5aH,llBH-Eudesman-lZ,cia-c.Iidc, 3-0x0 a 40.3 37.2 211.3 44.9 52.9 83.1 40.6 23.1 40.7 36.6 53.6 178.9 12.4 18.4 h 40.7 37.4 211.5 45.0 52.9b 83.2 53.6b 23.1 40.3 36.6 40.7 179 1 12.5 I 6 4 818 CI5H2203 4aH,SaH,ll~H-Eudesman-lZ,6a-nlide, 3-0x0 40.0 35.1 213.5 43.9 49.2 79.6 41.4 23.3 42.2 35.8 52.9 179 I 12.5 20.1 XI9 ClSH2203 4PH,5pH,11~H-Eudesman-12,6a-olide, 3-0x0 39.9 36.3 214.2 43.3 47.0 82.2 41.7 24.5 35.6 35.1 43.3 178.3 12.6 28.7 X10 C17H2604
136
370
X6
370
9'4
770
16X
c
370
167
i'
170
18 1
c
370
17.7
c
770
13.9 139
c
370
('
iJ
137
C'
370
IS K
~
c
770 ~
345
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 17.-ontinued Name / Chemical shifts C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-I0 C-11 C-12 XZO C I S H 2 2 0 3 4aH,5PH,I lpH-Eudesman-12,&r-olide, 3-0x0 4 0 0 36.4 212.6 41.7 50.8 81.9 41.4 24.1 30.6 35.7 44.2 178.4 X21 CISH2004 5a,ll~H-Eudesm-3-cn-12,Q-olide, lp-hydroxy-2-oxo X I 9 198.1 1250 163.2 53.Xb 79.2 51.8' 22.3 35.6 47.1 40.4 178.6 x22 C17l12205 5a,llpH-Eudesm-3-en-I2,~-olide,la-acetoxy-2-oxo X2 0 191.8 126.9 160.7 53.6 78.8 51.R 22.1 35.3 45.0 40.3 178.4
Yo.
Mol Ionnu13
C-I
31.0
33.4 66.0 63.6 76.6 48.5
22.9
Olhcr carbons: 797 Ac: 169.9 21.2: 804 Ac: a ; 806 Ac XI4 A c . 3 ; 816 Ac: 3 : 822 Ac: 170.3 20.6
noqq
""1
%
H
Sol
IW.
12.5 27.8
150
C
370
12.4
I1.X
246
C
377
12.4
13.4 24.3
C
377
12.3 19.4 20.7
C
245
Maritimin
X23 CISH2004
2107
C-I3 C-14 C-I5
""'
793
27.9 49.2
40.4 178.0 a
a , 808 Ac
R J C . k H; 5
800
R = OH
'I
"""
""
0-co
794
R = @-H
796
R = H
795
R = a-H
797
R = OAc
0 0-co
R = H
812 A (
,
0-co
""
799
a
0
0-co
0
810 Ac
,
802
801
798
R S : =- J c \0 - c o 803
R = a-OH
804
R
= a-OAc
805
R
=
806
R = 8-OAc
H R
8-OH
,,a,
i 0-CO
807
R = H
809
R = a-OH
813
R = a-OH
808
R = AC
810
R = a-OAc
814
R = a-OAc
817
R
811
R = @-OH
815
R = @-OH
818
R = 8-CH,
812
R = @-OAc
816
R = @-OAc
819
R = a-CH,
821
R = H
820
R = @-CH,
822
R = Ac
823
"
=
a-CH,
346
M. BUDESINSKY A N D D. SAMAN
Table 17 .--continued No X24 a h x25
826 X27 X2X 829
X30 831 832
X33 x34
835 X36 a h c
X37 a h
x3x 839 X40 841 842 843
X U 845 846 a
h E
d e X46A
Mol. formula c-1 C-2 c - 3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C - l l C-12 C-I3 C-14 C-I5 S<>I CISH220.3 Artesin X4 7 40.9 29.5 132.7 126.3 78.2 55.1 26.2 35.7 44.3 42.6 180.7 14.7 21 0 22.0 S 77 7 27.1 33 3 126.0b 128.gb 83.0 52.8 24.4 38.3 41.9 41.1 179.0 12.4 18.5 19.8 c' ~15~2203 ll~H-Eudesrn-4-en-12,6a-nlide, 3P-hydroxy 27.0 32.2 77.6 128.8 125.9 82.9 52.8 24.4 38.3 41.1 41.1 178.7 12.3 18 4b 19.7* C CZlH3208 Sonchuside C 24 3b 33.5' 82.8' 130.5 1250 83.5' 53.2 23.6b 38.7' 41 6 41.0 178.5 12.5 19.7' 19.5' I' CISH2204 Torrentin, deacyl 74 7 35.6 7 0 9 132.0b 127.P 82.5 53.3 245 37 9 43.0 41 2 178 5 12 4 I9 1 I5 2 (' CI7H2405 Torrentin 74 2 33.0 72.8 133.9' 125 I b 82.5 52.6 24.5 38.2 42.7 41.2 17X 3 12 4 1 x 4 I4 i C CIYH2606 Torrentin acetate 75 I 29.9 72.2 133.2' 125.7b 82.2 52.3 24.3 37.8 41.4 41.1 178 ? 12.4 I9 5 I4 5 i' CIXH2606 7aH,ll~H-Eudesm-4-en-12,6a-olide, l~-hydroxy-3~-propiimyIoxy 74.1 33.0 72.6 133.Xb 125.1b 82.5 52.5 24.5 38.1 42.6 41.2 178.5 12.4 18 4 I4 5 C C18H2605 7aH,11~H-Eudesm-4-en-12,6a-olide, la-hydroxy-3~-propionyloxy 73.0 32.4b 72.0 137.5'123.6' 82.3 54.0 24.7 31.5b 42.4 41.2 1784 12.4 24.0 1 6 0 C' CIS112204 Torrentin, 8-desacetoxy-3a-hydroxy 72.7* 39.2' 71.7' 127.6 134.3 83.0 53.8 24.8' 37.2' 43.3 41 3 17X 7 I ? 6 17 7' I X I i' CITH220.5 Torrentin, 8-desdcetexy-3a-hydroperoxy 72.9 38 I b 85.6 122.3 137.9 82.6 5 2 7 24 2b 38.1b 42.5 41 I I78 X I ? 3 I X j. 17 i L' CIS112004 Santonin, 1,2-dihydro-lP-hydrnxy 7 4 0 42.5* 197.6 129.0 153.2 82.1 52.2 24.3* 38.0h 43.9 41.1 178 0 12 3 11.2 I 7 5 i' CISfi2204 4~H,5aH,ll~H-Eudesman-l2,6a-ulide, lp-hydroxy-3-nxn 7 6 9 4 4 . 5 2 1 1 2 44.5 46.1 79.0 53.2 23.2 38.7 41.2 41.6179.2 12.6 13.8 140 C CISH2203 Reynosin, Ile,l3-dihydro C 7 8 2 33.6' 36.ObI43.0 52.6' 79.5 52.4' 2 3 1 31.3* 42.9 41.2 1796 12.5 11.7 1 1 0 2 C 78.2 31.2 33.5 142.8 52.5b 79.3 52.3b 23.0 36.0 42.8 41.2 179.4 12.5 I 1 6 1 1 0 3 C' 79.3 31.4 33 6 145.8 52 Zb 78.4 52.6' 29.7 36.1 41.2 42 9 175 7 12 5 I 1 7 1 1 0 J CISH2204 Artemin L' 7 1 8 298' 30.0'1452 76.7 8 2 0 45.5 ? 2 9 3 0 4 44.7 413 1796 I 2 5 1 7 3 1 1 2 4 ( 71X 30.Sb 300'1453 76X X2.9 4 5 5 29Xb 22gb 4 4 7 4 1 3 17'93 1 2 3 ' l 3 3 ' 1 1 2 7 ClT112204 GalliCddi(J1, iso 77.3 27.6' 29.1'1442 76.6 8 5 4 47.1 2 4 0 3 3 1 44.7 4 2 1 17x5 1 2 X I X ? 1 1 5 6 <' Cl5~I220.3 5aH,l1~H-Eudesm-3-en-12,~-olide,lL3-hydrox) 75 0 32.6 121.3 133.3 50.5* 81 4 53.6b 22.7 345 40.7 40.6 179 X I ? 4 I I 0 2 3 2 C' CIS112204 Il~H-Eudesm-3-en-l2,~-nlide,lp,Sa-dihydroxy 69.3 32.8 126.1 136.2 75.1 82.8 45.5 22.8 29.2 43.8 41 0 170 6 I 2 6 13 0 21 h L' CISH2204 Gallicadiol 7 5 9 32.9 123.0 1348 74.9 85.1 46.9 23.X 3 2 0 43 1 4 2 0 17x7 12X 1 x 9 ? I 7 C CI.iH2204 Erivanin 75 5 33.9 74 5 145.6 52.3 79.7 42.3 22.9 32 9 43.4 41 I 179 5 I2 5 17 7 I I?'1 C' CISH2204 Erivmin, 3-epi 75 2 39.4 68.8 147 3 45.8 79.6 51.9 23.0 33 0 42.7 41 2 179 5 12 5 I X 4 I O i '1 ( CI7H240S Erivanin, 1-acetyl 76.1 32.8 72.4 145.0 42.8 79.1 52.0 22.7 33.1 41.0 41.4 179 I 12 5 17 7 I I 3 7 i' C19H2606 5aH,7aH,11~H-Eudesm-4(15)-en-12,6a-olide, la,3~-diacetoxy 75 2 30.8 72.9 140.5 43.7 79.1 51.9 22.7 33.1 41.0 41.1 179 I 12.4 17.8 116 3 c' CISH2004 Vulgarin = Barrelin = Judaicin = Tauremisin c' 201.X 125.7 151.9 70.1 5 4 6 79.6 52.4 22 7 34 3 46 3 40.6 17X.4 I? 4 22 7 ? 3 C 201 6 125.7 151.6 70 1 54.6 79.6 52.4 22 7 34 2 46.2 40.6 178.7 I2 5 I9 X 23 X 201 2 125.4 152.0 70.0 54.6 79.5 52.3 22.6 34.2 46 3 40 5 17X 3 I ? 4 1'1 7 2 3 7 C' 201.6 125.7 151.7 70.1 547 7 9 6 52.5 2 2 7 34.3 46.2 4 0 6 17X 1 1 2 4 I 0 7 2 3 S i 201.6 125.1 152.0 69 8 5 4 4 79.3 52.2 22.6 34 1 46 3 40 4 17X 2 I ? 4 I'J 7 2 3 11 CISH200S Vulgarin, pernxy 201 8 127.6 151.0 81.3 4 6 9 79.1 52 2 22 6 34.2 46.9 40.7 179 7 I 2 4 _____. 20 5 I X 1 ('
447 447
'170 410
5h5
I S'J I XL) I S'J iJ
247 404
7'
I ?i,
J'J?
347
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 17.--continued Mol. formula Name / Chemical shifts C-1 C-2 C-3 C-4 C-5 C-6 C-7 847 CISH2004 Vulgarin, 4-epi
?&I.
C-8
C-9
C-10 C - l l C-12 C-i3 C-14 C-I5
a 203.1 125.3 150.2 68.2 51.0 79.2 52.3 22.8 32.5 45.9 40.1 179.0 h 203.1 125.3 150 2 68.2 51.0 79.2 52.3 22.8 32.5 45.9 40.8 179.0 848 C I S H I 8 0 3 ll~H-Eudesma-2,4-dien-12,Q-olide, I-0x0 2 0 3 6 1 2 3 . S 1 4 9 . 0 1 2 1 . 5 1 4 3 . 1 81.8 54.1 23.4 35.4 50.5 41.1 178.0 849 CISHI804 11~H-Eudesma-2,4-dien-12,6a-olide, 15-hydroxy-I-0x0 204 1 123.8 145.6 126.9 144.6 81.6 54.0 23.1 36.0 50.7 40.7 177.9 X50 C17HZOOS Il~H-Eudesma-2,4-dien-l2,6a-olide, IS-acetoxy-I-oxo 203 6 124.3 144.5 121.5 148.4 81.2 54.0 23.3 35.6 50.8 40.9 177.2 851 CIS111804 11~H-Eudesma-2,4-dien-12,6aslide,8a-hydroxy-I-oxo 2040 123.0 149.4 122.0 141.8 78.6 58.8 68.6 44.2 49.4 40.8 178.3
852 C I T H I X 0 3 a-Santonin 155.1 125.9 186.0 128.4 151.5 81.5 853 C I S H 1 9 0 3 N Santonin oxime 145.6 112.5 1507 122.5 139.5 82.3
54.0 23.3
39.3 41.7
12.5 20.6 31.7 12.5 20.6 31.7
C C
438 2
12.4 26.2
19.1
C
412
12.4 26.1 59.8
P
412
12.5 26.3 62.5
C
412
27.4
C
412
14.1
41.2 177.4 12.5
53.7 23 8 38.5 41.1 41.4 178.0
Sol. IW.
12.5
18.9
10.9 25 3
C27.459.521
12.2 26.0
459
C
Other carbons. 826 Glc: 102.0 75.0 78.5 72.0 78.0 63.1: 828 Ac: 170.8 21.2: 829 2xAc: 170.6 21 I 170.2 21.1; 830 Prop: 174.3 27.8 9.2; 831 Prop: 174.3 27.9 9.2; 844 Ac: 170.0 21.4 : 845 21Ac: 170.3 169 1 IS 2 21.2: 850 Ac. 170.7 20.9
R'
R'
824
OH
ti
825
H
OH
826
ti
OGic
827
OH
OH
828
OH
OAc
829
OAc
OAc
830
OH
OProp
831
832
R = H
833
R = OH
R
0-co
= 835
L
836
R = o-H
839
R = a-H
837
R = a-OH
840
R = a-OH
838
R = @-OH
841
R
R'
R2
846
R = a-OH
u4a
R = H
H
a-OH
846A
R = u-0OH
849
R = OH
843
H
@-OH
847
R = @-OH
850
R = OAC
844
A:
a-OH
845
A:
a-GAc
842
Ra 0-co
852
R = 0
853
R = N-OH
''4
834
851
=
8-OH
348
M. BUDESINSKY A N D D. SAMAN
Table 17 .-continued No 854 855 856 X57 858 X5Y
860 X61
862 863 864 865 866 X67 X68 X69
X70 a b X71 X72 873 874 875 876 X77 878 879
Mol. formula Name I Chemical shifts C - l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C - I 1 C-I2 C-13 C-14 C-15 C17H2405 Chrysanthemolide 73.0 137.7 123.1 70.0 49.5 80.7 52.2 22.9 35.3 39.0 40.6 175.3 12.5 20.0 24 5 ClSH2404 Colartin, Is-hydroxy 77.7 28.3 38.2b 71.2 56.0 80.8 53.2 23.4 39.3b 41.8 40.6 178.4 12.5 13.7 24.3 C I 7112605 Tauremisin, acetyl, tetrahydro 80.9 25.3 38.5 71.4 56.6 80.1 53.6 23.8 35.6 41.4 41.1 178.7 13.0 1 5 3 24.9 CISH2204 Santamarin, ll~,13-dihydro-3~,4u-epoxide 73.6 30.9 60.8 57.5 52.0 80.5 53.0 22.6 34.4 40.1 40.7 179.2 12.4 I I 7 21 5 C2lH3209 Sonchuside I 78.6 30.7 29.3 37.0 49.8 83.1 53.4 23.4 37.7 42.7 40.9 179.3 12 7 12.7 73 6 C2IH3409 Sonchuside H 84.5 28.6 26.8 39.1 49.8 83.2 53.3 23.1 37.5 41.7 40.9179.4 12.7 13.4 6 5 4 ClSH2204 Sonchucarpolide, Ilu,l3-dihydro 76.8 29.4 24.9 48.Bb 49.0b 81.6 52.8 23.1 37.3 41.8 41.3 178.3 12.6 12.1 203.2 C2IH3409 Sonchuside G 83.2 25.5 24.6 48.9 48.9 81.5 52.7 22.9 37.1 41.3 40.9 178.4 12.7 12 X 203 I C19H2806 5aH,11BH-Eudesman-12,6aslide,Zp-acetoxy-4u-methoxycarbonyl 44.2 68.9 41.3 50.6 43.1 79.2 43.5 22.8 35.4 52.3 39.3 179.2 12.3 174 2 1 6 Cl9H2806 SaH,lleH-Eudesman-12,6a-olide, 2p-acetoxy-4~-methoxycdrb1myl 44.8 68.9 40.9 56.1 42.6 82.0 43.2 31.0 36.Y 51.5 40.0 179 4 12.5 21 I 2 3 I CISH2203 Herbolide G 20.P 34.6* 121.1 137.8 51.2 80.2 49.6 32.9* a 40.7 38.2 180.1 9 7 11.1 2 3 3 CISHIBOS 11~H-Eudesm-3-en-12,6a-olide, I-oxo-Za,Sa-peroxy I' 204.0 78.3b121.1 149.7 83.5 78.1b 44.5 22.2 30.1 47.7 41.2 177.3 12.4 20.X 190 11SH-Eudesm-3-en-12,6a~lide, Ba-hydroxy-l-oxo-Zu.5a-peroxy CISHI806 c 202.6 78.2 121.6 149.0 82.7 75.7 50.8 68.1 39.8 47.2 41.0 177.2 14.2 21.8 lY.O CISH2203 ll~H-Eudesm-4-en-12,6a-olide, Ba-hydroxy 40.5 18.5 34.3 127.6b 128.2b 79.9 59.3 70.1 51.8 36.2 41.0 178.8 14.4 27 2 I 9 9 C21H3603Si 11~H-Eudesm-4-en-12,6u-olide, 8a-I-butyldimethylsilyloxy 40.5 18.5 34.4 127.2b 128.Sb 80.1 59.4 70.8 52.0 36.0 40.9 179.0 14.5 27.2 19.9 CISH2204 7aH,11SH-Eudesm-4-en-12,6u-olide, lp,Xa-dihydroxy 77.4 26.8 33.3 126.9b 127.3b 79.6 58.6 70.0 48.7 41.0 40.8 178.7 14.4 I9 h I!, 0 C17H2405 Torrentin = Gargantolide 74.2 33.0 24.5 125.Ib 133.9b 82.5 52.6 72.8 38.2 42.7 41.9 178.3 124 18.5 I4 5 77.2 26.7 33.2 126.9b127.3b 79.4 56.1 71.2 44.1 41.0 40.2 178.0 13.9 1 9 4 1 9 6 CI7H24OS Gargantolide, I-epi 73.8 24.9 28.9 127.2b 126.0* 79.6 56.1 71.5 39.2 40.8 40.3 178.0 14.0 27.1 2 0 0 C17H2403S2 Il~H-Eudesm-4-en-12,6a-olide, 3,3-ethylendithio-Xa-hydroxy c 39.6 39.2 72.7 128.Bb 133.7b 79.4 58.9 69.9 51.5 36.2 41.0 178.4 14.3 2 6 8 I 6 5 CISH2003 ll~H-Eudesma-2,4-dien-12,6cr-olide,So-hydroxy 40.8 123.Xb130.4b125.5'128.8' 79.2 57.3 69.8 52.5 36.7 40.7 178.7 14.4 24.4 I 9 I C27H4003SiSe Eudesm-4-en-12,6a-olide,Ba-r-butyldimethylsilyloxy-ll~-phenylsel~n~~ c 40.5 18.5 34.5 127.4b 128.2b 78.1 63.2 67.9 51.8 35.9 49.4 175.9 23.4 27 I 2 0 0 CI7H220S 4~H,5aH,11~H-Eudesm-I-en-12,6a-olide,la-acetoxy-3-oxo c 156.5 127.1 200.0 42.0 51.2 79.1 56.6 69.5 43.4 37.8 40.1 177.7 14.0 20.5 14 5 C21H3404Si 4PH,5aH,11BH-Eudesm-I-en-12,6a-olide, Ba-I-butyldimethylsilyloxy-3-~~1~ 1573 126.8 200.5 42.1 51.2 79.4 59.3 68.9 47.9 37.7 40.4 178.7 14.5 20.7 I 4 6 C15H2204 llpH-Eudesm-4-en-12,6a-olide, 3u,9p-dihydroxy c 32.4b 27.1 78.6 132.2' 129.4' 81.7 48.8 31.Zb 70.3 42.3 40.8 178.3 12.4 17.9 17 9 C17H2206 4BH,5aH,11~H-Eudesman-12,6a-olide, 8u-acetoxy-la,2a-epoxy-3-nxn c 63.3 55.9 207.7 42.6 44.4 79.6 55.8 69.6 41.9 36.8 40.1 177.6 13.8 17.8 17 9 C17H220S Artemisin acetate, y-tetrahydro C' 40.1 36.7 210.6 44.6 52.8 80.1 56.4 69.9 4 6 2 36.0 40.0 177.9 13.8 19.2 13.9
c
~
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
349
Table 17.--contznued Mol. formula C-I C-2 C-3 880 C I S H I 8 0 4 a 153.7 125.9 186.1 b 155.8 124.6 185.6 881 C I ~ H ~ O O S 153.2 126.1 185.8
No.
Name I Chernlcal shifts C-4 C-5 C-6 C-7 C-8 C-9 C-10 Artemisin 129.5 149.6 78.2 58.7 68.7 46.9 40.2 126.8 152.4 78.0 58.6 66.5 40.4 46.4 Artemisin acetate 129.8 148.7 77.9 56.2 69.6 42.6 40.0
C - l l C-12 C-13 C-14 C-15
Sol. Ref
40.9 117.3 14.2 26.5 10.9 39.9 178.1 25.9 14.1 10.7
C
409
S
126
40.3 176.6 13.9 26.4
c
409
10.9
Other carbons: 854 Ac: 170.5 21.1; 856 Ac: 171.1 21.7: 858 Glc: 104.8 75.5 78.0 72.0 78.0 63.0; 85Y Glc 102.2 75.3 78.3 72.1 78.7 63.3; 861 Glc: 102.2 75.1 78.3 72.1 78.6 63.3; 862 Ac: 169.8 21.4 COOMe177 R 53 4: 863 Ac: 170.3 21.4 COOMe: 176.2 54.4; 868 TBDMS: -4.2 -4.6 17.9 25.8(3); 870a Ac: 170.X ? I 2: X70h Ac: 170.4 21.0; 871 Ac: 170.5 21.2: 872 S-CH,-CH,-S: 40.0 41.4; 874 TBDMS: 26.013) 1 x 0 -3.R -3.9. SrP/i: 124.7 129.112) 138.212) 129.7; 875 Ac: 170.3 21.0; 876 TBDMS: 25.7(3) 17.9 -4.3 -4.6; 87X A(.: 170.3 21.0: 87Y Ac: 170.3 21.0; 880 Ac: 170.3 21.0
854
855
R = H
856
R = Ac
857
OH r 1
867
862
R = a
863
R = 8-COOCH,
R'
R'
H
H
a79
-
~
~
~
~864~
,
872
-
875
R = Ac
876
R
TBDMS
880
R = H
881
R = AC
=
865
R
866
R = OH
R'
R'
858
H
CH,OGlc
859
Glc
CH,OH
860
H
CHO
861
Glc
CHO
H
87 3
874
877
878
350
M. BUDESINSKY AND D. SAMAN
Table 17.--continued No. Mol. formula
Name / Chemical shifts C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14 C-15 Sol. Ref. 8x2 ClSH2004 IleH-Eudesm.l-en-12,6a-olide, Sa-hydroxy-3-0x0 409 38.3 33.2 198.7 129.1 151.0 78.6 58.2 69.4 51.6 37.3 40.9 177.6 14.3 25.2 11.1 XU3 C17H220S 4~H,5aH,11~H-Eudesm-2sn-12,Qslide, Sa-acetoxy-I-oxo C 201.2 125.4 154.1 33.1 50.7 79.6 56.0 69.9 38.5 45.3 40.0 177.9 13.9 18.5 20.1 409 8x4 CISHI804 IleH-Eudesm-Zsn-I2,6aslide, 4a,Sa-epoxy-l-oxo 1993 129.0 149.1 59.9b 67.8b 76.4 48.8 23.0 29.6 48.6 40.5 177.9 12.4 22.3 18.0 c 412 XX5 CISHI805 lIBH-Eudesm-2-en-12,6aslide, 4a,Sa-epoxy-Sa-hydroxy-I-oxo 198.8 128.8 149.4 60.4b 67.1b 73.5 54.6 68.8 39.5 48.0 40.4 178.1 14.1 23.3 17.8 c 412 886 ClSHlROS 11eH-Eudesman-12,6a-lide, 2a,3a$a,5a-diepoxy-I-oxo c 412 202.0 46.1 52.8 60.1b 69.2b 76.4 48.5 22.8 29.1 51.5 40.4 177.6 12.4 19.8 18.9 XX7 Cl5H2OOS Taurin, 4a,5a-epoxy-&-hydroxy C 437 209.4 41.3 27.9 65.0 64.0 73.7 54.4 69.0 33.1 48.6 40.3 177.7 14.3 19.3 21.3 XX8 CI5H2204 Herbolide I A a 20.2 a a 147.3 76.8 80.7 a 40.9 71.0 44.9 38.7179.6 9.2 12.8110.6 586 M 586 h 21.0 31.4b 31.1b a 78.1 82.8 30.9 42.0 72.6 a 39.9 a 9.6 13.6 111.8 XX9 CISH2204 5aH,7aH,ll~H-Eudesman-IZ,~-olide,8a-hydroxy-1~,4~-epoxy-lO-epi c 56') 85.0 25.6 36.3 86.0 59.0 76.4 52.2 70.8 41.6 46.9 41.6 179.2 1 4 0 25.6 I X 3 XYO CI 7H2004 7aH,ll~H-Eudesma-1,3,5-trien-12,6-olide, 3-aceloxy 137.5 120.4 145.4117.1 116.1 141.8 41.8 24.2 33.4 36.8 44.8 176.1 12.5 133 26.9 c 375 X Y I C17H2205 11~H-Eudesma-3,5-dien-12,6-olide, 8a-acetoxy-2-oxo c 400 51.7 197.0 127.5 145.8 115.4 151.4 50.6 69.6 43.2 38.3 39.8 174.8 14.4 27.3 2 3 6 892 C I S H Z O O ~ no name 76.3b 30.3' 38.6' a 57.7' 74.0b 57.3' 68.3b 46.9' a 40.5 a 14.3 13.5 il c I32 XY3 C25H3403 no name C 412 211 9 53.1 122.2 149.8 48.7b 84.0 48.1 22.7 33.4 47.6b 41.7 178.6 12.7 20.3 19.8 XYJ C2SH3403 no name 216.4 52.1 119.7 149.6 48.Xb 80.9 46.0 22.4 30.3 47.Yb 41.7 178.9 12.5 20.8 1 8 8 c 412 895 Cl5H2202 Costunolide, f3-cyclo, IlaJ3-dihydro c 564 41 8' 22.9' 36.0b 144.9 54.9 78.8 48.4 20.5' 40.0b 38.4 38.8 180.2 9 7 lX.O I O X 9 896 C,,H,,O, Reynosin, Ila,l3-dihydro i' 404 78.3 31.3 33.6 142.9 5 3 0 78.3 48.1 203 36.0 42.7 387 I 8 0 0 9.7 117 1 1 0 4 x w cis112203 Cadabicilone C I2 40.5 3 7 . 2 2 1 1 4 40.4 52.8 83.0 53.4 23.1 40.1 34.2 44.9 1789 13.8 18.3 I 2 4 XYX CISH2203 Santamarin, IlaJ3-dihydro c 564 75.4 32.8 121.1 133.7 51.1 80.2 49.5 20.2 34.5 40.6 38.2 180.2 9 6 11.0 -733 XYY C15H2203 Taurin, 11-epi c Sh4 213.6 36.0b 33.1b 130.0' 127.0' 80.9 48.4 20.8 34.7b 48.7 38.0 179 4 9.7 23 4 1') X YO0 ClSH2203 Artesin, 11-epi C' 404 7 7 7 27.1 33.3 126.0b 129.3b 82.1 48.2 21.2 38.2 41.7 38.0 179 8 9.8 1 x 4 1') 7 YO1 C17H2405 IlaH-Eudesm-4-en-12,6a-olide, 8~-accloxy-1~-hydrexy C' 417 77 8 26.6 33.4 128Xb 127.0b 77.4 48.9 68 6 43.3 41.4 37 3 178.7 1 1 5 20 9 2 0 0 YO2 C17H2205 Arlegallin c Sol 76.2 34.0 195.1 129.0 149.4 80.8 47.6 21.0 39.0 41.6 37.8 178.1 9.7 24 7 II 2 903 CIS111805 llaH-Eudesm-3-en-12,6a-olide, I-oxo-Za,5a-peroxy 412 203.9 78.3 121.0 149.8 83.8 77.2 39.8 194 30.0 47.5 37.9 178.0 9.2 20.7 I9 1 90.1 CISI118OS IlaH-Eudesma-2,4-dien-12,6a-olide, I-0x0 c 412 204.5 123.3 149.1 121.4 143.6 80.8 49.5 20.2 35.3 50.2 37.8 178.8 9.7 26.0 19.0 YO5 CIS111804 IlaH-Eudesma-2,4-dien-12,6a-olide, 8a-hydroxy-I-0x0 c 412 ? 0 3 . 7 1 2 3 . 2 1 4 9 . 2 1 2 2 . 2 1 4 1 . 5 78.0 55.1 64.4 44.0 49.5 3 6 . 6 1 7 8 0 9.3 27.4 18') YO6 ClSH2204 Torrentin, 11-epi, desacyl i7io c' 74.7 35.4 70.9 135Sb 127.Bb 81.6 48.8 21 2 37.7 42.8 38.1 179 4 9 X 19.4 15 3 YO7 C17H2405 Torrentin, 11-epi c S70 73.8 32.9 72.9 134.4b 124.Yb 81.7 47.8 21.1 38.0 42.4 37.9 179.2 9.7 I X 2 I4 3 YOU C19H2606 Torrentin, l,ll-diepi, I-acetate i70 c __ 7 4 9 29.2b 71.6 134.3' 124.4' 81.2 49.0 20.6 32.3b 41.0 38.0 179.1 9.8 24.7 15.6 __
C-l
c
c
35 1
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 17.-contku?d No.
Mol. formula I Chemicak shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-I1 C-I2 C-13 C-14 C-15 YO9 C19H2606 Torrentin, ll-epi, 1-acetate 7 5 2 29.9 72.3 133.7b125.6b 81.3 47.7 21.0 37.7 41.3 37.8 179.1 9.8 19.4 14.4
SIII
I<ef
C
570
Ollicr carbons. 883 Ac: 170.3 21 0: 890 Ac: 168.7 21.9 : 891 Ac: 170.3 21.1: 893 C-16 - C-25: 33.6 39.4 145.0 35.6 26.6 123.7 132.0 25.7 17.7 109.3: 894 C-16 - C-25: 26.1 40.6 145.3 35.5 26.6 123.8 1320 25.7 17.8 109.8: 901 Ac: 169.8 21.5: 902 Ac: 170.4 20.8; 907 Ac: 170.7 21.0: 908 2xAc: 170.9 21.2 170.5 21.2. YO9 21Ac. 170.5 21.1 170.2 21.1
. % , ,
1
"""'
0-co
= 883
882 0
on 887
qq =
(QAC
ox::p
0 %0 - c o """ 884
R = H
885
R = OH
888
889
892
893
""'
..,,0 = i
0-co 886
890
.OAc
0-co
.I,,
891
894
@ H
895 896
E0 - c o
0-co
R = H R = OH
898
a97
@ 0-co
0-co
YO
900
R = H
901
R = GAc
&
902
4cO
0-co
906
R = H
907
R = Ac
909
R = 8-OAc
p+
899
0-co
903
H
904
R
905
R = OH
=
352
M. BUDESINSKY AND D . SAMAN
Table 17.--continued No.
910 911 912
913 914 915 916 917 918 919 920 921 922 923 924 925 926 927 928 929 930 931 932 933 934 935
Mol. formula Name I Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14 C-15 Sol. Ref. CISH1803 6-Santonin 155.0 126.0 186.1 i28.8 151.9 80.8 49.5 20.3 38.2 41.5 38.2 178.3 9.9 11.0 25.2 C459.521 CISH2403 Colartin, ll-epi ' 43.2b 19.4 41.1b 71.6 57.8 80.3 49.3 20.7 40.Ib 37.3 38.0 179.3 9.7 19.8 24.2 C 564 ClSH2204 Colartin, ll-epi, IS-hydmxy 78.4 28.3 38.2 71.2 56.4 79.7 49.0 20.5 39.2 41.6 37.7 174.0 9.7 13.6 24.3 C 564 C15H2204 Colartin, 4,ll-diepl, IS-hydroxy 78.7b 27.1 38.0 71.1 54.7 78.8b 49.4 20.4 40.1 42.1 38.2 180.2 9.6 13.1 32.4 C 564 ClSH2204 Santpmarin, IIa,lSdihydro-Ja,4a-epoxide, 73.7 30.9 60.9 57.6 52.6 79.6 49.0 20.0 34.4 40.0 38.2 179.8 9.6 11.8 21.6 C 569 CISH2004 Herbolide E 21.2 29.8 72.9b126.9 134.3 81.6 48.1 42.3 71% 38.2 37.9 179.5 9.9 17.4' 18.W C 191 C17H2004 Eudesma-3,5,7(11)-t~en-12,60lide, 5acetoxy 37.2b 22.8 149.6 118.8'118.@ 143.8 148.5 20.1 37Sb 34.2 124.0 172.0 8.1 13.6 21.4 C 375 C16H2003 Eudesma-3,5,7(11)-trien-12,6-ol~ 5methoxy C 375 37.2b 22.8 158.0 110.7 116.1 141.7 149.5 20.1 37Sb 34.9 128.4 172.0 8.8 13.6 22.3 CISH1702C[ Eudesma-3,S,7(11)-trlen-l2,&olide, k h l o r o 36Sb 31.6 136.9 124.0 118.7 143.5 148.9 19.0 37.2b 34.3 126.6 171.3 8.1 18.1 21.2 C 375 C17H1804 Eudesma-1,3,5,7(11)-tetraen-12,6-olide,3-acetoxy 138.1 120.3 145.6 117.8 120.3 144.7 147.3 19.1 34.3 38.1 126.5 170.7 8.1 13.3 25.4 C 375 C16H1803 Eudesma-1,3,5,7(11)-tetraen-12,6-olide, 3-methoxy C 375 140.1 116.0 153.1 110.9 116.8 142.2 147.2 19.2 34.5 38.2 129.4 171.2 8.7 12.1 25.9 CISHIS02CI Eudesma-1,3,5,7(11)-tetrPen-l~6-olide, 3-chloro 137.6 124.4 131.4 126.1 118.6 143.6 147.9 19.2 34.5 38.2 125.7 172.3 8.3 17.6 25.4 C 375 C17H2005 Santomne, 4a-acetoxy 35.1b 38.2 205.3 78.1 120.5 144.4 147.9 19.5 35.6b 36.1 128.3 171.1 8.4 25.5 24.4 C 375 C17H2005 Santonene, 4S-acetoxy 33.4b 38.5 204.1 80.1 120.9 143.1 147.9 19.6 34.0b 36.4 127.3 168.6 8.4 25.6 24.4 C 375 CISHISO2C13 Eudesma-3,5,7(11)-trien-12,6-olide,laf~,3-trichloro 68.2 61.7 131.4 121.0 117.4 146.2 147.4 18.4 32.6 40.2 128.8 169.3 8.4 18.7 24.0 C 375 CISHI402CIZ Eudeuna-1,3,5,7(tl)-tetraen-12,6-ollde, 3,15-dichloro C 375 140.8 124.0 135.1 121.1b120.0b143.5 147.5 18.9 33.9 38.1 125.8 169.8 8.3 41.0 24.8 CI6H2405 SaH-Eudesm-3-en-12,6a-oiide, 1p,&-dihydroxy-13-methoxy 165 75.2 32.4 121.9 132.6 49.8 79.5 60.2 66.7 43.1 40.3 46.6 174.7 71.5 12.3 23.1 C C17H2205 Costunolide, a-cyclo, 8~-acetoxy-11~,13-epoxy 24.4 36.0 124.2 145.3 50.0 73.2 65.5 67:l 42.1 59.6 57.1 172.3 50.6 19.9 17.8 C 216 C22H3009 Eudesmd-en-12,6a-olide, 13-methoxy-lp,3a,&-triacetoxy 70.1 29.5 72.5 133.4 125.1 78.1 49.5 74.4 43.3 40.2 45.9 169.9 68.7 19.4 17.1 C 165 C24H32011 SaH-Eudffman-12,6a-olide,13-acetoxy-8~-(4-acetoxyangeloyl)-l~,l~a-dihydrox~3~~xo 318 77.2 44.2 210.1 55.9 43.0 72.4 47.4 67.0 42.6 40.7 75.3 174.6 63.2 13.8 15.9 C C19H2407 Eudesmaafraglaucolide 353 74.0 36.2 78.0 140.6 52.3 70.4 169.2 22.2 36.0 41.1 118.7 170.0 54.6 9.9 107.0 C C20H2606 Trichomatolide A 76.8 31.2 33.7 142.3 55.3 78.6 157.1 65.5 41.4 41.1 128.1 172.4 56.9 12.2 110.8 C 480 CI4H1604 Santonin, A'<"-13-nor, 4,s-dihydro-11-hydroxy -- 14.2 17.7 C 135 156.7 126.8 200.0 42.8 54.0 79.5 132.6 19.7 37.3 37.8 135.6 169.8 C14H1804 Santonin, A'."-13-nor, If;4,S-tetrahydro-ll-hydroxy 13.6 16.8 C 535 37.1 19.9 211.2 45.6 56.2 80.7 133.6 19.9 39.8 35.4 135.3 170.1 -C17H2404 Eudesm-7(11)-en-12,6aa-olide, 3,3-ethylenedioxy 37.8 22.7 110.5 40.9 53.7 82.2 162.3 31.0 40.5 35.2 120.2 174.6 8.3 12.2 17.0 C 30' CI7H2304Br Eudesm-7(11)-en-12,6a-olide, I3-bromo-3,3-ethylenedioxy 37.4 23.2 110.1 40.4 53.9 82.3 167.8 30.8 40.5 35.2 121.5 171.4 18.6 12.1 16.9 C 30'
CARBON-I3 NMR SPECTRA OF SESQUITERPENE LACTONES
353
Table 17.-continued Othercxbons: 916 Ac: 168.4 20.7: 917 OMe: 55.7; 919 Ac: 168.3 20.3; 920 OMe: 56.1; 922 Act 168.5 20.3. Y23 Ac: 168.4 20.3; 926 OMe: 59.3: 927 Ac: 169.4 21.1: 928 3xAc: 170.4 20.9 170.4 20.9 170.1 20.9 OMe: 59.1; 929 Atig-4-OAc: 165.0 127.0 142.2 63.0 19.7 171.1 20.9 Ac: 170.9 20.5; 930 2xAc: 172.8 2 0 4 170.9 20.1; 529 Tig: 168.2 128.2 140.0 14.8 13.0 934 O-CH,-CH,-O: 65.1 65.2; 935 O-CH,-CH,-O: 65.0 hS 2
R'
910
914
R2
911
ti
a-on
912 913
OH
a-OH
OH
b-oti
916
R = OAc
919
R = OAc
922
R = a-OAc
917
R = OCH,
920
R = OCH,
923
R = 8-OAc
918
R = Cl
921
R = CI
926
925
929
934
R = ti
935
R
= Bi
R'
Rz
R'
930
OAC
ti
AC
931
ti
OTig
ti
915
924
927
928
932
933
354
M. BUDESINSKY AND D. SAMAN
Table 18. Carbon-13 chemical shifts of eduesm-11(13)-en-12,8-olides. No 936 a h 931 a h C
d Y 38 a h Y 3Y Y40 a h 941 a h 942 Y43 Y44 945 946 Y47 948 Y4Y Y50 a h
951 Y52 Y53 954 a h 955 956 Y57 95R Y 59
Mol. formula Name I Chemical shifts C - I C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-I2 C-13 ClSH2002 Dlplophyllolide A 37.9 22.2 122.4 133.0 44.0 27.5 41.3 77.0 41.0 30.9 142.1 170.7 120.3 37.8 22.1 122.2 132.9 43.9 27.5 41.2 76.9 40.9 30.9 142.0 171.0 120.1 CISH2002 Ivangulin, 4-desoxy-8-epi 37.1 18.8 31.9 131.3 127.2 27.7 41.1 76.5 42.6 33.5 140.4 170.8 121 4 41.4 22.7 37.2 135.0 145.0 27.6 40.0 76.4 40.1 34.0 140.3 170.4 120.6 37.1' 18.7b 31.9' 127.1 131.2 27.6b 41.0 76.4 42.5 33.5 140.3 171.0 121.2 37.4 18.8 32.0 127.1 137.4 27.7 41.1 76.3 46.6 33.5 140.7 170.4 120.9 CI5H2002 Alantolactone, is0 41.3 22.7 37.9 148.9 44.0 27.5 40.6 76.8 41.0 34.3 142.3 170.6 120.1 41.3 22.7 36.8 148.9 46.0 27.5 40.3 76.7 42.1 34.2 142.5 170.1 119.5 C I SH2003 Asperilin 795 31.2 34.0146.9 44.1 26.7 40.1 76.3 37.8 a 142.1 a 120.2 CI 5H2002 Alantolactone 41.0 22.2 36.8 41.1 133.0 122.3 46.3 77.0 42.2 34.3 142.1 170.6 119.9 41.7 16.8 32.7 37.5 148.7 119.1 39.4 76.3 42.7 41.7 140.1 170.0 121 2 C15H2203 Septuplinolide 24.6b 19.3b 43.2' 71.6 41.1 43.3' 51.2 76.8 44.9' 33.1 141.0 170.7 120.1 17.3 24.9 44.4 71.2 41.1 41.5 48.8 77.0 42.0 32.5 142.2 I 7 0 6 120.1 CISHI803 Pinnatifidin 54 2 196.9 127.7 159.6 44.9 26.9 40.8 75.6 40.6 35.7 141.6 169.h 120.6 CISH2203 Yomogin, 1,Z-dihydro 42.5 34.7 197.8 130.0 158.7 29.7 39.6 74.6 35.2 33.9 138.6 169.7 123.1 CISH2003 ivalin 5 1 0 66.9 46.3 146.1 45.6 27.3 40.5 76.6 41.2 33.9 142.1 170 3 120 1 L'l.iH180.3 Alantolactone, iso, 3-0x0 40.4 36.0 201.2 147.3 44.8 27.3 39.6 76.1 38.9 32.1 141.6 1700 120.7 C15H2003 Telekin, iso, 3-epi 40.0b 32 1 73.0 151.0 44.6 27.5 40.3 76.7 41.0' 34.0 142.0 170.5 1203 CZOH2605 Alantolactone, iso, 3~-hydroxy-Ze-senecioyloxy 45.1 76.2 74.3 146.8 44.3 27.2 40.1 76.2 40.5 33.8 141.6 170.2 I 2 0 6 CI SH20O3 Telekin 35.6' 35 4* 33.Sb 150.1 74.2 21.7b 37.6 77.0 31.Xb 36.5 142.1 1706 120.2 C16H2204 Telekin, 5-desoxy, 5-methylperoxy 37 Xh 37.3h 32.2b 148.0 84.2 22.0b 37 8 76.9 28.4 37 3 141 9 1706 120 5 C I jH2004 Telekin, 5-desnxy, 5-hydroperoxy 35.8' 35.2h 32.0b147.2 84.9 21.Xb 37.4 77.1 27.Yb 37.1 142.0 170.9 120.4 35.Xb 21.8 32.2 146.3 85.Y 27.9 37.6 76.8 35.2b 37.3 141.9 170.5 120.6 CISH2003 Telekin, 5-epi 38.5b 34.5* 32.9b 151.1 75.8 21.Yb 37.8 75 4 32.4' 39.7 138.5 170.4 1209 C16H2204 Telekin, 5-epi, 5-desoxy, 5-methylperoxy 35.Xb 35.6b 32.6b 146.0 84.3 22.2b 38.7 76.1 30.1' 37.7 141.0 170 I 121 0 CISH2004 Telekin, 5-epi, 5-desnxy, 5-hydroperoxy 22.6b 35.7b 35.9b 144.9 85.5 22.0b 38.6 76.0 29.5' 37.9 141.1 171)O 1209 CISH1603 Encelin 159.3 126.6 188.5 144.2 44.6 26.7 39.5 76.0 37.4 36.0 141.1 169.8 121.1 160.3 127.2 189.1 145.0 45.3 27.4 40.2 78.1 38.0 36.7 141.9 170.5 121.9 CI 5H1803 Alantolactone, iso, 1,2-dehydro-k-hydroxy 124.5 142.4 69.6 148.7 40.4 26.8 40.6 76.6 38.4 36.5 141.6 170.3 120.7 CISHI803 SaH-Eudesma-1,4(15),Il(l3)-trien-12,X~~olide, 3p-hydroxy 127.5 139.9 70.4 148.6 44.1 27.1 40.4 76.4 38.4 39.6 141.6 170.3 120.7 CI 51118 0 4 Himeyoshin 6 3 9 56.2204.7 37.9 40.0 28.1 43.2 76.1 33.1 37.1 137.3 1115.5 121.0 C23H3209 Ahsinthifolide 36.9 18.6 28.9 127 5 139,s 27.6 41.7 76.3 42.6 34.1 140.5 171.4 121.7 CZYH28012 Ahsinthifolide 2',3',4'-triacetyl 37.1 18.5 28.4 127.2 139.4 27.7 41.8 76.0 42.5 34.0 140.5 170.4 121.4
C-14 C-15 -
17.3 21.1 17.2 21.0 26.8 19.2 I 7 3 21.1 19.2 26.8 19.1 26.8 17.7 106.6 17 6 IO6.4
113 10x1 172 285
176 226
19.6 22.5 20.0 30 4 18.3 21 5 11.2 25 0 18.7 10X.9 17.2 119.0 1 7 7 1035 I X 1 107 4
21.7 I0X.X 22 7 I 1 0 9
229 I l l X 23 0 113.3
?I
x
10') I
2 3 5 1127
233 I l 1 i 10.3 119.0 2 0 0 I19 6
19.2 111.7 20.6 105 3 15.5
I6X
27.u
(7x6
27 I
hX 1
355
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 18.--continued Mol. formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7
No
C-8
C-9
C-10 C-I1 C-12 C-13 C-14 C-I5
960 CISHIXO.1 Alantolactone, la,Za;3a,4a-diepnxy-5~,6-dihydro 60.5 48.0 56.0 53.4 3 7 2 25.7 4 0 4 75.8 36.2 33.4 141.4 170.1 120.8 17.3 19.5 961 CI5f12004 4aH-Eudesm-l1(13)-en-l2,8~-olide, Sa,6a-epnxy-Za-hydrnxy 4 6 6 63 I 39.0 38.0 66.2 60.8 37.0 74.5 39.3 33.6 136.3 169.8 123.9 24.9 18.7 962 C1 if12004 Micrncephalin, 1-deoxy-6a-hydroxy 41.7 18.7 44.1 73.0 54.2 69.6 50.1 77.4 42.3 35.2 139.0 170.2 122.4 20.5 23.1 963 C21fI2208N2CI6 Micrncephalin, 1-deoxy-6a-hydroxy + T A I
408
184 36.7 88.8 49.5 76.4 47.6
73.8 43.8
Sol llel
C:
317
C
1'9
C
126
37.1137.7168.9123.1 20.8 2 0 8
C
126
107 10.8
c' C
408
Yomogin
964 C-I.5H1603
a 155 2 126.3 185.5 131.0 154.4 29.9 41.8 h 155.2 126.5 185.6 131 3 154.4 30.0 42.0
75.3 75.4
38.8 38.5 140.3 169.5 121.9 25.6 39.0 38.6 140.5 169.7 122.0 25 7
35;
Oher carhunz. 937 Sen: 166 9 115.4 158.4 27.5 20.3; 949 OMe: 62.6: 952 OMP: 62.6: 958 Glc-6-Ac: 101.0 7 4 1 76.6 7 0 4 73.7 63.6 170.8 20.9: 959 Glc-2.3.4.6-Ac: 99.2 71.6 73.1 68.8 72.1 62.1 1702 2 0 5 I694 205 169 I 205 I694 20.5
- 0
936
937
945
r
R = H
939
R = OH
n
940
944
943
942
941
o
938
946
R = H
948
R = H
951
R = H
947
R = OSen
949
R = OCH,
952
R = CCHJ
950
R = OH
953
R = CH
q
o
q
o
CH,OR 954
955
R = a-OH
956
R = 0-OH
9 57
958
R = Glc-6-Ac
959
R = Glc-2.3.4.6-Ac
0
960
961
962
R = H
963
R = TAC
964
356
M.BUDESINSKY AND D. SAMAN
Table 18.-continued No
965 966 967 968 969 970 971 972 973 a b 974
975 976 977 978 979 980 981 982 983 984 985 986 987 988 989 990 991 a b
Mol formula Name / Chemical shifts C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-ll C-I2 ‘2-13 C-14 C-15 SOI I k l CISHI804 Pimatifidin, la-hvdroxv c 300 77.8 197.9 124.3 162.5 38.5 25.9- 40.4 76.7 33.6 38.6 141.4 170.2 120.9 17.0 22.0 CISH2004 Pimatifidin, 2-dihydro-la-hydroxy I’ 300 78.1 71.5 124.0 135.5 37.0 27.4 41.0 77.6 35.5 35.2 143.1 170.4 119.6 18.3 21.2 CI 7H2005 Pinnatifidin, la-acetoxy-Zdihydro 79.3 67.7 122.0 136.4 37.0 27.0 40.6 77.0 34.8 33.5 141.7 170.5 119.6 17.6 21.1 c 300 CI5HI604 Yomogin, laJa-epoxy 54.0 59.9 195.1 126.8 151.2 29.7 38.8 74.6 39.2 37.9 138.6 169.6 123.3 26.7 12.0 C 357 C15H1804 Eudesma-4,11(13)dien-12,8B-olide, laJa-epoxy-3a-hydroxy C 357 61.1 55.0 68.3130.1125.1 28.1 39.7 75.7 39.0 36.0139.4170.3122.3 25.0 14.2 C17H2004 Eudcsma-1,~15),11(13)-trien-l2,Sg6lide, 3g-acetoxy c 296 123.2 141.5 71.7 143.2 44.2 26.9 40.3 76.2 38.3 36.5 141.5 170.4 120.7 20.3 105.9 CISHI804 Alantolactone, h, la,Za-epoxy-k-hydroxy c 357 63.6 55.4 68.8146.1 34.5 25.9 40.1 76.4 36.3 34.3141.5l70.1 120.7 16.61143 ClSH2704 Carpesin, la-hydroxy = Ivasperin c 65K 85.2 72.2 44.3 147.5 45.6 28.3 41.4 79.0 39.3 39.5 144.3 172.9 121.3 13.3 109.9 C15H2004 Pulchellin C M 6SX 49.2 73.2 79Sb 150.1 45.2 28.6 41.2 78Sb 41.6 34.5 143.7 172.3 120.9 19.0 106.1 c 126 47.4 72.4 78.7b 147.4 44.4 17.2 40.2 76.P 40.7 33.9 141.6 170.3 120.7 18.8 106.0 CZOH260S Almtolactone, iso, 3~-hydroxy-2a-senecioyloxy c 126 45.1 74.3 76.2 146.8 44.3 27.2 40.1 76.2 40.5 33.8 141.6 170.6 120.6 18.4 107.4 CISHI704 Granilin M 65X 73.4 38.8 74.2 149.2 43.2 25.9 39.4 76.7 33.0 39.1 141.4 169.6 119.0 16.8 108.8 CZOH2605 Graniline, 3-angelyl c 543 74.1 32.6 75.1 144.3 34.8 26.6 40.2 77.3 33.4 39.0 141.9 165.6 120.4 17.8 114.6 CI9H2605 Gradline, 1-isobutyryl 76.0 32.5 72.8 148.5 34.6 26.6 40.0 76.6 33.5 37.7 141.6 170.2 120.6 17.6 111.4 c 543 C20H2805 Graniline, l-(l’-methylbutyryl) c 543 76.0 32.6 72.8 148.5 34.7 26.7 40.0 76.6 33.6 37.6 141.6 170.2 120.6 17.6 111.4 C20H2805 Graniline, 1-isovaleroyl c 543 76.1 32.6 72.8 148.5 34.6 26.7 40.0 76.6 33.6 37.6 141.6 170.2 120.6 17.6 111.3 C23H2808 Steiractinolide, la,J~diacetoxy-6-O-methacryloyl c ‘10 72.1b 29.9 72.8b135.8‘ 133.2’ 74Sb 44.9 71.2b 34.8 36.9 132.4‘ 166.2 124.1 17.4 21.8 C26H32010 no name c 292 72.5 29.7 67.6 135.7 138.8 71.3 45.1 74.4 34.5 37.3 131.2 168.3 124.9 22.0 60.6 CI7H2005 Eudesma-2,11(13)dien-l2,8~-olide,4p-acetoxy-I-0x0 c 62X 185.5 126.4 155.1 74.3 40.5 30.0 41.9 75.3 39.0 36.8 141.5 170.0 121.8 10.8 19 5 C17H2005 Eudesraa-2,11(13)dien-l2,8~-olide, 4a-acetoxy-l-oxo c 62X 185.5 129.9 154.4 75.3 38.6 28.5 40.5 75.8 38.3 36.8 140.5 170.1 120.7 11.0 17.3 CISHI804 Telekin, 2,Sdehydro-la-hydroxy C 357 73.0 128.8 127.7 145.8 73.8. 33.1 37.2 76.9 29.4 37.6 141.9 170.5 120.4 22.7 I44 C20H2806 Alantolactone, iso, la,2adihydroxy-3a-(Z’-methyIbu~noyloxy) c 503 77.9 77.3 77.0 143.4 34.1 26.8b 40.2 67.6 33.5 37.7 141.8 a 120.6 17.7 116.3 CISH2004 Pyrethradn, !3-cyclo, deacetyl 77.9 31.8 35.0 144.4 57.2 67.4 54.9 77.1 40.7 43.1 139.0 170.6 118.9 13.9 108.9 C+A 131 C17H2205 Pyrethrosin, ,8-cyclo c 131 78.3 31.5 34.5 142.4 54.3 68.0 53.1 76.4 40.0 42.6 136.2 170.9 119.6 13.7 108.9 C22H2807 SaH-Eudosma-3,11(13)-dien-l2,&-olide, lg-acetoxy-9f3-(4’-hydroxytigluyluxy) 77.7 29.4 120.3 131.9 47.1 23.0 46.4 80.6 76.2 42.6 138.0 169.5 118.3 8.7 21.3 C 602 C17H2406 5aH-Eudesm-11(13)-en-l2,&-olide, 6a-acetoxy-lg,4a-dihydroxy 71.9 27.9 43.2 72.4 57.2 69.7 53.6 76.4 41.5 41.7 136.6 17C.4 119.0 16.3 23 X C 121 C15H2003 Ivangustin, iso, 8-epi 75.7 32.7 120.3 133.7 46.9b 23.9 5O.Ob 80.1 38.8 a 139.4 a 117.0 21.1‘ 11.4‘ C 7!, CI5H2004 Pyrethrosin, a-cyclo, deacetyl = Sivasinolide 74.1 32.2121.2133.5 55.3 68.1 53.0 76.0 38.4 39.9138.0169.0117.0 11.6 22.4 C+A 131 C 24!, 77.6b 40.2’ 123.0 140.2 57.0 75.7b 54.7 69Xb 39.9’ 41.6 135.5 169.9 118.3 13.1 240
357
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 18.-continued Mol. formula Name / Chemical shifts C-I C-2 C-3 C-4 C-5 C-6 C-7 C-8 992 C17H2205 Pyrethrosin, a-cyclo 75.5 29.7 123.2 132.4 54.4 69.9 50.9 75.5 993 ClSH2002 Eudesma4,11( 13)-dien-l2,&-0lide 40.1 18.5 32.9 130.9 128.6 25.6 49.6 80.3 994 ClSH2003 Ivangustin, 8-epi 77.2 31.7 26.8b 129.8' 127.9' 26.0b 48.8 80.4
No.
C-9 C-10 C-11 C-12 C-13 C-14 C-15 32.9
Sol. Ref.
40.6 136.2 171.0 119.6 12.6 22.4
C
131
45.1 36.6 139.8 171.1 117.0 26.0 20.0
C
408
41.6 41.6 139.5 171.0 117.3 19.2' 19.7'
C
79
Other carbons 967 Ac: 170.2 21.1: 970 Ac: 170.0 21.0, 974 Sen: 166.9 115.4 158.4 27.5 20.3: 976 Ang: 170.4 126.8 139.9 15.8 20.7; 977 But: 175.5 34.3 19.0 18.9; 978 Mebu: 175.2 41.5 26.6 11.7 16.5; 979 t V d : 171.7 43.7 25.6 22Sb 22.C: 980 2xAc: 169.9 20.9 170.8 21.0 Mac: 168.4 135.9 126.5 18.3: 981 tiAc: 170.6 21.7 170.4 21.0 170.0 20.7 Tigr 166.7 128.1 139.1 14.6 12.2 982 Ac: 169.5 25.7; 983 Ac: 169.4 26.1: 985 Mebu: 176.1 41.4 26Sb 11.4 16.4; 987 Ac: 169.8 21.0; 988 rig-&OH: 166.0 127.9 141.6 59.6 12.6 Ac. 170.1 20.9; 989 Ac: 169.8 21.5: 992 Ac: 169.9 21.7
co
965
H
966
R =
967
R = Ac
968
969
HO
AcO - 0
970
R'O'"
971
973 R
972
974
&
-
Acg
0
co
co AcO
R' _~ _R' _ _
975
H
H
976
H
Ang
977
i8ut
978
Mebu
H H
979
(Val
H
981
HO
HO
984
= H
R = Sen
RQq 982
R = P-OAc
983
R = a-OAc
HO
985
986
R = H
987
R =
AC
co H OAc
9aa
989
f
R
n on
990
R
991
R =
992
R = OAc
=
993 R = H 994
R = OH
358
M. BUDES~NSKYAND D. SAMAN
Table 19. Carbon-13 chemical shifts of eudesman-12,8-olides (type 11-methyl). No. 995
YY6 YY7
YYS
YYY loo0 1001
1002 1003
IOU4 1005 1006
1007 I008 a b
IOU9 1010
1011
1012 I013
1014
1015 1016
1017 I018 a b
l0lY 1020 1021
Mol. formula Name / Chemical shifts C-I C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-ll C-12 C-13 C-14 C-15 Sol I k f CISH2202 4aH,5aH,7aH,ll~H-Eudesmnn-12,8~-olide, 3a-hydroxy 30.8 29.6 71.6 33.9 39.4 28.9 44.3 77.8 33.1 31.3 36.6 169.0 24.7 16.5 14 4 C 105 C17H2404 Ivangustin acetate, Ilp,l3-dihydro 75 7 27.9 30.6 126.6 130.2 23.4 43.1 75.8 37.2 37.8 41.8 179.6 21.3 14.3 18.9 C 7(X) C24H3209 Eudesm-4-en-12,8e-olide, lOa-methyl, 3~,15-diacetoxy-la-hydroxy-6a-tigloyloxy 70.9 32.7 69.7 132.7 140.7 68.6 48.0 73.7 37.3 39.7 36.5 178.1 14.5 18.1 61.4 c 292 C24H3008 Eudesm-4-en-lZ,8f3-olide, IOa-metbyl, la,l5-diacetoxy-6a-tigloyloxy 77.4 22.6 28.3 138.6 132.5 68.4 48.1 72.9 38.5 38.3 35.8 177.7 13.8 20.2 63 8 C 314 C26H34010 Eudesm4en-l2,8~-olide, 10a-methyl, la,3~,15-tri~cetoxy-6a-tigloyloxy 73.5 29.5 69.1 133.6 139.6 68.0 48.0 72.6 38.1 39.0 35.8 177.3 14.0 18.7 61.3 c 292 C21H2602Se Eudesm4-en-l2,8~-olide, Ilt3-phenylseleno 37.4 18.8 32.1 131.7 127.5 25.7 48.1 76.0 41.8 33.8 50.1 178.3 24.5 27.0 19.3 c 'lox CISH2202 5aH,7aH,llaH-Eudesm.3-en-I2,8~-olide 38.1 22.3 122.2 133.3 44.2 20.9 41.4 78.1 41.1 31.4 41.5 179.4 9.3 17.3 2 1 2 c 4ox CISH2102Br SaH,7aH-Eudesm-3-en-12,Sg-olide, Ila-bromo c 40s 37.8 22.3 122.8 132.5 44.1 22.7 50.8 77.4 40.8 31.2 60.1 174.3 22.4 17.3 21.2 CISH2202 7aH,llaH-Eudesm-4-en.12,8e-olide c 4ox 40.4 18.7 33.0 131.3 127.4 22.1 41.3 78.3 42.3 33.6 42.0 179.6 9.4 27.0 19 5 CISH2102Br 7aH-Eudesm-4-en-12.8B.olide, lla-bromo c 408 40.2 18.7 33.0 130.0 128.6 23.7 50.5 77.8 41.8 33.2 60.4 174.4 22.3 26.9 lY.4 C2IH2602Se 7aH-Eudesm-4-en-l2,8~-olide, Ila-phenyiseleno c 'lox 40.3 18.7 33.0 130.9 127.8 23.9 47 5 76.9 42.1 33.4 51.3 176.8 19.0 27 0 I9 4 CISH2002 Anthemidin c 19.4 137.4 120.4 122.0 136.8 41.0 20.2 41.5 78.5 38.7 33.8 43.4 179.0 9 3 I 6 4 2 0 0 CISH2003 7aH,llaH-Eudesmd-en-l2,8!3-olide, 3-0x0 c 'lox 37.3 33.3 198.3 130.4 157.6 24.4 40.9 76.6 42.0 35.0 41.8 178.7 9.6 24X I I 2 C/SHI803 Yomogin, Ila,l3-dihydro c 357 155.4 126.0 185.6 131.2 155.3 24.5 41.8 76.3 38.9 38.8 42.1 178.3 9.4 25.3 107 c 40s 155.3 126.0 185.7 131.2 155.4 24.6 42.1 76.3 38.9 38.9 41.8 178.3 9.4 25.3 108 C21H2203Se 7aH-Eudesma-1,4-en-l2,8!3-olide, 3-0x0-1la.phenyiseleno c JOX 155.3126.1185.5131.3154.7 26.2 48.2 75.1 38.9 38.7 50.6175.8 19.1 25.2 l0.X C17H2402S2 7aH,llaH-Eudesm-4-en-12,8~-olidc, 3,3-ethylenedithio c 4ox 39.2 39.3 71.9 137.6 128.7 23.6 41.2 77.6 42.3 33.7 41.8 179.2 9.4 26.6 16.5 CISH2203 5aH,llaH-Eudesm4(15)-en-12,8~-olide, 3fbhydroxy c 296 40 1 32.1 73.0 151.5 44.9 21.3 41.7b 76.6 40.1 34.6 41.2b 179.3 9.2 17.7 103.3 CISH2203 4aH,5~H,7aH,1laH-Eudesman-l2,&-olide,3-0x0 c 78 357 37.3 212.7 43.1 38.5 22.6 49.4 78.5 41.1 35.7 40.8 a 9.2 12.0 28.3 CISH2003 7aH,llaH-Eudesm-4-en-12,8-olide, 3-OxO c 40x 37.8 33.2 198.0 131.3 157.1 27.0 46.5 77.2 45.0 37.6 38.7 179.3 9.4 24.2 I I 5 CISH2202 4BH,SaH,7a~lleH-Eudesm-Z-en-lZ,&-olide C 7x 44.1 123.5 132.7 47.9 32.8 27.0 52.1 79.5 41.7 34.9 41.4 179.5 12.5 18.7 19.3 ClSH2203 4BH,SaH,7aH,ll~H-Eudesman-lZ,~-olide,3-OXO c 7x 37.1 43.9211.1 51.0 41.4 27.1 52.0 78.9 40.4 36.1 45.0179.1 125 11.7 17.9 C15H2203 4~H,SaH,7aH,llaH-Eudesman-l2,&-oIi~e, %OX0 c 7x 37.1 44.2 211.2 47.8 38.7 24.6 38.7 77.7 40.2 35.9 44.9 179.7 9.5 11.6 179 CI5H1803 7aH,llaH-Eudesma-1,4-dien-I2,&-olide, %OX0 c 4ox 1 5 4 . 5 1 2 6 . 1 1 8 5 . 6 1 3 1 . 8 l 5 4 . 7 26.7 47.3 76.8 40.7 40.9 38.8179.1 9.5 25.7 11.2 CISH2204 p-Cyclopyrethrcsin, desacetyl-11~,13-dihydro C 131 78.3 31.5 34.5 144.3 57.0 68.6 57.0 76.1 40.1 42.6 41.5 179.1 14.3 13.8 108.6 77.0 30.6 33.9 143.5 57.0 67.6 55.9 75.6 39.4 41.8 40.4 178.3 13.4 12.8 107.7 C+A 131 CISH2203 7aH,lleH-Eudesm-3-en-12,&r-olide, lp-hydroxy 79 75.7 32.6 120.1 133.7 47.1 25.3 52.6 79.8 38.5 40.3 41.4 179.4 12.5 21.0b 11.3b c CZI H2603Se SaH,7aH,-Eudesm-3-en-IZ,&~lide, I~-hydroxy-ll~-phenylseleno 79 75.6 32.6120.2133.6 47.1 29.6 57.1 77.1 38.5 40.3 49.2176.6 22.6 21.0b 11.3b c ClSH2203 7aH,11BH-Eudesm4-en-1Z,&-olide,le-hydroxy 77.3 31.8 26.7b 130.C 127.3' 27.6b 51.7 80.1 41.8 41.6 41.5 179.7 12.5 19.2' 19.6'' C 79
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
359
Table 19.-continued Olhercnrbons: 9% Ac: 170.9 21.3; 997 2xAc: 170.4 21.2 170.2 20.8 Tig: 166.5 128.2 138.8 14.6 I? I . YY8 2vAc: 170.4 21.1 170.4 20.8 rig: 166.5 128.5 138.3 14.5 12.1; 999 3xAc: 170.4 21.1 170.2 21.1 170.1 20.8 Tig: 166.3 128.2 138.9 14.6 12.2; loo0 SePh: 126.1 138.1(2) 128.9(2) 129.4; 1005 .%/'/I. I25.h 138.0t2) 129.1(2) 129.7; 1009 SePh: 125.1 138.0(2) 129.3(2) 130.1; 1010 S-CH,-CH,-S: 40.9 40.0: 1020 S e P h 138 2 129.7(2) 129.1(2) 124.3
q z AcO
HO" q
t
L
0
R2
'
1003
.
6Tlg
AcOCH,
=
R'
Rz
997
H
OAC
998
Ac
H
999
AC
Ac
996
995
co . -
1006
R = H
1000
1007
1004 R = Er 1005 R = SeC&
HO
1008
R
i
H
1009
R
=
SeC&
1012
1017
1010
1011
1013
1014
1018
1019
R = H
3025 R = SeC,li,
1015
R
=
n-CH,
1016
R
=
P-CHJ
1021
360
M. BUDESINSKY AND D . SAMAN
Table 19.-continued hlol. formula Name I Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-ll C-12 C-I3 C-I4 C-I5 1022 C211i2602Se 7aH-Eudesm-l-en-12,8a-olide, Il&phenylseleno
No
4 0 0 18.5 1023 CZIH2603Se 77 2 31.8 1024 C / S H 2 2 0 2 40 1 18.5 1025 C17H2402S2 39.1 39.4 1026 CISF11802 391 23.0 I027 C15H1803 33 0 22.1 102X CISH200Z 39 I 19.2 102') C15H2003 41 6 22.8
32.9 131.2 128.5 25.2 56.6 77.7 44.8 36.5 49.3 176.9 22.5 26.0 1'99 7uH-Eudesm4en-l2,8a-olide, I~-hydroxy-11~-phenylseleno 26.7b 130.1' 127.8' 25.6b 56.0 77.7 41.8 41.6 49.2 176.9 22 5 19.2d 19 7''
2C'
c'
7aH,11aH-Eudesm-4-en-12,8aa-olide 32.9 131.5 128.0 24.5 47.9 78.9 45.2
36.4 39.1 180.4
9.4
26.1
I09
C'
9.3 25.7
17 3
C
18.6 1075
C
8 6 23.X 109 X
C
7aH,llaH-Eudesm-4-en-12,8a-olide, 3,J-ethylenedithio 71.9 137.3 129.5 26.0 47.5 78.2 45.1 36.4 39.0 180.0 Atractylenolide I 36.2 148.0 48.4 22.7 148.3 148.1 119.1 38.1 120.5 171.2 Eudesma-4(15),7(11),8-trien-12,8-olide, 5a-hydroxy 31.1 148.8 76.6 30.6 145.7 147.7 115.0 42.4 123.5 171.1
8.5
Eudesmad,7(lI)-dien-l2,8~-olide
32.1 130.3 128.7 26.2 164.0 78.2 43.7 34.2 120.1 175.4 8 4 29.5 I!, X C Atractylenolide III 36.5 149.0 52.0 24.9 161.0 103.8 51.4 37.0 122.2 172.3 8 4 16 7 1lK1 h I. 1 0 3 0 C17H220.5 Eudesmad(l5),7(11)-dien-12,8a-olide, lp-acetoxy-Ep-hydroxy 79 8 23.7 27.0 146.0 49.5 33.2 159.9 103.1 47.2 39.9 122.4 170.6 8.2 I I 7 IOX.7 C' 1031 C17H2006 5~H-Eudesma-3,7(11)-dien-l2,8~-olide, 10a-methyl, la-acetoxy-8u-hydr11xy--2-11xci 82 7 192.1 126.4 158.2 49.4 23.2 159.7 102.6 46.1 42.8 123.5 170.4 8.3 12.3 21 0 A
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
361
Table 19.-continued Other carbons: 1022 SePIi: 138.2 129.6(2) 129.0(2) 124.3: 1023 SePlr: 138.2 129.7(2) 12'J.l(2) 124 3 I025 , S - C t l ~ - C l ~ 41.4 ~ - S ~ 39.8: 1 0 3 Ac: 172.1 21.0; 1031 Ac: 171.8 20.5 R
1022 R = H
1026
1025
1024
R
co
co
H
1028
R = H
1027 R = O r
1023 R = OH
1029
R =
n
1030 R = OAc
1031
362
M. BUDESINSKY AND D . SAMAN
Table 20. Carbon-13 chemical shifts of modified eudesmanolides.
Ill33
II1.U 1035 1036
1027 IO2X
103Y 1040 1041
I042 Ill43 II)U
I045 IIM 1017 IOJX
Nnmc / Chemical shifts C-7 C - 4 C-5 C-6 C-7 C-R C-9 C-10 Onuserinlide, R,9-dihydro 2 3 0 16X 23.4 149 7 5 0 4 21.8 1576 88.0 M.X 41 0 ('Xf12404 Onoserinlide senccioatc 2 7 0 1 6 X 23.3 149.7 50 4 22.9 157.5 64 8 29.7 41 0 C2OII240.5 Onoseriolide senecioate, Bp,Yp-epnxy 2 6 4 17.1 2 2 7 149.7 61.8 22.1 152.6 149.3 115.2 40.1 CISHI603 Chloranthalaclone Xi ? l o * 169 23.Yb 149 9 50.6 21.2 152.3 87.9 6 4 4 41.1 CIC11180.1 Shizukanolide C 27.2 169 22.1 463 60.3 23.0 148.6 149 5 120.2 42.1 ('I7H2004 Chlordnlhalactone C 2 7 2 16') 2 2 2 4 2 9 60.2 2 2 6 1482 149.5 119.9 41.9 CI.iHIX( )4 Shizukanolide F 2 7 2 170 2 2 0 46.0 59.9 23.0 149.2 151.3 123.7 41.9 C'IYH2206 Shizukanolide F, acetate 1 7 2 1 7 0 22.2 42 6 60.2 23.1 149 I 153.0 123.7 42.0 ('1 iHIKOJ Shizukanolide E 28.6 12.4 26.5 79 5 65 0 20.5 148.8 149 5 120.6 40.6 C17f12005 Shizukanolide E, acetate ? X 9 12.7 26.6 78.5 65 0 20.2 14R.3 149 3 120.5 40.6 ('17/1?005 Shizukanolide I) 24 6 16.6 22.4 42 5 4R.7 22.6 152.6 87.8 64.4 42.6 ('15HlOO2 Rrothenolidc 34.1 2 5 9 25.5 2 6 6 56.5 77.8 40.5 46.3 35 7 50.4 C19H2207 Scorpiolide 214 7 35.5 22.3 29.6 54.6 79.0 152.5 65 5 15 2 47 8 CISll2il02 Geigeranolide 45 9 26.2 33.5 26.5 52 8 27.9 41.5 77.5 39 0 49.8 Geigeranolide, dihydro C151i2202 46.0 26.3 2 6 3 26.4 53.4 33.6 44.4 78.1 39.0 50.2 C15H2202 Crispatanolide 30.8 28.3 26.2 26.2 35 6 32.4 86 3 34.9 27.8 58.6 Ratibinolide C15f11803 212.2 33.0 29.7b 25.9 55.1 79.9 52.0 20.5 29.9* 59.3
Sill I<el
127.9 168 2
549
1 7 0 1070
c'
76
127 X I6X 2
54
9
17.0 I 0 6 0
c
76
120.9 169 I
54.7
22.1 1069
c'
76
1290 170 7
9 0 IO6X
IhX
c
(744
1220 171 3
Xh
21 I
650
c
374
122.2 171 I
8.6
21 0
660
c
374
123.7 1705
54.7
21.0
64 3
c
374
120.2 169 1
55.4
21.0
660
c
774
122 9 1709
86
224
64 9
C'
174
123.0 170.8
87
22.3
666
C'
374
12X.9 170.4
89
16.1
65 Y
c'
374
141 8 171.3 119 5
204'
2O'lb
124.8 171 3
55.6
IX 2
2hY
c
666
141.8 170 5 1202
20.X
IX 5
c'
lox
44.41803
152
20.9
1x5
c'
691
50.3
17 I 178.3
I9 1
c'
43'
16.8
c
42x
17.1
138.1 1704 111.2
193
c 626 6-27
104Y C14f11402 1050 1051
1052 a h
I053 10S4 1055
1056 1057 105X 1OIY
Platyphillide 129.6 122.6 132.0 124.5 143.9 80.2 46.1 C14H140.7 Platyphillide, I-hydroxy 153.9 116.6 135.1 124.4 143.9 81.3 46.1 C f51/160.? Platyphyllide, I-methoxy 1463 I 1 I . X 134.3 124.4 143.9 79.3 45.9 C16H2204 no name (2 conformers) 172 4 34.8 120.4 136.6' 131.3' 82.3 49.3 172.3 34.6 118.9 134.8* 131.0b 80.1 48.7 C23H3409 no name 69.9 30.6b 28.4b 33.8 140.5 27.7h 37.3 C2Ytl40012 no name 69.4 30.7* 28.3' 33.8 1404 27.4b 37.3 Cl5H2004 Umbellifolide 17.6 36.6 43.1 207.8 212.2 4 0 7 37.2 C29H3208 Mortonin D 70.0 2 5 6 35.4 72.7 87.7113.1 35.A C2IH2606 Mortonin A 72.2 25.8 37.5 71.6 84.9 81.6 143.1 C24112R08 Mortonin B 7 0 6 69.1 42.9 71.0 84.9 82.3 142.9 C2IH2405 Mortonin A, anhydro 7 2 7 26.7 29.9140.5 8 0 9 81.2144.1
C - l l C-12 C-13 C 14 c' 15
25.6
26.5 148.5 133.5 I I 2 I
20 4 170 7
--
c
201
25.0
27.0 148.4 109.4 112 2
20.4 171 0
--
c'
261
24.7
36.6 150.3 111.3 1119
20.2 1682
--
c
261
22.9 22.9
31.3 130.9 41.8 179.5 31.3 130.2 41.5 179.5
12.3 12.3
19.2 18.7
24 3 22.5
c c
412 412
77.8
35.5 125.1 134.4 171.2 122.7
19.4
I90
C
2x4
77.2
35.6 125.1 134.4 170.5 122.3
19 3
19.2
c
2x4
80.0
37.9
4 5 7 138.0 164.2 123.4
22.8
299
c
35
r0.C
76.8
49.0
24.7
14.1
17.9
21.8
c
52x
121.7
85.8
49.8
32.8 172 2
22.8
20.4
26 8
C
528
121.9
86.1
49.6
32.9 171.7
23.9
21.0b 26.Y
c
52x
120.7
83.2
49.0
32.5173.4111.5
18.7
c
528
a
27.5
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
363
Table 20.--continued Name I Chemical shifts C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14 C-15 1060 CZ5H2005 Mortonin, 1-ketopboto 208.5 36.5 36.0 68.9 88.6 73.4 117.7 141.7 86.7 62.5 21.7 169.4 15.6 18.6 26.0 No.
Mol. formula C-1
C-2
Sol. Ref. C
528
Other carbons: 1033 Sen: 165.7 114.8 158.9 21.7 27.5; 1034 Sen: 165.7 114.8 158.9 21.7 27.5 ; 1037 Ac: 171.0 21.0; 1039 2xAc: 170.5 20.7 171.0 20.9; 1041 Act 171.2 20.9; 1042 Ac: 171.1 21.0; 1044 b A c : 170.4 20.6 169.2 20.3; 1051 OMe: 55.9; lOS2a O M : a ; 1052b OMe: a ; 1053 Glc-6-Ac: 102.5 73.5 76.2 70.1 73.5 63.8 171.1 20.9; 1054 Glc-2,3,4,6-Ac: 100.1 71.5 72.9 68.6 71.4 63.1 170.5 20.6 1700 20.6 169.3 20.6 169.1 20.6 1056 2xBz: 165.5 130.8 129.6(2) 128.6(2) 132.8 166.0 130.8 130.0(2) 128.0 (2) 133.2; 1057 Bz: 165.0 130.1 129.6 (2) 128.6 (2) 133.4 1058 Ac: 169.5 21.4b 61: 165.8 129.6(3) 12R.7 (2) 133.6 1059 Bz: 165.5 130.2 129.6 (2) 128.6(2) 133.3
*m
qq
co
co
CH'OH
la33
1032
.
--.
co
i. H-
R~OH,C
fi
CH,R' R'
R'
1036 H
H
1037 H
Ac
1038 OH
H
1039 OAc
Ac
.
AcOH,C i
W,OR
1040 R = H 1041
.
-
la44
1043
1045
1046
1048
-0
H'coo
&I ,,,f
co-0 1049
R = H
1050
R = OH
1051
R = OCH,
0-co
1052
1055
1053 R = Glc-6-Ac 1054 R = Glc-2.3.4.6-Ac
1056
"F
0-co
1042
R
a H p . . . , , r
1047
: H :
=
H
R = Ac
0
co
1035
1034
1057
R = H
1058
R = OAc
1060
364
M. BUDBSINSKY A N D D. SAMAN
other papers. The 11-methyl group was assigned to have a-configuration in maritimin [823] because of the chemical shift of C-13 carbon (6 = 12.3, ref. 245), as in gallicadiol [841] (C-13 at 6 = 12.8, ref. 246), while C-13 at 6 = 7.3 in grangolide [779] was as the argument for P-configuration of the methyl group. 1lp-methyl configuration was derived for eudesmanolides 896, 900 (C-13 at 6 = 9.7 and 9.8) when compared with lla-methyl epimers 836, 824 (C-13 at 6 = 12.6 and 12.4).404 Marco et al.408,409have described 13C NMR data of 56 eudesmanolides of natural and synthetic origin. The different effects - like cidtrans lactone ring closure, silylation with TBDMS group, double bond epoxidation, 1,2-double bond reduction, introduction of phenylseleno group - are discussed.408,409 The a-orientation of oxirane ring in maritimin [823] was assigned on the basis of shielding observed at C-7 (-4.6 ppm) when compared with reference compound 799.245Configuration of tertiary hydroxyl at C-5 was derived as p- and a- in gallicadiol [841] and isogallicadiol (8381 respectively according to the observed shielding effects on C-1 carbons (5.65 and 13C -0.9 ppm) when compared to compound 836 not having O H NMR spectra of natural C-5 epimeric hydroperoxides 950, 953 and corresponding pairs prepared by methylation 949, 952 and reduction 948, 951 have been described.37 5PH-epimers with a cis-decalin system were shown to exist in a single steroid-like conformation, which allows one to explain the observed spectral data.37 Series of isomeric 4a,5a- and 4p,SP-epoxy eudesmanolides have been synthesized and their 13C NMR spectra compared with those of corresponding 0 1 e f i n s . ~Surprisingly ~~ the observed substitution effects @-, y- and s-) could not be unambiguously correlated with the configuration of the oxirane ring. Geometry parameters which could be responsible for observed effects are analysed in ref. 130. 13C NMR data of some eudesman-12,6-olides with an unusual 5PH,6aH,7aH,10aCH3-configuration - isosilerolide [767], lasolide [769] and isolasolide [762] - have been described.322Possible conformations of cis- and trans-eudesman-12,6-olides are discussed using proton NMR parameters.”’ The characteristic features of 13C NMR spectra of a series of eudesma3,5,7(1l)-trien-l2,6-olides and of eudesma-1,3,5,7(1l)-tetraen-12,6-olides [890, 916-9251 are discussed in ref. 375. Miyase et al. have d e s ~ r i b e d 13C ~ ~ NMR ~ , ~ ~data ~ for eudesmanolide glycosides - sonchuside C - I [826,674, 683, 679,861,859,8581 and of some corresponding aglycons. X-ray structure analysis is described together with carbon-13 NMR data for some eudesrnan-12,6-olides: irazunolide [714],270 isosilerolide [767],322 isogallicadiol [838],247gallicadiol and 1-oxo-2a,5a-peroxyeudesm-3en-llaH-12,6a-olide [865];412 eudesrnan-12,8-olides: 3P-hydroxy-2asenecioyloxy-isoalantolactone [974];” and rnodiJied eudesmanolides: ratibinolide [1048]428and umbellifolide [lo551.35
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
365
14
Table 21
Table 2 2
&to
R2
Table 24
Table 2 3
CH2R'
Table 2 5
Fig. 22. Schematic representation of guaianolide structure types in Tables 21-25 and numbering of guaiane skeleton.
4.3.3. Guaianolides The guaianolides and sesquiterpene lactones with modified guaianolide skeleton represent one of the largest groups of sesquiterpene lactones. 13C NMR data on about 560 guaianolides collected from more than 180 original papers are presented in Tables 21-25. Tables 21 and 22 contain guaian-12,6olides which differ in substitution at C-11, similarly to Tables 23 and 24, containing guaian-12,8-olides. Finally, Table 25 shows modified guaianolides - namely seco-guaianolides - which are sometimes called xanthanolides. Schematic distribution of guaianolides into Tables 21-25 is shown in Fig. 22. There are only few papers dealing with NMR spectroscopy of guaianolides in a detailed manner.'28,526 In older papers the structure assignments of guaianolides are based on simple proton-decoupled I3C spectra, usually in combination with off-resonance decoupled spectra (e.g. refs 201, 219, 282, 299, 303, 329, 333, 335, 396, 481, 482, 492, 575, 680). The authors of later papers have frequently used more sophisttechniques like DEPT ,201,202,237,239,369,452,525,S96.S98,6O6 icated the APT exper~mentl28,219,403,525,S40,541,5S1,583,59Y,612 and/or the INEPT
366
M. BUDESINSKY AND D. SAMAN
in order to distinguish carbons according to the number of directly bonded protons. Long-range selective proton decouplings in 13C NMR spectra of lettucenin A [I5071 allowed its structure to be completed .625 Da Silva et aE.151 have assigned 13C NMR spectra of 18 guaianolides. The Eu[fodI3 induced 13C-shifts were helpful in the signal assignment of eremanthin [ 11771 and supported the predominance of distorted chair-like conformation of the seven-membered ring. 15’ TAC-derivatives of linichlorin B [ 10841, cumamrin B [l249], arctolide [1521], substituted slov-3-enolides [1336, 1321, 13251 and other compounds [1491, 1493, 1495, 1497, 1499, 15021 were used for structure determination and signal assignment in 13C NMR spectra.1253126,599 With deacylisomontanolide [I5611 a stepwise TAI acylation leading first to 8,lO-diOTAC derivative 115621 and finally to 8,10,11-triOTAC derivative [ 15631 was observed. 12‘ In recent papers various 2D NMR experimental techniques have been used in order to complete the assignment of individual peaks. Heteronuclear 13C-lH correlated 2D NMR experiments using delay times optimized for direct 13C-lH coupling have been used. 57,128,157,159.173,202,253,320,403,418,439,454,505,506,515.526,540,541,562,566,601,611.650 To resolve the ambiguities in the assignment of non-protonated carbons a ‘‘long-range’’ heteronuclear 2D NMR experiment was used either in a classical arrangement2s3~320~4s4~526,a1 or inverse modification.705Total assignment of ‘H and I3C NMR spectra of mikanokryptin [1525] was achieved using a variety of 1D and 2D NMR methods. DEPT spectral editing and a HETCOR spectrum allowed the assignment of all protonated carbons, while five quaternary carbons were assigned by a “long-range” HETCOR experiment .526 The complete assignment of 13C NMR signals in tannunolide A [ 13151 has been done by various NMR experiment^.'^ A selective INEPT experiment in combination with HETCOR spectra has been used to define position of ester group (isobutyrate and angelate) in hydruntinolide B and C [1244, 1243].173Standard HETCOR permits the assignments of C-7, C-11 and C-13 carbon atoms, while ‘‘long-range’’ HETCOR leads to the assignment of remaining carbons leaving ambiguous positions C-4 and C-5, which have been resolved by 1D-heteronuclear difference NOE experiments performed under selective irradiation of H-6 and H-15 protons. The ~ ~the shift configuration at C-11 in epimers 1315, 1314 was e ~ t a b l i s h e dby values of C-13 and C-8 carbons (6 = 9.88 and 24.44 in 11P-CH3 against 6 = 15.17 and 29.40 in lla-CH3 epimer). The stereochemistry at C-11 in 11,13-dihydrotomentosin epimers 1598 and 1599 was unambiguously determined. Upfield shift of P-oriented C(l1)-CH3 in second epimer is due to the y-gauche effect with C-6 which is also shifted upfield (from 6 26.3 to 21.9).391
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
367
The structure of guaian-l2,6-olide [1367] was established from 'H and 13C NMR spectra by means of 1D and 2D NMR techniques.253 One-bond C-H correlation served as the starting-point for the determination of C-C connectivities, which were inferred from a series of C-H correlation experiments with a systematically varied time period to obtain H-C magnetization transfer for the expected range of long-range J(C,H) (1.5 to 12 Hz). HETCOR spectra supported the structure and stereochemistry of isomeric epoxy guaianolides 1485, 1486 and 1488, finally confirmed by X-ray analysis.s06 The potential of 1D and 2D NMR methods in the structure analysis of sesquiterpene lactones was demonstrated on arctolide [1520].128 The senecioyl group was located into position 8 in compound 1331 by a COLOC experiment which showed a coupling between carbonyl carbon and H-8.601 Herz et ~ 2 1 . ~ have "~ described 13C NMR data of some xanthanolides [1572-1574, 15961. The peaks of 6 = 94.6 and 95.4 were found to be uniquely characteristic of an allylic carbon C-1 bearing a hydroperoxy group in peroxyeupahakonin A and B [1174 and 1125].333The position of the tertiary hydroxyl group at C-1 resp. C-5 in microhelenin E and F [1618, 16191 was determined3" by comparison with mexicanin E on the basis of a-, p- and y-effects (C(1)-OH: a-effect 29.8ppm at C-1, p-effects 9.4 and 6.3ppm at C-5 and C-10, y-effects -8.6 and -4.3ppm at C-9 and C-14; C(5)-OH: a-effect 31.2 pprn at C-5, p-effects 7.8 and 5.1 ppm at C-1 and C-6, y-effects -1.5, -2.5 and -5.1ppm at C-2, C-3 and C-7). Hydroxylation into position 9 a in ixerin F [1359I4l is supported by substituent effects derived from comparison with compound 1344 (downfield p-effects 3.9 and 8.4 ppm at C-10 and C-8, upfield y-effects -2.4, -5.7 and -2.4 ppm at C-1, C-7 and C-14). The position of caffeoyl group on glucose carbon C-2 in ainsliaside A [lo731 was deduced from observed shifts at glucose C-2 (l.Oppm), C-1 (-5.4 ppm) and C-3 (-3.1 ppm) when compared with glucozaluzanin C [ 10701.446 Connection of two glucose units in sesquiterpene lactone glucosides - macroclinisides B , D, E [1072, 1518, 15191 - was derived from glucose chemical shifts and stereochemistry of the glucose anomeric centre determined from J(C-l,H-l).4s1Miyase et al. have described 13C NMR data on series of guaianolide glycosides - crepisides A-I [1076, 1075, 1120, 1119, 1085, 1121, 1086, 1087, 1094],449macroclinisides F, G and I [1469, 1261 and 1074],448prenanthesides A-C [1262, 1284, 1354],450ixerins M-T [1095, 1097, 109P-1102, 1122, 1123],475hypochoreosides B-G and I [1396, 1203, 1204, 1218, 1219, 15571,490 cichorioside B [1395],591 cynaroside A [1475],s93 ixerisosides A-D [ll04, 1152, 1355, 11051 and tectroside [1103]665 frequently together with corresponding aglycons. To determine unequivocally the structure of studied compounds, particularly the configuration in positions 1, 4, 5, 10 and 11, many compounds were studied by X-ray diffraction analysis in combination with 'H and I3C NMR
368
M. BUDESINSKY AND D. SAMAN
Table 21. Carbon-13 chemical shifts of guai-ll(13)-en-l2,6,olides. Mol formula Name I Chermcal shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 1061 C I5H 2 0 0 j OsmitnDsin. 8a-hvdroxv ~. 5 1 9 24.7 38.8 137.4 i30.1 78.7 47.6 67.1 1062 CISIIIXOJ Osmitnpsin, la,lla-epoxy
Uu
C-9
C-10 C-ll C-I?
41.3
31.2 136.1 170.0 126.1
C-13 C-14 C-15 15.1 175
95.0 32.4 35.1 147.8 127.7 70.9 43.5 76.2 33.0 41.0 136.6 170.6 123.6 13.5 14.2 1063 ~ 1 ~ ~ 1 4 0 4 Leucodin, iso, dehydro, 9 ~ x n a 1378 2002 1350 168.5 38.4 79.8 49.8 45.5 196.0 141.4 137.1 172.1 124.8 19.3 12.3 I) 135.0 200.1 137.0 171.9 50.2 79.8 45.6 38.5 195.9 141.5 137.8 168.4 124.8 19.3 12.3 lOf14 C ISH I8 0 4 Osmitopsin, Ia,8a,4a,5adiepoxy4,5dihydrn 88.2 28.2 31.6 65.0 67.7 75.7 42.1 77.4 33.0 41.1 135.2 169.6 124.5 12.9 15.1 I065 C I S H I 8 0 2 Costuslactone, dehydro a 475 32.5 30.2 150.9 51.9 85.1 45.0 30.9 36.2 148.9 139.5 170.0 119.9 109.4 112.4 h 45.1* 30.3' 30.9'149.2' 52.0b 85.2 47.6 32.6' 36.3'151.36139.8 170.1 120.0 109.5'112.6' c 47.8 30.8 32.7 151.2 52.2 85.1 45.3 31.0 36.2 149.3 140.0 170.1 120.0 112.7 109.7 d 47.6 32.5 30.2151.1 52.0 85.1 45.1 30.8 36.1 149.2139.7169.5120.0112.51095 1066 C ISH I803 Zaluzanin C, 3-epi 4 5 6 36.7 84.9 154.1 44.2 74.6 49.6 31.0 39.9 139.4 148.5 170.1 120.5 113.3 113.2 1067 C17H2004 Zaluzanin C, acetate 4 5 0 34.3 83.6 147.6 44.3 74.4 50.0 30.4 36.2 139.4 147.9 170.5 120.0 114.2 114.1 106X ('15f11803 a 441 38.9 h 44.2 39.0
106Y C17H2004 44.6 36.5 1070 ('21H2808 a 449* 38.2 h 44X* 38.2 c 44.9' 38.2 d 445 37.9 c 448' 38.0 1071 CZOH2604 44.6 36.6 1072 C27H38013 44.Xb 3 8 0 11173 C301124011
45 0'
38 0
Ill76 C29fL34010
c
102
c
102
c C
583 255'
C
102
c c C
151 330 649
e
x
c
29*
C
207
83.7 49.9 34.0 30.5 139.7 147.8 169.6 119.9 114.3 111.2 83.9 50.0 34.2 30.6139.7148.0170.1 120.2114.4111.3
c c
464
83.8 50.3 34.5 30.6 139.6 147.6 169.9 120.4 114.4 13.6
c
29*
P
451
P
P
X 447 464 446
c
x
1'
451
I'
446
I'
448
I'
449
P
449
Zaluzanin C
73.4 152.8 45.5 73.6153.1 45.6
29*
Zaluzanin D
74.7 148.0 45.3 Zaluzanin C, X0.6 150.6 50.4 XO7 151.1 50.4 8 0 6 150.5 50.4 80.3140.7 45.1 80.5 150.3 50.2
gluco
83.7 83.8 83.6 83.5 83.5
45.3b 45.4b 45.4b 50.1 45.3b
30.7 30.8 30.7 30.6 30.6
34.2 149.0 141.1 170.0 119.4 114.0 112.5 34.4 149.0 141.1 170.2 119.6 114.1 112.4 34.1 148.9 141.1 169.9 119.2 114.0 112.5 34.1150.0148.6170.0119.5112.3113.9 34.1 148.8 141.0 169.7 119.2 113.9 112.4
P
P
Diaspanolide B
74.3 147.7 50.3 83.8 45.2 30.6 34.5 147.7 139.6 169.7 120.1 114.3b1134' Macrocliniside B 80.5 150.2 50.3 83.5 45.3b 30.7 34.1 148.8 140.9 169.8 119.4 114.0 112.5 Ainsliaside A
4 5 9 37.3 79.5 150.2 51.6 83.1 45.9 30.4 33.8 149.0 140.5 169.9 119.5 114.9 1 1 4 9 1074 ('J3114801X Macrocliniside I 44 8 33.0 80.5 150 3 50.4 83.6 45.3 30.7 34.2 148.8 141.0 169.9 119.3 114.0 112.5 1075 C29HJ4010
Sol Ref
Crepiside B
80.5 150.1 5 0 6 83.3 45.3b 30.6 33.9 148.8 141.1 169.9 119.1 114.0 112.9 Crepiside A
45.0 38 1 80.8 150.4 50.5 83.6 45.2 30.7 34.2 148.9 141.0 169.7 119.1 114.0 112.5 11177 I ' I S I I I 8 0 . ~ Zaluzanin C, 3-desoxy-7a-hydroxy 4 6 1 32.9 362 1504 45.9 87.9 75.7 30.0 34.1 142.7 151.8 169.9 122.8 111.5 108.8
C
207
I'l~lllX04 Cyannpicrin, 8-desacyl il 4 5 1 39.3 73.7 152.5 51.1 78.7 51.4 h 44 I * 39.9' 73.5 154.8 50.9b 79.9 51.5
c
120
I'
4x
c
'I
202
107X
7 2 0 41.3 142.7 138.0 169.6 123.0 117.0 113.1 72.0 45.1' 144.6 140.2 170.4 123.6 116.2 111.0 4 j 2 h 3 9 . 2 73.7 152.4 51.3b 79.0 51.0b 71.9 41.3'142.7 138.1 169.9 123.2 117.1 113.2
(1SJS,S~6~7~8S)-Guaia-4(15),10(14),11(13)-~ien-12,6-olide, X-angeloyIaxy-3-hydr[ixy 107Y ('2OH240S C 49 45.1 37.0 73.3 152.1 51.2 78.5 47.5 73.5 38.9 141.8 137.5 169.0 122.2 117.7 113 2 lOXl1 C19H2406 45 3 39.0 IIIXI <'lYII2607 IIlX2 a
h
45 6 36.1 C'lYll2206 51 3 39.0 45.3 38.3
Cynaropicrin, deacyl, 8-(3-hydrnxyisobutyrate)
73.5 152.1 51.4
78.0 47.2 73.4
36.5 141.9 157.3 169.6 123.0 118.1 1136
C
414
C
4hX
Grossheimin, 4,1S-dehydro-3aH-dihydro-8-(2',3'-dihydroxyisohutyrate)
73.6 152.1 51.8 78.2 47.4 75.6
39.2 141.8 137.0 175.0 123.5 118.2 113.9
Rcpin, IS-deoxy
73.8 152.1 45.3 78.3 47.7 75.2 36.8 141.2 137.4 169.8 122.3 118.5 113.7 73.2 151.8 51.5 78.1 46.9 75.2 35.6 141.6 136.8 169.5 123.6 118.1 113.8
C 126 C ?01.?02
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
369
Table 21.--continued Other carbons: 1067 Ac: 170.0 21.0: 1069 Ac: 170.8 21.3; 1070a Glc: 104.1 75.4 78.6 72.0 78.3 63.1. 1070h G k : 104.3 75.4 78.7 72.0 78.5 63.0; 107Oc Glc: 104.1 75.3 78.3 72.0 78.6 63.1. 107Ud G/c.: 1 0 3 9 72.9 78.2 71.5 78.0 62.7: 107Oe Glc: 103.9 75.1 78.4' 71.7 78.0' 62.9; 1071 iVal: 172.7 43.6 25.7 22 3 22.3: 1072 G/c(3-->I)Glc: 103.5 73.9 88.7 69.9 77.7 62.5 105.7 75.4 78.4 71.6 78.0 62.5: 1073 (;Ic-Z-UCinn-J',4'-OH: 98.5 76.1 74.9 71.8 78.2 62.6 126.7 114.9 148.2 147.3 116.3 122.1 166.4 11.5 6 145.9. 1074 Glc(3-->I)Glc(4-->I)G/c:103.5 74.1 88.5 69.8 77.8 62.5 105.4 74.7 76.3 80.9 76.6 61.X 104.8 75.1 78.3 71.5 78.1 62.5; 1075 Glc: 103.5 75.9' 75.6' 72.9 75.4' 62.1 Phac-4'-OH: 171 6 40.X 125.1 130.8(2) 116.2(2) 157.8; 1076 Glc: 104.0 75.1 78.2 71.6 75.1 64.9 Phoc4'-OH: 171.9 40.6 125.2 130.8(2) 116.2(2) 157.8; 1079 Ang: 166.7 127.0 139.7 15.7 20.3; 1080 ;Bur-3-OH: 175.1 42.4 6 4 4 13 5 : 10R1 inirr-2.3-OH: 169.2 77.2 68.1 21.9; lOE2a Mac-ep: 168.9 53.8 52.8 17.4; 1082b Mac-ey: 174.8 7 6 0 hX.l 21.6
1061
1065
1078
R = H
1079
R = Ang
1080
R = But-3-OH
1081
R = iEut-2.3-OH
1082
R = Mac-ep
1062
1063
1064
1066
R = H
1068
R = H
1067
R = Ac
1069
R = Ac
1077
1070
R = B-Glc
1071
R = iVal
1072
R = B-Gk
1073
R = B-Glc-2-OCinn-3'.4'-OH
1074
R = 8-Glc
1075
R = b-Glc-4-OPhoc-4-OH
1076
R = B-Glc-6-OPhoc-4'-OH
' 2 6-Glc
'-
B-Ck
'-
P-Glc
370
M. BUDESINSKY A N D D. SAMAN
Table 21.+ontinued No.
1083 1OX4
1085 a
h c
10x6 10x7 1088 1089 1090
1091
1092 Illy3 d
h c
1094 1OYs 1096 1097 1098 1099 1100
1101 1102
1103 1104
110s 1106
1107 I108
Mol formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 CY C-10 C-ll C-12 C-13 C-14 C-15 Sol Ref C19HZ 706CI Linichlorin B 5 1 7 39.1 73.7 152.0 45.6 78.1 47.3 75.9 35.8 141.4 137.5 168.8 122.1 118.7 114.1 c‘ 126 C22112308NC:14 Linichlorin B + TAI C 126 i? 4 36.0 76.9 149.5 45.9 78.0 47.6 76.1 35.2 140.4 137.1 168.6 122.8 IIX.6 119.5 C21H2809 Crepiside E M 320 47 5 38.9 80.2 150.2 53.8 81.0 50.2 73.9 42.2 144.9 141.1 173.0 122.4 117.3 115.7 P 450 46.0 38.4 80.5 150.0 51.2b 79.0 52.0’ 72.2 43.0 144.4 140.5 170.0 121.6 116.2 114.3 P 449 45.9 38.4 80.5 150.0 52.0b 78.9 51.2b 72.2 42.9 144.3 140.4 170.0 121.7 116.2 114.3 Crepiside G C29H34011 I’ 449 46 3 38.4 80.2 149.5 52.4 78.6 47.3 74.6 36.9 143.2 139.0 169.1 121.2 117.5 115 1 Crepiside H C29H34011 I’ 440 46.1 38.5 X0.9 149.8 52.1 79.0 51.3 72.2 43.1 144.5 140.5 170.0 121.7 116.3 114.5 C20H2606 (lS,3S,5~6R,7~XS)-Guaia~(l5),1q14),11(13)-trien-l2,6-olide,3-acetuxy-X-angeloyliix) 45.7 36.4 74.7147.2 51.7 78.1 47.8 73.4 37.4141.5137.6170.7122.4118.3116.0 C I9 C23K3009 Grnssheimin, 4,15-dehydro-JaH-dihydro-3-acetyl-8-(2‘-hydroxy-3’-acetoxyisohutyrdte) 4S3 365’ 75.3 147.1 51.7 77.5 47.4 74.8 36.2b141.1 137.5 173.4 121.9 118.5 116.0 C 46X CZYli34011 Grossheimin, 4,15-dehydro-3aH-dihydro-3-acctyl-8-(2’,3’-diacetoxyisehutyrate~ c 44x 45.4 35.8b 7 4 8 146.7 51.6 80.6 47.2 74.1 34.gbI40.7 137.0 170.0 122.0 118.2 115.9 Crepiside E, pentacetate 1-31ti38014 c 320 4 5 9 372 80.3 147.4 52.1 77.8 47.7 73.9 37.8 141.6 137.5 169.0 122.5 118.3 1163 (‘IS111804 Cynaropicrin, 8-epi, desacyl 1’ 590 44.1 39 0 731 155.2 50.5 78.8 50.1 66.0 44.2 145.1 137.7 170.1 120.9 115.9 109.0 Cynaropicrin, X-epi, desacyl, glycnside C2IH2X09 I’ 590 45.2 38.5 80.8 150.8 50.0b 75.5‘ 50.7b 66.1 43.7 145.0 137.7 170.2 121.0 116.1 I l l y 45.1 38.5 80.8 150.8 50.0” 78.2’ 50.7b 66.0 43.7 144.9 137.7 170.1 121.0 116.1 1119 P 450 45.1 38.5 R0.7 150.8 50.7 78.5 50.0 66.0 43.7 144.9 137.6 170.1 121.0 116.1 111.9 I’ 472 Crepiside I C29H.34011 I’ 449 45.2 38.6 R1.l 151.0 50.7 78.1 49.9 66.0 44.0 145.0 137.7 170.1 121.0 116.2 112.0 Ixerin M C26H360l I 4 4 9 38.4 80.7 150.3 50.4 78.9 48.1 68.4 40.3 143.7 136.2 169.1 121.3 117.2 112.3 I’ 472 Ixerin M, pentacetate CXH46016 45.2 37.9 81.2 150.3 51.3 78.5 48.3 69.4 40.3 143.7 135.6 170.5’ 122.3 117.9 112 8 P 472 Ixerin N ( ‘ 2 7113x01I I’ 472 44.8 38.4 80.7 150.4 50.3 78.8 48.1 68.4 40.3 143.7 136.2 169.1 121.3 1172 112.2 C37H48016 lxerin N, pentaacetate I’ 412 45.1 37.9 81.3 150.5 51 2 78.6 48.3 69.5 40.6 143.1 135.6 169.2 122.3 118.0 112.6 Ixerin 0 C34H4201.3 P 477 44.9 38.3 80.8 150.3 50.5 78.9 48.2 68.4 40.3 143.7 136.2 169.3 121.4 117.3 112.5 C34H42013 Ixerin P P 412 4 5 0 38.6 81.2 150.2 50.5 79.0 48.2 68.5 40.7 144.0 136.3 169.3 121.4 117.3 1123 Ixerin Q C35114401.3 P 412 44.8 38.2 80.7 1.50.2 50.4 78.8 48.1 68.5 40.2 143.6 136.2 169.1 121.3 117.2 112.4 Ixerin R C3SH44013 P 472 44.8 38.4 81.1 150.5 50.4 79.0 48.1 68.5 40.7 143.8 136.2 169.3 121.4 117.2 112.2 C29H.36012 Tectrnside 4 4 7 3 8 4 80.7 150.6 50.3 78.9 48.1 68.4 40.7 143.7 136.1 169.4 121.6 117.2 1122 I’ 665 C2Yt/14011 Ixerisnside A P 665 44.4 38.2 80.7 150.6 50.1 78.8 48.3 68.2 40.6’143.5 136.1 169.4 121.4 117.1 111.9 C2IH2808 Ixerisnside D P 665 40.7b 33.2 30.0 153.1 51.7 86.1 39.3’ 37.1 82.3 151.6 140.5 170.3 119.6 112.4 108.5 CISH1702Cl laH,5aH-Guaia~(lS),1~~4),1~(13)-trien-lZ,~-olide, 90-chloro C 151 45.4 32.9 30.7 150.5 51.4 85.1 43.2 41.9 62.5 148.5 137.6 169.3 120.8 109.3 113.1 laH,5aH-Guaia-4(15),~0(14),11(13)-trien-~Z,~-olide,9p-hydroxy CISHI803 P 8 43.9 33.4 30.7 152.7 52.2 86.1 41.7 40.6 74.4 155.1 140.1 170.1 119.8 108.5 108.5 C2llI2808 Diaspannside B 43.X 33.4 30.7 152J 52.0 85.8 41.8 39.1 79.0 150.0 139.8 170.0 1200 111.1 108 7 I’ Y
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
371
Table 21.---continued Mol. formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-ll C-I2 C-13 C-14 C-15 Sol. Ref. 1109 C16H2003 laH,5aH-Gual~-4(15),1~14),11(13)-trien-12,~-ol1de, 2@-hydroxy-13-methyl 44.0 34.4 73.5 153.1 46.4 83.2 49.8 39.0 30.9 148.2 130.1 169.7 136.6 113.8 111.0 C
No.
>
Other carbons: 1083 iBur-3-CI-Z-OH: 171.7 74.7 51.1 23.4; 1084 iBuf-3-Cl-2-OTAC: 167.9 81.6 46.7 20 6: 1085a Glc: 102.2 75.3 78.3 71.9 77.9 62.9; 1085b Glc: 103.4 75.3 78.2’ 71.9 78.5’ 63.0; 1085c Glc: 103.3 75.2 78.5 71.8 78.1 62.9; 1086 Glc: 102.8 75.1 78.2 71.9 78.2 63.0 Phac-4’-OH: 171.3 41.1 124.8 130.9(2) 116.5(2) 158.2; 1087 Glc: 103.4 75.1 78.3 71.7 75.1 65.0 Phac4’-OH: 172.0 40.7 125.3 130.9(2) 11632) 157.9; I088 Ang: 166.8 127.2 139.9 15.8 20.4 Ac: 170.7 21.2 1089 iBut-2-OH-3-OAc: 170.4 73.6 68.7 22.3 169.9 20.9 Ac: 168.4 20.4; 1090 iBur-2.3-OAc: 169.4 77.2 64.9 19.4 169.2 20.0 168.8 20.3 Ac: 168.1 20.6 1091 Glc-2 6-Ac: 98.4 71.4 72.9 68.6 71.7 62.1 170.5 21.2 170.1 20.7 170.0 2 0 6 169.5 20.6 Ac: 169.1 20.6; 1093a Glc: 104.6 75.3’ 78.5‘ 71.9 78.2‘ 63.0; 1093b Glc: 104.6 75.3 78.2’ 71.X 78.5’ 63.0; 109% Glc: 104.5 75.1 78.3’ 71.8 78.0b 62.9; 1094 Glc: 104.5 75.0 78.5 71.6 75.0 649 Phac-4’-OH: 171.9 40.6 125.3 130.8(2) 116.2(2) 157.8; 1095 Glc: 104.1 75.2 78.2 71.9 78.2 63 0 iVal-2-OH: 174.1 76.1 32.5 17.2 19.2; 1096 Glc-2,3.4,6-Ac: 100.6 72.2’ 72.6‘ 68.9 72.2’ 62.5 a !L’u/-2-0.41, 170.0b 77.2 30.1 17.3 18.7 a ; 1097 Glc: 104.1 75.1 78Sb 71.9 78.1b 63.0 Val-2-OH-3-Me: 174.1 75 5 39.1 24.5 11.6 15.7; 1098 Glc-2.3.4.6-Ac: 100.8 72.3’ 73.6* 69.0 72.3b 62.6 a Val-2-OAc-3-Me: 170.2 76 X 36.6 24.9 11.5 15.4 a : 1099 Glc: 104.1 75Sb 75.7’ 73.0 76.0‘ 62.3 iVal-2-OH: 174 I 76.1b 32.5 17 2 19.2 Phac-4’-OH: 171.8 40.9 125.3 131.0(2) 116.2(2) 157.4; 1100 Glc: 104.6 75.2’ 78.3 71.8 76.1 65 I [Val-2-OH: 174.2 75.3’ 32.5 17.3 19.3 Phac-4’-OH: 172.0 40.7 125.4 131.0(2) 116.3(2) 158.0: 1101 G k 104.1 75.4b 75.9’ 72.9 75.6’ 62.1 Val-2-OH-J-Me: 174.0 75Sb 39.1 24.5 11.6 15.7 Phac-4’-OH: 171 7 10.X 125.2 130.9(2) 116.2(2) 157.8: 1102 Glc: 104.4 75.0b 78.2 71.7 76.0 65.0 Val-2-OH-3-Me: 174.1 75.5‘ 3‘1.1 24.6 11.6 15.7 Phac-4-OH: 172.0 40.7 125.3 130.8(2) 116.2(2) 157.8; 1103 Glc: 104.7 75.4 78 6 71 7 78.5 62.9 Cinn-diH-2.4-OH: 174.3 72.8 39.8 128.5 131.3 116.2 157.7 116.2 131.3; 1104 Glc. 104.7 75 4 78.7 71.8 78.5 62.9 Phac-4’-OH: 171.6 40.4b 124.9 131.1(2) 116.3(2) 158.2; 1105 G l o 103.5 75.4 7X 6 71.5 78.5 627: 1108 Glc: 101.9 75.5 78.6 71.9 78.6 63.0; 1109 C-16: 13.8
R’O O *R2
R’O
H i
0.
co-
R’
R’
1092
H
H
iBut-3-CI-Z-OTAC
1093
Glc
H
8-Glc
H
1094
Gk-6-OPhoc-4’-OH
H
8-Glc
Phoc-4’-OH
1095
Glc
iVal-2-GH
1087
P-Glc-6-OPhac-4-OH
H
1096
Glc-2.3.4.6-Ac
1Val-2-OAc
1088 1089
Ac Ac
Ang iBut-2-OH-3-OAc
1097 1098
Glc
Val-Z-OH-3-Me
Glc-2.3.4.6-Ac
Val-2-OAc-
1090
Ac
iBut-2.3-0Ac
1099
Gk-4-OPhoc-4’-OH
bVal-2-OH
1091
8-Glc-2.3.4.6-AC
AC
1100
Glc-6-OPhac-4’-OH
Wol-2-OH
1101
Gk-4-OPhac-4’-OH
Val-2-OH-3-Me
1102
Glc-6-0Phoc-4’-OH
Val-2-OH-3-Me
I103
Glc
Ccnn-diH-2.4’-OH
1104
Glc
Phoc-4’-OH
R’
R’
1083
H
iBut-3-CI-2-OH
1084
TAC
1085 1086
HO
0.
1105
co
R = a-OGlc
= 8-Cl
1106
R
1107
R = 8-OH
1108
R = 6-OGlc
co 1109
3-Me
372
M. BUDESINSKY AND D. SAMAN
Table 21.--continued No.
1110 1111 a b c 1112 a
b 1113 1114 1115 1116 1117
1118 1119 1120 a
h 1121
1122 1123 1124 1125 1126 1127 1128
I129 1130 1131 1132 1133 1134
1135
Mol. formula Name I Chemical shifts C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-I1 C-12 C-13 C-14 C-15 Sol I k l CISHI804 Znluzanin C, 9a-hydroxy 41.3 39.0 73.1 155.3 49.3 85.0- 35.9 40.0 72.7 153.5 141.0 170.2 119.1 112.0 108.0 P 473 C2IH2809 Macroeliniside A 41.6 37.5 80.8 150.9 49.5 84.4 37.0 39.8 72.3 153.3 141.2 170.1 118.9 111.1 112.2 P 447.45 I 41.6 37.5 80.9 151.0 49.5 84.6 36.8 40.0 72.5 153.4 141.2 170.3 119.2 111.0 112.3 P 327 41.6 37.4 80.7 150.9 49.5 84.4 37.0 39.8 72.3 153.2 141.1 170.0 118.9 111.2 112.2 P 472 Znluzanin C, 9f3-hydroxy CISHI804 42.1 39.6 72.7155.2 49.6 84.8 40.9 40.7 74.6155.0140.1 170.1 119.7110.4107.3 P X 40.7 39.1 73.2 152.6 49.5 84.3 42.1 40.7 74.5 153.0 138.3 169.8 120.8 110.9 109.9 c 350 C21H2809 Dimpanoside A 42.9 38.1 80.7 151.1 49.6 84.4 41.4 40.7 74.6 154.3 140.3 169.5 119.1 110.5 1107 I’ x CI 7H2006 Salograviolide A 48.7b 36.0 74.5 147.3 47.1b 79.3 40.9 77.9 79.8 136.2 147.8 171.1 125.7 113.2’112.8’ C 157 C19H2206 Repdiolide 46.5 77.3b 47.9 73.8 35.8 a a 169.1 135.9’ 137.2’ 139.4‘ 51.4 78.8b 78.9b a C 612* CI 7H2005 Rupicolin B, 8-acetyl-1-desoxy 47.7 36.6 126.3 140.9 56.7 80.2 49.3 74.3 38.4 142.6 137.0 169.6 122.0 116.8 17.2 c 331 C20H2406 Eupahakonenin B 47.6 37.3 126.6 139.6 56.4 80.0 48.5 68.2 40.3 143.1 134.4 169.4 122.0 116.4 I 6 7 c 333 C15H1603 Ligustrin, 8-deoxy -2-ox0 56.2 206.2 132.6 177.5 53.2 83.3 46.1 31.2 36.4 144.1 138.5 169.3 121.0 117.3 l9.X c 162 C21H2809 Crepiside D 44.7b 34.8 153.4 112.9 54.2b 81.7 51.4b 72.8 45.0b 144.7 139.7 170.1 121.1 115.7 12 I I’ 449 C2IH2809 Crepiside C = Ixerin T, desacyl 45.7 35.6 151.2 112.3 54.1 80.3 50.0 65.9 43.2 144.9 137.8 170.2 120.7 115.8 11 6 P 419 43.2 35.7 151.3 112.4 54.2 80.4 50.1 65.9 45.7 144.9 137.8 170.3 120.8 115.8 11.7 I’ 472 C29H34011 Crepiside F 45.2 34.7 151.4 112.9 54.3 E!.2 47.5 74.8 41.2 143.3 138.2 169.2 121.8 117.3 12.2 I’ 44IJ C26H36011 Ixerin S 42.4 35.4 151.3 111.4 53.9 80.7 48.3 68.2 42.2 143.6 136.0 169.1 121.1 116.8 1 1 5 1’ 472 C27H38011 Ixerin T 42.5 35.5 151.3 111.5 53.9 80.7 48.3 6R.3 42.5 143.7 136.0 169.1 121 I 116X I I i I’ 472 C20H2407 Eupahakonin B 84.5 47.8 125.4 147.0 64.8 79.7 47.8 68.7 36.7 139.2 136.3 169.1 121.1 115.8 1 7 1 A 333 CZOH2408 Eupahakonin B, peroxy I’ 33-3 95.4 43.3 125.6 144.5 59.8 79.3 48.5 68.0 37.1 137.5 135.5 169.3 121.5 1 1 8 1 169 C20H2406 Preeupatundin, 8~-(4’-hydroxytigloyloxy) 52.5 78.4b 129.3 147.T 56.0 81.0b 47.8 68.2 38.6 141.6‘ 134.2’ 169.7 122.3‘ 119.3‘ 17.2 c‘ 17 C22H2608 Preeupatundin, 8p-(4’-hydroxy-S’-acetoxytigloyloxy) I. 631 53.8 79.1 129.9 147.3 56.4 81.3 48.3 69.0 39.3 142.1 134.9 169.6 122.2 119.4 174 C22H2607 Eupachifolin C c 112 50.7 80.3 126.3 148.2 56.0 80.0 48.0 68.0 39.0 139.1 134.0 169.2 122.4 120.1 17 Z C22H2608 Eupahakonesin (‘ 333 50.6 80.2 126.1 147.9 55.8 80.0 47.9 68.3 39.0 138.7 133.7 169.1 122.5 120 1 17 2 C25H3008 Pericomin c 307 46.9 37.4 126.9 143.Ib 48.6 80.3 56.1 67.7 41.2 134.4b139.4b170.3 122.8 116.4 592’ C25H3008 Pericomin, is0 c 367 47.2 37.3 126.8 143.1b 48.4 80.0 56.2 68.2 40.6 134.5*139.6b169.9 122.0 116.4 59.1‘ C20H2405 Achifolidien, is0 c 540 146.1b132.2 127.4 149.c 58.6 83.4 42.2 31.8 76.0 75.3 139.5 169.9 119.2 27.4 17.0 C19H2406 Cyclotagitinin C c I40 50.4 49.0 207.6 134.2 160.9 75.7 46.9 65.2 37.3 73.4 141.3 168.1 122.0 23.5 9.5 C19H2306CI Guaia4,11(13)-dien-l2,6a-nlide, la-chloro-10a-hydroxy-8P-isohutanoyloxy-3-1ixii 75.8b 47.0 203.4 132.9 162.8 75.0 46.9 65.4 39.1 75.9b 137.9 168.6 123.2 29.5 X.X C I40 C19HZZ06 Guaia4,11(13)-dien-12,6a-olide, la,l0a-epoxy-~-oxo-8~-isnbu~dnl~yloxy 63.2b 39.3 202.4 132.9 155.0 74.3 42.6 64.4 34.8 68Sb146.6 168.1 122.4 23.7 99 c‘ I40
373
CARBON-I3 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 21.4ontinued ~~
-~~
~
Mol. formula Name / Chemical shifts C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14 C-15 1136 C19H2206 Gunia4,11(13)-dien-l2,~-oiide, 1~,10~-epoxy-3-oxo-8~-isobutanoyloxy 64.9b 40.4 202.7 133.8 159.0 75.3 48.2 64.5 37.4 67.6b 141.4 167.9 122.5 25.7 9.0
No.
Sol
ICC!~
C
I?O
Other carbons: l l l l a Glc: 104.4 75.3 78.2 72.0 78.6 63.1; l l l l b Glc: 104.7 75.5 7X.7 72.0 7X.5 63.1 l l l l c Glc: 104.2 75.2 78.5 71.8 78.0 63.0 1113 Glc: 104.6 75.3 78.5b 72.2 77.9h 63.3; 1114 A c - 1701 21.0; 1115 Mac: 166.5 a 147.2' a ; 1116 Ac: 168.9 21.3; 1117 Tig-4,5-0H: 165.8 131.3 143.9 5 X X 56.9; 1119 Glc: 102.0 74.9 78.6 71.5 78.5 62.6; 112Oa Glc: 101.8 74.9 78.4 71.4 78.4 62.5. 112Oh (;/i 101.8 74.9 78.4 71.4 78.4 62.5; 1121 Glc: 102.1 75.0 78.7 71.6 78.6 62.6 P/iac-4'-OH: 171.2 41.2 125 (> 131.0(2) 116.5(2) 158.3; 1122 Glc: 101.6 74.8 78.3 71.4 78.3 62.4 iVal-2-OH: 174.0 75.9 72 3 17 (1 19.3: 1123 Glc: 101.7 74.8 78.3 71.4 78.3 62.4 Val-,?-OH- -3-Me: 174.1 75.5 39.0 24.3 I 1 5 15 X . 112-1 Tig-4.5-OH: 166.2 132.2 145.9 59.1 56.9; 1125 Tig-4.5-OH: 166.4 132.1 145.8 58.7 56 3; 1126 7 1 , y - 4 - ( J / / 166.8 127.5 141.6 59.3 12.5; 1127 Tig-4-OH-5-OAc: 165.5 127.4 147.6 59.6 58.2 171.4 21 0: 1128 Tig-4-OH: 166.5 127.8 141.1 59.6 12.7 Ac: a 21.3; 1129 Tig-4,S-OH: 165.8 131.1 144 0 5 X X 50 X A S 170.1 21.3; 1130 Ttg-4-OH: 167.4 127.2 142.0 57.9' 12.4 Sac 165.1 126.6 I48.Ob 59." 16.5: 1131 S i r , 165.0 126.5 147.9b 5 8 2 16.5 Mebu-2.5-en-4-OH: 166.9 136.6 35.0 61.1 128.0. 1132 Tig. 166.X 1% 3 I X 2 14.6 12.3: 1133 iBur: 175.7 34.2 19.1 18.9; 1134 iBut: 176.6 34.1 19.2 18.9; 1135 rllrrr. 175 0 31(1 I 0 I 18.9: 1136 iBut: 176.2 34.1 18.9 18.9 HO
* '4'
H (
1110
R = H
1112
R = H
1111
R = Gk
1113
R = Glc
1114
0.
co
v.
c0 '
1115
GlcO
1116
R = a-OAc
1117
R = 6-OTig-4.5-OH
R'
R'
1126
H
Tig-4-OH
1127
H
Tig-4-OH-5-OAc
1128
Ac
Tig-4-OH
1118
R = H
1130 R = Tig-4-OH
1119
R = a-OH
1124
R = H
1120
R = 6-OH
1125
R = OH
1121
R = a-OPhac-4'-OH
1122
R
1123
R = 6-OVol-2-OH-3-Me
1133
R = H R = Cl
-
1132
1131 R = Mebu-2.5-en-4-OH
1135
fl-OiVoi-2-OH
1134
1136
OMac
374
M. BUDESINSKY AND D.
SAMAN
Table 21.-continued Name / Chemical shifts
Mol. formula
No.
C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-I1 C-12 C-13 C-14 C-IS Sul-I(cl: 1137 ClYH2306CI laH-Guaia-4,11(13)-dien-12,6a-oliie, 2-chlor~l0a-hydroxy-E~-isobutanoyluxy-3-11~11 5 5 3 61.5 200.4 133.6 153.8 75.1 46.8 64.8 49.1 73.6 140.2 167.7 122.7 23.8 10.1 Zaluzanin C, 3-desnxy-4a,l5-dihydro-7a-hydroxy 1138 CISH2003 44.6 27.8 35.1 36.1 43.3 86.0 75.5 36.9 34.3 143.5 150.1 170.0 122.6 1 1 1 5 15.1 Estafiatone ll3Y CIS111803 39.9 43.9 218.8 47.0 50.8 88.7 44.1 31.8 38.5 148.7 138.9 169.7 121.0 113.0 14.3 1140 CISHI804 Grossheimin d 39.6 42.9 218.9 46.6 50.5 82.5 48.8 72.4 48.0 143.7 136.4 169.8 125.1 114.5 I4 4 h 404* 43.5’218.7 47.2 49.8’ 83.3 51.1 73.2 49.2‘145.4 138.7 170.3 124.5 114.4 15.0 c 45.9 47.1 218.1 39.3 48.5 82.0 49.9 71.7 42.4 144.4 137.7 169.6 123.2 113.8 14 2 C-l
C-2
C-3
1141 CliH200.5
43.2’ 46.8’218.2 1 I42 ClYH2407
Grossheimin, 8-0-acetyl 40.6 46.4b 82.2 51.1 74.3 43.0’142.4 136.0 171.1 124.6 116.7 Grossheirnin, 2’,3’-dihydroxyisobutyrate
40.7 42.3b218.2 46.7’ 51.5 80.6 46.5’ 75.9 40.7’14l.5 135.6 174.7 125.2 117.3 1143 C23H2809 Grossheimin, 2’,3’-diacetoxyisobutyrate 4 1 . 1 42.4b217 7 46.7’ 52.0 80.6 47.2‘ 75.8 40.0* 141.6 136.4 170.0 124.3 117 7 1144 CZOH2606
14.9 15 1 15 4
Ixerin S, aglycone
47.2 50.7 81.8 47.2 69.0 43 8 143 4 134.5 1686 122 7 1164 1-1 1 Zaluzanin C 3-dehydro-4~,15-dihydro-8~-(4’-hydroxy-5~-(4’~-hydroxytiglii~ Iiixy)tigIo>I i i x ? 79 8 43 9b219.5 47.1 50.1 82.7 47.1 67.9 44 3* 143.6 134 5 1699 123 4 116.3 I4 2 40.2 44.2b219.1 47.5 50.7 83.2 47.5 69.2 44.5b 145.6 136.6 1697 122 I I15 9 14 4 C17H2204 laH,SaH-Guaia-10(14),11(13)-dien-12,6a-olide, lS-ethoxy-3-oxo 4 0 0 45.7 217.7 44.6 44.2 88.8 52.9 38.4 31.8 139.0 148.9 169.8 121.2 113.0 681 0 CI5H1803 Estafiatin 44.8 32.9 62.2 65.0 5 0 7 79.4 43.8 28.8 2 8 . 5 1 4 6 . 6 1 4 0 . 4 I h X 3 l l X . 4 1 1 4 3 1 x 6 C20H2406 Eupatundin, 2-desoxy 58.1 74.3 6 4 3 67.1 80.3 78.5 41 9 6 8 7 37.7 139.2 174 5 16‘1 I 122 4 121 7 I5 X C20H2207 Eupatundin, dehydru 61.2 204.2 62 I 6 8 4 77.7 77.8 41.4 68.1 3 5 9 133 2 1346 1689 l 2 4 X 1 2 3 X I T 7 C‘ZjH3208 Zaluzanin C, 4~,1~-dihydro-R~-(5’-(5”-hydruxyti~loyluxy)-tiglii)loxy) 42 6 38.5 78.3 46.4 51.9 80.8 50.6 66.9 40.9 1423 1350 I69 2 121 5 I l h X 176 400
44.5 218.1
1145 C25H.3009
a h
1 I46
1147 I I4X 1 l4Y
1150
51 I 35.6 1152 C30HWOlZ
43.3‘ 38.5 1153 CI 5H2004
79.8 43.5
43.0
80.6 50.4 67.2 41.6 142 I 134.8 1693 122.0 117 I
Ixerisnside B
87.4 44.gb 51.4 81.6 49.9 67.8 41.6 143.5 136 3 169 3 121 2 116 X Grmheimin, 3-dihydro
51.0 81.6 53.6 72.8’ 46.6b 144.4 139.8 171.4 121.8 114.2 Grossheimin, 3-dihydro-3,S-di-O-acetyl 43.7b 49.8’ 80.0’ 35.6 43.5’ 80.5 5 1 6 74.4* 40.4‘ 141.5 137 4 169 7 I22 4 I17 I 1155 C19H2406 Subcordatolide A 85.7’ 140.2 134.6‘ 82.0’ 66.5‘ 67.3* 46.2 76.8 35.8 135.0 144.0 176.0 122 I I I h X I156 C20H2406 Subcordatolide A, 8-desaryl-8-tigloyl X5.8* 140.2’ 138.2’ 82.1b 66.Sd 67.6* 46.4 76.9d 36.0 134.8 144.1 169.8 122 6 1169 laH,5aH-Guaia-10(14),11(13)-dien-12,6a-olide, 3p,4a-dihydroxy 1157 C15H2004 38.8 34.3 78.3 80.5 53.9 83.7 47.4 3 1 6 39.1 148.9 140.4 170.1 119.4 112.5 Diaspannside C ll5X CZI H300Y 38.7 32.9 85.1 80.7 53.3 83.4 47.5 31.7 39.2 148.3 140.3 170.2 119.6 112.6 Michefuscalide = I,ipiferolide, p-cyclo 1159 Cl711220S a 44 0 26.1 44.8 79.9 55.4 78.7 49.2 74.3 39.8 141 I 135 5 I6X 5 127 7 115 7 h 44.2 26.4 404 79.X 5 6 4 77.9 5 0 2 6 5 6 43.7 141.i 134.8 Ih9O 1220 1167 Cebelin C 1160 C19112307CI 48.9 35.8 78.5 85.8 59.6 77.0 49 3 75 5 40.0 I41 9 I449 170‘1 122 7 I 1 7 6 Cebelin C, 3v,4’-diacetyl 1161 ( X H 2 7 0 Y C [ 46.7 35.2 78.4 83 8 57.9 75.6 46 8 74 I 36.2 140.9 1364 16X 4 123 I I I X 9 Chlororepdiolide 1162 C23H270iCI __ 5 8 4 83.3 84.1 83.9 60.1 77.6 47.2 74.4 3 6 . 7 1 4 2 . 8 1 3 8 . 8 1 6 9 . 0 1 2 0 . ‘ ~ 1 1 8 0 46.8
39.0h 77.5‘ 42.9
1154 ClYH2406
375
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 21.--continued Othercarbns: 1137 iBur: 175.6 34.2 19.1 18.9;1141 Ac: 169.4 21.0; 1142 iBur-2.3-OH: 168.9 75.5 67.9 21.8;1143 iBur-2.3-OAc: 168.7 78.6 65.4 20.0 169.3 20.6 169.8 20.8; 1144 iVnl-2-OH: 174.2 74.9 32.1 15.9 19.2; 1145s Tig-4-0H-S-OTig-4'-OH: 165.2 126.7 148.9 59.5 58.1 167.4 127.3 142.3 59.2 12.5: 1145b Tig-4-0H-li-OTig-4'-OH: 165.7 127.4 150.1 59.6 58.7 167.6 127.4 143.6 59.3 12.6;1146 OEI: 66.7 14.9;1148 Ang: 167.3 127.4 138.7 15.8 20.5; 1149 Ang: 166.9 127.1 139.1 15.8 20.5; 1150 Tig-S-oT~g-5'-OH: 165.4 127.6 145.7 14.4 56.4 166.8 131.6 141.4 14.0 57.5: 1151 Tig-4-OH-5-OTig-5'-OH: 165.2 126.8 147.9 59.2 56.4 167.0 131.6 142.1 14.3 58.1 Ac: 171.2 21.2;1152 Cinn-diH-2.4-OH: 174.4 72.8 40.9 128.7 131.2(2) 116.2(2) 157.7 Glc: 105.8 75.5 78.6 71.8 78.4 62.9;1153 2xAc: 170.9 21.1 169.9 22.0;1155 iBut: 169.7 34.0 19.0 18.8;1156 Tig: 166.9 138.8 134.8 14.4' 12.W;1158 Glc: 104.6 75.9 78.7h 71.8 78.5' 62.9;ll59a Ac: 169.3 21.0 1159b Ac: 170.3 20.9;1160 Mnc-4-OH: 166.6 139.3 126.0 61.6: 1161 Mnc-4-OAc: 164.3 135.0 129.4 62.2 169.2 21.2 Ac: 170.3 20.8;1162 Mnc: 166.5 136.7 126.3 IK.3 0
*
OiBut
0.
co
1137
1138
-
1139
R
1140
R = OH
1141
R = OAc
1142
R
1143
R = OiBut-2.3-OAc
=
H
1144
R = iVol-2-OH
1145
R = Tig-4-OH-5-OT!g-4'-OH
OiBut-2,J-OH
R'
Rz
R'
R2
1147
H
H
1150
H
lig-5-OTig-5'-OH
1148
OH
OAng
1151
Ac
Tig-4-OH-5-OTig-S-OH
1152
Glc
Cinn-diH-2.4
1146
R'
Rz
1155
R
1153
OH
H
1156
R = lig
1154
OAc Ac
=
1149
-OH
R'
R2
R'
R2
R'
1157
OH
H
1160
H
H
Mac-4-OH
1158
OGlc H
1161
H
AC
Mac-4-0Ac
1159
H
1162
OH
H
Mac
iBut
OAc
376
M. BUDESINSKY AND D. SAMAN
Table 21.4ontinued Nu
1163 1164
I165
1166 1167 a h 1168
1169 1170 1171
1172
1173 1 I74 1 175
I 176
1177 a h c
Mol formula Name I Chemical shifts C-I C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-LO C - l l C-I2 C-13 C-14 C25H2Y010CI Cebelin C, 38,4,4‘-triacetyl 46.6 34.8 76.7 92.8 54.5 75.3 47.0 74.0 36.0 140.4 136.3 168.4 123.1 119.3 C19H2207 Sublutenlide 45.4 37.6 75.1 68.2 97.7 75.9 52.8 75.6 36.5 141.4 136.6 168.9 118.4 123.2 ClYH2207 Repin 46.0 38.9 75.5 69.2 53.1 77.5 47.8 75.3 36.4 142.7 138.6 169.0 121.1 118.0 C20H2407 Sublutenlide, 8-desacyl-8a-(4‘-hydroxytigloyl) 48.1 47.6 74.1 68.2 45.6 76.9 53.0 76.1 36.6 141.4 137.1 169.1 122.7 118.5 ClYH2207 Janerin 46.3 36.8 76.0 69.0 53.5 77.6 48.2 74.7 38.9143.5139.1 169.3121.5118.1 47.Yb 37.6‘ 74.2’ 68.2 45.7b 76.7‘ 53.1 76.3‘ 36.5’ 141.4 137.0 168.9 122.7 118.6 C191f2207CI Acroptilin 46.7‘ 36.1‘ 76.2* 69.0 54.0 76.3 48.Ib 76.2‘ 39.2’ 143.3 139.0 169.3 121.9 118.5 C19H2307C1 Costuslactone, dehydro, 2a,3~dibydroxy-4a-epoxy.&r-tigloyloxy 49.2’ 73.1 77.2 65.4 47.1b 77.4‘ 51.7 78.9’ 36.7 135.2 136.9 168.4 121.9 119.4 CI5HIBO2 Eremanthin, is0 47.9 38.1 125.5 143.3 54.9 86.1 45.0 30.0 119.5 137.3 139.3 170.0 119.3 17.8 C17112004 Cumambrin A, 9,lO-dehydro 47.5 37.9 125.6 138.2 55.1 79.5 46.8 73.1 121.6 142.7 136.6 169.7 122.9 27.7 CISHIR04 Rupicolin A 83.3 46.3 123.1 141.9 64.2 78.2 50.0 71.0 127.6 139.0 137.7 169.8 123.6 29.4 CZOff2407 Eupahakonin A 83 4 47.7 123.6 145.5 66.4 79.0 48.2 67.8 119.6 142.2 135.9 169.0 121.2 24.9 C20H2408 Eupahakonin A, peroxy 94.6 44.2 123.4 142.7 60.7 78.9 48.2 67.9 122.8 141.7 135.6 169.0 121.6 24.4 C25H3009 Rupicolin A, 8-epi, 8-(5’-(4”-hydroxytigloylnxy)-tigloyloxy) X3 3 47.0’ 119.2 141.7 47.6b 65.5‘ 66.9’ 76.8 123.0 144.5 134.2 169.7 122.6 24 3 C19112206 Helipterolide, 14-acetate-3f3-acetoxy I41.0 37.9 82.0 146.2 53.1 76.4 51.6 2 6 0 30.5 140.8 132.0 168.7 1178 66.7 ClS111802 Eremanthin 47.1 29.2 30.5 150.4 52.7 83.2 45.3 29.7 121.2 138.2 140.7 170.1 119.4 27.2 47.1 29.2 30.6 150.3 52.7 83.2 45.3 29.7 121.1 138.0 140.4 169.9 119.3 27.9 47.0 30.5 29.1 149.9 52.5 83.1 45.2 29.6 120.8 137.8 140.1 169.7 119.1 27.9
1178 C24113009 ~ 4 n4 1 2 1179 C2611iZOlO
C-15 42.7
C
48.3
C 453*
48.6
P
48.4 48.5
c+s
51.4 47.3
E
424 34
E
424
c+s
34
28 0
c
IS1
17.6
c
333
17 6
c
705
17 9
A
333
I7 8
A
333
17.5
c
I99
116.3
13
699
110‘9 1109
c c
229
1107
c
305
Eremanthin, 3~-hydroxy-8a-(2’,3’-diacetoxy-2’-methylbutanoylnxy~ 72.1 152.2 51.1 77.2 48.8 67.2 119.9 145.2 134.6 168.9 122.1 28.4 115 2 Eremanthin, 3~-acetoxy-8a-(2’,3’-diacetoxy-2’-methylbutanoyloxy~
c
343
c
343
c
343
c
343
P
633
c 40.3 145.4 137.8 170.6 122.8 115.7 17.2 la,lO~-dihydroxy-3~-is0butanoyloxy-3-nxo c 40.3 81.3 138.4 168.2 123.6 22.5 86
705
C
162
c
402
44.0 38.6 11x1 C24112809
73.5 147.3 51.5 76.9 49.2 65.6 120.6 144.1 135.5 168.9 121.3 28 3 117.7
809 46.2 11x2 (‘20112207
72.6 147.0 60.9 76.6 47.6 65.5 120.9 144.6 134.9 168.9 121.9 2 4 8 118.2
Eremanthin, Eremanthin,
151
3P-acetoxy-8a-(4’-acetoxyangeloyloxy)
3~-acetnxy-8a-(5’-acetoxyangeloyloxy)-la-hydrnxy
Montacephalin
135.6 193.3 134.8 173.1 78.4 84.4 48.5 70.1 11x3 CIS111804 Rupicolin B 8 4 0 45.2 124.5 140.0 64.6 79.8 50.9 72.2 1 1x4 CIYII2407 Guai-4,11(13)-dien-12,6a-olide, 74 X 46 3 204.1 132.6 161.9 73.9 48.1 63.9
~~
613
C+S 34
73.2 147.3 51.3 76.4 48.6 67 I 120.1 144.6 134.4 168.7 122.1 28.2 117.6
132 0 195.6 I 1x6 c1s1116i04 a 134.2 195.5 h 132 R IO6.O 11x7 (‘20112206 a 174 2 I04 7 h 132.hb194.9
126
48.5
44 0 38.4 I I X O (’241126‘08
11x5 (‘1511160.~
Sol. Ref
74.8 148.0 139.1 169.3 121.9 13.1
156
140
Leucndin, dehydro
135 6 169.4b 53.0 84.4 53.1 24.5 37.2 151 7 138.6 169.0b118.6 21.8 I9 7 Matricarin, 1l,l3-dehydro, desacetyl = Lactucin, 14-deoxy 1360 170.7 52.0 82.5 5 8 3 6d.2 49.4 146.2 139.2 169.5 121 8 21 3b 198’
A 705 135.2 170.6 51.4 81.6 57.5 67.0 48.5 146.7 136 7 169.6 122.7 19.5 21 3 5aH-C.uai-1(lO),3,11(13)-trien-l2,(nr-~lide, X~-(2’,3’-epoxyangeloyl1~xy)~2~11~1~ c‘ 21‘9 135.5 168 7 54.5 78 4 52.6 65.4 40.6 145.4 132.4 169.0 120.0 22.8 18 7 135.9 169.1‘ 53.0 78.6 55.1 65.6 41.1 145.8 134.3b 167.8 120.4 23.2d 19.7’’ C 262
377
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 21.-continued Mol. formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-ll C-12 C-13 C-14 C-15 Sol I
No.
~
Olhei carbons: 1163 Mac-4-OAc: 164.3 135.0 129.4 63.9 169.5 21.9 2xAc; 169.2 21.2 169.2 20 h. 1164 M o c - ~ p .170.0 53.7 52.8 17.2; 1165 Mac-ep: 170.2 54.3 52.9 17.5; 1166 Tlg-4-OH: 166.5 12X.O IJI 7 5‘) X 12.7; 1167a Mac-4-OH: 165.9 141.8 125.0 61.3; 1167b Mac-4-OH: 165.3 135 2 1266 h2.2: 1168 i / t i i f - 2 - 0 / / -3-C/: 173.3 75.8 48.5 24.0; 1169 Tig: 166.5 128.1 138.2 11.9 14.4: 1171 Ac: 169.0 21.2; 1173 ?ig-4.5-0// 166.5 132.0 145.9 59.2 57.0; 1174 Tig-4.5-OH: 166.4 131.8 145.9 59.2 56.9: 1175 Tig-4-0WS-Ofi,q-4 -011
165.2 126.6 148.2 59.4 58.0 167.3 127.3 141.7 59.0 12.2; 1176 2xAc: 169.6 20.4 170.0 20.8; 1178 Mebii-2,3-OAc: 168.6 81.7 72.4 16.3 14.6 169.5 21.0 170.0 20.9; 1179 Mebu-2.3-OAc: 168.4 81.6 71 X 16.5 14.5 170.8 20.8 169.4 20.9 Ac: 169.2 21.0; 1180 Ang-4-OAc: 165.8 128.0 139.9 62.8 19.7 170 X 20.9 Ac: 170.7 21.1; 1181 Ang-5-OAc: 164.8 127.0 146.1 16.0 65.3 170.9 2 0 7 Ac: 1704 21.2; IlXZ .Seii 165.9 115.8 158.5 20.1 27.1; 1184 iBur: 176.1 34.0 18.9 19.1: 1187a Epang: 167.7 59.0 59 4 13 3 1‘1 3. l l X 7 h Epyafig: 169.0’ 59.3 59.8 13.7 19.0d: 1188 Afin: 166.8 1269 139 8 15.X 204: l l X Y M P / I I I - ~ . I - O / / 175 7 77.4 71.4 16.5
1163
R’
R2
R’
R2
R’
R2
1164
ti
Mac-ep
(2s)
1170
a-H
H
1172
ti
a-OH
1165
H
Mac-ep (2R)
1171
6-H
OAc
1173
H
@-OT,g-4.5-0h
1166
ti
Tig-4-OH
1174
OH
B-OTig-4.5-OH
1167
ti
Moc-4-OH
1175
ti
8-0T~g-4-OH-
1168
H
iBut-2-OH-3-CI
1169
OH
Tig
R = Mac-4-OAc
CH20AC
H
-OH
u l ,#“OR’
R’ ACQ*
-5-0719-4
AcO
‘-101
OAng-5-OAc
i
0.
0.
co R’
1176
& H Z
0. 1183
co
0.
co R2
co
1181
1177
H
H
1178
OH
Mebu-2.3-OAc
1180 1179
OAc
Mebu-2,3-OAc Ang-4-OAc t ”B; c l ; .
0
0.
,
eR H
0. 1184
co
1182
i
0.
co
co
1185
R
1186
R = a-OH
1187
R = 8-OEpang
1188
R = 8-OAng
1189
R
=
ti
= 8-OMebu-2.3-OH
378
M. BUDESINSKY AND D. SAMAN
Table 21 .-continued No
1190 1191 1192 1193 1194 a b
1195 11%
a b C
1197 1198 1199 1200 a b
1201 1202 a h
1203 1204
1205 1206 1207 1208 1209 1210 1211 1212 1213 1214
Mol formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-I4 C-IS Sol I
162.1 185.7 Cl5H1604 131.0 195.6 131.0 195.2 C17H1805 130.8 194.2 CZlH2609 131.8 194.9 131.8 194.9 131.7 194.9 C23H28010 133.4 194.5 ClSH1604 77.2 200.6 ClSH1805 59.0 206.6 CI5HI60S 133.2 194.8 133.2 194.8 C19H2006 132.7 194.2 C2IH26010 133.0 194.6 133.0 194.6 C25H35011 133.5 194.3 C30H33011 133.5 194.6 CZ9H32012 133.4 194.2 CI5H1804 136.7b 38.5 C21H2809 136.2b 38.5 C29H3401 I 136.1b 38.5 C29H34011 136.0b 38.5 CZ9H34011 136.3b 38.6 ClSHI803 142.0 35.0 C2CH2406 125.2 37.9 C25H3009 137.2b 37.8 C2OH2006 126.7 37.0
137.4 147.4 50.8 77.9 52.9 71.3 75.1 131.9 133.3 168.1 121.8 57.2 176 C 656 Jacquinelin, llJ3-dehydro = Lactucin, Sdeoxy 132.7 172.6 52.4 83.8 49.6 24.0 37.0 153.5 138.1 169.2 119.1 21.7 61.8 C+M 126 133.2 171.7 49.8 83.9 52.7 24.2 37.3 153.3 138.4 172.0 119.3 21.9 6 2 4 C 369 Lactucin, ll-dewxy, acetate 133.6 165.9 52.7‘ 83.5 50.6’ 24.3 37.4 153.4 138.4 168.2’ 118.9 22.0d 63 2 C 575 Crepidiaside A 134.6 169.1 50.1 84.1 52.6 24.4 37.2 152.5 139.7 169.1 118.2 21.6 68.8 I’ 9 134.6 169.1 50.1 84.1 52.5 24.4 37.2 152.5 139.7 169.1 118.2 21.5 6X.7 I’ 7 134.4 169.1 50.1 84.0 52.5 24.4 37.1 152.5 139.6 169.1 118.2 21.5 6X.7 I’ 447 Lactucin, 8-acetyl-15f3-D-glucopyranosyl 135.2 168.4 54.3 78.4 48.6 69.4 44.1 145.4 137.2 169.9 121.2 20.9 68 7 I’ 3X Leucodin, dehydro, lf3,lOg-epoxy 133.2 171.6 52.7 80.4 49.6 20.5 34.4 67.0 136.1 169.5 116.6 20.8 18.9 C 529 Hieracin Il 130.0 180.0 50.8 83.2 48.7 22.7 41.0 72.3 138.8 169.3 120.4 32.2 63.1 C+M411 Lactucin 133.2 175.0 49.6b 81.6 58.2 67.7 49.Ib 146.4 138.9 169.1 121.9 21.4 62.5 P 646 133.2 175.0 49.6 81.6 58.2 67.7 49.1 146.4 138.9 169.1 121.9 21 4 62 5 P 474 5aH-Guai-1(10),3,11(13)-trien-I2,~-olide,15-hydroxy-8a-methacryli~yloxy-2-11~0 133.6 171.2 48.4 80.8 54.9 69.3 44.3 146.0 135.9 168.0 122.2 21.3 62 1 C 490 Picriside A 134.7 169.3b 49.6 81.6 58.0 67.6 49.0 146.8 138.8 169.0b122.0 21.4 68.7 P 646 134.7 169.3 49.6 81.6 58.0 67.6 49.0 146.8 138.8 169.0 122.0 21.4 68.7 P 474 Hypochoeroside C 134.9 169.3 48.6 81.2 54.6 69.8 44.0 145.1 137.4 168.3 I209 21.0 68 6 P 490 Hypoehoeroside D a 169.4 48.7 81.3 54.5 69.7 44.3 145.6 137.3 168.6 121.3 21 I 6X.X P 490 Lactucopicriside 134.8 169.0 48.5 81.1 54.3 69.8 44.0 145.3 136.9 168.2 121.4 2 0 9 6X 5 I’ 471 Youngiaside A, sglycone 124.8 147.0 52.7 85.4 44.3 32.9 71.5 134.7b141.5 169.5 1164 22.4 61 7 P 7 Youngiaside A 128.1 141.8 52.3 85.4 44.0 32.8’ 71.5 134.Xb141.2 169.9 116.9 22.4 68.1 P 7 Youngiaside B 128.5 141.7 52.1 85.5 44.0 32.8 71.5 135.0b141.3 169.7 116.6 22.4 68.1 P 7 Youngiaside C 128.1 141.7 52.2 85.4 44.0 32.8 71.4 134.9b141.2 169.7 116.6 22 3 68.2 I’ 7 Youngiaside D 128.1 142.0 52.4 85.5 44.2 33.0 71.6 134.gb141.5 169.6 116.5 2 2 4 68 1 P 7 Babia HI, dessarracinyl 121.0 147.0 33.0 52.0 67.0 59.0 80.0 132.0 169.0 210.0 136.0 15.0 18.0 A 470 Eupdhakonenin A 125.4 139.9 56.4 79.9 55.3 66.7 37.6 136.7 135.2 169.1 119.5 24.1 17.7 c 333 Zuubergenin, desacetyl, 8f3-(5’-(4”,5”-dihydroxytigloyloxy)~’-hydroxytiglo)l~~xy) 126.7 135.4b 56.6 80.1 55.4 66.8 36.0 131Sb137.2b169.7 120.2 24.1 17 5 C 439 Guaiagrazielolide, 8B-angeloyloxy 122.4 133.9 58.5 74.0b 48.7 78.4b 63.4 150.0 133.3 167.6 126.1 160.9 162 C 103
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
379
Table 21.-continued No
1215 1216 a
h
Mol. formula Name / Chemical shifts C-8 C-9 C-10 C-l C-2 C-3 C-4 C-5 C-6 C-7 C29H34011 Crepidiaside E 136.9 37.5 127.8 141.3 53.0 82.5 58.9 68.8 46.6 126.6 CISHI803 Eregoyazin 47.5 42.4 218.0 38.4 52.4 84.1 43.9 29.8 122.1 135.5 38 5 42.4 218.4 47.6 52.5 84.2 44.0 29.9 122.2 135.4
C-lI C-12 C-13 C-14 C-15 139.8 169.9 121.3 23.0
SI)I Ref.
69.0
I’
139.9 169.5 120.1 27.0 15.3 139.9 169.6 120.3 15.5 27.1
C
C
‘1
305 151
Other carbons: 1192 iBur-Z-OH-3-Cl: 172.2 75.3 50.3 23.4: 1193 Tig: 167.5 127.3 140.5 14.7 12.1 Ac. 171 4 20.7. 1195 Ac: 169.8’ 20.6’; 11960 Glc: 104.2 75.1 78.5 71.7 78.3 62.8: 1196b Glc: 104.2 75.1 78.jh 71.6
78.2’ 62.7: 1196~Glc: 104.1 75.1 78.2 71.5 78.4 62.7: 1197 Glc: 104.2 75.1 78.3b 71.3 81.2* 62.5 Ac: 169.9 20.8: I201 Mac: 165.8 135.6 127.0 18.2: 1 2 0 2 ~Glc: 104.1 75.1 78.4 71.6 78.2 62.7: 1202b G l r . 104.3 75.1 78.4 71.6 78.2 62.7; 1203 Glc: 104.2 75.2 78.4 71.5 78.4 62.6 Mac: 166.0 136.3 18.2 126.8: 1204 Glr: 104.1 75.1 78.3 71.5 78.3 62.6 Cinn: 165.8 117.9 146.5 134.8 128.8(2) 129.4(2) 131 I ; 1205 Glc: 103.9 7 3 9 78.1 71.4 78.0 62.5 Phac-4’-OH: 170.9 40.7 124.3 130.9(2) 116.4(2) 158.0: 1207 Glc. 103.1 74.9 78.2’ 71.5 77.7’ 62.6: 1208 Glc-3-OPhac-4’-OH: 102.8 72.9 79.5 69.7 77.8 62.1 172.0 40.9 125.4 130.8(2) 116.0(2) 157.6; 1209 Glc-4-OPhac-4‘-OH: 103.1 75.1 75.6 72.7 75.6 61 9 171.6 40.7 125.1 130.8(2) 116.1(2) 157.7: 1210 Glc-6-OPhac-4’-OH: 103.2 75.0’ 78.3 71.6 75.1‘ 65.0 172.2 4 0 5 125 4 131.0(?) I16.2(2) 157.8; 1212 Tig-4.S-OH: 165.9 131.1 144.1 58.7 56.7: 1213 Tig-4-0H-S-O7is-4’.5’-I)/I: 165.3 125.2 147.9 58.9 58.4 166.6 126.0 144.6 59.1 58.8; 1214 Ang: a : 1215 Glc-2-OP/iai.-4’-(11/. 101 5 75 6 76.0 72.0 78.3 62.5 171.4 41.0 125.4 131.0(2) 116.2(2) 157.8
1190
R = OH
1191
R = CI
R’
R’
R’
1194
R = H
1192
But-2-OH-3-CI
H
H
1195
R = AC
1193
Tig
OH
OAC
1196
R = Glc
1197
Q H
i
0.
co
1198
R’
R‘
1206
R = H
1200
H
H
1207
R
1201
Mac
ti
1208
R = Glc-J-OPhac-4’-0-
1202
ti
Glc
1209
R = Glc-4-OPloc-4’-Or
1203
Mac
Glc
1210
R = Clc-6-OPhcc-4-3r
1204
Cinn
Glc
1205
Phac-4’-OH
Glc
1199
= Glc
9, G
O
A
n
g
H i 1211
R = H
1212
R = lig-4.5-OH
1215
R = Tig-4-OH-5-OTig-4’.S-OH
ROH&
1214
i
0.
0-CO 1215
co
R = Glc-2-OPhac-4’-~H
0. 1216
b=
cn
380
M. BUDESiNSKY AND D. SAMAN
Table 21.--continued b’o
Name I Chemical shifts C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-ll C-12 C-13 C-14 C-IS Sol Ret 1217 C19H2206 laH,5aH-Guai-3,11(13)-dien-lZ,~~lide,15-hydroxy-8a-methacryloyloxy-Z-oxo C 490 49.1 206.9 130 I 179.8 49.7 78.0 52.8 71.7 40.0 30.5 135.3 168.6 125.2 16.6 62.5 1218 C25H3301l Hypochoeroside E a 17.0 69.0 P 490 48.X 207.1 131 I 178.1 50.0 78.5 53.3 72.5 40.1 30.9 137.3 169.0 1219 C3OH.35011 HypochoerosideF P 490 48.9 207.1 131.0 178.1 50.0 78.5 53.2 72.1 40.4 31.0 137.2 168.9 a 16.9 69.0 Mol tomula
C-l
C-2
C-3
1220 C17H2205 Lipiferolide, a-cyclo 125.6 30.2 38.3 80.4 58.8 77.7 52.0 65.0 39.3 132.9 134.9 169.1 121.1 22.8 24.5 1221 C20H2007 Eupatundin, dehydro, is0 158.4 194.5 64.6 66.2 a a 47.7 66.4 38.8 134.0 134.7 167.9 120.1 25.3 15.8 1222 C20H2207 5s 6s 7Q8 Z’R’ 3’R*)-Guai-l(lO) 11(13)-dien-12,6-olide, a
S,4!e~xy-8~~,3’-;poxyPngeloyloxy~-z-o~o 132.4b196.6 63.1 62 1 50.5 74.6 56.0 66.0 40.6 151.8 135.1b167.2’119.0 24.04 18.6‘
b 132.0h 196.6 63.1 62.3 50.7 74.9 56.4 66.2 41.1 154.5 134.Zb167.6‘ 120.2 1223 CISHI604 Ludartin, 2-0x0 131.1 197.6 63.1 62.3 5 4 1 80.3 50.4 24.8 37.3 159.0 138.5 186.7 118.4 I224 C20H2407 ZS 3s 4 5s 6s 7R,8R]-Guai-1(10) 11(13)-dien-12,6-olide, $-a~g~Io~ox~-3~4-epoxy-Z-hydrox~
1374h 7 2 5 67.2 65.2 52.9 76.1 BacchariolideA 136.9’ 72.6 66.0 65.5 51.1 77.5
C
680
c
28‘1
B
24.4‘ 18.6’
C
262 262
1 8 7 22.8
c
95
56.7 65.3 38.6 137.0b134.9 168.2 120.0 2 3 6
19.2
C
239
55.9 69.3 76.7 136.3‘ 138.0b 168.6 122.1 14.7
IX 8
C
505
34.0 134.Yb139.4 169 5 117.8 22.6 19 0
c
6Oh
1225 CZOH2407
1226 ClSH1803 133 Yb 33.6 1227 CI 7112005 a 132.2 7 4 4 h 1326 74.6 122R C19112405 132 5 74.3 122’9 CZOH240.5 1325 7 4 5
Ludartin
63.8 67.1 52.5
80.9 54.1 249 35.0143.5138.9 168.9118.2 22.3 80.9 54.1 25.0 35.1 143.3139.4168.9117.9 2 2 3 Kauniolide, 3a,4a-epoxy-2a-isobuta~yloxy 64.2 64.5 52.2 81.1 54.2 25.0 35.0 142.3 139.0 169.0 118.1 2 2 5
64.3 64.6 52.1 81.0
542
250
C 161 C+D 161
19 2
C
I61
19.2
c
I61
1x6
c
633
15.3 15.X
c
633
35.0 142.1 138.2 168.1 118.1 22.3
624
66.5 56.1
77.5
51.1 69.7 75.8135.4136.7169.1122.5
15.0
Tomencephalin, 5-hydroxy
625
69.6 80.0 79.0 4 7 6
70.6 73.4 133.6 137.2 169.9 122.3
Helipsolide, desacyl, 9-O-acetyl-8-O-angeIyl-Za,3a-epoxy
123.1 20.0
21.1
c
35X*
120.2
2X
J
c
151
119.6 49.9
2X.O
c
151
121.4 52 2
17 6
c
2x1
36.3 56.2 134.2 169.2 122.4 52.2
17 1
c
2x1
81.0 600 180.0 207.0 1320 54.0 35.7 55.7 134.1 169.0 122.5 52.1
17 0
A
76.8 54.3 74.5 54.1 72.9 75.5 135.3 135.7 168.5 laH,SaH-Cuai-9,ll(13)-dien-12,6a-olide,3a.4a-epoxy 61 0 65.4 48 8 83.5 46.3 29.2 121.4 137.3 139.0 170.1 laH,SaH-(;udi-9,l1(13)-dien-12,6a-olide,4a.lS-epoxy 7 28 7 66.1 53.2 82.3 45 4 29.5 120.3 138.4 139.6 169.4 1235 CICHl804 Rahia I 46 8 31.X 125.9 140.8 56.1 78.6 53.5 66.6 38.0 57.7 135.5 a
61.8
19.1
Rahia 11
47 8 32.6 1262 141.2 56.1 79.8 49.8 66.9 1237 CZOHZ006 Bahifolin a 51 0 37.0 122.0 147.0 34.0 50.0 68.0 57.0 h 4X 8 32 9 126.0 142.0 56.1 80.0 49.3 66.5 1238 (‘251iWO9 55 4 76.4 l23Y c 2 ; 1 1 1 2 0 9 5 3 6 78 7 I240 (‘27112608 51 2 78.8 1241 (‘70112407 60 3 74.4 1242 C l Y l l Z 4 0 7 5 5 1 7X I
194
Tomencephalin
1233 ( ‘ I C H I X O 3 4 1 2 34.0
1236 C20112407
192
Kauniolide, 3a.4a-epoxy-Za-tigIoyloxy
1231 C20112407
135.7 32.9 1232 C22112608 131.2 48.X
54.5 25.8
64.1 64.7 52.7 6 4 2 64.7 52.2
1230 CZOH2406
130.3 3 3 6
80.7
Kauniolide, Za-acetoxy-3a,4a-epoxy
17 2
c
170 2x4
Spicatin, desacetyl
81.2 47.6
67 5
36.2 56.1 1342 169.6 122.5 56.3” 17.4
r
29‘)
X0.2
47.5
67 2
35 7 55.2 1 3 . 7 169.9 123.0 56.6b 17 5
c
200
125 4 150.6 55 5 Euparotin
X0.4
46.6
67 0
35.8 55.2 133.7 169.4 123.1 56.2
17 5
c
112
129.1 149.8 84.4
X2.5 42.2
669
37.0 55 7 134.1 169 4 123 8
54.8
13 6
c‘
?XI)
75.5 1403 1707 1200 2 6 7
1X I
c‘
171
129.0 149 5
52.4
Spicalin
:?5 1 1506 51 2 Eupachifolin II
Hydruntinolide A
125.7 151.8 54.4
84.4
41 4
31.0 75.6
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
381
Table 21.--continued Mol. formula Name / Chemical shifts C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14 C-15 1243 C24H3009 Hydruntinolide C 54.2 77.9 126.1 151.4 54.4 80.6 46.9 71.2 72.2 76.3 137.5 170.4 121.4 26.6 18.1 1244 C23H3009 Hydruntinolide B 54.3 78.0 126.3 151.6 54.5 80.6 47.0 71.6 72.3 76.6 137.6 170.6 121.4 26.7 18.2
No.
Sol. Ref. C
173
C
173
Other carbons: 1217 Mac: 165.8 135.8 126.5 18.2; 1218 Glc: 104.4 75.3 78.5 71.5 78.5 62.6 Mac: 166.1 a 126.6 18.4 1219 Glc: 104.4 75.3 78.5 71.5 78.5 62.6 Cinn: 165.8 118.3 146.2 134.7 128.8(2) 129.4(2) 131.0 1220 Ac: 170.5 21.1; 1221 Ang: 166.7 126.7 140.1 15.8 20.5; 1222a Epang: 168.8' 592 59.6 13.9 19.2'; 1222b Epang: 168.9' 59.3 59.9 13.6 19.w. 1224 Ang: 166.8 127.0 139.4 15.8 20.4; 1225 Ang: 166.6 126.5 141.2 15.9 20.5; 1227n Ac: 170.8 20.7; 1627; 1227b Ac: 170.9 20.7: 1228 iBur: 177.1 34.1 19.1 18.9; 1229 Tig: 167.9 128.2 138.2 14.3 12.0 1234 Sen: 165.4 114.5 160.4 20.5 27.6; 1231 S e x 165.4 114.5 160.1 20.4 27.6; 1232 Ang: 166.0 126.4 141.3 16.0 20.5 Ac: 168.9 20.9; 1236 Ttg-4.5-OH: 166.1 131.6 144.6 58.9 56.8; 1237. Fur: 205.0 177.0 127.0 146.0 153.0; 1237b Fur; 162.1 118.4 105.7 144.0 148.1; 1238 Tig-5-0Tig-S'WH: 165.4 127.6 145.5 14.5 57.4 166.6 131.7 141.9 14.2 56Sb; 1239 Tig-5-0Tig-S'-OH: 165.3 127.6 145.6 14.5 57.5 166.7 131.9 141.1 14.2 56.2b Ac: 169.1 21.3; 1240 Tig-4-OH: 166.5 127.5 141.6 59.5 12.7 Ac: a 21.4 1241 Ang: 166.9 127.3 138.6 15.8 20.5 : 1242 A(.: 170.0 21.3' 170.0 20.9b; 1243 Tig: 166.8 126.6 140.0 20.6 15.7 Ac: 168.7 21.2' 168.9 2O.Zb; 1244 iBw; 176.2 34.2 18.9 19.2 2xAc: 168.8 21.3' 168.9 20.4'
R'
R'
R'
Rz
1217
Mac
H
1221
OAng
OH
1218
Mac
Glc
1222
OEpang H
1219
Cinn Glc
1223
H
1225
1220
H
1226
R = H
1230 R = H
1227
R = OAc
1231
1228
R = OiBut
1232
R = OH
R = OTig
1229
U
1233
1224
I
1234
R'
R = H
1236
R = Tq-4.5-OH
1238 H
Tig-5-0Ttg-5'-OH
1237
R = Fur
1239
Tig-5-OTtg-5
AC
1240 Ac
1241
1242
R = H
1243
R = OTig
1244
R
=
OiBut
R'
1235
Tiq-4-OH
-OH
382
M. BUDESiNSKY AND D . SAMAN
Table 21.--continued h i
1245 1246 1247 1248 124Y 1250 a b 1251 1252 1253 1254
1255 1256 1257 1258 1259
1260 1261 1262 1263 1264 1265
1266 1267 1268 1269
1270
1271
hlol lormula Name / Chemical shifts C - I C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 C-13 C-14 C-15 Sol llct CI5HIXOZ laH,SaH-Guai-3,11(13)-dien-l2,6a-olide, 9a,l0a-epoxy 47.5 34.8 125.1 144.8 53.3 85.4 39.9 29.0 62.0 63.0 138.8 169.7 119.4 18.0 26.4 C 151 CISH2003 Cumambrin B, 10-epi-8-deoxy 48.9 33.6 126.1 141.7b 56.2 84.1 50.5 23.2 40.3 73.6 140.3b 170.4 118.7 33.0 17.7 C 606 CISH2003 Cumambrin B, 8-desoxy 55.0 34.1 126.4 142.8 55.0 84.6 44.2 25.5 35.7 73.0 142.2 170.0 118.4 30.2 17.4 P 448 CISH2204 Cumambrin B 54.7 33.5 125.1 143.3 54.7 80.6 51.1 71.4 39.9 74.2 139.7 170.0 120.5 33.0 17.6 C 126 C21H2008C16N2 Cumambrin B + TAI 52.5 32.8 124.8 143.5 53.8 78.9 46.0 75.7 34.9 87.3 137.5 168.7 122.3 26.6 17.8 C 126 Cf7H2205 Cumambrin B, 8a-acetoxy = Cumambrin A 54.2 38.8 125.2 143.3 54.2 73.2 46.3 80.1 33.4 73.3 138.2 169.1 121.0 33.2 17 8 c 269 54.2 38.8 125.2 143.3 54.2 73.2 46.3 80.1 33.4 73.3 138.2 169.1 121.0 33.2 17.8 C 159 C2OH26OS Cumambrin B, 8a-angeloyloxy 54.2 38.9 125.4 143.7 54.4 72.9 46.8 80.3 33.5 73.6 138.7 169.4 121.1 33.5 17.8 C 269 ClYH2605 Cumambrin 8, 8-isobutanoyloxy 54.2 33.6 125.7 143.7 54.5 80.4 46.9 73.2 38.8 73.7 139.6 169.4 121.1 33.8 17.8 C 159 C2OH2606 Cumambranolide, 8P-sarracinoyloxy 5 5 0 34.0125.5143.4 55.1 80.8 46.6 67.9 38.6 73.1 135.3170.21219 32.9 17.7 c 232 C22H2807 Cumambranolide, 8~-acetylsarracionyloxy 55 0 34.1 125.4 143.5 55.2 80.5 46.8 67.5 38.6 73.4 135.2 169.9 121.7 32.8 17.6 C 232 C2OH2606 Cumambranolide, 8~-(2’-(1”-hydroxyethyl)acryloyloxy) 55.0 34.1 125.4 143.5 55.2 80.6 46.7 68.0 38.0 73.1 135.1 170.0 121.7 32.9 17.6 C 232 C20H2605 Cumambranolide, 8P-angeloyloxy 55.0 34.1 125.4 143.5 55.2 80.7 46.8 67.1 38.5 73.2 135.3 170.0 121.7 33.0 17.7 C 232 C2OH2606 Cumambranolide, 8~-(2’R,3’R-epoxyangeloyloxy) 54.9 34.1b 125.5 143.4 54.9’ 80.4 46.5’ 69.0 38.4b 73.1 135.2 170.0 121.8 32.8 17.6 C 232 C2OH2606 Cumambranolide, 8P-(2’S,3’Sspoxyangeloyloxy) 54.9 34.1b 125.5 143.3 54.9‘ 80.4 46.5’ 68.8 38.0b 73.1 135.1 170.0 121.4 32.7 17.6 C 232 C22H2808 Cumamhrin B, 8~-(4’-hydroxy-5‘-acetoxytigloyloxy) 55.Ib 34.3 125.8 143.4 55.3b 80.1 47.1 68.5 38.6 73.4 135.4 170.1 121.5 32.7 17.6 L 631 CISH1404 Poreladiolide, dehydro, is0 163 3 84.5 125.8 150.3 45.1 85.0 51.1 2 2 4 27.2 a 138.1 173.6 120.1 168.4 16.9 B 639* Macrocliniside G C2IH3008 54.8 31.0 125.4 143.9 53.4 84.3 43.1 24.8 34.1 80.7 142.7 170.1 118.2 28.1 178 P 448 C19H2407 Prenantheside A P 450 50.4b 32.1‘ 151.4 113.6 52.6b 85.5 44.0 25.5 37.2‘ 73.2 142.0 170.1 118.5 28.9 12.1 C22H2708CI EupachifolinD 50.8 78.1 125.8 151.9 54.8 81.3 47.2 66.9 36.3 73.0 134.3 169.6 122.2 54.6 18.1 C 332 C2SH31OYCI Spicatin, desacetyl, hydrochloride 54.7 74.7 128.9 149.1 51.9 82.1 47.2 67.3 36.2 73.6 134.7 169.9 121.8 54.9 18.0 C 299 C29H38012 laH 5crH-Guni-3,ll 13 -dien-l2,6aslide 2~,16ar-dihydroxy-d-(~~-hyd~x~~~oylo~y)-8~-(S~-(S~~-hydrox~igloyloxy)tigloyl~xy~ 54.8 74.8 129.0 149.2 52.3 82.1 47.3 67.4 36.0 77.3 134.8 169.9 121.7 71.4 18.0 C 299 C2OH2407 laH,SaH-Guai-3,11(13)-dien-12,6aslide,8~-(2’,3’-epoxyangeloyloxy)-lO~-hydroxy-2~ 59.6 206.2 134.4 178.6 48.7 76.9 53.4 67.7 46.1 73.7 132.2 168.7 121.8 31.2 18.8 C 219 laH,5aH-Guai-3,11(13)-dien-lZ,~slide, 3,10~-dihydroxy.2-oxo-8~-tigloyloxy C2OH2407 5 3 9 203.5 150.7b 148.3b 49.7’ 77.5 47.6‘ 65.1 45.7 74.6 133.9 168.9 122.4 27.2 14.4 C 284 Athamontanolide, 8a-isobutyryloxy C2IH2607 124.1 129.6 144.2 84.4 57.3 79.8 34.1 75.5 71.5 142.2 136.4 175.8 122.0 21.7 25.3 C 94 i21H2607 Athamontarrolide, 4-ep1, 8a-isobutyryloxy 121.4 131.9 142.1 83.5 53.6 79.8 34.1 76.0 71.5 143.6 136.5 175.7 121.4 21.6 29.5 C 94 CIYH2207 Athamontanolide, 4-epi, 8a-acetoxy 124.8 132.0 142.2 83.6 53.6 79.8 34.2 76.0 71.5 143.7 136.6 175.8 121.5 21.6 29.5 C 94 C2OH2607 Tunefulin 91.3 134.2 139.6 82.9 65.9 78.6 39.0 82.4 31.4 82.4 141.0 169.2 121.1 23.0 23.9 C 452
383
CARBON-I3 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 21.--continued No.
1272 1273 I274 1275
Mol. formula Name I Chemical shifts C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C17H2007 Ezomontanin 77.4 125.2 130.2 70.9 43.7 77.3 42.4 73.7 C20H2407 Athanadregeolide 98.7 133.6 137.6 74.2 41.8 71.8 29.7 30.5 C22H2609 Athanadregeolide, 8a-acetoxy 98.6 133.4 137.6 74.9 47.7 71.1 29.7 70.8 C20H2407 Achifolide, iso, p-proxy 92.0* 136.8 139.6 96.9b 69.1 76.9 41.1 29.7
C-9
C-10 C - l l C-12 C-13 C-14 (2-15
46.4
71.0 173.5 171.0 120.6 20.2 30.5
Sol l k l
C
3x0
69.8 93.6 139.5 169.3 119.7 21.8
13 7
69.6 93.7 136.9 168.4 121.3 21.7
13.7
C
94
73.7 74.9 139.2 169.6 119.8 24.4
13.5
C
S41
C
'14
Othercarbons: 125Oa Ar: 169.8 21.3; 1250b Ac; 169.8 21.3; 1251 Ang: 166.8 127.1 139.7 15.8 20.6. 1252 i h ! : 176.0 34.1 18.8 18.9; 1253 Sac 166.6 131.6 140.5 15.8 64.4: 1254 Soroc: 165.2 127.4 145 4 15'1 65.4 170.7 20.8: 1255 Acr-2-CH(OH)CH,: 166.0 124.6 66.9 22.4 121.7; 1256 Ang: 167.3 127.5 13X.X 15 9 20.6: 1257 Epang: 169.3 59.8 60.0 13.9 19.3; 1258 Epang: 169.3 59.8 60.0 13.9 19.3; 1259 Tig-4-OH-5-OAc: 165.6 127.1 147.7 59.4 58.2 171.3 20.9 1261 Glc: 98.3 75.1 78.7 71.9 77.6 63.0; 1262 G i c 101.8 75.0 78.7' 71.5 78.5' 62.6; 1263 Tig-4-OH: 166.7 127.6 141.5 59.5 12.7 Ac: a 21.5: 1264 Tig-5-0TIg-S'-0H: 165.7 127.5 145.8 14.6 57.5 166.8 131.4 142.3 14.3 56.2; 1265 Tis-5-00: 165.8 127.6 145.7 14.6 57.5 Tig-5-OTig-5'-OH: 166.8 131.gb142.3' 14.3 56.1' 167.5 131.5b 142.2' 56.3': 1266 Eparig' 168.9 59.6 60.0 13.6 19.6; 1267 Tig: 166.5 127.7 138.7 14.4 12.1; 1268 ;Bur: 168.8 45.3 18.5 18 8 A r . 170.0 20.8: 1269 ;Bur: 168.5 46.0 18.5 18.8 Ac: 169.7 20.8; 1270 2xAc: 169.8 20.8 a ; 1271 A w : 166.8 126.8 137.9 15.9 20.6; 1272 Ac: 170.6 20.3; 1273 Ang: 166.9 127.2 140.0 15.9 20.5: 1274 A I I , ~ :165.7 126.2 141.9 15.9 20.1 Ac: 170.3 21.0; 1275 Tig: 166.9 128.3 138.5 14.6 12.2
w-CO 1245
1246
1247
R = ti
1253
R = Sor
1248
R = OH
1254
R = Sarac
1249
R = OTAC
1255
R = Acr-E-CH(OH)C+,
1250
R = OAc
1256
Ang
1251
R = OAng
1257
Epanq(2.R.3 R)
1252
R = OiBut
1258
Epong(Z'S.3 5 )
1259
Tig-4-OH-5-OAc
Q
OTig-5-
H i
0.
-OTiq-5-OH
co R'
R2
R'
Rz
1261
H
P-Glc
1263
Ac
Tig-4-OH
1262
OGlc
H
1264
H
Tig-5-OTig-5'-OH
1260
I
1265
.OAc
R'
0-co
0-C6
O-cS,
R'
R2
R'
R2
R'
'R
1266
H
Epong
1268
a-OH
iBut
1272
OAc
H
1267
OH
Tig
1269
@-OH
iBut
1273
H
OAnq
1270
@-OH
AC
1274
OAc
OAnq
1275
H
OT,?
1271
384
M. BUDESINSKY AND D . SAMAN
Table Zl.+ontinued Mol formula Name / Chemical shifts C-I C-2 C-3 C-4 C-5 C-6 C-7
No
C-8 C-9 C-10 C-11 C-12 C-13 C-14 C-15 1276 CISHI805 TanaDarthin a-wroxide 93 5b 133.9' 137.3' 99.ib 69.6 79:5 42.9 22.9 33.1 71.1 170.0 139.9 119.6 27.7 13.7 Apressin 1277 C17112007 74,I*133.3 137 6 78.5b 41.7 72.1 69.7 30.4 98.4 93.7 139.3 169.2 119.7 21.6 13.6 1278 C20H2407 Achifolide, a-peroxy 93.5* 133.3 137.3 98.4b 69.5 78.4 41.6 30.2 71.8 74.1 139.0 169.3 119.8 21.7 13.7 127Y C I S H I 8 0 3 laH,SnH-Guaid(15),1I(l3)-dien-12,6a-olide, 9a,lOa-epoxy 46.6 27.6 28.3 148.4 52.0 81.5 40.9 28.2 61.5 63.3 139.5 169.4 118.9 110.9 26.2 1280 ('21H.7008 Brachynereolide 52.3 26.2 29.0 149.9 51.6 81.0 43.3 23.4 30.4 81.1 141.8 171.1 118.9 27.6 109.8 12x1 CIS112004 Cynaropicrin, &desacyloxy, 10,14-dihydro-lOa-hydroxy 4 9 9 37.8 72.7 155.3 49.6b 82.9 44.8 25.2 36.9 73.6 142.2 170.1 118.5 28.8 108.8 12x2 C21H3009 Ixerin D a 50.2b 35.3' 79.7 150.5 50.6' 81.8 44.5 24.9 35.4' 73.4 142.6 170.0 118.2 30.1 112.9 h 50.3b 35.7 79.9 150.9 50.7b 82.2 44.8 25.1 35.7 73.7 142.8 170.5 118.7 30.2 1129 c 503 35.4 79.8 150.7 50.7 81.9 44.5 24.9 35.5 73.4 142.8 170.1 118.2 30.3 112.9 12x3 C30H36012 IxerinU 50.9* 34.5' 80.5 150.5' 50.6b 81.7 44.5 24.8 35.8' 73.4 142.9 170.1 118.1 30.9 113.5 12x4 C2YH3009 Prenantheside B 503* 34.8' 79.9 150.3 50.8' 81.7 44.5 24.8 35.6' 73.4 142.7 170.1 118.3 30.6 113.5 12x5 C'20112607 Breviarolide 43 7 31.2 125.7 143.0 56.6 80.5 47.0 68.6 28.9 38.1 134.4 169.5 122.2 66.0 17.3 1286 CISH1903Br laH,SnH-Guai-9,11(13)-dien-l2,6a-olide, 15-bromo4p-hydroxy 43 2 30.6 38.9 81.5 54.2 82.1 45.7 29.9 120.5 135.6 138.9 169.3 120.2 43.6 27 2 1287 ClSH2004 Cumamhrin, 10-epi, 8-deoxy-k,4aspoxy 46.4 30.8 64.6 67.3 46.2 82.7 52.5 24.9 43.3 71.8 139.4 170.1 119.9 32.6 17.2 l 2 X X CISHI804 laH,SaH-Guai-l1(13)-en-12,6a-olide, 3a,4a;9a,lOa-diepoxy 40.2 31.3 5 9 4 64.8 48.0 82.3 38.7 28.4 60.9 62.6 138.2 169.2 119.4 19.3 26.8 I Z X Y CISHI804 laH,5aH-Guai-11(13)-en-12,6a-olide, 4a,15;9a,lOa-diepoxy 4 5 0 26.4 28.1 65.6 52.2 81.3 40.8 28.3 61.3 63.2138.61692119.3 49.8 25.8 1290 CZOf12407 Eupachifolin E 50 2 72.8 65.3 65.8 50.8 77.3 48.8 6 7 8 36.7 56.3 115.2 168.9 121.6 56.2 18.8 1291 C22H2609 Graminiliatrin 49.4 72.9 64.6 65.8 50.1 77.2 48.1 67.9 36.2 55.7 134.3 169.4 122.7 56.4 1Y.7 1292 C20H2607 laH SaH-Guai-ll(13)-en-12 6a-olide
Sol. IW
C
71
C
640
C
541
C
151
C
689
P
500
P P P
590 450 41
P
590
P
450
c
4x5
c
151
c
596
c
151
c
151
I'
332
c
306
18.4
c
306
37.2 54.6 133.9 172.3 123.6 53.4
18.4
c
306
36.1 56.4 133.4 168.6 122.8 56.4
18 I
c
332
57.1 72 6 42.5 57.4 49.5 23.5 33.0 71.5 140.9 169.3 118.9 19 2 27 0 5 8 4 73.Xb 50.4 78.4 44.8 23.8 34.2 79.Yb 169.5 139.7 120.3 27.3 19.5
s
396
C
71
s S
492 396
c c
430' 37"*
k,4h;lOa,I4-diepoxy-Z~-h~droxy-8~-(~~-methylbutanoyloxy~
73.1 1293 CZOH2607
64.5 65.9
49.1 73.1 1294 C22H2608 48 4 74.9 I295 CI5IIIRO5 a 79 6 78.4 b 72.Sb 58.8 1296 ClfiHlXOS a 81.8 X64 h 77 7 82 7 1297 ('17H2007 a 70 I 58.6
64.5
49 I
70.1 56.') 129X ('151/2006 h
S0.4 76.7 48.1 65.5
37.2 54.6 133.9 172.3 123.6 53.9
laH 5aH-Guai-11(13)-en-lZ 6a-olide 3a,4h;1Oa,14-diepoxy-2p-h~droxy-8~-isovaleroyloxy
65.9
50.4 76.7 48.1 65.5
Eupachifolin E, acetate
61.9 65.9
50.2 75.9 48.2 66.7
Canin
Artccanin
61.1 74.4 48.1 10.0 46.6 57.0 70.4 44.0 56.0 42.5
26.3 40.7 74.3 143.7 173.9 122.8 23.6 309 22.2 36.9 70.2 139.6 169.9 118.7 19.5 26.9
Yomogiartemin
56.9 49.0 44.8 76.5 44.1 71.6 29.7 71.4 137.5 169.2 121.5 21.3 58.6 71.4 49.9 76.5 44.8 71.6 441 29.7 137.5 169.2 121.5 26.7
267 21.3
5aH-Guai-11(13)-en-l2,~-olide, lp,2P-epoxy-3P,4a,10aa-trihydruxy c 3-12 45.1 23.6 35.1 83.4 139.3 169.4 119.9 22.1 26.5 IZYY ~'lSH1905CI 5aH-C.uai-11(13)-cn-12,~-ulide, 3 ~ ~ - c h l o r o - 4 a , l 0 a - d i h y d r o x y - l c r , 2 a - ~ p 1 1 ~ ~ c 663' .~. X4 J 58 X X0.4 72.8 65.2 66.7 45 9 24.4 36.6 73.7 140.7 P 120.0 2 2 6 27.4
73 3 64.4
64.1 72.2 57 9 79.9
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
385
Table Zl.+ontinued Other carbons: 1277 Ac: 170.1 20.8: 1278 Tig: 166.8 127.8 138.8 14.6 12.2: I280 Glc: 96.9 73 5 70.7 70.2 75.3 61.8: 1282a Glc: 103.5 75.1 78.3 71.8 78.0 62.9: 1282h Glc: 103.9 75.4 78.4' 72.0 7X.h' 63 I . I282c Glc: 103.6 75.2 78.4 71.9 78.1 63.0; 1283 Glc-bOCinn-3;4'-OH: 103.9 75.1' 78.2 71.8 75.3' 6 4 6 167.4 115.8 145.9 126.9 115.0 150.2d 147.5 116.5 121.9; 1284 Glcd-OPhac-4'-OH: 103.3 74.9 78.0 71.5 74.9 64.8 171.9 40.6 125.2 130.8(2) 116.2(2) 157.7: 1285 Tig-4-OH: 166.6 128.0 140.9 59.6 127: 1290 rig: 1667 128.2 137.7 14.1 12.1: 1291 Ang-4-OAc: 165.8 128.4 138.6 63.0 18.3 171.1 20.8: 1292 MrOrr: 176.0 40.9 26.5 11.4 16.7; 1293 r V d : 172.4 43.2 25.5 22.2 22.2: 1294 Tig: 166.5 127.7 1380 14 4 12 I Ac: a 21 1: 1297a A c , 169.9 20.3; 1297h Ac: 169.9 20.3
R'
R'
1281
R = H
1276
ti
ti
1282
R = Glc
1277
OAc
H
1283
R = Glc-6-OCinn-3'.4'~0H
1278
OH
Tig
1284
R = Glc-6-OPhac-4-OH
1279
1286
1285
HO"'
co
OH: (lp.2p-epoxy)
1298
R =
1299
R = CI. (la.2~-epoxy)
1287
R'
R2
1290
ti
Tig
1291
H
Ang-4-OAc
1292
H
Mebu
1293
H
iVal
1294
Ac
Tig
1289
0.
1280
1295
1288
1296
R
1297
R = OAc
=
ti
386
M. BUDESINSKY AND D. SAMAN
Table 2l.
No.
Z~,lbadihyd~oxy-~,4a-epoxy-S~-(Z~-me~hylbuta~yloxy~
1302 1303 1304 1305 1306 1307
51.8 72.3 64.0 65.9 49.7 77.8 47.4 67.0 39.9 72.8 135.0 170.0 121.3 33.3 19.2 Cl5Hl 705CI Chloroklotzchin 78.5 79.1 65.4 72.5 50.0 62.5 42.8 22.5 33.7 70.2 140.9 169.8 118.7 27.0 25.3 CISH2207 5aH-Guai-11(13)-en-l2,6a-nlide, la,2a,3a,4a,lOa-pentahydroxy 87.0 77.3 64.6 74.2 59.0 79.8 48.6 22.6 37.4 72.1 138.6 169.6 120.0 27.8 24.3 C17H2305CI laH,5aH-Gu0i-11(13)-en-12,6a-olide,SP-acetoxy-lOa-ehloro-4a-hydroxy 49.0 26.8 38.7 80.7 57.9 76.5 51.9 66.1 47.0 74.4 134.3 168.8 122.1 31.3 24.9 ~ 1 ~ ~ 2 0 0 4 Prenanthelide A 46.4b 40.3 218.9 48.2b 50.6 85.8 44.5 25.8 40.3 73.1 141.3 169.7 119.3 27.2 15.8 C17H22OS Prenanthelide A, acetate C 43.7 39.0 217.5 47.5 50.7 85.5 44.3 25.5 31.8 82.8 140.2 169.9 120.2 24.6 1 6 2 C19H2607 laH,ScrH-Guai-ll(13)-en-12,6a-olide,4P,lOa-dihydroxy-SP-isobutyryloxy-3-0 xo c 45.4 47.1 214.2 77.3 53.3 76.5 47.7 65.4 39.4 71.3 135.0 171.8 120.8 32.1 22.9 C20H2608 l a H SaH-Guai-l1(13)-en-l2 6a-olide ~
1308
~~~
306 427 02') hSO
450 450 701
2~,1~;3a,4a-diepo~y-Za,l~~ihydr~xy-S~-(2~-methylbutanuyloxy)
58 0 114.2 64.6 66.0 51.3 75.4 49.8 65.8 38.6 81.9 134.0 168.2 122.2 X0.5 1309 ~ 2 0 ~ 2 6 0 8 l a H SaH-Guai-11(13)-en-l2,~-olide
19.0
C IIX.illh
58.0 114.2 1310 C20H2205 397 30.1 1311 C20H2508CI 53.0 70.2 1312 C20H2208 57.2 71.4
IY.O
c' IJX.3ilh
2~,1~;3a,4a-diepoxy-2a,1Oa-dihydr~xy-8~-isovaleroyloxy
64.6 66.0 51.3 75.4 49.8
65.8
38.6 81.9 134.0 168.2 122.2 XO.5
laH,ScrH-Guai-11(13)-en-12,6a;l4,4P-diolide, Ea-angcloyloxy 38.1
89.1 44.7 72.0 50.1 74.8 37.7 46.2137.2168.6123.1 170.1 21.7 Eupachlorin, 3a,4a-epoxy 62.8 67.3 81.0 79.4 41.1 67.3 36.5 74.0 135.2 169.7 121.6 55.6 16.2 Euparotin, %&-epoxy 64.1 67.3 80.8 78.5 42.0 67.8 36.6 55.2 134.6 169.5 1226 55.4 15 7
I3
'is
C
2x9
C
2x9
Othercarbons: 1300 N u / : 172.8 43.3 25.6 22.4 22.4; 1301 Meba: 176.5 41.1 26.6 11.6 1 6 X . 1304 A( 170.0 20.9: 1306 Ac: 169.1 22.3; 1307 iBur: 176.4 34.0 19.2 18.8; 1308 Mebrr: 175 4 41.4 2 6 6 I 1 6 1 6 s . 1309a IVUI: 171.7 43.4 25.7 22.3 22.3: 1309b iVaI: 171.7 43.4 25.7 22.3 22.3: 1310 Afig' 165.5 127 3 139.7 15.9 20.6; 1311 Ang: 167.3 127.6 138.2 15.8 20.6; 1312 Arlg. 167.1 127.5 13X.4 15 X 20.5
CARBON-13 NMR SPECTRA OF SESQUITJZRPENE LACTONES
387
Table 21.--continued
CAC
1300
R
1301
R = Mebu
1305
R = H
1306
R = Ac
1311
= (Val
1302
1307
1312
1303
1308
R = Mebu
1309
R = (Val
1304
1310
388
M. BUDESINSKY AND D. SAMAN
Table 22. Carbon-13 chemical shifts of guaian-12,6-olides (type 11-methyl) NO.
Mol. formula
__ C - l C-2
C-3
1313 C15H2002 a 47.7 34.6 125.5 b 47.7 34.6b 125.4 1314 CISHI802 140.7 123.1 132.5 1315 C15H1802 140.2 122.8 131.4 1316 C20H2405 129.7 195.4 135.4 1317 C20H2405 129.8 195.2 135.4 1318 C22H2607 129.0 195.0 136.1 1319 C25H3007 129.0 195.0 136.1 13211 C20H2805 51.3 33.5 125.8 1321 C23H2807NC13 50.9 33.2 126.0 1322 C2SH3407 49.2 32.0 125.6 1323 C24H3208 a 49.0 31.5 125.5 b 49.2 31.7 125.6 1324 C22H3007 a 56.0 32.2 125.9 b 49.0 31.9 125.6 1325 C25H300YNC13 53.0 32.0 125.3 1326 C27H3608 49.0 31.4 125.4 1327 C24H3408 49.0 31.6 125.5 1328 C22H3006 a 53.2 32.4 126.0 b 52.8 31.8 125.0 1329 C24H320Y 58.0 73.1 130.3 1330 C24H3409 58.4 77.1 130.3 1331 C24H3209 57.5 71.3 129.9 1332 C26H36010 52.4 79.4 126.8 1333 CZ6H34010 51.9 79.9 126.7 1334 C2Yff40010 52.6 78.8 126.9 d h 52 7 77.1 127.2 1335 C2711.ZXOY 53.0 78.6 127.0 1336 C3OH38011NC13 52.4 78.8 127.1 1337 C24H3209 52 3 130.3 139.0 133X C26111009 4X 4 37.6 216.1 ~
Name / Chemical shifts C-4 C-5 C-6 C-7 Grilactone 143.0 51.9 84.4 38.9 142.4 51.9 84.4 38.0 Tannunolide B 146.3 122.4 78.1 41.3b Tannunolide A 145.3 121.8 77.3 42.2 Badkhysin, is0 166.2 48.5 76.1 47.2 Badkhysin 169.7 49.0 80.7 45.1
C-8
C-9
C-10 C-I1 C-12 C-13 C-14 C-15
Sol Ref
19.4 19.4
33.8 147.6 37.8 179.4 33.8b 147.7 38.9 179.3
11.0 111.9 11.0 111.9
17.3 17.3
C C
118 13
29.4
34.0 152.9 45.2’180.0.
15.2 24.2
14.0
C
57
24.4
34.0 153.2 39.1 178.9
9.9
23.6
13.1
C
57
67.6
41.1 143.8 40.6 177.2
10.2
16.3
19.8
C
118
67.0
43.5 145.2 37.2 178.0
13.2
19.6
20.4
C
118
C
550
5~H-Guai-1(10),3-dien-l2,6~-olide, lla-acetoxy-8a-angelnyloxy-2-nxo 169.1 48.0
78.4
47.3
67.0
44.0 145.2 77.9 173.3 20.0
20.6
20.3
5~H-Guai-1(10),3-dien-12,6fJ-nlide,8a,lla-diangeloyloxy- 2-oxo 169.4 48.0 78.6 47.5 67.0 44.3 145.0 77.8 173.5 19.9 20.5 20.2 C 118 SlovJ-enolide, lla-angeloyloxy-log-hydroxy 142.3 49.5 82.8 42.4 21.9 40.2 73.1 76.7 175.7 20.4 32.2 18.4 C 557 Slov-3-enolide, lla-angeloyloxy-log-hydrnxy + T A I 141.5 51.3 81.9 42.3 21.1 33.5 89.2 79.4 175.5 20.1 26.9 18.3 C 557 Gradolide = Slov-3-enolide, 8a,lla-diangeloyloxy-l0~-hydroxy 146.9 47.3 78.1 55.7 66.6 43.5 71.1 78.2 174.1 20.1b 30.8 18.6 C 39 Montanolide, iso, acetyl = Slov-3-enolide, 8a-angetoyloxy-1O~,1la-diacetoxy 145.8 47.7 77.5 53.5 64.0 40.6 82.6 78.1 173.7 20.0 24.5 18.3 C557.118 146.0 47.9 77.6 53.4 64.1 41.0 82.6 78.2 173.8 20.2’ 24.7 18.1 C 39 Montanolide, iso = Slov-3-enolide, lla-acetoxy-8a-angeloyloxy-l0~-hydroxy 147.1 49.4 78.3 47.5 66.9 43.6 71.3 78.5 174.1 20.2 31.1 18.8 C 557 146.7 47.2 78.0 55.7 66.6 43.2 71.0 78.0 173.7 20.7b 30.8 18.5 C 39 Montanolide, is0 = Slov-3-enolide, lla-aeetoxy-8a-angeloyloxy-l0~-hydroxy + TAI 146.6 48.9 77.4 47.6 64.2 41.9 86.9 78.3 173.8 20.0 24.9 18.6 C 557 Slov-3-enolide, l@p-acetoxy-8a,lla-diangeloyloxy 145.8 47.7 78.0 53.4 63.6 40.6 82.5 77.8 173.2 20.1b 24.5 18.3 C 39 Slov-3-enolide, 10~,1la-diacetoxy-8a-(2’-methylbutyryloxy) 146.2 47.8 77.6 53.7 64.2 40.8 82.5 78.2 173.8 20.2 24.6 18.5 C 557
lpH,5pH-Guai-3-en-l2,6~-0lide, log-acetoxy-8a-angeloyloxy 147.0 50.9 80.8 47.3 65.7 41.4 83.5 36.8 180.0 13.8 25.4 18.4 C 23 145.9 50.0 80.1 46.4 64.8 40.5 82.7 36.2 178.9 13.5 24.9 182 C 52 Slov-3-enolide, 10~,11a-diacetoxy-2a-hydroxy-8a-angeloyloxy 147.1 50.2 77.2 48.0 65.3 44.2 82.1 78.2 173.7 20.8 25.9 17.9 C 118 Slov-3-enolide, l0~,lla-diacetoxy-2~-hydroxy-8a-(2‘-methylbutyryloxy) 147.1 50.1b 76.6 47.9b 65.1 43.8 81.Y 78.1‘173.5 26.3‘ 22.3‘ 17.9 C 559 Slov-3-enolide, 10g,lla-diacetoxy-2p-hydroxy-8a-senecioyloxy 146.5 49.6b 76.5 47Sb 64.0 43.6 81.7’ 11.7’173.2 26.9‘ 21.9* 17.3 C 559 Slov-3-enolide, 2~,1O~,lla-triacetoxy-8a-(2’-methylbutyryloxy) 148 5 50.2k 76.4 48.3* 65.5 44.5 80.7‘ 78.2’ 174.8 26.3d 22.9‘ 17.8 c‘ 559 Slov-3-enolide, 2fJ,lO~,lla-triacetoxy-8a-senecioyloxy 149.5 50.2b 76.3 48.4b 64.7 44.9 80.7’ 78.0’ 175.0 26.@ 21.2d 17.4 C 559 Archangelolide 148.8 49.8 76.7 47.9 65.2 43.8 80.8 78.0 173.4 26.0 20.2 17.5 C IIX 148.9 50.1’ 76.8 48.1b 65.4 44.2 9 0 9 79.0‘ 173.0 26.3’ 22.3d 17.7 C 559 Slov-3-enolide, 10~-acetoxy-2a-angeloyloxy-lla-hydroxy-8a-(2’-methylbutyryloxy) 148.8 49.3 77.4 53.2 64.8 43.6 81.1 73.2 178.6 22.4 26.4 17.4 C IIX Slov-3-enolide, l0~-acetoxy-2a-angeloyloxy-lla-hydroxy-8a-(2’-methylbutyryloxy~+TAI 148.6 49.9 76.9 48.0 65.0 43.8 80.8 80.7 172.4 20.3 26.4 17.4 C 557 Slov-2-enolide, l0~,lla-diacetoxy-8a-angeloyloxy 52.9 a 74.8 47.8 66.2 44.6 85.8 78.5 a 20.3 24.9 25.5 c‘ IIX 4aH-Slovanolide, 8a-benzoyloxy-10~,11a-diacetoxy-3-oxo 46.7 44.7 75.2 47.9 65.0 40.0 78.0 81.8 173.3 25.7 20.6 16 2 C ilh
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
389
Table 22.--continued - ~-
Othercarbons: 1316 Ang: 166.5 128.5 138.5 14.5 19.8: 1317 Ang: 166.6 127.0 140.0 15.9 20.2: 13211 An:. 166.5 126.9 140.2 16.0 20.3; 1321 Ang: 166.6 126.6 140.7 16.0 20.3: 1322 ZxAng: 165.6 1270 1406 15.8 20.0b 166.3 126.6 140.0 15.7 20.0b; 1323a Ang: 165.9 127.2 138.2 15.4 20.1 2xAc: 170 I 22 1 169.3 20.6: 1323b Artg: 166.0 127.3 138.5 15.2 20.2b 2xAc: 170.3 22.6 169.5 20.8b, 1324a Ang: I67 2 127.1 140.7 16.0 20.4 Ac: 169.7 21.0; 1324b Ang: 167.0 126.7 140.4 15.7 20.1b Ac: 169.2 15.Y*: 1325 h g : 166.0 126.7 140.4 15.8 20.2 Ac: 169.7 20.8; 1326 2xAng: 165.9 127.2 140.2 15.6 20.0b 1659 1265 138.3 15.4 19.Sb Ac: 169.6 22.3: 1327 Mebu: 174.8 41.3 26 4 11.6 16.4 2xAc: 170.2 20.8 169.5 22 5 . 1328a Ang: 167.5 128.6 138.4 15.7 20.5 Ac: 171.3 22.7; 1328b Ang: 166.2 127.4 137.7 15.5 20.3 Ar 170.2 22.4; 1329 Ang: 166.0 127.0 139.9 15.8 20.3 2xAc: 169.8 20.8 170.1 22.5: 1330 ZxAct 170 3 ?I2 169.6 20.4 Mebu: 174.8 41.3 26.3 16.6 11.5: 1331 2xAc: 170.3 21.2 169.9 20.4 Sen: 164.3 157.7 I I 5 3 20.3 26.9; 1332 3xAc: 170.3 21.2 169.9 20.4 169.6 20.2 Mcbu: 174.8 41.3 26.3 16.6 11 5: 1333 ? ! A ( 170 3 21.2 169.9 20.4 169.6 20.2 Sen: 164.3 157.7 115.3 26.9 20.3: 1334a Mebrc: 174.6 41.1 26.2 I I J 16.2 2xAc: 169.8 20.7 169.8 22.1 Ang: 167.2 127.6 137.6 15.5 20.3: 13341, 2xAc: 1703 21.2 1 W h 2 0 4 Ang: 167.4 126.6 138.0 15.7 20.4 Mebu: 174.8 41.3 26.3 16.6 11.5: 1335 Ang: 167.4 127.6 138.0 15.6 20.4 Ac: 170.1 22.3 Mebur 175.2 41.1 26.2 11.5 16.2; 1336 Ang: 167.2 127.6 137.7 15.6 20.4 Ac 170.0 22.2 Mebu: 174.6 41.1 26.2 11.6 16.2: 1337 Ang: a 126.8 140.6 15.9 20.4 ZxAc: 170.0 20') 170.2 22.5: 1338 ZxAo 170.2 22.5 169.8 20.5 Bz: 164.7 139.4 128.5(2) 129.6(2) 133.5:
Ox0
1313
--
1314 R 1315 R
1320 R = H 1321
co
&R
R = TAC
R'
R'
1329 1330 1331
a-OH
Anq
@-OH
Mebu
@-OH
Sen
1332 1333 1334
8-OAc
Mebu
8-OAc
Sen
8-OAng
Mebu
1322 1323 1324 1325 1326
1335 1336
a-CH,
p-cti,
R'
R'
ti
Anq
Ac
Ac
ti
AC
TAC
Ac
Ac
Ang
R = H R = TAC
1316 1317
R = a-H R = B-H
1327
1337
1318 1319
R = AC R = Ang
1328
1338
390
M. BUDESINSKY AND D . SAMAN
Table 22.--continued - ~. Yo
h l d lonnul.i
C-l
C-2
1339 CIYf12405
Name / Chemical shifLs C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-ll C-12 C-13 C-14 C-I5 Zaluzanin C, Ilal3-dihydro-8a-melhacryloyloxy 73.7 152.6 4 9 8 79.0 50.7 72.0 40.4 142.2 38.1 178.3 11.3 117.0 112.7
C-3
So1
Ilcl
c
562
C
562
c
562
N
562
16.1 110.7 114.1
s
394
80.4 it 50.3 83.3 42.2 32.3 35.9149.5 49.8178.1 13.3113.2111.9 80.5 150.7' 50.2' 83.4 42.2b 32.3 36.0 149.6' 50.V 178.2 13.3 113.2 112.0 C 44.2b 37.9 80.6 150.4 50.3 83.6 42.3b 32.5 36.1 149.5 50.1 178.4 13.4 113.3 111.9 1345 C20H2804 Diaspanolide A 4 4 0 36.4 74.3 148.6b 50.3 83.7 50.0 32.3 36.1 148.4b 42.0 178.3 13.2 113.4'1131' Costuslactone, IlflH-11,13-dihydrodehydro-8a-hydroxy 1346 CISH2003 4 7 2 32.3 30.1 151.1 52.5 80.2 55.4 75.1 47.0 144.5 41.6 179.1 16.1 109.7 114.3 Costuslactone, ll~H-11,13-dihydrodehydro,8-0-p-D-glucoside 1347 C21H?#08 4 6 7 31.9 2 9 3 152.1 52.2 79.2 53.3 82.9 43.9 145.2 40.3 178.8 16.1 108.6 114.0 Zaluzanin C, l l p , l I d i h y d r o 1518 ClSH2003 43 5 38.7 73.4 153.2 50.8 83.7 49.5 32.3 35.9 148.7 42.0 178.4 13 I 114.3 113 5 1WY CISH2004 Cynaropicrin, desacyl, I l ~ , l 5 d i h y d r o 44.2' 39.0' 73.6 153.0 50.7' 79.1 56.0b 74.9 44.8'143.2 42.0 a 15.9 116.2 112.0 Cynaropicrin, desacyl, 1Ip,lJ-dihydro, 8p-D-glucoside 1350 C2 I H?#09 44.2 39.6 73.1 155.2 50.7 80.0 54.8 84.5 43.7 144.9 41.8 179.4 17.1 115.8 109.7 1351 C22H?OO6 l a H S a H 11 H Guai-4 15) 1 14)dlen-12,6a-olide,
I' P P
473
C
X
c
3'11
s
39-I
c
x
3.
202
I'
593
437
386
1340 CIYfl2406
438 1.341
38.6 73.8 152.5 49.9 78.8 50.7 72.2 40.3 142.3 38.1 177.3 11.3 117.3 1131 Zaluzanin C, lla,l3-dihydro-3~-methacryloyloxy 75.9150.3 50.6 79.5 53.5 70.4 36.5145.4 39.1179.2 11.2115.0113.5
C19fi7405 44.3 46.7 1342 C I 9112406 4 4 4 46.6 1-33 C21HMO9
431
Zaluzanin C, lla,l3-dihydro-i3a-(2'-hydroxymethacryloyloxy)
40.1
1344 C21H3008 a 4 4 0 37.8 b 44.2* 37 8
Zaluzanin C, lla,l3-dihydro-3~-(2'-hydroxymethacryloyloxy)
75.6150.1
50.2 79.1 53.6 70.8 36.5142.2
39.1179.2
11.2115.0113.6
Costuslactone, ll~H-11,13-dihydrodehydro-3a-hydroxy, 8-0-p-D-glucoside
76.9 155.0 49.9 79.6 53.5 83.0 44.7 144.8 39.1 178.8 Zaluzanin C, Ila,l3-dihydro, 3-0-P-D-glucoside
41
590
8a-~~xy~e~yiacrylo~ox~-~-hydr~xy
44.5
38.7b 73.3 152.4 52.2' 78.7' 51.0' 77.7' 39.0b 141.8 41.3 178.4
1352 C31tl40013 44.4 36.3 I353 C21f13009 44 4 37 9 1354 C30H34012
45.2
373
Cynaropicrin, desacyl, 11!3,13-dihydro,
74.7 147.9 50.9 78.9
15.2 117.5 112.8
C20I ,202
8p-D-glucoside pentaacehte
53.9 85.1 42.6 142.6 41.5 177.9 16.1 116.8 114.3
c
l5X
f'
450
I'
450
Prenanlheside C, desacyl
80.5 150.8 50.8 79.4 56.3 75.l* 46.6 145.1 42.3 179.0 16.5 115.1 112.3 Prenantheside C
74.9
463144.1
42.5 179.0
26.1
35.6 151.l
73.9 178.3 22.1 113.Ob1I2.Ob
P
665
40.6177.1
53.2107.9111.1
s
394
83.8 48.6 40.4 74.5 153.2 41.6 178.0
13.1 110.3 110.0
C
356
73.3 155.7 49.3 84.5 35.7 41.0 73.0 153.9 45.2 178.6 13.3 111.4 1079 lxerin F 80.7 151.3 49.5 84.0 36.6 40.8 73.0 153.6 45.4 178.4 13.3 111.0 111.6 80.6 151.2 49.4 83.9 36.5 40.7 72.9 153.5 45.3 178.4 13.2 110.8 111.6
P
473
P
474
I'
41
M
48
367 150.2 77.7 179.9 63.9 112.6 108.8
A
525
36.2 148.9 30.4 1770 4 4 4 1147 112 2
C
525
4 3 6 38.6 73.4 152.6 50.1 82.6 42.5 28.5 35.1 148.0 59.1 173.1 50.1 114.4 1112 13M C16t/200.1 no name 43 5 38.7 73 4 153.2 44.5 84.7 49.9 35.7 29.6 148.5 24.9 179.6 12.4 113.6 1105
C
52i
C
464
1355 CZIH300Y
43.9 38.0 1356 C20H2704 46.3 32.1 1357 CIS1l2004 406 38.7 1358 ClSH2004 41.8 39.0 1359 C2IH3009 a 41.9 37.4 b 41.8 37.3 1360 C21H2604Se 46.6' 39.9 1361 ClSH2OOS 43.1 38.6 1362 C15/11J04C/
43 8
39 I
1363 CISHI804
79.7b150.1 51.7 79.3b 56.6
16.3 115.9'114.3
Lxerisoside C
80.8 150.1 49.7
82.9 43.9
Involucratin
29.5152.4
51.6 84.7 45.3
28.6 36.6150.4
Zaluzanin C, llP,13-dihydro-9~-hydroxy
7 3 1 153.1 49.4
Zaluzanin C, llp,l3-dihydro-9a-hydroxy
Cynaropicrin, 8-deacyl-llH,lIphenylseleno
75.4' 133.4 49.0b 81.3 50.8 73.6' 44.3 145.1 52.8 179.0 28.6 115.9 110.0 Sobtitialin
73.1 154.0 50.3 83.0 52.8 26.9 Solslitintin, 13-cliloro
74.1 153.2 50.7 83 4
53.2 27.1
Solstitialin, Il,l3-epoxy
391
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 22.--continued Mol. formula Name I Chemical shifts C-1 C-2 C-3 C-4 C-5 . C-6 C-7 C-8 C-9 C-10 C-I1 C-12 C-13 C-14 C-15 1365 C16H2ON203 no name 43.2 36.1 72.9154.6 49.2 84.7 52.2 39.1 23.3149.2150.0172.9 26.4113.3109.3 1366 C16H2ON203 no name 43.0 38.6 72.7 153.9 48.7 84.1 49.4 35.7 22.0 149.0 96.5 173.8 27.9 113.3 109.6 1367 CI 7H2407 SuH-Guai-l-en-12,6a-olide,So?-acetoxy-3u,4a,lO~-trihydroxy 151.2 126.5 78.8 79.7 56.8 76.4 56.8 70.9 45.0 69.3 40.7 177.5 15.0 29.8 21.2 No.
SJI. k t .
P
464
P
464
C
253
Other carbons: 1339: 166.4 136.2 126.1 18.2; 1340 Mac-4-OH: 166.8 144.3 126.3 62.3; 1341 Mac I67 2 137.6 126.2 18.4; 1342 Mac-4-OH: 165.8 145.4 123.2 61.3; 1343 Glc: 103.6 72.3 76.4 70.0 73.6 61 I . 1344a Glc: 104.1 75.1 78.4 71.7 78.1 62.8; 1344b Glc: 104.1 75.2 78.5 71.8 a 63.0: 1344c Glc. 104.4 75.4 78.7 72.0 78.4 63.1; 1345 iVal: 172.7 43.6 25.7 22.3 22.3; 1347 Glc: 103.8 73.9 11.1 70 I 76 7 61.2: 1350 Glc: 105.5 75.5 79.0 71.8 79.0 63.0; 1351 Mac-ep: 175.0 75.9 68.0 21.8; 1352 Glc-2.3,4./i-A<: 101.3 71.9 73.1 68.5 72.0 62.2 170.6 21.2 170.4 20.7 170.2 20.7 169.3 20.6 Ac: 169.0 20.6; 1353 C;lc: 104.1 75.3b 78.2' 71.8 78.5' 62.9; 1354 Glc-2-OCinn-3',4'-OH:99.2 76.1 74.9 71.8 78.1 62.5 166.4 115.5 145.8 126.6 115.0 148.7 147.4 116.5 121.9; 1355 Glc: 105.0 75.3 78.6 71.8 78.4 62.9: 1356 Pro: 667 31.4 23.5 44.0 173.8; 13591 Glc: 104.6 75.3 78.5 71.9 78.1 63.0; 1359b Glc: 104.3 75.2 78.4 71.X 7 S O 62.9: 1360 SePlr: a 132.2(2) 129.9(2) 127.7; 1364 C-16: 10.6; 1365 C-16: 78 8: 1366 C-16: 78 3: 1367 A1 169.6 21.2
RO
-
R'
R'
1346
H
OH
Mac-4-OH
1347
H
OGIC
Mac
H
1348
OH
H
Mac-4-OH
H
1349
OH
OH
1350
OH
CG C
1351
OH
Mac-ep
1352
OAc
Glc-2.3.4 b-A:
1353
OGlc
CH
1354
OGlc-Z-OC8nn-
CH
R'
R2
1339
H
Mac
1340
H
1341 1342
1343
1344
R = Glc
1345
R
iVd
--3',4'-OH
R'O
HO
0-co 1356
1355
COOH
R'
R2
1357
H
@-OH
1358
H
a-OH
1359
Glc
a-OH
0. 1360
HO
1361
R = CH20H
1362
R = CH2CI
1363
1364
R = CHZCH2
1365
R = CH,CH,N=N
1366
R = N=NCH2CH,
1367
CH2SePh
co
392
M. BUDESINSKY AND D. SAMAN
Table 22.--continued No
1368 1369 1370 1371 1372 1373
1374 1375 I376 1377
1378 1379 13x0
13x1
13x2 13x3 1384 13x5 1386
1387 13x8 Y
h c
1389 1390 1391 I392 a
h
1393
Mol. formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-ll C-I2 C-13 C-14 C-15 ClSH2003 Artabsin 137 2 124.0 45.5 150.9 134.0 82.0 52.4 25.9 39.9 70.7 41.5 178.8 i2.8 30.1 15.0 Achillicin C17112205 137.8 1245 45.6 149.8 134.0 78.2 40.5 73.5 46.5 69.4 55.9 178.2 14.9 30.4 15.5 ClSHlX02 Tannunolide B, 6.epi 140.0 121.8 133.8 142.0 125.2 82.0 49.2 25.4 35.5 148.4 41.0 178.9 15.2 24.2 12.8 CISHIX02 Tannunolide C 1400 134.7 136.1 130.4 52.3 81.4 49.5 24.7 35.0 150.9 40.6 179.3 10.0 22.6 1W.0 CISH2003 Tannunolide D 136 3 128.7 140.9 82.6 59.3 82.7 53.3 27.0 35.8 129.2 40.9 176.8 12.2 23.4 25.0 C15fI2003 Tannunolide E 135 5 130.5 139.5 84.0 60.0 83.0 48.8 24.8 35.8 130.4 39.6 179.7 10.4 23.7 25.4 CISH2003 Mntricin, desacetoxy 138.0 131.5 139.0 83.2 56.3 81.2 49.9 24.4 35.6 129.9 39.1 177.4 9.9 23.4 29.9 C171i2205 Matricin 136.7 1297 140.5 84.0 58.7 79.2 56.5 71.7 42.4 123.6 40.3 177.5 15.3 23.4 25.1 C17H2205 Matricin, 4-epi 1389 132.1 138.9 83.3 57.6 79.1 54.8 71.5 42.4 124.7 4 0 3 177.4 15.2 23.3 20.5 C17H2205 Tannunolide E, 8a-acetoxy 137.7 130.0 140.5 84.5 58.5 79.0 53.3 68.3 41.8 1244 38.2 178.2 10.0 23.6 25 6 C29H.16011 Crepidiaside D 1363 37.5127.5141.5 52.8 82.2 62.4 70.3 46.4126.8 42.1178.4 16.1 23.0 69.0 C2Ili.IOOY Crepidiaside C 136 5 37 5 129.0 142.2 52.3 82.5 62.9 70.4 46.5 126.9 42.2 178.5 16.1 23.0 68.2 CI 7112206 Neoezoguaianin 85 4 140.8 136.4 82.4 67.3 78.0 40.3 76.4 36.3 143.3 50.6 178.0 16.0 117.2 24.6 CISHI803 Leucodin, epi, dehydro, 11,lIdihydro 133.1 196.3 134.9 168.2 52.7 80.2 42.1 25.3 34.3 142.7 55.2 177.3 12.3 19.8 23.2 C16H2405 SaH,IluH-Guai-2-en-12,6a-olide, 4~,1Op-dihydroxy-la-methoxy 76.5 123.9 143.1 94.5 54.8 82.3 40.0 22.7 35.8 79.2 39.2 180.5 10.6 29.0 25 X C19H2807 5aH,ll~H-Guai-2-en-lZ,6a-olide, &-isohutyryloxy-Ia,4a,lOa-trihydroxy 9 0 2 135.2 140.7 83.5 52.8 75.0 43.9 66.1 41.2 79.3 50.6 180.6 16.5 24.4 23 3 ClSH2203 laH,5aH,ll~H-Guai-2-en-l2,~-olide,l0a-hydroxy 59 2 129.7 138.7 50.2 46.5 87.4 52.6 27.0 44.2 75.5 41.8 178.6 13.0 23.1 20.6 CISHI803 Leucodin, dehydro, 11,13-dihydro 131 9 195.8 135.5 169.9 52.6 84.2 56.4 26.0 37.6 152.1 41.1 177.5 12.3 21.6 19.8 CI>HI~O~ Matricarin, desacetyl 133.1 195.0 135.7 170.0 51.7 81.1 61.6 69.6 41.4 145.3 41.4 177.5 15.5 21.6 19.X CI 7H200S Matricarin 133.3 195.1 135.8 169.6 51.6 81.1 59.1 70.4 44.7 145.0 40.7 176.6 15.0 21.1 19.8 Ci5ifiao3 Achillin 131 6 195.9 135.4 170.1 52.8 83.4 51.8 23.5 37.5 152.2 39.2 178.4 9.8 21.5 19.7 1 3 1 8 195.7 135.4 170.1 52.9 83.5 51.9 23.6 37.6 152.1 39.3 178.3 9.9 21.5 19.7 131.8 195.9 135.5 170.3 52.9 83.6 51.8 23.5 37.6 152.4 39.3 179.6 10.0 21.5 19.8 C15HIX04 Achillin, &-hydroxy 132 3 195.1 134.7 170.6 50.8 80.0 56.8 63.7 47.6 146.3 37.6 178.2 8.8 20.9 19.2 C17H2207 Ezomontanin, 11,13-dihydro X0.X 126.8 133.3 75.2 45.1 83.5 52.0 73.4 46.6 72.8 54.0 173.0 15.2 20.5 28.5 C21H2809 Lactuside C 1 3 2 . 9 1 9 6 7 1 3 5 . 4 1 7 1 . 6 5 1 3 84.3 46.5 29.5 80.6150.1 409177.9 12.4 19.8 19.5 C15111804 Jacquilenin 131.1 195.1 133 2 171.6 49.5 83.7 56.1 25.8 37.7 153.5 41.3 177.2 12.2 21 8 62.5 1309 195.7 132.6 173.0 49.2 83.6 55.7 25.5 37.4 153.8 41.4 177.8 11.9 21.5 61.8 C21112809 Crepidiaside B 131.7 195.0 134.4 169.5 49.8 83.8 55.6 25.9 37.5 152.8 41.3 177.2 12.2 21.4 68.8
Sol. Ref. C
66
C
47
C
55
C
55
c
55
C
55
C
55
C
31
c
31
c
55
I’
0
P
0
C
162
c
210
c
317
M
312
C
126
c
4IX
c
41X
c
4IX
C JO5.4Oh C 41X 492
c s
3%
c
3x0
P
327
c 369 C+M I26 I’
9
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
393
Table 22.+ontinued Name I Chemical shifts C-I C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 1394 ClSHlBOS Lactusin, llp,l3-dihydro 133.1 195.1 133.1 175.2 49.6 81.4 61.9 69.3 49.3 147.0 1395 CZIH28010 Cichorioside B 1327195.2132.7169.9 49.7b 81.5 61.8 69.1'49.3b147.7 1396 CZSH33011 Hypochocroside B 133.5 194.5 134.8 169.6 48.7 80.8 58.5 71.0 44.4 145.6 No
hlol. lomula
C - l l C-12 C-I3 C-14 C-15
Sol. Ref.
41.9 177.8 15.9 21.5 62.5
P474.646
16.1 21.6 69.3'
I'
591
41.0 176.7 15.1 21.0 68.8
I'
490
42.1178.1
Othercarbans. 1369 Ac: 170.0 21.2: 1375 Ac: 169.8 21.1; 1376 Ac: 169.7 21.1; 1377 Ac: 170.0 21.1: 1378 G/c-~-OBZ/-~'-OH: 101.5 75.6 75.9 71.8 78.1 62.4 171.3 41.0 125.3 130.8(2) 116.2(2) 157.7; 1379 Glc: 103 2 75.1 78.6 71.8 78.2 62.5; 1380 Ac: 170.2 21.1; 1382 OMe: 50.2: 1383 iBuI: 177.7 35.4 19.6 19.1; 1387 Ac: 169.7 21.3: 1390 Ac: 171.9 21.7: 1391 Glc: 103.5 75.1 78.6 71.6 78.6 62.7; 1393 Glc: 104.1 7S,0 78.3 71.5 78.1 62.6; 1395 G k : 104.4 75.4 78.6 71.7 78.6 62.8: 13% Glc: 104.2 75.3 78.5 71.6 78.5 62.1 Mac: 166.0 a 126.6 18.3
R'
R'
1368
H
0-OH
1369
OAc
a-OH
1370
1372
R'
R'
1378
R = Glc-2-OBzI-4'-OH
1375
8-CH,
a-CH,
1379
R = Glc
1376
a-CH,
a-CH,
1577
p-CH,
P-CH,
1382
1371
1390
1373
6-CHI
5-CH,
a-CH,
6-CH,
1381
1384
R'
OAC
0.
CO
1391 1392
R?
U-Ch,
1374
1380
1383
G'
P-CH,
R'
R2
H
H
1393
H
Glc
1394
OH
ti
1395
OH
Glc
1396
OMaC
Glc
R2
1385
H
a-CH,
1386
OH
a-CH,
1387
OAc
a-CH,
1388
H
O-CH,
1389
OH
6-CH,
394
M. BUDESINSKY AND D. SAMAN
Table 22.--continued h4ol formula C-l C-2 C-3
No
Name / Chemical shifts C-4
C-5 C-6 C-7 C-8 C-9 C-10 C-ll C-12 C-I3 C-I4 C-I5 \iil* 1397 C16H2203 laH,SaH,11~H-Guai-3,9-dien-12,6a-olide, 13-methoxy 48.0 37.8 125.3 144.4 54.2 86.6 47.4 31.1 120.0 137.1 43.6 176.1 69.2 17.8 27.8 C 151 laH,5aH,llBH-Guai-3,9-dien-12,6a-olide, 13-dimethylamino I398 C17H25N02 48 1 37.9 125.5 144.4 54.6 86.4 46.3 31.3 120.5 136.7 44.9 177.2 58.7 17 9 27.9 C lil 1399 CISH200.5 Hieracin I 59.2 207.0 129.8 180.4 50.7 83.3 52.7 23.8 41.0 71.9 41.7 177.9 12.7 32.3 63.1 C' 369 1400 C2SH35011 Hypochoeroside G 50.3 207.5 130.9 178.7 52.8 77.6 54.5 73.1 40.9b 31.8 40.6b 177.5 15.8' 16.1' 68.9 P 490 1401 C20H2608 I~H-Guai4-en-12,6~slide, 3a-angeloyloxy-7~,11~-epoxy-Z~,8a,lO~-trihydrox~ 64.9 78.9b 88.6b 134.4' 140.9' 74.6b 71.4' 65Sb a 74.4 63.6'174.1 9.3' 25.3' 13.T M I41 leH-Guai4-en-12,6 slide 1402 C24H3209 3a-angeloyloxy-8a-~utyro~loxy-2~,lO~-dihydroxy-7~,l le-epoxy
65.5 79.3b 89.0' 134.6 a 75.0b 70.1' 67.7b 1403 C2XH40011 1 H Gun14 en 12 6B-olide
a
74.5 65.1' 173.3
10.6* 26.0'
15 2*
hl
111
l~~~acetox~-~-a~geloylo~y-7~,~1~-epoxy-?~-hexanoylox~8a-hydroxy 9.2 24.1 I 3 U 51 141
59.8 79.2b 86.lbI33.7'l42.3' 73.8' 71.1 65.2' 43.5 86.3 63.9'174.4 1404 C32H44011 1 H Guai4-en-l2,6~-0lide
I~~~aeetoxy-3a-angeloyl~~y-7~,11~-epoxy-2~-hexanoyloxy-~a~~~tyroylox) 9.6' 23.7' 13.V h? 1-11
59.9 79.1b K O b 133.3' 143.C 73.Xb 69.4' 67.0b 41.2 85.6 64.8' 173.1 1405 C30H42010 1 H Guai4-en-12 6B-olide
l~~~acetoxy-3a-a~geloylo~y-7~,ll~-epoxy~8a-hydroxy-2~-~tanoyl~~xy hl 111
1406 1407 1408 1409 1410 1411
1412 1413 a b
1414 1415 1416
1417 1418 1419 1420 1421
59.8 79.2b 86.1b133.7'142.3' 73.8' 71.1' 65.2b 43.5 86.3 63.Y174.4 9.2' 24.1' 13.0' C34H48011 Thapsigargin, 7,ll-epoxy 59.9 79.1 86.0 133.3 143.4 73.8 69.4 67.0 41.2 85.6 64.8 173.1 9.6 23 7 13.0 CISHI804 Aehillin, IeJOP-epoxy 67.Ob2O1.0 133.2 176.7 49.7 79.7 51.8 19.8 34.6 65.2b 39.3 179.1 9.9 18 9 209 CISH1804 Matriearin, l@,lOP-epoxydesacetoxy 67.0 201.0 133.1 176.6 49.3 80.3 56.2 22.1 34.6 65.3 40.8 178.1 12.3 1 8 9 2 1 0 C19H2606 laH,llaH-Guai4-en-IZ,~-olide, 10a-hydroxy-8~-isobutyroyloxy-3-oxo a 237 49.9 49.4 207.3 144.2 160.9 75.8 44.5 66.5 37.1 44.9 38.5 177.1 11.3 C15H2003 Cichoralexin 55 7 206.8 131.4 173.6 52.0 86.7 57.0 20.7 35.6 30.3 41.2 178.5 21.8 12.2 19.7 CISHI804 Matricarin, deaeetoxy, la,lOa-epoxy 67.4 201.5 132.6 177.1 53.0 85.9 54.4 24.6 38.9 66.3 41 2 178.5 12.4 17 3 21 4 CISHIX0.5 Aehillin, la,lOa-epoxy-8a-hydroxy 65 2 201.1 132.3 177.7 56.4 77.0 47.4 62.4 43.7 65.2 37.5 178.5 8.8 20.3 18 5 C27H38010 Trilobolide S2.6 33.3 81.2 142.8 134.5 78.7 79.7 67.7 39.8 87.0 79.5 178.4 15.9 23 4 13 2 50.5 32.0 79.7 131.6 143.0 77.6 78.6 66.5 38.5 86.0 78.7 175.9 16.2 22 4 13 0 C32H42012 Trilobolide diacetate 51.1 33.1 81.3 144.5 132.6 78.7 83.8 68.0 39.5 86.0 a 179.7 19.9 244 13 4 C26H36010 Trilobolide, nor 51 1 32.2 79.5 143.9 130.9 77.2 78.7b 66.5 38.5 85.5 78.Xb 175.1 15 9 18.0 13 I C24H34010 no name 63.5 74.1* 88.0b 133.7' 139.6' 78.9* 79.6 67.7b a 79.3 79.6 17R.3 15.Yd 2 4 2 13.1' C32H42012 Thapsivillasin H 59.1 79.5 85.8 141.4 133.1 78.4 79.7 67.7 39.5 86.3 79.7 178.7 16.2 23.4 13.2 C34H.54012 no name 59.1 79.5 85.8141.4l33.1 78.4 79.7 67.7 39.5 86.3 79.7178.7 16.2 23.4 13.2 C27H3609 Trilobolide, 7,11-epoxy 51.8 31.9 79.3 131.3 144.0 72.7 67.6 65.6 40.0 84.6 62.5 170.0 9.1 21.6 12 X 215H2203 laH,llbH-Guai4-en-lZ,~-olide, I0a-hydroxy 58.1 25.3 37.7 143.5 129.0 82.0 49.2 23.9 45.0 75.2 41.6 178.6 12.4 21 3 15 7 CIXH2205NC13 laH,11eH-Guai4-en-12,6a-olide,IOa-hydroxy + TAI 55.0 24.7 37.7 144.8 127.6 81.4 49.0 24.0 38.4 92.1 41.5 178.1 12.3 19.6 a
hl
141
c JiIi.wi
c
hll
c
573
"
454
c
611
s
3'16
hl
141
c
I26
h1
475
c
600
M
141
h?
142
M
I42
c
I26
c'
I:(>
C
I26
395
CARBON-I3 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 22.-continued Other carbons: 1397 OMe: 59.1; 1398 NMe,: 45.7; 1400 Glc: 104.5 75.3 78.5 71.5 78.5 62.6 M a c . 166 3 ii 126.4 18.4: 1401 Atlg: 169.2 128.8 140.0 16.4 20.9; 1402 Ang: 169.2 128.8 140.0 16.4 20.9 Bur: 174.4 37.7 19.2 14.7; 1403 Hex: 174.5. 35.4 25.9 32.6 23.6 14.6 Ac: 172.7 23.0 Ang: 169.2 128.8 140.0 I6 4 20.9; 1404 Hex: 174.5 35.4 25.9 32.6 23.6 14.6 Bul: 174.4 37.7 19.2 14.7 Ac: 172.7 23.0 Aug' 169 2 128.8 140.0 16.4 20.9; 1405 Ac: 172.7 23.0 Ang: 169.2 128.8 140.0 16.4 20.9 Ocr: 174.9 35.4 26 1 V1.l 30.1 32.9 23.7 14.3; 1406 Ocr: 174.9 35.4 26.1 30.1 30.1 32.9 23.7 14.3 Bur: 174.4 37.7 19.2 I4 7 A(' 172.7 23.0 Ang: 169.2 128.8 140.0 16.4 20.9; 1409 iBur: 175.2 34.4 18.8 18.8; 1413a Ac: a Mehrr. a Atig: a ; 1413b Ang: 167.7 127.8 138.4 16.2 20.7 Mebu: 175.5 41.4 26.1 11.6 15.8 Ac: 171.1 22 3. 1414 Ails: a 3xAc: a Mebu: a ; 1415 Ac: 170.6 22.4 Bur: 172.4 36.6 21.9 13.7 Atlg: 167.7 127.11 138.5 16.4 20.7; 1416 Bur: 174.4 37.7 19.2 14.7 Ang: 169.2 128.8 140.0 16.4 20.9: 1417 ZxSeri. I66 2 117.1 158.8 20.4 27.4 Ang: 169.2 128.8 140.0 16.4 20.9 Ac: 172.7 23.0 1418 Ocr: 174.4 35.3 26.1 30 I 30.1 32.9 23.1 14.3 Mebu: 176.3 42.7 27.3 12.0 16.7 Bur: 174.4 37.7 19.2 14.7 Ac: 172.7 23.0. I l l y h g . 161.4 127.6 138.5 16.3 20.6 Mebu: 174.7 40.9 26.4 11.4 15.8 Ac: 171.0 22.3
"-C6 1397
R = OCH,
1398
R = N(CHJ2
1399
1400
1401
R = H
1402
R = IBUI
"4
?,OAc
R'O
LJ-4
r i H I
0. "-C6
co
0.
"-C6
R'
R'
1407
R = 8-CH,
1403
Hex
H
1408
R = a-Cti,
1404
Hex
But
1405
Oct
H
1406
Oct
But
co
1410
1409
R'
R'
R'
Q2
R'
1411
H
a-CH,
1413
H
Mebu
1417
Sen
Sen
hnq
1412
OH
8-CH,
1414
Ac
Mebu
1418
Gct
MeDu
But
1415
H
But
1419
1416
1420
R = ti
1421
R = TAC
396
M. BUDESINSKY AND D.
SAMAN
Table 22.--continued No.
1422 1423 1424 1425 1426 1427 1428 1429 1430 1431 1432 1433
a h 1434
a b 1435 1436 1437 1438 1439 1440 1441 1442 1443 1444
1445 1446 1447 1448
Mol. formula Name / Chemical shifts C-8 C-9 C-10 C - l l C-12 C-13 C-14 C-15 C - l c - 2 C-3 C-4 C-5 C-6 C-7 C34HS0012 no name 59.1 79.5 85.8 141.4 133.1 78.4 79.7 67.7 39.5 86.3 79.1 178.7 16.2 23.4 13 2 Thapsivillosin J C31H44012 59.1 79.5 85.8 141.4 133.1 78.4 79.7 67.7 39.5 86.3 79.7 178.7 16.2 23.4 13.2 C3lH42012 Thapsivillosin I 59.1 79.5 85.8 141.4 133.1 78.4 79.7 67.7 39.5 86.3 79.1 178.7 16.2 23.4 13.2 C35H54012 Thapsivillosin G 59.1 79.5 85.8 141.4 133.1 78.4 79.7 67.7 39.5 86.3 79.7 178.7 16.2 23.4 13.2 C32H46012 Thapsitranstagin 59.1 79.5 85.8 141.4 133.1 78.4 79.7 67.7 39.5 86.3 79.7 178.7 16.2 23.4 13.2 C36HS6012 Thapsivillosin E 59.1 79.5 85.8 141.4 133.1 78.4 79.7 67.7 39.5 86.3 79.1 178.7 16.2 2 3 4 13.2 C36H54012 Thapsivillosin D 59.1 79.5 85.8 141.4 133.1 78.4 79.7 67.7 39.5 86.3 7 9 7 178.1 16.2 23.4 13.2 Thapsivillosin C C35HS4012 59.1 79.5 85.8 141.4 133.1 78.4 79.7 67.7 39.5 86.3 79.7 178.7 16.2 23.4 13.2 C32H44012 Thapsivillosin B 59.1 79.5 85.8 141.4 133.1 78.4 79.7 67.7 39.5 86.3 79.7 178.7 16.2 23.4 13 2 C32H42012 Thapsivillosin A 59.1 79.5 85.8 141.4 133.1 78.4 79.7 67.7 39.5 86.3 19.1 178.7 16.2 23.4 13.2 C32H46012 Thapsigargicin 59.1 79.5 85.8 133.1 141.4 78.4 79.7 67.7 39.5 86.3 79.7 178.7 16.2 23.4 13.2 C34HSOOI2 Thapsigargin 58.4 78.6 84.8 140.9 132.3 76.9 79.3 66.5 38.6 84.7 78.9 175.9 16.0 22.9 12.6 59.1 79.5 85.8 133.1 141.4 78.4 79.7 67.7 39.5 86.3 79.7 178.7 16.2 23.4 13.2 C3OH44011 no name 58.7 79.4 85.7 133.1 139.2 77.9 80.2 69.8 40.5 86.5 80.3 177.3 16.0 22.8 12.X 57.5 84.3 77.1 130.6 140.6 78.2 85.7 68.7 39.1 79.4b 79.6b 176.0 16.1 22.6 12 X C34H50012 no name 59.1 79.4 86.1 136.4 139.0 a 81.6 67.4 39.2 86.3 75.8 101.9 17.6 22.7 12.9 C39H56014 Thapsiprgin diacetate 57.6 79.2b 85.Sb 142.5 128.9 78.0 84.8‘ 67.8 38.9 89.2 83.2‘ 174.2 20.5 25.4 13.4 ClSH2002 Eremanthine, llp,l3dihydro 47.3 29.3 30.3 150.2 52.7 83.2 48.9 29.8 121.3 137.9 42.2 177.8 12.9 110.3 27 X C16H2203 laH,~H,ll~H-Guaid(lS),9sn-12,6a-olide, 13-methoxy 47.1 29.4 30.2 150.2 51.9 83.2 47.9 30.1 121.5 137.6 43.7 175.5 68.9 110.2 27.8 l a ~ ~ l l p H - G u a i ~ ( 1 5 ) , 9 - e n - 1 2 , 6 a - o l i d 13-dimethylamino e, C17H2502N 47.1 29.5 30.3 150.3 52.2 83.1 46.6 30.4 121.8 137.5 45.9 177.0 58.8 110.4 27.8 l a ~ l ~ H , l l ~ H - G u a i ~ l S ) ~ n - 1 2 , 6 a - oSa-hydroxy lide, CISH2203 43.6 31.1 35.2 144.4 86.5 78.8 48.3 26.9 25.4 41.6 41.9 178.0 12.6 18.9 114.7 ClSH2203 Ixerin V, aglycone 52.2b 22.5 31.1 152.2 51.3b 84.2 41.5 26.1 39.5 74.4 43.1 179.7 10.9 25.8 107.4 C21H2809 Ixerin E 48.7 35.3 79.9 151.5 49.7 82.6 39.0 26.4 35.2 73.6 43.2 178.5 13.3 28.1 110.6 Ixerin V C21H3208 52.4b 21.4 30.6 152.9 51.9b 82.8’ 39.8 26.4 35.3 81.3 42.6 179.8 11.2 25.4 105.1 4aH,5aH,ll~H-Guai-l(lO)-e~l2,~~lide CISH2202 130.0 27.2 35.4 36.4 52.2 83.9 53.7 30.9 32.0 134.4 42.1 179.2 12.5 24.8~ 14.6 4~H,5aH,ll~H-Guai-l(lO)-en-12,~~lide CISH2202 130.0 27.3 34.5 40.1 55.8 86.2 54.4 31.7 34.1 138.2 41.9 178.8 12.3 23.5 20.8 Michelliolide, dihydro C15H2203 132.0 35.2 38.4 80.2 58.2 84.0 53.5 27.0 29.9 131.0 41.1 178.2 12.2 23.6b 23.7’ Ludartin, llp,l3-dihydro CISH2003 133.4b 33.4 63.6 67.0 51.8 80.3 57.6 27.4 34.2 134.9b 41.2 177.7 12.1 22.3 18.9 ( 3 s , 4 % 5 ~ 6 s , 7 S , l l S ) - G u ~ i - l ( l O ) ~ n - l ~ ~3,4-epoxy lide, CISH2003 133.7b 34.7 64.1 67.4 51.8 82.1 55.2 27.0 34.7 133.9b 41.5 178.0 12.1 23.6 18.9
~
Slll.
I
M
I42
M
142
M
I42
M
I42
M
142
hl
I42
M
142
hl
I42
I\I
142
M
42
hl 141.142 N 143 h.1 141-143
c
141 I96
M
475
M
475
C
lil
c
151
c
151
c
so6
C
590
P
41
I’
590
c
126
c
126
C
501,
C
606
C
ho6
M
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
397
Table 22.--continued Othercarbons: Othercarbons: 1422 Ocr: 174.4 35.3 26.1 30.1 30.1 32.9 23.7 14.3 Ang: 169.2 128.8 140.0 16.4 20.9 But-j-en: a Ac: 172.7 23.0; 1423 iVol: 173.4 44.2 27.2 22.8 22.8 Ang: 169.2 128.8 I400 16.4 20.9 Bur: 174.4 37.7 19.2 14.7 Ac: 172.7 23.0; 1424 2xAng: 169.2 128.8 140.0 16.4 20.9 Ilirr: 174.4 37.7 19.2 14.7 Ac: 172.7 23.0; 1425 Hep-&Me: 174.3 35.2 27.2 27.9 39.8 29.0 23.0 23.0 Aii,q. 169.2 128.8 140.0 16.4 20.9 Mebu: 176.3 42.7 27.3 12.0 16.7 Ac: 172.7 23.0; 1426 IVol: 173.4 44.2 27.2 22.8 22.8 Ang: 169.2 128.8 140.0 16.4 20.9 Mebu: 176.3 42.7 27.3 12.0 16.7 Ac: 172.7 23.0: 1427 Oci-6-Me: 174.1 35.6 26.3 27.7 35.2 37.5 30.6 11.8 19.6 Ang: 169.2 128.8 140.0 16.4 20.9 Mebrr: 176.3 42.7 27.3 12.0 16.7 Ac: 172.7 23.0 1428 Ocf-6-Me: 174.1 35.6 26.3 27.7 35.2 37.5 30.6 1 1 2 19.6 Ang: 169.2 128.8 140.0 16.4 20.9 Sen: 166.2 117.1 158.8 20.4 27.4 Ac: 172.7 23.0: 1429 Ocr: 174.4 35.3 26.1 30.1 30.1 32.9 23.7 14.3 Ang: 169.2 128.8 140.0 16.4 20.9 Mebu: 176.3 427 27.3 12.0 16.7 Ac: 172.7 23.0; 1430 ZxAng: 169.2 128.8 140.0 16.4 20.9 Mebu: 176.3 42.7 27.3 12.0 16.7 Ac: 172.7 23.0 1431 2xAng: 169.2 128.8 140.0 16.4 20.9 Sen: 166.2 117.1 158.8 20.4 27.4 Ac. 172 7 23.0 1432 Ang: 169.2 128.8 140.0 16.4 20.9 Hex: 174.5 35.4 25.9 32.6 23.6 14.6 Ac: 172.7 23 0 h l 174.4 37.7 19.2 14.7; 1433~Oci: a Bur: a Ac: a Ang: a ; 1433b Oct: 174.9 35.4 26.1 30 I 30.1 32.9 23.7 14.3 Ac: 172.7 23.0 But: 174.4 37.7 19.2 14.7 Ang: 169.2 128.8 140.0 16.4 20.9; 1434a A q : 169.2 128.8 140.0 16.4 20.9 Ocr: 174.9 35.4 26.1 30.1 30.1 32.9 23.7 14.3 Ac: 172.7 23.0; 14341, Ally. 167.4 127.4 138.9 15.8 20.5 Ac: 171.5 22.6 Oct: 172.8 34.3 24.8 29.1 29.1 31.7 22.6 14.1: 1435 A,.: :I Afig: a Bur: a Oci: a ; 1436 Ac: a Afig: a Mebu: a Ocr: a ; 1438 OMe: 59.1; 1439 NMu; 45.6 1442 Glc: 104.0 75.3 78.5 72.0 78.2 63.0; 1443 Glc: 98.3 75.3 78.9' 72.0 77.8' 63.1
1422
H
R'
R'
R'
R'
1437
R =
oct
But-3-en
1435
H
But
1438
R = OCH,
1436
Ac
Mebu
1439
R = N(CH&
1423
;Val
But
1424
Ang
But
1425
Hep-6-Me
Mebu
1426
iVol
Mebu
1427
Oct-6-Me
Mebu
1428
Oct-6-Me
Sen
1429
oc t
Mebu
1430
Ang
Mebu
1431
Ang
Sen
1432
Hex
But
1433
o ct
But
1434
o ct
H
0.
1440
0
0.
co4
,,,
co
R'
R'
R'
1444
R = a-H
1447
3o.4o-eporj
1441
H
8-CH,
H
1445
R = 8-H
1448
39.4@-epodr
1442
OGlc
a-CH,
H
1446
R = a-OH
1443
H
8-CH,
Glc
398
M. BUDESiNSKY AND D . SAMAN
1659 X I 5 2 9 8 83.1 38.8 75.8 48.2 66.9 45.6128.3 56.9177.7 11.6 175.0 2 6 2 1450 ('I5lll604 Porelladiolide 42 3 81.5 125.9 147.0 44.0 84.5 56.9 34.2 137.8 127.9 40.5 177.9 13.5 170.3 15 I 1451 CI5Hl60.5 Porelladiolide, 3a,&-cpoxy 42 3 79Oh 64 5 68.0 38.6 79.3b 53.2 34.3 133.6 127.8 44.3 177.7 13.5 170.3 16.2 1452 Cl5H2003 Eregoyazidid B 47.X 42.6 218 0 39.2 51.7 84.1 48.3 3 0 3 122.6 135.9 42.3 178.0 13.0 27.3 15 7 h 39 2 42.4 218.6 47.8 51.7 84.1 48.3 30.3 122.6 135.8 42 7 176.6 13.1 15.7 27.4 1453 CI5ff2OOS Artahsinolide A I43 7 2066 51.0 75.4 166.1 76.3 47.8 23.8 35.8 71.7 42.6 176.4 12.8 27.2h 26.9' 1454 CISH2005 Artabsinolide B
s
2xx
c
44
c
44
C
305
c
IS1
c'
66
24.2 36.2 71.6 42.8 1766
13.0 27.5b 29.Sb
c
66
24.5
12.6 28.4
27.4
c
66
81.7 138.9b 80.6 49.7 25.8 39.2 71.2 41.5 177.7 12.5 29.5' 29.0' llaH-Guaia-1(5)-cn-lZ,6~-olide, 3~,4~-dihydroxy-Za,lOa-dimethoxy 89.2 83.3 140.5 77.9 38.8 20.5 35.7 76.8 40.5 178.9 10.3 27 8 23.9 1458 CISH2202 laH,4pH,SaH,I l~H-Guai-10(14)-en-lZ,~-oIide 47 6 3 0 5 34.9 39.9 52.4 86.6 52.8 32.7 37.0 150.4 42.2 179 2 12.9 111.7 20 X 1459 ('15112202 1pH,4pH,SpH,l l~H-Guai-10(14)-en-l2,6u-olide 4 2 9 31.4 3 3 5 3X.4 47.4 85.9 47.9 32.0 36.1151.4 42.7178.7 1 3 7 1 1 4 7 I 6 X
c
66
c
347
c
I26
c
126
117113.6 I X R
c
596
19.? 79.8 55.7 83.9 51.6 26.3 40.2b 148.7 41.4 178.2 13.2 112.0 24.1 1462 C l S f I 2 0 0 3 laH,4pH,5aH,11pH-Guai-10(14)-en-lZ,~-olide,3-OX0 47.2 44.0 219.1 48.6 39.7 88.5 50.9 39.0 32.9 149.1 41.7 178.1 13.3 112.5 1 4 0
C
506
c
464
C
IZi
c'
I4
s
4x
s
4x
142.3 205.5 1455 CI7H2405 145 S* 76 4 I456 C17Ii24OC I49 I' 77.0 1457 C17H2606 142 5 77.1
52.8 77.1 168.6 78.4 460
82.2 143.Ib 79.4 48.9
38.7
71.6 42.0 177.4
Artabsinolide D, acetate
47.4
Estafietin, Ila,l3-dihydro
1460 C I S H 2 0 0 3
43.8 31.9
48.6
Artahsinolide C, acetate
63.1
63.1
50.7 80.8 46.0
1461 C15H2203 44.1 32.9
Compressanolide
1463 CI.5H2004
Grandolide, 3-0x0
27.1
32.5141.2
38.5179.4
47 I 44.0 219 0 36.5 4 4 2 88.0 50.7 40.5 74.3 152.7 41.4 177.9 13.2 I 0 9 4 13 7 I464 CISH2005 Zaluzanin, dehydro, 4~,1S,11~,13-tetrahydro,8a,9a-dihydroxy 3 8 4 43.1 219.3 30.5 50.9 77.4 44.4 72.3 83.2 147.5 47.5 1795 1 1 . 1 114.9 I 4 3 1465 C17H2405 Grosheimin, 11,13-dihydro-13-ethoxy 47.1 47.1'2?11.1 39.5 47.1 83.7 50.7 74.4 43.7b146.0 4 9 . 0 1 7 6 7 68.1'113.8 I 4 5 1466 CZIH2404Se Grosheimin, 11,13-dihydro-13-phenylseleno 46.4* 48.6'221.7 38.9 46.6b 83.3 49.9' 73.7 43.1'145.2 50.1'176.6 27.7 113.4 13.8 1467 ClSH2206
lsolipidiol 43.0b 39.4 78 0 47.7 51.6 82.2 58.9 146R C19H2606 lsolipidiol acetate
41.3b 35.6 1469 C21H3209 43.1 3 8 0 1470 C3IH42014 41.4 37.4 1471 CISH2204 48.1 38.0 1472 C21H3009 41 5 32.8 1473 C17/I2?06 47.2 43.8 1474 ClSH2205 42 7 39.4
79.8 44.2
48.7 145.8 42.6b 179.0
16.7 113.9
18.6
I'
44x
80.9 55.2 76.7
42.9 143.4 43.0b 177.5
15.7 115.7
18 1
P
44))
75.8 48.3145.3 42.4178.7
16.5114.1
1x7
I'
4'lx
15.7 1158
18.3
I'
44x
13.1 109.7
17 5
C
125
15.7 117.2 6 4 1
C
15X
14.2
C
120
I90
I'
593
37.5 150.7 85.0 180.3 64.8 112.3 19 2
I'
593
Macrocliniside F
87.0 45.3
51.0
81.8 58.5
Macrocliniside F, acetate
87.7
45.1
50.7
81.0
55.2
76.8 43.0 143.3 42.6 177.5
Grandolide, 38. hydroxy
78.3
39.9 46.8 85.4
50.6 40.3
74.4 153.7 41.8
a
Saussureolide, triacetate
78.2 81.4
55.0 76.9 53.7 75.4 42.0 140.5 40.5 176.8
laH,4~H,5aH-Guai-lO(14)-en-lZ,6u-olidc, Ila-ocetoxy-13-hydroxy-3-oxo 218.4 39.7
51.5
86.7 49.8
27.3 38.4 148.8 75.6 175.9 64.1 112.9
Cynaroside A, aglycone
78.1
1375 .. . CZIH?ZO/O ~ . ~~~
42 9
50.7
76.1
38.3 87.3
47.6
52.6 78.6 55.8 28.0
Cvnaroside A ~ . ~
45.6
52.0 78.4
37.8 150.9 85.2 180.3 6 4 8 112 I
~
55.6
27.8
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
399
Table 22.-continued Orhercarbons: 1449 rig: 166.7 122.7 138.8 14.4 12.0; 1455 Ac: 178.4 21.4; 1456 Ac. 170.2 21.4; 1457 ZrOMe: 58.1 50.1; 1465 0.9: 66.4 15.4: 1466 SePk: a 128.8(2) 126.4(2) 127.5; 1468 2xAc: 1699 %'I 170.6 20.9; 1469 Glc: 105.6 75.3 78.5 72.0 78.1 63.1; 1470 G/c-2,3,4,6-Ac: 102.0 72.2 73.5 69.5 72 2 62.6 169.4 20.4 169.6 20.4 169.8 20.4 170.1 20.4 170.2 20.9: 1472 3xAc: 170.4 21.1 170.3 21 I 170.0 20.9: 1473 Ac: 170.3 20.6; 1475 Glc: 105.9 75.5 78.6 71.9 78.6 63.1 n--CO
"-cO 1451
1450
1449
1452
Qq 0.
co
..,,,,
1453
R = ol-OH
1454
R = @-OH
"-cO 1457
R'
R=
1455
a-OAc
a-OH
1456
P-OAC
8-OH
0.
co
,111
OH
K1
H
H
1463
H
@-OH
1464
OH
a-OH
AcO
HO
R'
R2
H
1468
Ac
AC
1465
R = OEt
1469
Glc
H
1466
R = SePh
1470
Glc-2.3.4.6-Ac
AC
1473
R'
1462
1461
1460
1459
1458
1474
R =
1475
R = Glc
H
0-co 1471
1472
400
M. BUDESINSKY AND D. SAMAN
Table 22.--continued No
1476 1477 1478 1479 1480 14x1 1482 1483 1184
Mol. formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-I1 C-12 C-13 C-I4 C-15 -Sol. R C f C2IH2604Se Grasheimin 3-dihvdro-11H.lfohenvlseleno c 18 48.2b 46.6' 78.4 38.5 47.1; 81.4 -50.5 75.2 '42.6'143.8 54.5 171.3 .27.9 15.3 18.1 C23H280SSe Grosheimin, 8-acetyl-11H,13-phenylseleno c JX 43.5b 47.1 218.3 39.4 46.Xb 83.3 51.0 75.8 43.5 142.8 44.3 175.4 28.1 16.0 14.2 C2SH3006Se Grosheimin, 3-dihydro-3,8-diacetyl-llH,l~phenylselen c 4x 43.7b 42.8' 79.Y 35.3 47Sb 81.1 50.8 76.2' 42.6'142.0 50.8 175.3 27.9 16.4 17.9 C16H220S IlaH-Guaian-12,6a-olide, la,%c;3a,4a-diepoxy-lOg-methoxy 78.6 28.6 67 I 66.3 61.6 80.8 39.4 19.1 32.2 81.3 42.6 178.8 9.9 17.4 23.4 c 347 C17H2207 Ezoartemin 78 2 57.4 57.7 71.2 40.8 79.0 43.2 72.3 47.4 69.5 52.5 178.1 15.8 20.8 27.2 I' 350 C17112207 Yamayomoginin s J?t)' 77.2 56.4 56.7 70.4 39.4 77.9 41.9 71.0 45.8 68.4 50.8 177.8 15.5 19.5 2 6 6 ClSH200S 11~H-Guaian-12,6a-olide, la,2u$a,Sa-diepoxy-lOp-hydroxy c 66 6&9* 62.5 3 1 . 5 70.4 65.3b 75.6 46.1 23.8 36.0 75.6 39.3 176.6 11.0 25.8 15.0 C2OH2808 5aH-Guaian-12,6a-olide, & - a n g e l o y l o x y - 1 ~ ~ ~ ~ ~ x y - 3 ~ , ~ , l 0 a - t r i h y d r o x y 72.9 64.2 64.4 83.1 57.3 76.5 41.5 72.2 43.2 71.5 51.6 177.2 15.9 22.2 26.9 C 342 C17H2408 Ezoyomoginin C 462 79.9 63.6 63.8 72.4 41.7 74.7 49.4 73.1 43.2 71.0 50.8 177.4 15.0 24.1 27.6
14x5 C l S H 2 2 0 4 70 3 29.0 37.0 14x6 ('IS1l2204 a 69X 29.4 3 7 4 h 70 2 29 8 38.5 1487 C I S H 2 2 0 3 45.2 28.5 34.7 14x8 C I S H 2 2 0 4 4 2 2 28.7 38.8 I489 C l S H 2 2 0 3 44Y 27 3 34.9 1490 C1S112204 45.4 39.7 219.7 1491 C l M i 2 2 0 6 N N 3 43 2 39.3 217.7 1492 CIS112403 51.9 27.3 33.8 14Y3 C l X H 2 4 0 S N C O 48.7 27.4 32.7 1194 C I S H 2 4 0 3 51.4 26.2 32 6 11% C 1 8 f f 2 4 0 5 N C I 3 48 5 25.4 32 0 I496 CIS112403 54.0 28.7 35.4 1497 C18f1240SNCI3 52 7 28.6 35.3 14YX C15112403 5 0 4 27.2 33.2 l 4 Y Y ('lX11240SNCl.i 501 27.1 3 2 6 1500 C I S H 2 4 0 4 4X.2 34.2 73.3 1501 C I S H 2 4 0 3 52.3 28.7 34.7 1502 ('IXlI24OSNC13 4 9 5 280 343
5aH,ll~H-Guaian-12,6a-olide, la.lOa-epoxy4a-hydroxy
c
506
c
506
[I
506
20.4
c
126
23.9
c
506
34.7 58.3 42.2 178.8 13.0 54.3
21.3
c
126
48.3 48.2 86.3 49.9 26.4 41.9 73.6 42.0 178.3 12.8 25.5
15.2
c
I26
13.0 24.3
15 8
c
126
13.0 26.6
20.6
c
126
13.0 25.0
21.2
c
126
12.9 24.5
15.1
c
1?6
15 7
c
126
1 2 9 32.8 21.0
c:
126
12.7 26.8
209
c
126
51.2 25.4 42.4 73.0 42.3 179.5 12.9 32.2
I4 8
c
126
12.8 26.2
146
c'
I20
74.7 42.2 178.6 13.0 25.4
8.7
c
126
35.4 75.2 42.0 179.3 13.4 35.1
19.3
c
I?(>
194
c
12f>
80.6 59.5 79.7 50.9 23.9 34.0 63.0 42.0 177.8 12.6 24.3 21.8 5aH,11pH-Guaian-12,6aa-olide, Ip,lOg-epoxy&-hydroxy
79.6 55.2 81.6 53.1 23.1 33.4 62.1 40.7178.0 79.7 55.4 81.8 53.4 23.7 33.7 62.4 40.7 178.2
12.4 23.2 23.2 12.4 23.3b 23.2'
laH,4~H,SaH,11pH-Guaian-12,6a-olide, 10a,l4-epoxy 40.9 51.0 86.3 52.8 26.5 36.9 58.6 42.0 178.4 13.2 49.0 laH,5aH,llaH-Guaian-12,Q-olide, 10a,l4-epoxy4a-hydroxy 79.6 54.7 83.4 50.8 25.7 39.1 58.0 41.2 a 13.1 47.9
laH,4~H,5aH,ll~H-Guaion-12,6a.olide, lOg,l4-epoxy 40.8
52.7 85.8 52.9 25.8
a-Santonin, dihydro, isophoto a-Santonin, dihydro, isophoto
+
TAI
48.1 47.8 83.8 50.0 25.5 33.7 90.1 42.8 177.7 laH,4pH,5aH,1lpH-Guaian-l2,6aa-olide, 10a-hydroxy 3 9 8 49.7 85.7 53.5 26.2 40.9 74.9 42.5 178.9 laH,4pH,5aH,II~H-Guaian-12,6a-olide, I0a-hydroxy 38.8 48.7 84.0 53.2 25.3 33.6 91.6 43.0 178.4 laH,4aH,5aH,11~H-Guaian-12,6a-olide, I0a-hydroxy 36.0 49.0 82.5 50.8 26.3 43.8 74.7 42.1 178.8 laH,4aH,SaH,11pH-Guaian-12,6a-olide,l0a-hydroxy 36.8 48.9 81.4 50.2 26.4 36.1 92.2 42.1 178.4 Artabsin B, tetrahydro 41 6 52.5 86.2 50.9 Artahsin H, tetrahydro
41.2 53.6 85.6
25.0 41.7 73.7 42.1 179.4
+
+
TAI
+
TAI
12.9 23.4
TAI
52.3 25.5 38.0 90.2 41.9 178.7
Artabsin C, tetrahydro
35.6 49.1 83.4
Artabsin C, tetrahydro
35.5
+
TAI
50.7 82.4 50.8 25.8 38.7 89.0 42.1 178.6
laH,4aH,5aH,11~H-Guaian-12,6a-olide, 3,10a-dihydroxy 40.3 46.6
82.0 50.8 26.2 43.0
Artabsin A, tetrahydro
37.6 42.6 84.8 47.6 Artahsin A, tetrahydro
376 423 843 475
26.4
+
TAI
266 334 923 4 1 8 1 7 8 6
132 2 x 4
401
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 22.--continued No
Mol. formula C-1 C-2 C-3
1503 'CISH2403 45.9 31.3 1504 ClSH2403 49.3 23.4 1505 ClSHI802 49.6 34.8 1506 CISH1803 48.6 29.4 1507 ClSH1203 147.1 34.6
35.2 30.7 126.9 30.7 31.3
Name I Chemical shifis C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-I2 C-13 C-14 C-15 Artabsin F, tetrahydro 36.6 47.4 84.9 52.8 26.8 35.5 75.2 42.5 179.1 13.2 34.8 22.0 l ~ H , 4 a H , S a H , 1 1 ~ H - G u a i n ~ l ~ ~ ~10a-hydroxy lide, 34.7 50.8 82.6 51.4 25.3 41.5 74.2 43.7 178.8 12.8 21.5 16.3 lSH,SfULGuaI -3,7(11),10(14)-trkn-12,~~i~ 142.5 53.8 83.4 162.8 31.9' 30.4'149.4 174.1 122.6 8.5 112.8 18.1 Zaluzanin C, 7,11-dehydro-3-daoxy-11,13-dihydro-13-hydroxy 149.0 51.1 81.2 207.2 28.8 30.4 148.8 125.3 165.7 54.8 113.3 112.3 Lettucenln A 157.9 134.8 153.3 149.9 128.4 143.8 143.4 99.6 168.8 185.4 25.7 121.6
Sol. Kef. C
126
C
126
C
136
C
207
C
625
Other carbons: 1476 SePL: a 133.6(2) 129.3(2) 127.5; 1477 Ac: 169.7 20.8 SePh: a 133.4(2) 129.2(2) 127.5; 1478 2xAc: 169.7 20.3 169.7 20.3 SePh: a 133.6(2) 129.2(2) 127.5; 1479 OMe: 48.9; 1480 Ac: 169.8 19.9; 1481 Ac: 169.2 20.7; 1483 Ang: 166.8 126.9 140.3 15.1 20.6; 1484 Ac: 170.1 21.3
R'
R'
1476
H
H
1477
H
Ac
1478
Ac
AC
1479
1484
1483
1489
-
1490
R = H
1491
R
TAC
1480
R = a-CH,
1481
R = P-CH,
1482
1485
lo.10a-epoxy
1487
R = 8-H
1486
l@,lO@-epoxy
1488
R = a-OH
R'
R'
R'
R'
1492
a-cn,
H
1496
a-CH,
n
1493
a-CH,
TAC
1497
a-CH,
TAC
1494
8-CH3
H
1498
P-CH,
H
1495
@-CH,
TAC
1499
P-CH,
TAC
co R'
RZ
1501
a-CH,
H
1502
a-CH,
TAC
1503
P-CH,
H
1500
& "
1506
4- co
co 1504
\$CHO
1507
1505
402
M. BUDESINSKY AND D. SAMAN
Table 23. Carbon-13 chemical shifts of guai-11(13)-en-12,8-olides. No. 1508 1509 1510 a b 1511 1512 1513 1514 1515 1516 1517 1518 1519 1520
Mol. formula C-1 C-2 C23H3209 50.1 35.7 CISH2004 55.8 71.1 C17H220S 53.3b 73.9 51.5 80.4 ClSH2004 142.8 70.3 CI7H2205 135.7 72.0 C21H3006 41.9 36.4 C17H2206 48.0 27.9 CISH1803 42.7 38.0 ClSH2003 46.9 26.3 C2IH2808 45.1b 37.5 C27H38013 45.Zb 37.4 C27H38013 45.2b 37.6 CI 7H2006 52.2 30.4
Name /Chemical shifts C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-I1 C-I2 C-13 Lemmonin A 25.0 87.4 53.8 29.7 41.6 81.3 40.1 144.7 139.6 170.0 123.0 Floriledin 50.4 79.1 50.8 29.5 42.2 80.5 40.0 141.2 139.5 169.9 122.7 Florilenalin, 2-acetoxy 49.2 78.5 51.7b 29.6 39.7 80.3 29.9 139.9b 139.3b 169.7 122.5 40.9 78.3 53.1 29.7 42.1 73.9 39.5 140.0 139.2 169.8 122.6 S a H ~ u ~ i - l ( l O ) , l l ( l 3 ) d i e n - l 2 , 8 ~ ~ i2p,4adihydroxy de, 51.1 76.8 53.0 25.9 43.0 79.7 37.5 129.0 140.7 170.1 121.0 Inuchinenolide B 46.8 77.1 52.1 25.1 41.9 78.6 36.7 131.2 138.2 169.6 121.7 Pleniradin, 2deoxy-4-O-a-L-rhamnopyranoside 25.7b 86.9 47.7 25.Y 41.1 77.9 122.6 139.V 137.5' 170.4 121.3 Pleniradin, 14-acetoxy-2-deoxy 38.8 79.1 51.1 26.2 44.0 78.5 124.0 137.4 139.8 170.0b 121.3 Achalewlide 207.9 138.1 168.3 32.0 38.5 78.0 36.6 30.1 138.4 169.0 123.5 Inuviscolide 41.1 80.3 59.1 29.9 45.4 82.4 40.7 146.7 139.6 170.3 120.5 Macrocliniside C 80.3 153.4 47.6 28.6 44.gb 85.0 42.3 144.4 1407 170.0 118.1 Macrocliniside D 80.4 154.2 47.7 28.6 44.gb 84.9 42.4 144.4 140.8 170.0 118.0 Macrocliniside E 80.6 154.4 47.7 28.7 44.gb 85.0 42.4 144.5 140.8 170.1 118.0 Arctolide 72.3 153.9 79.6 38.8 40.6 81.3 39.3 55.6 138.8 169.8 120.4
Sol Ret.
'2-14 C-15 23.0
C
220
115.1 25.0
C
227
115.6 25.3 115.5 25.2
C C
315 97
22.9
A
224
21.6 22.6
C
329
22.5
20.6
c
515
67.1
24.3
c
224
14.9
8.2
C
4x7
111.7 24.1
c'
566
116.4 107.7
P
451
1164 107 7
P
451
116.5 107 8
P
451
112.2
21.7
c
50.6 111.4
1521 CZOH2008NC13 Arctolide + TAI 48.0 30.1 72.3 148.7 90.2 36.3 41 I 81.5 39.8 53.9 138.1 169.5 120.4 49.6 1522 C18H2206 Arctolide, desacetyl, 3-propionyl 52.4 30.6 72.2 154.0 79.7 39.1 40.6 81.3 39.3 55.8 138.8 169.8 120.5 50.9 1523 CZOH2606 Arctolide, desacetyl, 3-(2'-methyl)butyryl 52.5 30.7 71.9 154.1 79.9 39.1 40.6 81.3 39.4 56.0 138.7 169.7 120.6 51.2 1524 C1SH1803 Xerantholide a 442 40.3 207.0 139.8 169.7 30.0 45.1 81.3 41.5 33.0 139.2 169.8 120.0 12.7 b 45.2 40.4 206.9 139.9 169.3 30.1 44.2 81.2 41.5 33.0 139.0 169 5 120.1 12.8 1525 CISHI804 Mikanokryptin 45.2 41.3 208.0 143.5 170.9 63.5 50.9 75.2 40.5 33.1 136.2 169.9 120.9 9.0 1526 CISH2003 Inuviscolide, lOa,I4a-dihydro-4a,Sa-epoxy a 47.5 32.6 40.2 69.8 69.5 28.8 44.2 82.4 30.4 34.4 138.9 169 8 119.6 14.5 b 47.1 28.7 32.4 68.0 68.7 30.0 43.7 81.1 40.0 34.2 139.6 168.8 117.9 13.9 1527 ClSH2004 Guai-5,11(13)-diene-l2,~-olide, la,lO~-dihydro-2a,4-dihydroxy 48.1 73.9 47.0 77.2157.6119.5 57.9 80.4 44.9 34.1138.6169.8118.9 20.8 1528 C23H3209 Florilenalin, 2-desoxy, 8-epi, 4-O-~-D-(6'-acetyl)glucopyranoside 46.3 37.6 26.6 87.7 57.6 30.0 40.7 82.3 45.2 146.3 139.4 170.0 120.7 112.0 1529 CIS112203 Inuvixolide, 1-epi, 1Oaa,l4-dihydro 36.2 24.2 34.3 80.9 53.5 30.1 40.6 82.2 37.4 28.6 141 7 169.9 118.0 19.8 1530 CI 7112406 Arnimollin, acetate 56.4 74.1 46.5 72.4b 50.1 28.3 43.2 81.9 44.9 78.7b 139.5 170.0 119.6 30.8'
125,12x, 552
113.X
c 12x352
111.7
c
1117
c' l25.SS2
125.552
8.1 8.2
C'
442
c'
126
12.8
c+s
526
15.4 14.9
c
u
126 650
28.0
c'
6XX
22.2
c
220
20.6
13
634
C
403
24.4
~~
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
403
Table 23.-continued
Q?
R'Ow H -
=
R &
co
co RJ
-
R'
Rz
1511
R
1508
H
Clc-6-Ac
1512
R = Ac
1509
OH
H
1510
OAc
H
1516
R'
H 1513
Rho
1514
H
@
R1
1515
H OH
.H
OAc
1517
R = P-Glc
R'
R'
1524
R = H
1518
R = @-Glc'~@-Glc
1520
Ac
H
1525
R = OH
1519
R = p G l c '28-Ck
1521
Ac
TAC
1522
Prop
H
1523
Mebu H
... 0 I,
OGlc-61526
1530
1527
1528
Ac 1529
404
M. BUDESINSKY AND D . SAMAN
Table 24. Carbon-13 chemical shifts of guaian-12,8-olides (type 11-methyl). No
Mol formula C-l C-2
1531 C21fl3208
Name I Chemical shifts
C-3
C-4
C-5
C-6
C-7
C-8
C-9 C-10 C-11 C-12
C-13 C-14 C-15
Lemmonin C
5 1 5 36.7 26.5 86.8 56.6 24.1 43.6 81.2 39.7 145.9 40.3 179.1 11.3 111.3 1532 CZH3409 Lemmonin B 50.7 36.0 25.6 87.2 55.9 23.5 42.6 81.1 39.3 143.8 39.7-179.4 11.2 111.9 1533 CISH2005 Carolenalone 159.4 39.7 75.7 80.9 50.9 25.6 42.1 85.5 198.3 130.2 37.2 179.9 12.8 14.7 1534 C20H2606 Carolenalone, 3-0-tigloyl 155.3 36.7 77.6 79.7 51.0 25.0 41.1 84.9 197.5 130.9 37.0 179.5 12.7 14.8 1535 C20H2606 Carolenalone, 3-0-angeloyl 155.1 37.0 77.7 80.0 51.4 25.1 41.4 85.0 197.8 131.5 36.8 179.7 12.7 14.9 Carolenalol 1536 C15H2205 I409 38.5 76.0 80.3 49.8 23.7 40.2 83.6 73.8 127.8 37.9 180.9 12 3 20.5 1537 C23H3409 Lemmonin D 48.4 32.4 29.1 77.2 151.5 116.5 42.4 86.4 39.5 36.7b 37.Llb 179.1 11.6 20.6' 1538 CIS112204 Hymenoratin G 57.7 75.7 42.1 78.7 154.2 115.8 47.6 77.0 38.3 29.6 35.1 1789 11.4 20.2 1539 CISHI802 Geigeriafulvcnolide 146.2 127.2 128.2 139.3 132.6 130.6 42.8 78.6 38.4 28.6 47.1 177.9 14.7 21.4 1540 Cl5H1802 Stevisamolide 126.2 133.8 119.2 137.1 143.7 27.2 43.5 79.5 36.8 144.5 39.0 179.1 14.7 24.6 1541 C15H2003 Achalensolide, lla,l3-dihydro 4 6 8 3 7 . 2 2 0 7 4 1 4 0 . 4 1 6 8 . 3 26.1 44.7 80.0 33.4 27.5 3 6 . 5 1 7 8 0 13.7 19.6 1542 ~1.if120o.z Achalensolide, lla,l3-dihydro 4 1 6 38.4 2082 138.3 169.1 25.7 38.2 78.9 37.5 3 0 2 37.8 178.0 15.3 I O X 1543 CISH2003 Geigerin, desoxy 49.9 41.8 207.8 137.1 170.7 30.8 42.5 80.7 36.7 39.3 40.4 178.0 14 I 22.6 1544 CI7H2204 1aH,SaH,ll~H-Guai-3,10(14)-dien-l2,8~-olide, 15-acetoxy 5 0 0 35.1b 128.7 142.8' 47.6 29.9 45.7 79.5 35.2b 141.7' 44.0 179.4 15.7 115.8 1545 C20H2605 1~,5~,10~,ll~H-Guai-3-en-l2,8~-olide, 1-0x0-6a-senecioyloxy 50.9 209.1 134.4 165.1 50.2 75.1 48.5 71.5 34.6 27.2 39.7 177.9 19.7 27.7 1546 C151f2204 Carolenalin 39 7 34.6 77.8 80.1 46.8 21.5 40.5b 79.6 122.6 !37.6 38 3b 1799 12.8 23.0 1547 C20H2805 Carolenalin, 3-0-tigloyl 39.3 32.0 80.0 79.8 46.8 21.1 40.0b 7 9 2 122.8 136.1 37.9'1799 1 2 8 22Y 154X C?OIf2XOS Carolenin 3 9 5 32.1 79.9 79.9 46.9 21.2 40.1' 79.2 122.9 136 I 37 Y b 179 9 12.9 22 Y 1549 1'21H?209 Carolenalin, 4-0-~-D-glucoside 38.1 33 0 75.2b 87.4 43.8 21.2 39.3' 79.3 123.4 136.5 37.6 180.0 13.1 22.1 1550 C311142014 Carolenalin, 3-0-acetyl4-(tetra-O-acetyl-~-D-glucosyloxy) 3Y 9 32.6 77.9b 86.2 46.8 21.3 40.8' 78.gb 122.3 136.4 38.1b 1794 12.5 23.2 1551 C20H2805 Hymenoratin F 56.7 76.4 41.5 70.1b 69.4b 28.3 36.9 77.7 39.7 29.7 39 6 1786 15.9 22.2 I552 C20112805 Hymenoratin E a S4 5 a 39.5 6 9 . 9 67.Xb 24.4 38.9 a 35.6 29.8 38.8 178 2 10 3 20.8 h 54.6 77.3' 39.3 69.0' 70.0 24.4 38 8 766' 35.6 29.9 38.5 177 I 10.2 20.6 1553 L.2OH3005 Hymenosignin 548 77.3 39.1 69.7 68.0 24.5 3 9 6 77.4 35.9 29.8 38.9 1780 1 0 4 20X 1554 ('ISH2OOJ Xerantholide, 11J3-dihydro I 40 3 206.X 139.9 169.3 31.2 48.0 X I 2 41.2 32.9 42.0 1779 12 9 12 X 0 40 3 207 I 139.2 171.0 31.1 47.9 81.2 41.2 32.9 41.9 178 I 12.7 12.7 I555 ~ ' 1 5 / 1 2 0 0 2 Xerantholidc, lla,l3-dihydro 45 2 40 7 206.9 139.5 170.2 27.9 42.6 81 0 41.1 42.8 49.6 178.8 1 0 8 12 7 I556 ClS111603 Grossmisin, anhydro 161 5 194.9 132.1 1403 145.9 118.8 50.3 77.8 44.6 127.5 41.5 177.5 21.4 13 1 1957 ('21112909 Hypochoeroside 1 100 205.1 131.3 169.1 1431 120.0 5 3 6 7 6 7 4 7 3 20.8 4 1 3 17x8 116 129
Sol I<et
226
c
220
221
c
220
20.3
P
335
20.2
C
335
20.3
C
31s
20 3
I'
735
26.6
c
220
261
c
221
12 2
C
690
12 7
c
698
86
c
4x7
X I
c'
ss7
76
c
690
61.6
C
237
205
c
690
21 9
I'
377
216
c'
335
21 7
c'
335
18.2
I'
135
1x5
c 335
15 X
C
227
IS 3 I6 1
C
n
227 227
153
c'
2x2
c C
126 442
X I
C
442
I4 I
c
300
651
I'
4I)O
X 2 8 I
405
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 24.4ontinued Othercwbons: 1531 Glc: 99.2 74.9 77.2 71.9 78.2 63.1: 1532 Glc-6-Ac: 98.1 73.4 76.3 70.5 73.7, 63 8 171.6 21.0 1534 Tig: 167.2 128.0 138.1 14.4 12.1; 1535 Ang: 167.6 127.4 139.1 15.9 20.6; 1537 Glc-6-Ac: 97.7 73.3 76.5 70.5 73.5 63.9 171.4 20.9'; 1544 Act 170.8 20.9; 1545 Sen: 175.8 114.6 1607 1.5.3 22.0: 1547 Ttg: 167.3 128.2 137.6 14.4 12.1; 1548 Ang: 167.3 127.4 138.3 15.8 20.6; 1549 Glc: 99.5 75 2b 78.2 71.3 78.5 62.4; 1550 Glc-2.3.4.6-Ac: 96.2 71.3d 72.7d 68.6 71.6 62.2 168.1 169.0 169.7 169.9 170.1 20.5 20.6 20.6 21.0 21.0 1551 Ang: 167.6 127.9 137.7 15.8 20.5; 1 5 5 2 ~Ang: 167.8 127.9 137.8 15.8 20.6; 1552b Ang: 167.4 a 138.2 15.2 20.9: 1553 Mebu: 176.3 41.6 26.7 11.5 16.4; 1557 Glc: 104.4 75.1 78.7 71.6 78.5 62.8
@ n
co
1531
R = Glc
1533
R = H
R'
R2
1532
R = Glc-6-Ac
1534
R = Tig
1537
H
Glc-6-Ac
1535
R = Ang
1538
OH
H
&? 1539
1536
co
1540
1541
R = a-CH,
1542
R = P-CH,
1543
co
R'
R'
R'
1546
H
H
1551
Ang
a-CH,
1547
Tig
H
1552
Ang
P-CH,
1548
Ang
H
1553
Menu
P-CH,
1549
H
Clc
1550
AC
Glc-2.3.4.6-Ac
1545
1544
R 1554
R = u-CH,
1555
R =
8-CH3
1556
1557
406
M. BUDESINSKY AND D . SAMAN
Table 24.--continued N(> 15%
1559 1560
1561 ' i
h 1562
MOI. romuiu
C-l C-2 C-3 CISH2203 47.5 32.7 40.6 Cl5H2204 58.5 36.1 125.6 C22H2807 119.0 130.0 143.5 CISH2205 57.6 36.3 126.7 52.0 36.0 126.2 C2IH2209N2C/6 55.5 34.9 126.4 C24H22OllN3C19 54.7 34.8 126.7 49.2 35.2 125.7
1563 a h 1 564 C22H3009 1565 1564
1567 156X
51.0 32.1 C3OH44011 56.5 78.3' C17H22OS 4 3 9 216.1 C17H22OS 5 0 2 215.4 C17H2205 46.3 215.9
1569 C151ilX03
Name / Chemical shifts C-4 C-5 C-6 C-7 C-8 C-9 C - I 0 C-lI C-12 C-13 C-14 C-15 S I I 1.11Inuvkcolide, 4a,5a-epoxy-10a,14,11,13-tetrahydro 69.9 69.8 28.6 42.2 82.0 28.8 34.5 39.9 179.6 10.2 14.5 15.5 C 126 1~H,S~H,11aH-Guai-3-en-l2,&r-olide, 6P,lOP-dihydroxy 139.4 52.0 67.3 45.8 75.2 40.9 74.7 40.5 179.7 11.6 32.9 15 5 C 52 SaH,7aH,llaH-Guai-l(lO)~-dien-lZ,&r-olide, 9a-acetoxy-6a-angeloyloxy-4a-hydr~xy 84.5
57.1
79.0
45.0
68.5
75.4
a
37.9
a
9.5
22.0
25.6
C
372
32.3 320
15.4 15.4
A C
I26 I?(>
27.8
15 2
A
I?(>
27.7 27.8
15.0 14.9
A
c
126 I26
22.8
13.2
c
12h
1\1
111
17 3
"
1x7
14 7
c
1x7
Montanolide, iso, desacyl 139.4 138.6
52.5 52.1
74.7 66.9
53.2 55.9
67.2 41.1 73.6 76.2 176.4 21.4 74.7 40.2 76.4 73.4 176.0 21.4 Montanolide, iso, desacyl t T A I (8.10-diOTAC denvatwe) 139.9 50.8 74.0 50.3 71.3 40.2 86.2 75.0 176.4 21 8 Montanolide, iso, desacyl + TAI (8.10.1 I-uiOTAC derlvaiive) 139.8 50.6 74.7 50.8 71.2 40.2 86.8 80.0 172.6 24.0 139.6 51.0 70.9 54.6 74.3 40.4 87.4 80.3 171 7 24.1
Trilobolide, desacyl 75.5 136.6 141.4 68.9
79.8
83.3
37.6
82.5
78.4 1767
23.5
71.3' 79 8b 84.3' 40.4
82.3
77.3' 179.6
24.Y 240d 12 Xd
Thapsigargin 86.4' 134.Y4137.8
laH,4aH,S~H,lOaH-Guai-7(1l)-en-12, 8a-olide, 5a-carhoxymethyl 47.5
43.8
55.5
32.7 159 4
78.6
38.2
28 5 126.4 173 2
8.8
17 7
laH,4aH,SPH,lOaH-Guai-7(1 I)-en-12, Xa-olide, 5P-carhoxymcthyl 47.4 44.9
43.0 59.0 36.6 158.8 79 I 42.3 28.6 127 3 172.8 9.C I X 4 1 PH,4aH,5PH,lOaH-Guai-7(11)-en-12, 8a-olide, Sa-carhoxymethyl 45.2
57.4
31.1 155.8
80.2
38.3
27.1 126.3 174.1
10.2
217
205
c
387
X.9
19 X
X4
c
4x7
laH-Guaia-4,7(11)-dien-l2,8~-olide,3-0x0
46 7 37.2 206.8 139.3 166.3 27.4 157.2 83.0 1570 C20H2807 Dugaldiolide, Za-tigloyl 57.4 77.8 43.5 79.4 87.9 31.2 46.3 80.9 1571 C2OH2806 Hymenoratin D 57.7 78.6 46.5 77.6 85.0 31.8 48.1 81.0
33.9
28.8 123 2 173 h
38.3
26.6
98.2 1751
61.6
20.5
21 I
c'
220
38.2
26.6
97.8 1752
21.1
212
206
c'
227
Other c;iibons. 1560 Airs: 166.4 126.9 140.3 15.8 20 4 Ac: 169.9 22.0. I564 Aqi. 167 6 127 6 I 1 K '1 I i S 2 0 6 Ac: 170.1 22.3: 1565 Ocr. 174.9 35.4 26.1 30.1 30 I 32 9 23.7 I4 3 Afi,q 169 2 I 1 X X I 4 0 0 1 6 4 20.9 A i 172.7 23.0: 1566 COOMe: 170.5 52.4, 1567 COOMe: 171 2 52 6. 156X COOM? 170 3 57 3 1570 71,s. 167.9 128.7 137 6 14.4 12.0: 1571 Any 167 7 127.7 13R 2 15 7 20 5
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
407
Table 24--continued
co
co
co OAng
1558
1560
1559
1564
1565
I
CH,R' R'
'R
1570
Tig
OH
1571
Ang
H
1569
1566
R = n COOCH,
1567
R = @-COOCHJ
R'
R'
R'
1561
H
H
H
1562
TAC
TAC
H
1563
TAC
TAC
TAC
1568
408
M. BUDESINSKY AND D. SAMAN
Table 25. Carbon-13 chemical shifts of modified guaianolides. No 1572 1573 1574 1575 1576 1577 1578 157Y 1580 1581 1582 1583 15x4
Mol lormula Name I Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-I1 C-12 C-13 C-14 C-15 Sol Ref ClSH2004 Parthemollin 143.6 65.7 50.7 206.6 120.5 78.7 37.9 28.3 29.8 32.4 139.8 169.3 122.2 16.5 30.5 S 303 C17H2205 Ivalbatine, acetate 139.2 25.6 41.0 207.1 123.5 78.0 38.9 34.7 72.5 33.9 140.0 169.0 122.5 13.5 29.6 S 303 ClSH2204 Ivambrin 145.1 66.3 46.8 63.3 119.5 78.9 38.1 28.5 30.2 32.8 139.1 169.4 j21.9 16.6 24 I S 303 C2OH2607 Ratiferolide, 4,S-seco, Sa-angelate-%-hydroxy 82.4 197.7 125.5 145.6 78.5 77.5 41.7 37.0 70.9 34.7 138.0 166.8 123.0 12.7 18.5 C 193 C2OH2607 Ratiferolide, 4.S-sec0, Sa-(2'-methylbutyrate)-9-0~0 8.6 18.6 C 193 81.5 199.0 125.6 148.8 77.6 76.5 41.0 44.0 206.4 49.3 137.0 167.8 124.2 Inusoniolide CISH2003 145 9 33.0 41.6 207.7 123.6 81.3 47.6 23.8 30.7 37.4 139.9 170.2 118.6 15.6 2 9 9 C XO Inusoniolide, 8p-acetoxy C17H2205 C 680 145.4 32.5 36.0 207.4 125.2 75.6 50.2 68.5 42.0 36.6 135.8 169.3 120.6 19.1 30.0 C2OH2806 (1S.5S,6R,7S,10S,11R)-Xanth-3-en-12,601ide, 5-angeloyloxy-I-hydroxy-2-0x0 C 295 84.4 201.7 129 2 145.1 79.7 79.6 38.6 26.9 19.4 35.1 37.7 177.9 10.3 15.7 18.5 C2OH2807 (lS,SS,6R,7S,9R,lOS,llR)-Xanth-3-en-l2,6-olide,5-angeloyloxy-1,9-dihydroxy-2-oxo C 295 86.7 199.2 125.8 145.6 79.2 79.2 33.5 31.1 69.7 41.4 37.8 178.6 9.9 12.5 18.5 C2OH2607 (1S,5S,6R,7R,8R,9S,lOS,11R)-Xanth-3-en-12,6-olide, S-angeloyloxy-8,Y-epxy-1 -hydriixy-2-~ixii c 295 84.4 201.0 125.5 146.6 80.6 79.0 42.6 55.7 50.6 40.0 38.0 176.9 10.2 12.2 18.7 C2OfiJO07 (lS,4R,5S,6R,7S,10S,11R)-Xanthan-l2,6-olide,S-angeloyloxy-1,4-dihydroxy-2-oxi1 c 295 85 1 216.7 49.1 63 6 79.7 79 2 38.6 26.6 19.3 35.5 37.6 177.7 10.2 16.1 22 5 C2UH3007 (lS,4S,SS,6R,7S,lOS,11R)-Xanthan-l2,6-olide, 5-angeloyloxy-1,4-dihydruxy-2-i~x~i 85.1 216.8 49.1 63.8 79.7 79.1 38.6 26.4 19.2 35.5 37.6 177.9 10.1 16.0 22.6 c 295 ~ 2 ~ ~ 3 2 0 8IS 4 5s 6R,7 8R 9s 10s 11R)-Xanthan-12 6-olide,
84.4 213.6 1585 C22H.3208 84 3 212.6 1586 C2OH2606 93.5 204.2 15x7 CISH2203 I45 7 33.2 15x8 CIS~IZOO~ 135.8 34.4b 158Y CISH2003 a 144.6 30.6 h 1445 30.4 1590 C17H220S 142.5 30.0 1SY1 ClSH2003 145 6 30.4 15Y2 C17H2405 144.9 27.8 15Y3 C15H2003 22 9 23.3 15Y4 ClSH2203 145.6 32.8 15Y5 ClSf11804
62 7h 146.5 15Y6 ClSH1304 1.50.1 76.4
!%a$oy/oxy-&dox;-4-dthoxy-l-hydro 48.8 72.0 78.9 78.6 42.9 55.7 50.7 39.6 37.9 176.9 1s 4s SS 65 7R,8R,9S 10s lIR)-Xanthan-lZ 6-olide, ~-a~gdIo~o~y-8,9-epo~y~thoxy-l-hydroxy!2-0~0 47.8 71.4 78.9 78.6 42.4 55.6 50.7 39.6 37.8 176.9 no name 105.2 190.5 72.0 77.8 38.8 27.1 18.9 34.3 38.0 177.6 Parthemollin, 6-epi, 2-desoxy-llp,l3-dihydro 41.7 207.7 123 8 81.0 51.0 31.4 25.3 37.4 42.3 178.7 no name 40.4 207.1 176.5 76.3 46.3 25.4 32.4b a 41 7 178.3 Xanthalongin = Tomentosin 42.7 207.8 120.2 26.7 42.2 79.2 36.8 35.6 139.2 170.1 42.6 208.0 120.1 26.6 42.1 79.2 36.6 35.4 139.0 170.2 lnuchinenolide A 42.2 207.0 125.5 70.0 42.2 76.7 36.9 35.0 135.6 169.5 Tomentosin, 10-epi 42.7 208.0 120.4 25.5 45.4 78.1 34.1 33.8 140.0 a Tomentosin, IOa-hydroxy4H. acetate 36.3 70.5 121.8 28.0 41.6 76.6 43.7 73.7 139.3 171 2 Carabrone 43.6 208.6 34.2 30.7 37.7 75 6 37 3 17.2 129 0 a Tomentosin 4 H 38.0 67.5 119.9 26.7 42.2 79.5 36.7 35.0 139.1 170.4 Xanthatin, 8-epi, lp,SP-epoxide 129.5 197.5 65.8b 28.2 39.3 79.2 32.0' 31.5' 138.9 168.9 lvalhin 44.6 65.1 122.6 24.7 48.3 82.4 36.8 28.7 140.0 169 7
9.9
16.0
197
C
295
9.9
16.0
19.3
C
295
10.0
14.7
16 5
c
295
12.4
15.8 29 9
C
506
146
17 X
29 9
C
506
121.9 21.0 122.0 20.9
29 8 29 9
c c
403 391
124.7 20.6
30.0
C
329
122.1
19.3
30.0
C
391
122.4
304
21 4
C
h1J0
122.6
18.2
20 I
c
156
122.1 21.0
23.8
C
566
123.3
18.6
31.2
c
391
118.2
19.5
23 9
s 303 ~-
Other carbons: 1573 Ac: 170.1 21.0: 1575 Aug: 168.8 126.7 140.5 18.3 15.6. 1576 Mebrr: 176.X 36.2 26 3 (1.4 l6.I: 1578 Ac: 170.1 21.0: 1579 Aitg: 168.3 126.8 140.6 15.9 20.2: 1580 Ang: 167.5 1267 1406 15 X 2 0 I : 1581 Arq: 168.9 126.6 141.9 16.0 20.2: IS82 Arig: 1688 126.5 141.8 15.8 20 3: 1583 Arls 16X.7 126.5 141.6 15.8 20.3: 1584 Arrg: 167.4 126.6 141.3 15.4 20.3 OEt: 64.1 12.5: 1585 ArrS: 167 3 125 7 141.1 15.4 20.3 OEI: 64.1 12.5; 1586 Attg: 165.9 126.9 139.8 15.8 20.3: 1590 Ac: 1689 21 0 . 15Y2 /I<' 170.2 20.0
409
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 25.-continued
& ,p2
O'CO
R'
R'
1572
OH
H
1573
H
OAc
1574
1575
1576
:?'t o g
AngO"'
O-co
co
1577
R
= H
1579
R = ti
1578
R = OAc
1580
R = OH
1581
1582 [ 4 R ] 1583 [ 4 S ]
Jq
AngO"'
0.
1584 [4R]
1586
1587
1588
1585 [4S]
co
1589
R = ti
1590
R = OAc
co
1591
1593
1592
/pQ
co
co
1594
1595
1596
co
410
M. BUDESINSKY AND D. SAMAN
Table 25.--continued Mol formula Name / Chemical shcfrs C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C - l l C-12 C-13 C-14 C-15 -<<Jl I
No
~
146.5 129.1 a 66.2 29.2 39.Xb 79.6 CISH2203 Xanthalongin, llj3J3-dihydro = 144.7 30.4 42.7 a 119.7 26.3 45.1 79.1 144.7 30.4 42.7 208.1 119.7 26.3 45.1 79.2 CISH2203 Tomentosin, lla,l3-dihydro 144.1 31.0 42.7 208.2 122.6 21.9 42.3 80.5 CISHI805 Tanaphillin 7 6 4 44.4 203.7 137.2 138.5 71.6 42.7 27.5 CI6H2005 Tanapartholide, 3-methoxy 205.7 38.7 75.2 126.4 129 6 X I 4 42.2 28 7 CISHI805 Tanapartholide A, seco 202 6 131.0 166.8 78.7 62 7 X0.3 42.1 28.7 CISH1805 Tanapartholide R, scco 204.7 133.1 165.8 78.1 58.2 80.6 4 0 9 284 C19H2207 no name 113.0 37.3 123.0 135.6 61 4 X0.2 42.9 72 3 CI9H2207 no name 113.6 37.4 123.4 136.2 60 3 7'1 ? 4 7 c t 7 CI9H2307CI no name 55.8 4 6 6 171 2 204.0 87.2 a 44.0 65 5 54.9 46.2 170.1 203.5 86.3 76.P 43 8 65 6 B
1598 a
3 1 3 28.7' 38.8'
a
10.3
1Y 2
30 5
c
391
Tomentosin, llpJ3-dihydro 35.5 35.3
35.4 35.5
39.3 179.2 39.3 179.4
14.0 20.6 14.0 20.7
29 x 30 0
c
403
c'
391
36.9
32.9
38.9 179.1
10.9
21.3
29 9
C
301
39.6 207.8 138.5 173 8 122 7
14.1
30 0
c
40.1 202.2 138.6 170 2 121 6
28.9
13 7
I3
-1V
39.7 207 7 169.8 137 6 124 8
300
25 2
C
71
39.5 207.7 169.5 137.9 124 3
30.0
28 9
c'
71
111.9 153.7 141 I 170 1' 125.9
20')
I7 9
c'
300
41 I 152.6 139.X 16') Xh 124 1 104 f,
I7 6
c
300
30.1 300
76.1 132.9 167.0 124 I 23 8 76.7b 133 7 166 7 123.2 23 5
10h 70 0
C'
1607 C29H36013 Hypocretenolide, 11,13-dihydro-14-O-P-D-glucopyranoside tetraacetate 151.0 192.5 134.8 168.4 8 8 7 33.8 34.8 25.2 33.8 137 1 3 8 0 173 5 12.7 67 5
I3 x
c'
26s'
x
C'
(,'A1
13 1
c
66
13 7
c'
JXX
li 3
"
JSX
I0 2
c'
i4i
23 0
('
2-1-1
3
c'
2-14
18 6
c
3x7
20 7
"
1s:
('
371
"
:'I
c
371
c
3l(l
c'
Ihh
b
1599 1600 1601
1602 1603 1604
1605 1606 a h
I608 CI 7H2205 502
36.5
1609 CI4H1804 130.4 136 6
1610 CI6H2006
I40 140
Axivalin 70.9
39.1
78.1
75.5
44.3
23.1
17.9
52.9
25.6
40.2
18.2142.417161216
70
24
Egelolide, 8-desoxy
--
147.2 117.0 76.7
69.3
41.5 178 9
12.5
30 2
Egelolide, 8-acetyl
115 9' 136.3 -- 147.3 129.0b 74.9 56.4 72.8 46.7 67.6 405 177 9 15 4 29.8 1611 CI9H2406 Egelolide, 8-angeloyl 116.0' 136.2 -- 147.3 129.2' 75.0 56.4 7 4 0 47.0 67 8 4 0 4 178 0 I S 3 29'9 1612 C14t11804 laH,lOcLH-Cuai-7(11)-m-12,8a-olide, I3-nor, 4a,Sa-epox)-Il-h)droxy 48.5 25.7 32.4 70.0 69.4 25.8 137.4 88.0 40.0 33.0 130.0 169 5 -15.6 1613 CI4112004 no name 5 6 4 21.1h 40.9 80.7 5 1 9 ' R 5 3 505' 223b 42.8 2W15 3 9 2 1 7 7 12.5 -1614 CI4H2004 no name 53 8 28.7 40.3 79.9 50.5* X 3 5 504' 23 0 44.3 210.6 41.1 177 4 13 5 -1615 C I 6 H I 8 0 5 4aH,5PH-Guai-1(10),7(1l)-dien-12,&r-olide,14-nor, Sa-carhoxymethyl 138.7 202.6 45.6 44.9 47.7 32 2 158.0 7 9 0 33.7 131.8 126.6 172 9 R.9 -. 1616 C16H1805 4aH,S~H-(;uai-l(10).7(11)-dien-lZ.Ri-olide, 14-nor, 5p-carboxymeth) I 140.0 202.8 45.6 46.3 50.6 33.5 157.6 7X I 3 5 6 132.3 126.8 173 0 XY -. 1617 C14Hl603 Mexicanin E 53.5 166.4 132.9 210.2 48 I 7 1 4 44X 7 x 4 3x5 273 141 2 1 7 i l O I21 7 * I 5 1618 CI41i1604 Microhelenin E 83.3 163.6 132.6 206.4 57 5 31 Y 44 X 7X 4 ? Y '1 33.6 140 h I O X 0 122 I1 I / > 1619 C I 4 H I 6 0 4 Microhelenin F 61.3 164.9 130.4 210.9 80.0 36 7 39 6 78.3 38.0 27.4 141.5 170 7 1220 21 5
1620 CISH2004
I$
(,i?*
Tenulin, deacetyl, neo
173 2 138.4 207.0 37.2 44.0 66.0 58.4 75.8 38.1 1621 C17H1205 Heienalin, acetyl, neo, llp,l3-dihydro 170.7 140.4 206.4 39.1 43.0 68.4 58.0 76.2 40.8
31.3
41.2 17X 0
20.6
31.5
38.3 177.1
20 3
8.1'' 1 2 0' 12.6
X 7
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
411
Table Z.--continued Oilicrcarbns. 1601 OM?; 58 2: 1604 2xAc: 169.1b 22.5 169.Ib 22.3; 1605 2xAc: 168Xb 22.2 168.7b 21.0: 1606d )/Ifif: 175.4 34.0 19.0 18.8:1606h ~Aur: 174.9 34.0 18.9 18.7; 1607 Glc-2.3,4.6-A~: 1OO.Y 72.8 71.7 Nj.2 71.2 61.7 169.3 20.6 170.5 20.6 170.0 20.6 169.4 20.6: 1608 Ac; 169.9 21.1: 1610 Ac: 169.9 21 2: 1611 ,411.q 166.6 127.2 139.8 15.9 20.5. 1615 COOMe. 169.3 525; 1616 COOMet 170.7 52.6; 1621 Ac: 170.5 21.0
a 1
co
R
1597
1598
R = a-CH,
1599
R = @-CH,
1601
1600
q,oAc q,oAc H j
0.
1602
R = a-OH
1603
R = 8-OH
H j
co
O'CO
1604
1606
1605
CH,OR I
OH
1607 R = Glc-2.3,4.6-Ac
1608
1612
1609
R = H
1610
R = OAc
1611
R = OAng
R'
R'
1620
R = @-OH
1617
ti
H
1621
R = rr-OAc
1618
OH
H
1619
H
OH
$qq
Ho"'
iir
0.
\ Lo
,,,,,,
co
= o-COOCH,
1613
R = a-H
1615
R
1614
R = @-H
1616
R = @-COOCH,
412
M. BUDESINSKY AND D. SAMAN
spectra: guaian-12,6-olides: 7a-hydroxy-3-desoxyzaluzanin C [10771,2”7 salograviolide A [1114],lS7 chlororepdiolide [1162],614 eregoyazin [12161,3”5 Bahia I [12351,284 10-epi-8-deoxy cumambrin B [12461,606 cumambrin A [12501,159 yomogiartemin [I29771,379 3P-chloro-4a7 lOa-dihydroxy-la,2a-epoxy5aH- guai-11(13)-en-12,6a-olide[12W],6638a-benzoyloxy-1O~,11-diacetoxy3-oxo-4aH-slovanolide [13381,551 3a-hydroxy-ll~H-ll,13-dihydrodehydro costuslactone 8-O-P-glucoside [13431,394 leucodin [ 13851 and achillin (13881,418 7,ll-epoxythapsigargin [1406],141 1,lo-epoxyachillin [1407],405 eufoliatorin [1449],288 la,l0-epoxy-4a-hydroxy-SaH,ll~H-guaian-l2,6aolide [1485] and l0a,l4-epoxy-4a-hydroxy-laH,SaH,ll~H-guaian-l2,6aolide [1488] guaian-12,8-olides: achalensolide [1515]487and 5a-carboxyrnethyl-laH,4aH,SPH-guai-7( ll)-en-12,8p-olide [1567];387 and rnodijied guaianolides: 5-angeloyloxy-l-hydroxy-2-oxo-( 1s,5S ,6R,7S, 10s,11R)-xanth3-en-12,6-olide [1579],295 ivalbin [1596I3O3and compound 1614.244 4.3.4. Pseudoguaianolides
Carbon-13 NMR data of 158 pseudoguaianolides are divided according to the structure features into Table 26 (pseudoguai-12,6-olides), Table 27 (pseudoguai-12,8-olides) and Table 28 (modified pseudoguaianolides). Pseudoguaianolides contain a 5,7-ring skeleton with a methyl group at the C-5 ring junction. Two major types of pseudoguaianolides - ambrosanolides and helenanolides (Fig. 23) - have trans-annelled five- and seven-membered rings and they differ in configuration of methyl group at C-10 and the position of lactone closure which is typically at C-6 in ambrosanolides and at C-8 in helenanolides. Nevertheless, compounds with cis fused 5,7-rings [1639, 1644, 1736, 1737, 17501 and unusual ambrosan-12,8-olides [1655, 1656, 1658, 1665-1668, 1669, 1685, 1719, 1728-17311 have been described (for references see Tables 26 and 27). One of the first 13C NMR studies on sesquiterpene lactones was made by Herz and Sharma310 on tenulin [1741] and its derivatives 1738, 1740, 1743-1745, 1748. Proton decoupled 13C NMR spectra of tenulin [1741] and dihydrotenulin [1743] afforded two sets of lines with greatest differences for C-16 and neighbouring carbons C-8, C-11, C-12 indicating the mixture of C-16 epimers in both chromatographically pure samples. The conclusion was confirmed by “spectroscopic homogeneity” of dehydration products 1740 and 1745. SFORD experiments and chemical shift comparison within series of compounds were used for structure assignment of carbon signals.31” l ~ ~ 13C NMR spectra of a series of pseudoguaianDelgado et ~ 1 . measured 12,8-olides [1644, 1647, 1674, 1682, 1720-1723 and 17491. They found that C-14 and C-15 methyl signals were very sensitive to the reduction of 2(3)and ll(13)-double bonds, probably due to induced conformation changes of the seven-membered ring from chair-like to boat type.
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
413
H i '
12
AMBROSANOLIDE
HELENANOLIDE
Fig. 23. Ambrosanolide and helenanolide type of pseudoguaianolides and numbering of pseudoguaiane skeleton.
13C NMR data on pulchellin [1687] and its derivatives 1660, 1670, 1688, 1689, 1691-1693, 1699, 1702, 1703, 1768 and 1769 have been described.688 It was shown that chemical shifts of C-8 of 6a-oxygenated pulchellins [1688, 1689, 1691, 16931 (6 = 76.8-79.7) were very different from those of 6P-oxygenated pulchellins [1692, 1699, 1702, 17031 (6 = 64.0-67.4). Comparison of 13C NMR spectra in a series of pseudoguai-12,6-olides [1623, 1625, 1627-1630, 16361 provided data on the substituent effect of OH group in position 1, 2 and 8.46 The long-range deshielding effect of OH group in compounds having syn-axial interactions between 6-substituents (e.g. 2P-OH and C-14 and C-15 methyl carbons) was demonstrated. 13C NMR data for some other groups of pseudoguainolides can be found in the literature. 113,240,274,304,175,516,227,598 1D NMR methods - DEPT and/or APT - have been extensively used in structure assignment of pseudoguaianolide carbon signals (e.g. ref. 46, 225, 264, 486, 524, 621, 651, 653). Selective proton decouplings allowed identification of some carbon signals.516TAI-Induced acylation shifts in helenalin [1647] were described.*l Recently 2D-HETCOR spectra have been measured to assign unambiguously methyl carbon signals in hymenolin [1636],46all protonated carbons in desacylligulatin C [1633] and rudbeckin A [1642],651rudmollin diacetate [ 16681,653 helenalin acetate [16491 and its difluorocyclopropane derivative 1754,'75hymenoratin B and C [1779, 1770].277 X-ray structure analysis has been described together with carbon-13 NMR ambrosin [1623], damsin [ 1626],328 data for some pseuduguaian-12,6-ulides: parthoxetine [1635]499and 3a-acetoxy-llaH,l3-dihydrodamsin[1641];82and pseuduguaian-12,8-ulides: cooperin [16461,621 rudmollin [16651,3w geigerinin [1686],81 6a-hydroxypulchellin 4-0-angelate [ 1691]688and britannin [ 16951.lo
414
M. BUDESINSKY AND D . SAMAN
Table 26. Carbon-13 chemical shifts of pseudoguaian-12,6-olides. No
Mol lormula Name I Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7
1622 a h 1623
CISHI803
a h c d
C-8
149.2 124.4 39.9 213.9 58.5 79.8 43.5 24.0 149.3 124.4 39.9 213.9 58.5 79.8 43.5 24.0 ClSH1803 Ambrosin 48 4 163.6 131.2 210.7 56.6 47 I 163.8 130.2 210.5 55.5
80.9 79.8 47.6 163.4 131.0 210.8 56.1 80.1 47.7 163.4 131.2 210.7 56.2 80.2
1624 CISH1703Cl Ambrosin, 3-chloro 47 3 180.4 137.3 210.9 56.2 80.3 1625 C1SH1804 Parthenin a 83.4 162.8 130.8 209.8 58.2 78.5 b 83.8 163.4 130.9 210.7 58.6 78.7 1626 CISHZ003 Damsin a 46 2 24.0 36.0 218.2 55.0 81.8 h 45.9 25.5 36.0 218.9 54.8 81.6 c 4 6 0 25.6 36.3 219.0 54.8 81.7 d 46 1 24.0 36.1 219.0 54.9 81.8 1627 CISH2004 Coronopilin a 84.8 31.8 32.5 213.0 59.0 80.0 h 8 4 5 32 3 32.1 218.6 58.8 79.9 16ZX CISH2004
5 1 4 73.8 1629 CISH2004
C-9
C-10 C-11 C-12 C-13 C-14 C-15
Sol I<ef
Ambrosin, neo
30.2 38.8 139.1 169.9 119.6 21.1 30.2 38.8 138.9 169.9 119.9 21.5
14.8 15.0
C
C
27X 22
30.4 28.9 29.5 29.6
17.4 16.6 17.1 17.2
C C C C
278 46 328 22
44.3 24.8 29.6 33.7 138.5 170.9 120.9
17.6 15.3
C
22
43.8 27.6 29.2 39.8 140.1 170.4 120.2 43.7 29.4 27.9 40.0 140.1 170.8 121.3
16.7 17.4 16.8 17.9
C C
5x9
120.4 15.9 13.8 120.8 15.7 13.6 120.8 15.8 13.7 120.9 15.8 13.2
C C C
278 359 328 22
44.5 27.4 30.0 42.2 135.8 165.8 116.5 14.2 16.8 44.5 30.0 27.5 42.1 141.1 170.8 121.4 17.1 14 4
C C
589 46
17.Y
A
46
45.0 43.9 44.4 44.5
44.6 44.2 44.3 44.4
25.3 24.0 24.6 24.8
25.9 23.8 23.8 25.7
33.6 33.2 33.1 33.4
34.1 33.0 33.6 33.8
34.5 34.1 34.2 34.3
139.0 137.7 138.0 138.2
140.1 139.5 139.5 139.7
170.7 170.2 170.4 170.5
170.0 170.1 170.2 170.3
119.8 119.3 119.9 121.2
17.6 16.9 17.3 17.4
C
46
Ripinnatin
49.4 218.3 53.8 82.5 45.2
36.6 27.2 36.1 142.1 170.4 120.3 17.7
Ivoxanthin
47.6 67.8 46.3 215.0 51.6 82.2 45.2 33.8 26.5 30.5 141.6 170.6 1630 CISH2004 Confertillorin, desacetyl 46.9 24.3 36.6 217.3 55.3 81.4 52.1 67.0 44.5 32.4 139.2 170.4 1631 C15HZ005 Coronopilin, 8p-hydroxy 86.0 33.4 29.0 208.0 59.6 82.5 46.0 81.0 29.0 42.8 145.0 172.0 1632 CISH2005 Coronopilin, 20-hydroxy 86.0 68 8 41.8 218.0 62.7 81.8 46.5 28.8 31.5 38.4 143.0 173.0 1633 CISH2204 Ligulatin C, desacyl 4R.4 22.3 29.7 83.9 53.5 90.1 43.4 32.3 24.8 32.8 139.9 170.2 16.34 C15H2004 laH-Pseudoguai-7(1l)-en-l2,6~-olide, 13-hydroxy4-oxo 43.9 23.7 37.4 217.6 52.6 85.3 165.1 23.2 32.6 32.9 126.7 174.0 I635 C19H2408 Parthoxetine 94.3 34.9b 31.6b 77.5 61.0 105.7 161.6 23.3 29.Ib 36.2 127.1 169.7 1636 CISHZ004 Hymenolin 84.1 163.3 130.9 211.2 58.7 79.2 47.4 29.5 25.8 41.5 40.3 180.6 1637 C15IIZOOS Parthenin, 11,13-dihydro-13-hydroxy X3 X 162.0 130.8 207.5 57.6 78.8 41.8 25.4 28.4 38.4 45.8 170.0 163X CISII2004 Hymenin, 11,13-dihydro 8 0 9 I624 131.2 208.7 58.3 76.8 42.4 28.3 29.1 42.2 54.9 175.3 1639 (‘15112204 Hymenin, 2,3,11,13-tetrahydro 8 1 1 32.2 34.3 215.7 57.2 78.1 44.7 26.9 31.2 43.1 53.2 174.2 I 6 4 0 C15112204 Damsin, 3a-hydroxy-lla,13-dihydro 4 2 0 31.5 69.6 218.7 54.3 80.9 46.6 18.7 36.9 34.7 39.7 178.6 1641 C I 7 H 2 4 0 5 Damsin, 3a-acetoxy-lla,l3-dihydro a 42.4 30.5 71.3 214.0 54.8 80.9 46.8 18.6 37.0 34.7 39.8 178.5 b 42.1 30.3 71.2 213.7 54.6 80.7 46.6 18.4 36.8 34.6 39.6 178.3 I f 4 7 :/.‘HZ405 Rudbeckin A 46.9 22.7 27.2 82.7 60.2 85.7 44.0 31.9 42.4 85.3 53.0 179.4 1643 C17H240S Rudmollitrin 47.6 24.5 37.4 215.7 56.7 81.6 46.2 24.8 32.0 33.9 40.0 168 3 Iciw CIS112204 Helenalin, allo, tetrahydro, I-epi 52 0 I 9 0 39 2 219.0 51.3 80.0 52.0 6 4 5 38.0 25.5 37 5 178 5
120.1
16.0
15.4
A
46
122.0
16.0
13.9
A
46
123.0
15.8
16.6
A
589
122.5
15.7
17.0
M
589
118.9 14.0 61 8
C
651
54 I
17.3 11 3
C
159
54.7
15.7 59.6
c
499
16.1
17.6
18.3
C
46
61.4
17.0 19.0
C
589
13.2
16.5
18.5
C
240
14.1 15.2 17 3
c
240
16.0
10.3 I6 0
C
82
16.0 15.8
10.2 16.3 10.1 16.2
C 82 C+B 126
68.9
C
651
14.7
15.6 63 6
C
304
26.5
13 5
C
166
16.6 24.3
23 5
415
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 26.--continued ~~
Mol formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-lI C-12 C-I3 C-14 C-15 1645 Cl7H1602F4 Parthenin, di(difluorocyc1opropane) 76 3 159.6 130.5 208.5 54.0 81.6 41.3 23.8 36Y 28.2 37.5 169.5 19.2 23 4 17.8
~
No.
Si)IXC
(Ahercnrbons. 1635 2xAc: 170.6 21.0 169 1 20.4: 1641a Ac: 170.1 20.7; 164lb Ac: 169 9 20.5. 1643 A < 20.7: 1645 C-la: 107.0 C-13a: 115.0
& co
1622
R*
Qk O-co
co
O
0.
1623
R = H
1624
R = CI
1625
171 16'1 X
co 1626
9 = H
1627
R = OH
Qk Qk 0-co
1628
R = @-OH
1629
R = a-OH
0
0-co
R'
R'
1630
H
u-OH
1631
OH
8-OH
1633
aR2 co
CH20H
1636 1634
1635
R'
R'
a-OH
a-CH,
1637
u-OH
CH20H
1638
8-OH
CH,
co 1639
Q; ..,,,
1640
R = H
1641
R = Ac
F
1645
1642
1643
0.
1644
co
416
M. BUDESINSKY AND D. SAMAN
Table 27. Carbon-13 chemical shifts of pseudoguaian-12,8-olides. Miil tiirmuki Nane / Chemical shifts C - l C-2 C-3 C-4 C-5 C-6 C-7 1646 CISHIX04 Coowrin \(I
-
C-8
C-9
I 5 0 2 148 2 201.7 46.7 40.9 35.4 38.2 76.4 40.7 IM7 C15111804 Helcnalin a 5 1 4 163.7 129.7 211.9 47.8 74.1 50.9 78.2 39.5 h 5 1 . 4 164.1 129.8 212 3 57.9 74.1 50.8 78.3 39.5 c 5 1 2 162.9 129.7 211.1 57.6 74.1 51.2 77.6 39.5 d 5 2 . 4 1 6 4 0 1 2 9 . 7 2 1 1 . 5 5 7 8 74.1 51.9 79.2 4 0 4 e 52.3 163.8 130.0210.8 57.7 75.0 52.1 79.1 40.8 f 53.0 165.9 130.3 213.8 58.5 75.4 52.7 80.6 41.1 IMX C18HI806NCI3 Helcnalin + TAI 53.2 162.5 129.3 208.5 55.6 81.7 47.1 78.1 40.2 IMY C17H200S Hclenalin, 6-acetate a 52.8 162.3 129.1 211.4 57.4 74.7 59.9 80.7 41.7 h 53.2 161.7 129.6 208.5 55 4 77.7 47.8 78.0 40.2 1650 CI 7H2005 Mexicanin A, 6-acetate 154.3 121.9 39.5 215.9 54.7 78.9 60.1 73.7 40.9 1651 CZ(JH2406 Fastigilin C 49.7 161.6 129.9 208.6 55.3 77.0 45.7 83.4 77.8 I652 C20H2406 Multigilin 50.1 161.9 129.8 208.9 55.4 79.2 45.7 83.4 77.0 1653 C20H2206 Multiradiatin 51 6 159 1 132.4 207.6 55.4 70.1 46 5 78 3 205.6 I654 CZOff2206 Multistdtin 51.4 158.9 132.4 207.5 55.6 71.1 46.8 78.2 205.4 1655 C I S N 2 0 0 2 Confcrtin 45 9 21.2 35.8*2192 50.6 36.Y 39.0 79.4 38.0 I656 CISH2004 Peruvin a 83.8 32.7 35.6216.2 54.8 31.6 38.9 80.7 36.7 b 83.6 31.4 36.6 216.4 54.8 32.6 38.8 80.8 35.5 1657 CISH2004 Helenalin, 2,3-dihydro 48.2 24.6 33 9 218.3 54.3 72.2 57.4 79.8 42.4 1658 C17H2205 Rudmollitrin, 11,13dehydro 46.3 21.4 36.6 214.8 53.9 36.2 37.8 79.0 34.4 1659 C23H32010 Paucin 51.8 76.6b 44.8 215.3 50.9 35.3' 38.2 79.2' 36.0' 1660 CI5H2204 Pulchellin, nco 46 8 77.1 44.5 81.3 40.8 39.8 54.9 77.4 35.9 1661 C17H2405 Chamissonolide, 6-desoxy 51 I 79.5 40.6 77.5 47.0 42.4 41.4 80.8 36.2 1662 Cf 9H2606 Chamissonolide, 4-O-acetyl-6dewxy 51.6 77.0 39.3 83.1 45.3 39.3 40.5 70.3 35.1 1663 CISH2204 Cumanin 41 3 40.8 68.4 77.1 44.1 35.0 37.7 80.1 36.4 1664 CISH2204 Hymenoratin 46.4 38.4 77.2 85.8 44.8 34.5 39.7 77.5 35.3 1665 CISH2204 Rudmollin 44.2 23.1 30.2 79.4 48.6 36.1 37.8 80.1 36.5 1666 C17H2405 Rudmollin, 4-acetoxy 44.4 23.5 27.1 76.7' 48.9 36.0 37.4 79.9b 34.6 1667 C I 7H2405 Rudmollin, 15-acetoxy 44.6 23.0 29.4 77.6 47.3 36.0 37.2 79.9 34.1 1668 C19ff2606 Rudmollin, 4,15-diacetoxy a 44.6 23.3 26.8 77.8 47.4 35.9 37.2 79.3 34.2 h 44.1 23.3 26.8 77.6 47.3 34.2 37.0 78.9 29.9 1669 CI7H2404 Rudmollin, 4J5-acctal a 44.3 23.0 22.1 80.3 41.6 39.0 38.1 79.3 36.8 h 44.0 23.0 22.3 80.1 41.4 39.1 37.9 78.9 36.7
C-I0 C-lI C-12 C-I3 C-14 C-I5
{iil-&L621
27.8 138 7 169 5 122.8
19.6 2X 7
26.2 26.1 26.0 26.5 27.0 27.4
122.7 123.1 121.9 121.9 122 I 123.3
20.1 202 19.7 20.2 20.4 20.5
1X.7 18.7 18.7 I8 8 18.9 19.3
A $1
26.1 137.2 169.3 125.5
19.8
18 3
c
XI
27.4 135.4 169.8 123.1 19 X 26.2 137.5 169.3 124.4 2 0 0
169 18.4
c' C
240
295 135.3 174.1 124.7
18.4 174
"
2.10
33.1 137.7 169.0 126.3
15.9
IX 2
c
510
33.0 137.6 169.3 126.2
15.9
IX I
C
516
44.7 1326 167.9 121.7
16.4 17 9
c'
516
44.6 132.4 167.8 121.9
164
17 X
c
5111
30.6 139 3 169.4 123 3
20.0
17 7
c'
524
41.1 141.3 170.4 122 5 18.8 22.7 41.0 141.2 1705 122.6 22.6 18 8
c.
4x6
c
x2
27.9 134.7 169.7 121.9 14.7 l9.X
c
240
30.4 139.5 168.9 123.0 17.3 65 1
c
704
28.6 140.0 1700 122.2
137.9 137.9 138.7 139.7 140.2 140.4
160.6 169.9 169.1 170.4 170.2 172.2
('
c c I$ I'
Ihlr
XI 54x 54x 54X
s'tx
175
19 4
20 6
c
284
29.0 140.4 170.1 122.3 20 7
22 2
c
6XX
142.5 169.0 121.5 22.2
20 8
A
679
28.8 140.0 169.4 122.4 20.4
21.2
c
67X
30.1 139.8 169.8 122.9 16.7
17.8
c
486
29.7 140.1 170.0 122.8 16.0
19.9
C
227
30.5 141.7 169.5 121.4 16.6 64.6
c'
304
30.2 140.3 169.4 122.5 16.4 63.6
c
304
30.2 140.2 169.7 122.8
15.8 64.3
c
704
30.0 139.7 169.1 122.8 35.9 140.6 168.8 122.1
16.0 63.8 15.9 64.0
c
304 653
30.1 139.6 169.4 123.1 30.0 140.5 169.0 121.9
17.1 72.0 1 6 9 71.7
C
264 264
a
c B
417
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 27.4ontinued Other carbons: 1649a Ac: 201.3(?) 20.1; 1649b Ac: 169.1 20.9: 1650 Ac: 202.l(?) 19.3; 1651 Serf. 165 2 I I5 3 159.1 30.4(?) 27.5: 1652 Ang: 166.5 127.1 140.0 15.9 20.4; 1653 Sen: 164.7 114.7 160.2 20.5 27 5 . 1654 Aiig: 1659 126.7 140.8 15.8 20.3; 1658 Ac: 170.2 20.6: 1659 Glc-6-Ac: 103.6 73.3 76.7* 70.1 73 7 h i J 168.9 20.6; 1661 Ac: 170.0 21.2; 1662 2xAc: 170.6 21.2 170.2 21.6; 1666 Ac: 170.5 21.0; 1667 A< ’ 171 0 21.1: 1668a 2xAc: 170.8 21.0 170.3 21.0: 1668b 2xAc: 170.5 20.6 169.8 20.6. 166Ya CH,-CH. 20.9 ‘ J I 5 . 1669b CH,-CH: 21.2 91.6
:
HO
co
co
co 6R
1646
1647
R = H
1648
R = TAC
1649
R = AC
1653
R = Sen
1655
R = H
1654
R = Ang
1656
R = OH
6-Ac-Glcq
1650
~
co
R = 4nq
1658
.leCo OH
6R2
R’
R’
R’
R’
R‘
R’
1660
H
H
1663
8-OH
8-CH3
1665
H
ti
1661
AC
H
1664
u-OH
a-CH,
1666
4c
H
1662
Ac
Ac
1667
H
hi
1668
PIC
AC
1659
1669
R = Sen
1652
1657
?
co
1651
418
M. BUDESINSKY AND D. SAMAN
Table 27.--continued Mol. formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 1670 Cl5H2205 Neopulchellin, 6a-hydroxy
No.
C-9
12-10 C - l l C-12 C-13 C-14 C-I5
Sol. Ref.
46 8 76.7 42.2 76.7 52.9 79.9 51.8 76.7 35.8 28.6 136.9 170.3 126.0 '19.8 20 3 C 68X Chamissonolide 1671 C17H2406 49 7 80.0 41.0 77.8 52.6 77.0 47.6 80.6 36.9 a 138.7 170.2 125.5 20.0 20.6 A 679 1672 C19H2806 Chamissnnolide, 2-deacetyl-2-isnbutyryl 49.0 79.0b 40.1 76.5' 51.6 76.6' 46.9 79.Sb 28.6 35.9 137.0 170.0 126.1 19.9* 20.Sd C 221 I673 C19H2607 Chamissonolide, 4-acetyl 5 0 3 7 7 . 2 39.1 76.0' 50.9 76.4' 45.7 7 8 . 6 28.3 35.7 136.9 170.5 125.7 19.8' 20.3' C 224 1674 C18HZ406 Helenalin, 6-acetyl-2,3-dihydro-2a-methoxy 52 2 80.4 39 I 216.0 54.0 76.8 52.2 78.5 41.5 24.1 138.7 169.3 124.5 18.7 19.9 C 166 1675 ClSH2005 Villosin B 53 4 69.5 49 5 215.1 59.2 77.6 47.1 79.9 40.6 28.0 140.7 170.7 123.0 22.2 15 8 A 224 Hymenograndin 1676 C19H2607 50.8 76.9 76.2 80.6 41.8 39.4 38.2 72.6 34.9 28.9 139.4 171.2 123.0 17.6 20.2 C 282 1677 CZlH2808 Hymenograndin, acetyl 51.1 76.4 72.1 79.9 41.4 39.1 39.1 71.9 34.4 28.8 138.9 171.0 123.3 18.4 20 2 C 282 1678 CISHZUOS Autumnolide 51.6 59.2 6 1 7 75.6 58.6 75.2 45.2 73.5 34.3 26.0 136.3 1692 126.1 16.9 199 C 2x2 1679 CZOH3006 laH,lO~H-Pseudoguai-1~(~3)sn-12,8~-nlide, 2a,4~-dihydroxy-l5-(2'-methylhuIdn11).l11xyl 55 9 72.9b 42.6 75.4b 49.0 35.1 37.9 16.7 34.2 29.3 139.2 169.4 123.3 21.0 64.8 C 275 1680 C25H3007 laH,1O~H-Pseudoguai-2,11(13)-dien-l2,8~-nlide, 6a-angeloyloxy4-oxo-9~-seneci1~).I11~). C 225 49.8 160.5 129.9 207.9 55.4 78.1b 46.2 80.3 77.Zb .30.9 140.0 166.9 125.5 15.3' 20.3 1681 C15H1804 Mexicanin I C+hl X I 53.4 163.0 130.2 215.2 57.1 65.1 53.0 76.1 44.4 27.2 135.2 166.6 123.0 20.9 19 X 16x2 CI7H2005 Mexicanin I, acetyl = Linifolin A a 51 9 160.9 130.2 210.7 55.4 65.8 53.0 75.8 44.1 27.3 134.6 169.3 122.6 20.7 1 9 6 C I66 h 52.8 160.6 129.7 210.4 54.9 65.3 51.4 75.3 43.7 28.7 134.0 168.Yb1222 21.0 19.2 c 59x c 51.9 160.6 130.3 210.7 55.3 65.5 53.3 75.6 44.0 27.1 134.0 169.0 123.0 20.7 1 9 6 c XI 1683 C2OH2405 (1S,5R,6S,7R,8S,10R)-P~udn~aia-2,~~(~3)-dien-~Z,S-nlide, 6-angeloyloxy c 59s 53.9 162.1 130.5 208.6 56.4 72.4 52.1 76.0 44.1 27.0 137.2 168.6 121.6 22.2 19.4 Pseudoguai-ll(13)-en-12,8a-olide, 6a-hydroxy4-oxo 1684 CISH2004 c 23 45.2 2 4 6 37.7 223.8 57.7 75.4b 52.1 76.0b 44.2 30.2 139.0 169.6 121.8 20.1' 19.1' Cdrpesiolin 1685 CISHZ004 c 422 52.4 24.6 37 8 223.2 57.6 76.1 45 3 75.4 44.3 30.2 139.4 169 5 121 3 20.0 19 0 Neohymenoratin = Geigerinin 1686 CISH2204 A 220 a 4 6 2 39.3 7 5 2 82.1 45.7 35.0 45.1 9 1 0 45.7 30.7 143.1 1701 118.5 20.9 1 9 0 hl XI b 46 I * 45 3 83 4 90.7 46.0 39.4 465' 75.3 36.9' 31.1 143.0 172.2 119.8 20.9 19 1 Pulchellin 16x7 ('15//7204 C 6XX 4 8 1 75.5 45.9 80.9 4 4 3 42.1 56.3 82.3 33.8 28.6 140.8 1704 119.5 21.2 25.9 16x8 ClSH2ZO5 Pulchellin, 6a-hydroxy C hXS 52 3 75.4 43.9 79 7 5 4 5 81.4 52.5 78.5 41.2 28.6 138.5 1705 123.7 21.1 24.4 16XY CZOH2806 Pulchellin, 6a-angeloyloxy c' 6XX 48 0 75.2 43.9 79 5 55.3 80.1 53.5 79.5 40.7 28.0 137 1 169.1 123 3 2 0 8 23 7 Flexuosin A I6YO C17//2406 c 5% 5 6 9 77.4 41.8 79.5 52.5 67.9 50.3 75.3 44.0 28.8 1360 I694 120.7 21 2 IS 3 16Y1 C2OH2806 Pulchellin, 6a-hydroxy, 4-angelate A hXX 49.8 73.9 45.1 82.2 55 4 81.6 53.3 79.3 41.4 28.3 137.1 170.4 123.7 20.X 23 0 Pulchellin, 6P-acetoxy, 4-angelate 16Y2 C22FlWO7 c 6XX 5 0 0 74.7 44.3 82.3 51.3 76.8 58.0 6 7 4 40.3 2 8 . 7 1 3 6 . 0 1 7 0 2 1 2 0 . 7 20.5 20.1 Pulchellin, 6a-angcloyloxy, 4-isovalerate 16Y3 CZSH3607 c (IXX 164 7 3 2 4 3 7 80.4 51.3 81.9 55.2 76.8 40.4 27.3 136.5 169.4 113.4 29.0 21.5 Inuchinenolide C 1694 C19H2607 C' 32'J a 4 9 7 7 5 6 43.9 75.6 51.9 74.7 53.6 74.2 35.0 30.1 139.1 169.3 121.0 17.1 206 c I26 h 40 7 75 Xh 43 9 75 9' 52.0 74.8 53.7 74.2 35.0 30.1 139.3 169 7 121 4 17 I 2 0 6 16Y5 c'IY112607 nritannin ( 1 0 761h 4 4 0 753' 5 1 1 7 6 6 5 2 4 7 2 9 3 6 2 3 0 2 1386 1688 1200 1 5 9 204 C 10
419
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 27.--continued ~~
Mol. formula C-l C-2 1696 CI 7112406 51.Yb 78.2’ l6Y7 C19112607 51.Xb 77.3 1698 C19112607 51.7 77.5
No.
C-3
Name / Chemical shifts C-4 C-5 C-6 C-7
~
~~
~
Sol
&-
17.7
C
5YX
21.2’
17.5
C:
598
44.0 28.8 135.8 169.2 120.7 21.1
17.9
C
598
C-8
C-9
C-10 C-I1 C-I2 C-13 C-14 C-I5
51.2’ 75.8
44.1
28.8 136.6 169.9 120.8 21.0
Altcrnllln 39.7
78.5’ 52.3
63.9
(1S,2S,4H,SS,6H,7W,XS,IOH)-Cuul-l1(13)-cn-12,8a-ulide, 2,441 37.15 82.4
51.4 64.9
39.5
79.0 51.7
67.8
-
52.7b 75.2
Flexuusin A, 2-ucelyl
50.1 76.3
44.0
28.9 136.7 169.5 120.’)
Otber cilibon:. 1671 Ac: 170.8 21.2; 1672 fUuf: 177.0 34.2 18.9 18.8; 1673 2xAc: 169.5 21.2 169.5 21 4, 1674 Ac: 169.4 21.0 0Me: 56.7; 1676 2xAc: 169.8 20.6 169.6 20.6; 1677 3xAc: 169.7 20.9 169 5 205 169.3 20.5; 1679 Mebu: 176.7 41.2 26.5 16.4 11.6; 1680 Ang: 169.1 127.3 137.4 15.8’ 20.3 SCII. 165 0 115.4 158.7 27.2 17.9; 36820 Ac: 169.0 21.4; 1682b Ac: 168.6b 20.3; 1682c Ac: 169.4 21.4; 1683 A~ig: 165.7 127.0 138.6 20.0 15.4; 1689 Ang: 165.9 125.9 142.3 15.9 20.3; 1690 Ac: 170.8 20.2; 1691 Aug: 167.3 129.7 139.5 15.9 20.8; 1692 Ac: 169.1 17.9 Ang: 166.rl 127.7 138.3 15.7 20.9; 1693 (Val: 171.9 29.6 25.5 22.5 22.5 AJig: 166.9 126.7 140.8 15.7 20.2 3694a 2xAc: 170.0 21.1 172.3 21.1; 16Y4b 2xAc. 172.9 21.2 170.5 21.2; 1695 2xAc: 172.9 21.2 170.2 21.2; 1696 Ac: 170.3 20.4; 1697 2xAc: 170.5 20.4 1703 21.0’: 1698 2xAc: 170.9 20.4 170.5 20.2
R’
R’
R’
R’
1676
R = H
1670
H
H
1674
u-OW,
a-OAc
1677
R = AC
1671
Ac
H
1675
@-OH
@-OH
1672
iBut
H
1673
AC
Ac
1678
R’
,
co
1679
R = CHaOMebu
1680
1686
1681
R = @-OH
1682
R = B-OAc
1683
R
=
a-OAng
R’
R’
1687
u-OH
H
1694
OAc
u-OH
1688
a-OH
a-OH
1695
@-OH
~-OAC
1689
u-OH
a-OAng
1696
u-OH
@-OH
1690
u-OH
8-OAc
1697
a-OAC
@-OH
1691
u-OAng
a-OH
1698
a-OH
8-OAc
1692
u-OAng
@-OAc
1693
u-OiVd
a-OAng
R’
co
R‘
R’
1684
a-OH
a-CH,
1685
8-OH
B-CH,
420
M. BUDESINSKY AND D . SAMAN
Table 27.--continued hlol IiJrmuln
Name / Chemical shifts C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-lI C-12 C-I3 C-I4 C-15 I6Y9 CIY112608 Pulchellin, 6P.9P-diacetyl 45.7 74.6 42.4 80.0 52.6 78.7 52.3 68.3 79.4 35.0 136.6 170.6 120.5 16.5 17.4 1700 C22H.3008 IS 2s 4R.S 6&7S 8R 9blOS Pseudoguai-11(13)sn-8,12-olide,
Nil
C-I
C-2
C-3
~
Rcl 6XX
6-a;.et~xy-2-;ngelo;lo~y~,6di~ydroxy
1701 1702 a h
4X.3 78.0 C2OffZ807 49 7 80.5 CZOIf3007 49.5 80.4’ 47.1 81 0
1703 C22H.WOX 4 6 4 80.0 I704 C25H.<608 49.8 77.1 1705 C2SN3808 499
77.1
1706 C20H3006
5 6 3 72.7 1707 C20113006 56.5 72.6 17OX CISH2004 a 52.1 163.3 h 55.5 161.5 1709 C20H260S 54.2 161.4 1710 C20H2605 54.0 161.9 1711 CISH2004 52.7 161.2 1712 C I 7 H 2 2 0 S 53.8 162.1
77.4 79.3
34.9 135.6 167.6 122.6 16.7 17.8
c
217
81.3 79.5
38.2 138.3 170.0 121.0
18.3 17.9
A
326
79.Zb 53.3 64.8 47.6 81.3b 79.4b 38.1 138.3 170.0 121.0 18.3 17.8 80.0 52.9 79.0 49 1 64.4 78.9 37.7 137.9 172.4 120.7 22.4 22.3
A
c
326 6nn
40.2 78.6 52.2 63.9 46.9 Pulchelloid A
41.4 79.3 53.3 64.8 47.6 Pulchelloid
41.3 43 9
B = Pulchellin, 6p,9fbdihydrnxy, 2-isovalerate
Pulchellin, 4-0-acetyl-6P,9pdihydroxy,
2-angelate
38.0 82.3 51.3 79.7 49.8 64.1 79.0 36.4 135.7 170.5 122.2 171 1s 2s 4 5s 6R 7s 8R 9R,lOS)-Pseudoguai-ll(l3)-en-12,8-olide,
17.6
c
6XX
38.0 81.9 51.4 64.5 46.5
17.7
c
217
~-a~ghlo~nx~-6~9-dihyhroxy4~valeroyloxy 80.1 79.7 36.1 135.8 167.2 122.2
16.6
3 8 1 81.9 51.3 64.5 46.5 80.1 79.6 36.2 135.8 167.2 122.2 16.9 17.7 Pseudoguai-11(13)-en-12,8a-olide, 2a,lS-dihydroxy-4~-(2’-methylbutyrylcrxy) 39.2 81.8 50.1 32.3 44.6 81.7 44.1 28.5140.2169.8119.8 20.7 64.8
217
275
Pseudoguai-11(13)-en-12,8a-olide, 2a,4~-dihydroxy-15-(2’-methylbutyryloxy)
41.9 80.5 4 9 5
33.4 44.6 81.6 44.1 28.8 140.1 1696 1199
20.6 65.1
27i
Plenolin
129.4 212.3 57 4 69.0 50.9 79.9 40.4 25.7 4 0 2 178.6 130.1 212.0 58.8 67.3 48.1 78.0 38.3 27.8 35.7 178.5
I I 4 19.7 10.0 20.1
IX0 19.1
22 1
73i
Plenolin, 6-0-angeloyl
129.3 208.9 54.8 71.7
48.8 79.3
41.0
25.8 40.4 178.5
11.0 19.7
17.6
335
129.3 209.3 54.8 70.9 48.9 79.6 40.9
25.9 40.5 178.9
11.1
19.8
17.7
68I*
19.7 14 8
240
Plenolin, 6-0-senecioyl Helenalin, Il~,l3-dihydro
1302 210.5 56.4 71.3 55.1 75.8 44.7 28.2
50.2 178.2 20 1
Arnicolide A
129 4 209.5 54.7 72.0 48.9 79.4 40.8 25.8 40.4 Arnicolide B 53 8 162.0 129.3 209.3 54.6 71.6 48.9 79 4 40.8 25.7 40.4 C19H2406 Radiatin 49.5 161.7 130.0 209.0 54.5 72.2 47.0 84.7 78.1 32.8 40.5 CZOH2606 Fastigilin A 49.7 161.5 130.0 209.2 54.5 71.6 47.2 84.8 78.0 32.7 40.5 CZOH2606 Fastigilin B 49.3 161.5 130.0 209.2 54.4 70.6 47.2 84.8 77.9 32.8 40.5 CI S H I 904Cl Aromatin, 11,13-dihydro-13-chloro-l lp-hydroxy 44.6 159.4 130.4 212.0 51.3 26.9 54.5 78.5 35.4 26.7 76.7 CISHZZ04 Helenalin, 2,3,11,13-tetrahydro 47.3 24.3 35.1 217.7 54.3 69.8 53.6 76.7 44.9 29.5 50.2 C17H2405 Confertin, 2a-aeetoxy-1laJ3-dihydro 389 69 I 4 2 5 213.7 5 1 7 36.2 48.2 79.5 28.4 26.4 38.3 CISH2004 Helenalin, dehydro, tetrahydro 50.5 21.8 33.5 218.2 65.5 203.1 55.3 76.5 40.2 28.2 37.8
c
178.8
10.9
19.6 17 5
1789
10.8
19 6
17 5
I26
178.0
10.8
15.8
17 3
516
178.2
10.8
15.7
17.3
516
178.1
10.8 15.7
17.4
516
126
1713 C20H2805
1714 1715 1716 1717 1718
1719 1720
1721 CISH2204 46.0 22.3 1722 CI iNZ4OS 47 9 22 5 1723 C18H2606 52.0 79.5 1724 CZOHZR06 54 9 69.0
18.9
c
-454
19.8 15.8 17 3
c
240
175.6 48.2 176.2
25.3
178.0 10.3 21.3
17.4
C
99
177.3 21.2
10.0
C
166
19.9
Helenalin, tetrahydro
36.3 221.1 55.4
70.0 50.4 80.2
38.5 27.0 40.0 179.5 20.3
11.0 12.5
c
I66
39.0 27.3 40.2 178.0 20.3
10.5
12.1
c
I66
10.5 15.6
C’
I66
Helenalin, tetrahydro, aettyl
35.2 217.0
53.6 72.9 48.1 79.5
Helenalin, trahydro, acetyl, 2a-methoxy
40.3 217.0
53.0 73.6 48.2
77.0 39.0 29.2 41.5 178.5
19.7
79.3 39.7
10.5 21.4
Arnifolin, 11.13-dihydro
45.4 212.9
56.4 71.8 47.6
27.0 40.1 178.8
14 I
C 33.5
421
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 27.4ontinued Mol. formula Name / Chriiiical shifts C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 Flexuosin B 1725 CZOH2806 54.5 69.5 45.4 213.0 56.5 71.1 47.7 79.5 39.6 27.1 1726 CZOH2806 Plenolin, 2,3-dihydro-Za-O-senecioyl 52.0 72.2 44.6 215.1 57.5 67.0 43.2 77.2 37.6 29.4 1727 C20H2806 Autumnolide, lla,l3-dihydro, 4-0-tigloyl 50.3 60.0 60.0 76.6 59.9 69.2 49.1 79.4 37.9 25.1
No,
C-11 C-12 C-13 C-14 C-15
Sol Ref.
40.2 179.1 10.6 21.5 14.2
C
677
35.1 178.9
9.5 20.6
14.0
C
221
39.4 179.3 10.8 21.3
13.8
C
335
Othercarbons 1699 2xAc: 168.3 19.8 169.8 20.4 1700 Ang: 169.6 127.4 138.7 15.7 20.4 Ac: 170.7 21.0. 1701 Ang: 167.9 129.2 137.3 20.7 15.8; 170211 iVal: 172.7 44.3 26.3 22.7 22.7; 1702h iVal: 169.7 40.9 25.9 17.9 17.5; 1703 Ac: 169.0 21.1 Ang: 167.3 127.4 138.0 15.6 20.3; 1704 Ang: 168.9 127.3 138.6 15.7 20.4 iVal: 172.4 43.5 25.7 22.4 22.4 1705 Mebu: 175.9 46.4 22.3 17.0 11.8 iVal: 172.4 43.5 25.7 22.4 22.4; 1706 Mebu: 175.8 41.2 26.8 16.6 11.5; 1707 Mebu: 176.4 41.3 26.6 16.5 11.6; 1709 Ang: 165.9 127.0 138.6 15.6 20.4; 1710 Sen: 164.8 115.3 158.0 20.4 27.5; 1712 Ac: 169.6 21.0; 1713 iVal: 171.6 43.3 25.6 22.3 22.2 1714 Mac: 166.0 136.0 126.2 18.1; 1715 Ang: 166.3 127.3 139.3 15.7 20.4; 1716 Sen: 165.0 115.3 158.5 20.4 27.3; 1719 Ac: 170.6 20.8 1722 Ac: 169.4 20.9; 1723 Ac: 169.2 20.9 OMe: 56.8: 1724 Ang: 165.8 127.0 138.9 15.8 20.7; 1725 Sen: 164.9 115.4 158.6 20.4 27.4: 1726 Sen: 166.0 115.0 158.7 20.2 27.3: 1727 Tig: 167.5 127.7 138.5 14.5 12.0
R'
R2
1699
H
AC
1700
Ang
H
R'
R2
1701 1702
Ang
n
1703 1704 1705
Ang
Ac
Ang
iVal iVal
1706 1707
iVal H
Mebu
R'
R2
Mebu
H
H
Mebu
1708 1709 1710
R = ti R = Ang R = Sen
co 1711 1712 1713
1714 1715 17%
R = H R = Ac R = iVal
1718
1717
R = Mac R = Ang R = Sen
AcQ
co
co 0
0
1719
0 1720
1721 R = n 1722
o,,:qco TigO
& 1727
R = AC
R'
R'
1723
CH3
AC
1724
ti
Anq
1725 1726
ti
Sen
Sen
H
422
M. BUDESINSKY AND D . SAMAN
Table 27.-continued No
1728 1729 1730 1731 1732 1733 1734 1735 1736 1737 1738 1739 1740 1741 a h 1742 1743 1744
hlol. formula C-l C-2 CISH2404 42.4 22.5 CI7H2605 45.5 22.3 CI 7H2605 43.0 22.7 C19H2806 43.2 23.0 C21H3008 50.2 76.6 C2lH3008 50.0 77.3 C20H3007 49.5 77.8 C17H2205 153.7 119.1 C151f2004 59.9 165.0 C17H220S 598 164.7 C17HZ205 52 7 161.1 C30H4405 49.6b 161.5 C17H2004 150.1 122.7 C17H2205 543 162.6 54.1 161.4 5 4 7 162.3 C17H2405 48 3 2 4 7 48.6 24.2
Name I Chemical shifts C-4 C-5 C-6 C-7
C-8 C-9 Rudmollin. lla.13-dihydro 29.6 80.7 47.7 26.1 38.4 80.4 36.5 Rudmollin, 15-O-acetyl-llaJ3dihydro 29.7 82.3 53.5 90.1 43.4 83.9 24.8 Rudmollin, 4-O-acetyl-lla,lMibydro 25.3 80.2 46.7 36.3 38.3 78.5 29.2 Rudmollin, lla,l3-dihydro, diacetate 24.5 80.0 46.6 36.0 38.0 78.0 26.4 Hymenolane B 80.1 72.0 41.1 41.3 37.6 72.1 34.4 Hymenolane 72.2 80.3 41.0 34.9 37.9 72.6 29.5 C-3
C-10 C - l l C-12 C-13 C-14 C-15 37.4
29.2 178.8
10.5
17.4 65.9
C
653
32.8
29.9 170.2
10.9
17.0 61.8
C
653
37.1
29.7 179.5
10.5
16.8
65.1
C
653
37.3
29.0 178.4
10.3
16.4 63.7
C
653
38.8
42.0178.4
17.0 18.4 20.3
C
227
29.5
37.9 178.0
10.2
c
282
18.5
20.5
laH,10pH-Pseudoguaian-l2,8~~lide,Za-tigloyloxy4~,lla,13-trihydroxy 42.5 78.4 45.5 29.3 40.7 81.0 Heleniamarin, is0 40.1 215.8 59.3 69.4 53.0 76.9 Tenulin, desacetyl, 1-epi, is0 54.9 72.6 53.1 77.3 133.4 a Tenulin, 1-epi, is0 133.3 210.4 54.1 72.8 52.2 77.7 Tenulin, iso 130.3 210.6 54.5 66.0 55.1 75.8 Aestivalin 129.3 209.2 54.7 70.8 53.1b 83.8 Tenulin, pyro 39.7 217.6 53.5 78.6 60.2 75.5 Tenulin (C-16 epimers) 130.4 212.7 56.3 77.4 63.3 76.5 130.6 212.8 55.9 76.0 63.2 77.2 130.0 212.3 55.3 74.0 63.8 76.0 Tenulin, dihydro (C-I6 epimers) 34.6 221.6 54.5 78.4 61.7 76.1 34.5 221.2 53.5 74.8 62.0 75.6
Sol Ref.
35.4
29.5
79.0 176.8
66.5
20.9
21.7
c
220
43.6
28.2
38.5 177.2
12.3
19.6
20.5
c
186
36.9
28.3
39.2 178.0 23.6
23.0
12.1
C
185
36.5
29.2
39.4 177.2 23.6
22.8
11.8
C
I85
447
27.2
37.0 177.4 20.6b 19.7
13 9
s
310
.78.0
32.1
55.9 179.9
17.4
C
307
41.3
29.8
56.5 175.4 21.2b 16.2 19.2b
C
310
42.9 42.4 42.5
28.4 27.9 28.0
58.8 176.4 18.3b 19.6b 19.9* 58.3 176.0 18.3 19.4 19 8 58.8 176.4 19.0b 20.4b 204b
C C
310 126 310
42.4 42.0
30.8 30.3
58.5 175 6 58.3 177.6
18.0b 13 7 I Y 8' 18.5b 13.8 19.6'
c
310
C
310
21.3'
13.7 I 9 7'
C
310
20.6'
14.8
13.8
C
310
23.4
26.0
120
C
1x5
20.1
14.8
18 7
c
310
21.7
8.6
14 5
C
I66
21.4
9.6
275
c
11.4
12.4 20.3
C
175
11.8
20.9
17 8
C
175
11.7 20.9
17 7
C
I75
20.5
170
C
I75
28.1 207
17 3
C
I75
30.0
17.4
C
175
1745 C17H2204 Tenulin, anhydro, dihydro 48.4 24.4 34.4 220.3 53.4b 49.1 59.6 75.3 41.8 30.3 54.4b 75.4 1746 C17H2405 Tenulin, dihydro, is0 47.3 24.3 35.1 219.8 54.3 67.5 53.6 75.9 44.9 29.5 37.0 177.6 1747 C17H2405 Tenulin, dihydro, 1-epi 524 20.2 36.5 219.1 54.2 72.0 52.6 77.2 34.9 27.9 39.4 177.4 I748 C15H2004 Tenulin, dihydro, iso, 6-desacyl-6-0x0 47.8 23.0 35 8 209.7 61.0201.6 61.8 76.5 44.9 29.2 36.8 177.2 1749 C15H2004 Helenalin, iso, 2,3-dihydru 43.3 22.5 39.7 221.0 54.6 68.1 161.6 78.2 37.4 29.8 125.8 174 2 1750 CISH2003 1~H,1O~H-Pseudoguai-7(ll)-en-12,8~-olide, Lox0 65.1 218.0 34.4b 35.8b 44.4 32.5b159.1 82.1 35.6b 25.8 125.8 174.6 1751 C18H2405 Helenalin acetate, Z,J-dihydro, cyclopropane 4K.O 22.4 35.0 216.2 53.7 76.6 48.0 78.8 39.0 27.3 26.6 178.8 1752 ClXH2205 Helenalin acetate, cyclopropane 53 3 I 6 1 9 129.3 209.0 54.7 75.6 48.9 78.6 40.2 26.0 26.6 178.9 1753 ClliH2005D2 Helenalin acctate, (13a,13a-di2H,)cyclopropane 53.4 161.7 129.4 208.9 54.8 75.6 46.9 78.6 40.3 26.1 26.5 178.9 1754 C18H2UOSF2 Helenalin acetate, difluorcyclopropane 53.4 162.0 128.9 208.5 54.4 74.7 43.9 79.8 40.2 25.8 37.5 170.8 1755 ('18H2005CI2 Helenalin acetate, dichlorcyclopropane 53 5 162.0 129.0 208.4 54.6 75.3 48.9 79.5 40.3 25.9 42.3 171.1 1756 CIXH2005Br2 Helenalin acetate, dibromcyclopropane 53.6 161.8 129.2 208.6 54.9 75.4 52.0 79.3 40.5 26.0 40.5 171.8
30.2
18.0
15.6
20.5
C
387'
423
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 27.--continued ~
Orher carbons: 1729 Ac: 170.9 21.1; 1730 Ac: 170.8 21.2: 1731 2xAc: 170.9 21.0 170.7 21.0: 1732 169.2 20.0 169.4 20.2 170.7 20.6; 1733 3xAc: 170.9 20.5 169.6 20.5 169.6 20.5; 1734 7 q : 167 X I28 5 137.7 14.4 12.0: 1735 Ac: 170.1 20.0; 1737 Ac: 170.2 20.6 1738 Ac: 169.2 20.0b; 1739 Auy: 1 6 4 . X 127 2 138.4 15.4 20.1 C - 1 ' - C-10': 147.4 121.2 38.3 42.9 29.4 36.8 19.9 72.8 29.2 26.0; 1740 C 1 6 . CI7: 161.4 83.7: 1741a C16 - C17: 108.4 24.7; 1741b C16 - C17: 108.2 25.0; 1742 C16 - C17: 105.2 27.3; 17433 C16 - C17: 107.6 24.6; 1744 C16-CI7: 104.4 26.8; 1745 C16-Cl7: 162.0 82.7; 1746 Ac: 169.2 19.P. 1717 Ac: 170.2 20.6; 1751 C-130: 20.4 Ac: 169.2 20.9; 1752 C-130: 18.9 Ac: 169.4 19.7; 1753 C - I ~ O :n Ac.. 169.5 19.8; 1754 C-130: 110.4 Ac: 169.1 19.3: 1755 C-130: 62.3 Act 168.8 19.5: 1756 C-130: 2X 3 A <
168.7 19.6
co
R'
R'
1732
R = a-CH,
H
H
1733
R = 6-CH,
1729
H
Ac
1730
Ac
H
1731
AC
AC
1728
1734
1735
, i
1736
R = H
1737
R = Ac
1738
$,
1739
1740
on
CG
0 R'
R'
R'
R'
1746
R = a-H
1741
CH,
OH
1743
CH,
OH
1747
R = 8-H
1742
OH
CH,
1744
OH
Q3 .
&
1749
1748
CH, =CH2
1745
0
:
\ co
\ co
1750
1751
1752
R = ti
1753
R
1754
R = F
1755
R = CI
1756
R = Br
= D
424
M. BUDESINSKY AND D. SAMAN
Table 28. Carbon-13 chemical shifts of modified pseudoguaianolides. Mol lormula Name I Chemlcal shifts c.1 c-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-ll C-12 C-13 Altamisic acid 1757 ('ISH2005 133 X' 25.4 34.W 179.0 76.9 85.7 41.7 34.5' 25.4 132.5b138.4 170.2 120.1 1758 ( ' r 7 l ? W S Altamisin a I34 3 25.7 34.3 173.9 86.5 85.9 41.9 35.0 25.7 132.4 138.8 170.2 120.1 h 134,(1' 25.6 34.0'173.7 77.9 85.7 41.7 34.8' 25.6 132.3b138.5 170.1 120.0 175Y ('17N2606 no name 134.0 26.4 34.7 174.2 76.6 86.6 40.1 34.7 25.6 132.6 45.9 a 69.9 1760 CISNIX04 Psilostachyin B a 133.3 25.2 34.8 170.9 80.7 83.5 41.5 30.0 26.0 126.1 138.5 169.8 120.6 b 133.0 25.0b 34.6 170.5 86.7 83.2 41.3 29.7 25.8' 125.9 138.3 169.5 120.3 1761 C I S I f 1 6 0 S Paulitin 61.5 140.3 127.3 160.3 85.8 81.2 39.2 31.1 25.6 66.8 138.9 169.1 121.9 1762 CISHI605 Paulitin, is0 62.0 146.9 123.6 160.0 85.6 82.0 41.7 32.0 22.8 71.0 137.6 169.0 121.1 1763 CISH2004 Psilostachyin C 43.0 22.6 31.6 168.8 89.8 86.2 41.3 30.9 24.0 35.3 138.3 169.4 120.2 1764 C/5//2005 Psilostachyin 79.4 24.4 27.5 177.1 93.6 83.4 41.6 30.2 26.9 40.1 138.8 169.5 121.6 1765 ClSH2005 Canambrin 78.3 22.5 29.1 176.5 91.7 82.3 41.4 29.3 26.7 40.6 138.5 169.3 121.3 1766 CISHZOOS Cordilin 77.7 23.2 28.5 176.7 92.0 83.3 41.0 28.8 26.4 39.8 140.0 169.7 120.4 1767 CISH220S Ambrosan-12,6-olide-3-oicacid, 4-nxo-3,4-seco 43.5 30.7 176.7 203.7 55.9 85.3 41.6 23.4 29.4 37.1 40.6 178.4 10.5 1768 CI 7H240.5 Pulchell-Sene, neo, 4-0-acetyl4,5-seco 56 I 69.0 34.9 62.2 138.9 121.6 45.0 80.8 36.6 27.6 138.6 171.3 116.6 1769 C17H2405 PulchellJ-ene, neo, 2-0-acetyI4,5-seco 53.2 71.0 35.9 58.5 138.6 122.0 44.7 80.2 36.9 28.0 138.2 170.9 118.9 1770 ClSH2004 Hymenoratin C 36.5 102.8 138.1 99.8 35.8 41.9 38.8 77.0 34.6 28.2 140.5 170.4 122.9 1771 CISH220S Hymenoxon, 3-epi 32.1 42.1 93.1102.0 36.6 32.4 38.6 76.9 35.1 30.3140.5170.3122.8 1772 C17H2805 Hymenolide, 3-epi 32.8 42.3 93.2 107.4 36.8 33.1 38.3 76.7 35.0 30.7 140.8 170.1 122.2 1773 C19113006 no name 39.6 38.7 97.2 91.5 39.1 31.0 37.7 76.3 35.2 30.3 139.9 169.5 123.0 1774 C15H220S Hymenoxon 37 6 41.5 90.7 102.0 37.9 33.9 38.6 76.9 34.9 30.3 140.6 170.3 122.6 1775 CI9H2607 Hymenoxon diacetate 37 5 30.5b 90.4 99.9 38.6 40.4b 38.7 76.0 34.8 30.3 139.9 169.3 122.7 1776 Cl711280S Hymenolide 3X 3 41.6 90.8 107.6 37 8 34.2 38.8 76.7 34.9 30.4 140.4 170.0 122.2 1777 C19H3006 no name 387 40.5 97.4100.6 37.8 31.8 38.6 76.2 34.8 30.5140.1169.3122.5 1778 C19H2607 Hymenovin B, diacetate 37.8 30.1b 92.3 94.6 43.0 38.2' 39.0 76.0 35.1 30.8 139.5 169.3 123.3 1779 C20H3006 Hymenoratin B 47.9 65.2 65.7 98.0 40.9 36.4 43.4 86.2 42.9 28.5 139.5 170.2 119.0 No
C-14 C-15 -Sol Ref 24.4 22.6
C
458
24.7 22.8 24.5 22.6
c C
108 458
24.9 226
C
597
23.7 23.1 23.5 22.8
C
c
458
24.2 21 0
c
I08
20.Y
21 9
c
108
18.9 144
c
108
21.6
15.1
C
lox
21.4
15.0
c
lox
20.3
15.1
c
597
22.0 21.0
108
P 21,610
23.4 26.4
C
635
23.1 25.8
C 615
19.4 19.Y
c
20x
20.1
19.6
c
252
20.0
19.6
C
252
20.7
13.8
C
252
20.1 20.1
C
252
20.0 21.0
c
208
20.0 20.0
C
252
20.1 20.1
C
252
20.8
14.6
c
208
20.0 22.6
c
208
Othercarbons: 175th 0 E f : 60.2 14.3: 1758b 0.9: 59.9 14.1: 1759 2xOMe: 51.3 59.1: 1768 Ac: 170.2 20.7; 1769 Ac: 169.7 20.8; 1772 0 E f : 64.9 15.1; 1773 OEf: 63.0 14.9 Ac: 170.1 21.0; 1775 2xAc: 169.1 20.0 169.3 21.0; 1776 OEf: 63.5 15.1: 1777 0 E f : 64.5 15.0 Ac: 170.3 21.0; 1778 2xAc: 168.7 21.0 169.6 21.0, 1779 Mebu: 175.4 41.7 26.4 11.7 16.7
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 28.--continued
ROOC
H&OOC*
0-co 1757
R = H
1758
R = Et
CH,OCH, 0.
o&
0. co
co
O-co 1760
1759
la.10a-epoxy
1762
18.108-epoxy
1767
1766
1764 [lS]
1763
1761
1765 [lR]
R'
1770
R'
R'
R2
1768
H
AC
1771
a-OH
a-OH
1769
Ac
H
1772
a-OH
a-OEt
1773
a-OEt
8-OAC
1774
@-OH
a-OH
1775
8-OAc
a-OAc
1776
8-OH
a-OEt
1777
8-OEt
a-OAC
1770
B-OAc
P-OAC
~
~
1779
425
426
M. BUDESINSKY AND D . SAMAN
4.3.5. Elernanolides Carbon-13 chemical shifts of 51 elemanolides (cis or trans lactonized into position 6 or 8 and some with modified skeleton) are summarized in Table 29. The biogenesis of elemanolides most likely involves Cope rearrangement of g e r r n a c r a n ~ l i d e which s ~ ~ ~ had also been frequently used in preparation of some elemanolides or in structure elucidation of germacranolides. 13C NMR spectra of common elemanolides show characteristic signals of olefinic carbons C-1, C-2, C-3, C-4 of two vinyl groups (see Table 29 and ref. 133). Data on a series of natural and synthetic eleman-12,6-olides [1782, 1783, 1790-1793, 1795, 17961 are described and substituent effects discussed in ref. 133. Pedro et had also synthesized a series of eleman-12,8-olides [1798, 1804, 1807, 1810, 1811, 1814, 18151 from eudesmanolide artemisin [880] as starting-material and described their 13C NMR data. Herz and c o - w ~ r k e r s ' isolated ~~ unusual dihydrooxepin-type elemadien-12,8-olides [1825-18291, which were characterized by 13C NMR data. Data on other elemanolides in Table 29 are split over refs 32, 33, 58, 79, 122, 132, 150, 170, 171, 213, 237, 281, 316, 321, 497, 563, 616, 636 and 648. X-ray structure analysis is described together with 13CNMR data for two elernan-l2,&olides: dehydroelemanshkuhriolide [1818]171 and micordilin [ 18231.316
4.3.6. Erernophilanolides Carbon-13 NMR data of 55 eremophilanolides are given in Table 30. Most of these compounds have cis-annelled six-membered rings and 7( 11)-double bond. The configuration at C-8 then determines the stereochemistry of the molecule as 8P-steroidal or 8a-nonsteroidal (Fig. 24). Naya et ~ 1 synthesized . ~ some ~ ~ pairs of 8-epimeric eremophilenolides [1835-1838, 1841-1844, 1870, 18731, from furanofukinol and proposed a procedure to distinguish the stereochemistry of the epimers from 'H NMR (interproton homoallylic coupling between Me-13 and H-6a indicates 8a-configuration) and I3C NMR (upfield chemical shifts of olefinic carbon C-7 in 8P-epimers reflect shielding arising from cis-type arrangement in steroidal conformation). 13C NMR data of a large series of eremophilenolides were described by Sugama et The signals were assigned by mutual comparison of data, selective proton decouplings and shift calculations using Beierbeck's parameter^.^^" Chemical shifts of C-1, C-4, C-5, C-7 and C-10 appeared upfield in 8P-series. Carbon signals in six natural eremophilenolides [ 1851, 1862, 1863, 1866, 1871, 18721 were assigned by HMQC and HMBC correlation experiments.425 The most important correlations were found between the high field CH, Me-14 and Me-15 protons and quaternary carbons C-4 and
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
( 8 8 ) STEROIDAL
427
(8a) NONSTEROIDAL
Fig. 24. Steroidal and nonsteroidal conformation of furoeremophilenolides with SPand Sa-configuration.
C-5. Considerable variation of a-effects and some conflicting P- and y-effects were noticed. C,H-COSY and COLOC experiments have been used for the assignment of carbon signals of istanbulin B [ 18471,455 3P-angeloyloxy-1OPlop-epoxyhydroxyeremophilenolide [18521,3 3P-acetoxy-6P-angeloyloxy-lp, 8P-hydroxyeremophilenolide [18651,'04 and 6a,8P-dimethoxy-lOPhydroxyeremophilenolide [18671. 3 Bohlmann et ~ 1 . described ~ ~ ' I3C NMR data of unusual natural 8-epimeric dilactones [1879, 18801 which afforded 8,9-seco derivatives 1881a, 1881b, 1882 by methanolysis and compounds 1883a, 188313 through following methylation. X-ray structure analysis has been described together with 13C NMR data €or tollucanolide C [ 18531.509
428
M. BUDESiNSKY AND D. SAMAN
Table 29. Carbon-13 chemical shifts of elemanolides. Mol formula
No
1780 1781 1782 1783 1784 1785 1786 1787 1788 1789 1790 1791 1792 1793 1794 1795 1796 1797 1798
1799 1x00
1801 1x02
1x03 1x04 a
h 1x05
IXIM ~.
Name I Chemical shifts
C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-I0 C - l l C-12 C-13 C-14 C-IS Sol kf CISH2004 5aH-Elema-1,3,11(13)-trien-12,QI-olide, 8aJ4dihydroxy C 616 143.2 114.4 124.1 143.2 44.2 75.0 46.4 69.9 32.6 29.7 138.3 170.1 115.2 ‘64.9 26.0 C17H2205 5aH-Elema-1,3,11(13)-trien-1Z,Qslide, 14-acetoxy-&-hydroxy C 616 142.3114.2124.3l42.3 41.8 75.1 46.2 70.0 33.1 29.7138.0l70.6115.3 66.6 26.1 ClSH2004 Melitensin, dehydro C 133 146.1 112.7 114.9 143.9 50.6’ 78.8 55.0’ 67.5 49.8 41.9 137.4 169.7 120.5 18.9 67.3 C19H2406 Melitensin, dehydro, 8-0-(4’-hydroxymethacryloyl) 145.6 113.2 115.2 143.6 50.6b 78.6 52.3b 69.7 45.0 41.9 136.6 a 120.2 18.7 67.4 c 133 C2OH2607 Melitensin, dehydro, 8-0-(2’-(1”,2”-dihydroxyethyl)acryloyl) 145.6 113.1 15.1 143.6b 50.6 78.7 52.4 69.7 45.0 41.9 139.0b 169.1 120.1 18.4 67.3 c 122 ClSH2003 5aH-Elema-3,11(13)-dien-12,6a-olide,243x0 55.1 201.9 17.6 139.2 55.8 80.8 49.2 21.8 38.3 39.8 140.4 170.2 117.4 21.4 22.3 c S63 ClSH2003 5~H,lOaCH,,Il~H-Elema-l~,-dien-l2,6~-oIide, 8-0x0 144.0 112.5 15.6 141.3 54.4 79.2 55.4 206.3 50.1 41.0 37.7 176.3 14.3 18.8 25.1 c 33 CISH2203 5~H,10aCHl,11~H-Elema-1,3dien-12,6~-olide, &-hydroxy 147.1 111.4b 15.2’ 141.6 50.0 77.9 53.1 67.9 41.9 39.8 37.4 178.5 14.4 21.2 24.5 c 32.33 C20H2804 5~H,10aCHl,ll~H-Elema-1,3dien-12,6f3-olide, Sa-angeloyloxy 146.6 111.7b 1S.lb141.3 47.5 77.1 53.5 69.0 38.2 39.9 36.7 1774 14.0 20.2 24.6 c‘ 12.37 C22H3006 Laserolide, iso 145.6 116.3 11.4140.1 5 3 0 75.6 46.2 6 7 3 40.1 389 77.8174.2 20.9 22.5 2 2 9 C 321 CISH2203 Epitemisine 148.1 115.6 21.5 140.7 59.Xb 75.9 56.6b 65.5 46.1 42.7 36.9 178.9 12.3 21.2 23 5 C 133 ClSH2203 Il~H-Elema-1,3-dien-l2,6a-olide, Su-hydroxy 146.9 111.9 15.8 140.3 58.3b 78.6 55.2’ 69.1 49.6 42.0 41.5 178.7 14.4 19.7 23.8 C 133 11~H-Elema-l,3-dien-12,6a-nlide, 8aJS-dihydroxy CISH2204 146.4 112.6 14.6 144.4 50Sb 78.7 58.4‘ 68.9 49.6 41.7 41.6 178.4 14.4 19.0 67.4 C 133 C19H2606 Il~H-Elema-1,3-dien-l2,6a~lide, 8aJSdiacetoxy 145.7 113.1 16.7 138.9 51.3b 78.0 56.0b 69.9 45.0 41.6 41.0 177.7 13.9 18.9 67 2 c 133 5aH,11~H-Elema-l,3,-dien-12,6a-olide, Yp,lS-dihydroxy ClSH2004 C 132 144.5 115.1 16.8 144.0 49.3’ 80.2 48.9b 29.8 74.7 48.4 41.5 178.6 12.5 1 0 4 67 3 C2IH3403Si ll~H-Elema-1,3-dien-12,6a-olide, 8a-r-butyldimethylsilyloxy C 171 147.2 111.6 15.4 140.4 58.3b 78.6 55.2b 69.5 49.7 41.8 41.2 178.8 14.4 19.5 23 6 11~H-Elema-1,3-dien-l2,6a-olide, 8a-r-butyldimethylsilyloxy-15-uxo C2IH3204Si C 133 146.0 112.3 137.7 145.3 46.6b 77.4 58.6b 69.5 49.4 41.7 41.4 178.6 14.4 1 8 3 1937 C19H2207 Vernndalin, Ilp,l3-dihydro C 213 139.2 116.1 164.5 129.8 40.5 ‘17.0 53.8 68.9 38.0 40.0 45.7 176.8 13.8 7 0 0 1348 CISH2002 SaH-Elema-1,3,11( 13)-1rien-l2,S&nlide c 7x 148.1 111.2 112.9 146.0 48.9b 30.1 40.2b 76.1 40.1 39.3 141.1 170.5 120.8 1 9 2 2 4 4 CISH2003 5aH-Elema-1,3,11(13)-trien-I2,8~-olide, 6a-hydroxy c 5x 147.8 111.7 114.2 143.1 57.1 69.4 47.1 76.6 39.3 39.6 138.9 170.2 123.4 1 9 6 26X C19H260S Zempaolin A r sx 146.1 112.6 113.6 144.3 50.6 70.3 46.4 76.5 38.9 40.1 138.2 169.3 122.8 1 8 9 67 3 CI9H2S05 Zempaolin B c 5x 145.5 113.0 136.9 145.8 43.5 69.3 46.3 76.7 38.7 40.4 138.1 169.2 122.9 175 1939 CZOH2806 Schkuhridin A C 170 142.2 115.6 114.3 142.3 56.3 69.7 46.5 75.0 33.0 42.2 138.2 169.8 124.0 6 7 3 259 C24H3208 Schkuhridin, diacetyl C 170 142.0 116.6 114.8 140.2 54.3 71.0 45.3 75.0 32.6 42.4 137.2 168.9 123.6 6 6 9 248 CISH2002 5aH-Elema-1,3,11(13)-trien-12,Su-olide c‘ 7x 147.9 111.3 113.9 145.3 52.6b 27.7 49.4b 79.7 42.8 41.9 139.3 170.7 117.5 1 8 9 217 C’ 4‘J7 148.0l13.0111.0137.3 46.1 26.5 40.2 75.8 39.2 a 145.7 a 120.3 I 6 4 I!, 3 C19H2407 Elcman-1Z,Rcr-olide, 6a,l4-diacetoxy-15-hydroxy C‘ IF0 I41 6 114.9’ 115 9’ 142.9 50.6‘ 78.4 51.7’ 69.1 40.7 44.3 136.5 169.2‘ 120.2 67 2’ 66 7 (JIY112207 Zinaflorin I11 55 4 44.6 194.1 146.2 31.3 71.5b 43.0 71.6b 74.Sb 40.5 135.8 170.4 119.1 12.8 139 5 c‘ 2x1
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
429
Table 29.--continued Okercarbons: 1781 Ac: 170.8 20.8; 1783 Mac-4-OH:
a a 126.7 62.3; 1784 Acr-2-CH(OHJCH20H-165.2 136.7 71.2 64.8 127.5; 1788 Ang: 166.4 127.3 138.8 15.7 20.4; 1789 Ac: 169.8 21.0 Ang: 166.7 126 7 140.6 15.9 20.2; 1793 2xAc: 170.6 21.0 170.2 21.0 1795 TBDMS: 25.7(3) 17.8 -4.4 -4.1; 1796 TUUMS: 2533) 17.9 -4.4 -4.7; 1797 Mac4-OH: 162.9 138.4 125.8 60.8; Is00 B u t : 175.8 34.1 19.0 19.0; 1R01 ; B u t 175.7 33.9 19.0 18.8; 1802 iVal-2-OH: 174.7 75.4 39.1 15.4 11.7; 1803 iVal-2-0Ac: 169.7 76.4 36.6 15.3 11.4 170.5 20.7 Ac: 169.6 20.5; 1805 2xAc: 170.04 21.0 170.4' 21.0; 1806 Mac: 166.3 135.2 1266 18.3
1780
R = H
1782
R = ti
1781
R = Ac
1783
R = Mac-4-OH
1784
R = Acr-2-CH(OH)CHZOH
1787
R = H
1788
R = Ang
1785
...*
11,
1786
ROHZC
6-CO
R =
1793
R = Ac
0-CO
HOHZC
H
1792
1794
R'
R'
1802
R = H
1798
CH,
1803
R = Ac
1799
CH,
H OH
1800
CH,OH
OiBut
1801
CHO
OiBut
HOC
1806
1789
R
6-CO
1795
R = CH,
1796
R = CHO
1804
1790
R
1791
R = o - 3 ~
1797
1805
=
p-c'i
430
M. BUDESINSKY AND D. SAMAN
Table 29.--continued No
Mol formula
1807 1808
1809 1810
1811 1812
1813 1814
1815 1816
1817 1818 1819 1820 in21 1822 1823 1824
1825
Name / Chenucal shifts
C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C - l l C-I2 C-13 C-14 C-15 Snl Re1 CISH2202 SaH,11~H-Eiema-1,3-dien-l2,8~rslide c 7x 148.4 111.1 112.8 146.0 49.5 29.6 43.7b 76.7 39.9 38.6 42.9 a 14.3 18.7 24.5 CISH2202 Cailitrin 147.5 110.9 113.2 145.5 46.3 26.4 42.0 75.4 41.3 39.9 35.6 179.0 13.3 16.2 24.6 C 237 C20H3006 SaH,llaH-Elem-3-en-12,8~rslide, 6a-hydroxy-l4-(2'-hydroxyisovaleruyloxy) 31.3 7.9117.2142.4 57.0 68.0 47.0 75.1 32.8 39.7 41.6178.7 11.0 6 6 2 23.7 C 170 CISH2202 5aH,ll~H-Elema-1,3-dlen-12,&-olide 148.1 l 1 1 . 1 113.7 145.4 52.Xb 29.2 52.1b 79.4 42.3 41.9 41.4 179.3 12.5 18.8 24.5 c 7x C2IH2602Se krH-Elema-l,3-dien-l2,&-olide, 11s-phenylseleno 147.7 111.2 113.9 145.2 52.9b 27.1 56.6b 77.1 42.3 41.9 49.3 176.6 22.5 18.8 2 4 7 c 78 CISH2203 5aH,ll~H-Elem-I-en-l2,&-olide, 3,4-epoxy 147.2 111.8 56.1 57.0 53.Xb 26.0 51.Sb 78.9 43.6 41.4 41.4 179.1 12.5 1 9 . 6 ' 2 0 0 c 79 CISH2204 SaH,ll~H-Elem-1,3-dien-l2,&rslide,6a,lS-dihydroxy C 132 146.4 112.4 116.8 145.3 57.6b 76.4 57.4b 71.3 42.1 a 41.6 179.0 14.3 19.8 67.5 CISH2604 SaH,11~H-Eieman-l2,&rslide, 2,3-dihydroxy c 7s 43.9 58.0b 66.@ 41.8 33.1 23.6 51.6 80.0 41.7 38.8 41.5 179.9 12.4 13.7' 22.X C27H3202N2Se2 SaH,11~H-Eleman-l1,&-olide, 2,3-di-(o-nitrophenylseleno) c 7x 19.9 34.5b 40.1' 47.5 29.9 23.8 51.6 79.3 41.4 40.3 41.5 179.1 12.5 18.1' 21 6 CISH2202 5aH,11~H-Elem-3-en-12,&-olide, lp,2B-epoxy 5 8 8 44.5 114.8 144.6 50.1b 28.9 51.6b 79.1 37.0 38.8 41.3 179.1 12.4 23.6 16.7' c 70 CISHI603 Linderalactone, is0 143.6 114.8 123.7 136.6 46.8 72.2 113.6 152.6 34.9 40.9 119.8 138.6 8.2 18.7 206 c' 636 CISHI604 Elemamchkuhriolide, dehydro 133.1 118.4 115.7 141.0 53.3 80.9 42.7 72.9 39.8 47.6 134.1 168.4 124.1 176.2 2 1 3 C 171 CISH1804 Elemanwhkuhriolide 137.4 116.0b114.0b143.5 56.6 81.2 46.6 75.2 38.5 50.5 136.6 1702 122.5 101.7 25.0 C 171 CI9H2207 no name 81.8 65.5103.2142.9 31.4 69.5 43.1 74.0 68.6 42.0136.0169.6119.1 17.7 116.3 s 2x1 no name ~20~2407 81.8 65.5 103.2 142.9 31.4 69.5 43.1 74.0 68.6 42.0 1360 169.6 1191 17.7 1163 s 2x1 CI 7H2407 Micordilin, tetrahydro s 716 81.6 92.9 107.6 39.8 34.3 26.3 36.7 76 5 28.8 37.6 40.2 1696 8 9 63.0 I I 4 CI 7H2007 Micordilin s 316 82.0 93.3 104.2 144.3 35.7 24.0 35.4 75.3 27.1 38.2 141.2 169.2 108.2 61.9 120.9 CI 7HI807 Micordilin, dehydro 75.0 171.6 105.3 139.1 38.2 24.0 37.8 75.0 26.9 38.2 141.1 169.Zb113.8 61.1 121 6 s 716 CI9H2206 * 7R* 8R* 10R*)-Elema-l 3 11(13)-trien-12,8-oiide, 1~~-hpox3-15-lsobutanoyloxy-i49xo
104.4 142.5 143.8 115.8 41.8' 34.2' 40.4b 74.9 32.4' 53.2 141.0 169.4 20.7 1987 6 6 6 1826 CI9H2206 7R* 8s' 10S*)-Elema-1,3 ll(l3)-trien-12,8-olide, 1~~pox;-l5-:sobutanoyloxy-lqsxo I040 144.3b 144.5b 117.5 43.2 29.0 49.5 78.7 37.6 56.6 138.2 169.9 17.8 197.3 66 S 1827 CI9H2406 SS*,7R*,8S* lOS*)-Elema-l 3,l l(13 -trien-12,8-olide,
i'
176
C
176
109.3 142.2 144.4 117.5 43.1 29.0 49.6 79.8 39.5 46.7 138.8 170.5 17.3 70.4 67 2 1828 CI7H2006 SS*,7R*,8S*,lOS*)-EIerna-l,3,1 1(13)-trien-12,8-0lide,
C
176
70.7 65.5
C
176
712
66X 71.4' 667
C
176
1%
17:)
21.3
c
04s
1,3spoxy-14-hydroxy-15-lsobutnnoysx;
1.3-e~xy-14-acetoxy-lS-hydroxy .
1829
a b 1830
.
108.0 142.1b142Xb117.5 42.9 29.2 49.7 79.4 40.0 44.7 138.7 170.8' 117.5 C21H2607 *,7R*,8S*,lOS*)-Elem~a-l,3,ll(l3)-trien-l2,8-olide, f S3-epoxy-14-acetoxy-lS-isobutanoyioxy 108.4 142.6 144.4 117.6 43.9 29.1 49.6 79.3 40.0 44.7 138.6 170.5 117.5 108.7 142.1 144.3 117.5 44.0 29.2 49.4 78.7 40.1 44.6 139.6 169.5 116.1 CISHI803 Smyrnicordiolide 110.8 141.5 139.4 119.4 52.3 28.3 161.5 76.5 47.8 39.3 119.8 174.8 8.2
30.8
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
431
Table 29.-continued Otbercarbons: 1809 1Vul-2-0H: 174.7 77.1 39.2 15.4 11.7; 1811 SePh: 124.3 129.0(2) 129.6(2) 138.1; 1x15 ZxSel'h(2-NOJ: 125.4 126.3 128.6 131.2 133.6 146.3 125.6 126.5 128.7 131.4 133.7 146.7; 1820 Mac 166.2 135.7 18.2 126.2; 1821 rig: 166.7 127.9 137.8 14.5 12.3: 1822 Ac: a ; 1823 Ac: 169.9b 20.4: 1x24 Ac: 170.0b 20.6; 1826 ;Bit!: 176.7 34.1 18.9 18.9; 1827 iBuf: 176.9 34.0 18.9 18.9; 1828 Ac: 170.4 2 0 % 1829a rBiri: 176.8 34.1 19.0 19.0 Ac: 170.3 20.8: 1829b ;Bur: 176.2 34.3 19.0 19.0 Ac: 1696 20.3
y"-" p.
1807
1808
1810
1809
1811
R = R =
-I
SePh
...o, o* 1813
1812
1814
R = OH
1815
R = SePh(Z-NO,)
1816 OH
n co-0 H
$&co
H
i
H 1818
1817
R'. R' = 0
1820
1822
R = Moc
o/=--.q+o $HO
-
.
n
CH,OiBut 1823
R', R 2 = 0
1824
R' =
OH: RZ =
*o
-
.
H
CH,ORZ
R'
R2
1826
CHO
iBut
1827
CH,OH
iBut
1828
CH20Ac
H
1829
CH,OAc
#But
1825 H
1830
432
M. BUDESINSKY AND D. SAMAN
Table 30. Carbon-13 chemical shifts of eremophilanolides. No
1831 1832 1833 1834
1x35
Mol formula Name I Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-ll C-12 C-13 C-14 C-15 ('/jH2002 Eremophilenolide, epi, 3.4-dehydro 25 7 26 I 1226 139.6 40.8 36.7 160.8 77.8 40.4 36.7 121.0 174.5 7.9 18.6 22 7 ('/jH2002 Eremophilenolide, 3P-dehydro 2 3 I 21 5 122.5 135.8 41 3 35.7 160.6 80.2 34.8 38.6 119.2 174.9 8.7 19.5 25.7 ('/51//803 lstanbulin C 2 1 1 2 3 9 4 24.8 144.2 49.1 37.1 160.5 70.0 34.1 48.0 120.8 174.2 16.8 110.6 8.3 C.ljH2004 lstanbulin D 77 9 48.9 24.7 148.8 42.4 31.5 162.0 105.0 34.4 50.0 121.7 172 8 11.6 108.3 8.9 'IjH2202 Eremophilenolide. epi
2 9 1 26.6 1836 ( ' l S H 2 2 0 2 ii 30 8 20 X b 307 206 1837 C I S H 2 2 0 3 250 30.1 1838 ( . l J H 2 2 0 3 ii 21 7 28.3 b 22 3 29.1 1839 C l j H 2 0 0 3 211 7 37.0 1840 C2OH280.I
27.1 41.4 40.3
31.0 163.0 78.0
Sol
Ref
C
169
C
469
S
647
s
647
36.1
42.9 121.6 1750
8.0
160
24.4
C
469
35.3 35.2
40.1 120.5 174.7 40.3 120.6 174.8
83 8.2
21 4 16 0 16.0 21.6
P
c
622 469
35.1
39.6 120.9 174.8
8.2
111
22.9
C
469
35.0 35.4
39.9 120.4 174.8 34.3 120.2 174.9
8.2 8.4
12.3 25 1 25.4 13 0
c P
469 622
8.4
209
14.9
C
455
Eremophilenolide
26.7 26.7
30.0 300
39.7 36.2 161.4 80.4 39.8 36.5 161.0 80.3
Eremophilenolide, fa-hydroxy
72.4
38.1
41.0 36.6 160.5 8 0 2
Eremophilenolide, 3b-hydroxy
71.6 70.7
33.9 40.3
39.9 37.4 161.0 80.2 40.2 37.4 161.7 80.4
lO~H-Eremophil-7(11)-en-12,8a-olide, I-oxo 30.4
29.2
42.6 36.0 158.9 78.5
33.6
56.8 121.9 174 1
10~H-Eremophil-7(11)-en-lZ,8a-olide, la-angeloyloxy 41.2 36.8 160.0 7 9 9
29.6
43.9 121.2 1744
8.2
21 5
I5 2
C
169
1841 ( ' l i H 2 0 0 3 Eremophilenolide. epi, 3-oxo 28 1 34.0b213.6 55.4 42.6 34.4b 160.2 77 1 1842 ( ' l j H 2 0 0 3 Eremophilenolide, 3 - 0 ~ 0
36.9
35.3 122.7 174 I
8.0
13.9 23 1
C
469
C
469
706
26.1
29.3
29.4
26 9 35 0'211.0 45.6 44.5 36.8b 159.1 7 9 6 36.1b 39.5 1843 ( ' / j H ? 2 0 3 Eremophilenolide. epi, 3a-hydroxy 2 2 % 289 73.9 4 4 7 38.9 35.1 163.3 78.1 35.1 36.8 1x44 ( ' 1 1 1 1 2 0 3 Eremophilenolide, epi, 3f3-hydmxy 27 3 29 2 68.6 44.7 41.0 34.7 162.1 77 7 33.7 35.5 1845 ( ' / 5 H 2 2 0 3 Eremophilenolide, 6B-hydroxy 26 1 20 2 3 0 9 30.9 43.2 68.7 163.8 7 8 6 3 5 4 342 1816 ('l.51f2003 ToluccanolideA 1290 23') 277 36.0 4 5 9 78.2 161 7 7 8 7 403 134.4 I847 Cliff2003 Istanbulin B 211 4 41 3 31 2 4 2 6 44.4 38.6 159.0 800 29.3 54 4
121.8 174.1
8.4
7.6
121.0 1752
8.0
152
254
C
469
122.0 174.7
8.0
7.5
25 0
c
469
120 I 174 8
85
16 jb 16Jb
P
622
1225 175 1
9I
175
13 9
c
5110
122.8 176.6
8.3
12 1
14 9
c
455
2 1 1 2 4 1 1 3 1 1 4 2 1 4 4 8 3 3 8 1 5 7 . 9 1 0 8 7 3 7 0 5 4 . 3 1 2 3 9 1 7 1 9 8.1 1 1 5 147 1849 ('7011805 10~H-Ercmophil-7(lI)-en-l2,8a-olide, la-angeloyloxy4b-hydroxy 70 h 20 1 29 2 290 41.7 33.8 158.8 103.8 35 3 43.4 1226 172.7 8.1 21 4 I5 2 1850 ('2011780j Eremophil-7(11)-en-lZ,8a-otide. la-angeloyloxy-lO~-hydroxy 75 8 27.8 28.5 32.9 46.3 32.3 160.7 78.3 35.2 76.9 121.0 174.8 8.3 15.8 14 8 1851 ('/.5/f2203 Eremophilenolide, lOp-hydroxy 364 22.3 29.7 33 5 44.9 31.8 161.4 78.7 41.0 75.0 120.5 176.0 8 3 14.7 I6 0 I852 ('201/2805 Eremophilenolide, 3~-angeloyloxy-1O~-hydroxy 324 29.6 72.1 36.5 44.6 31.8 1607 7 8 4 4 0 7 74.6 120.7 1731 8.3 121 1 7 8 1853 ( ' l j H 2 0 0 J Toluccanolide C 128 5 24 6 28.6 37.3 46.8 77 7 160.7 103.1 4 5 0 135.5 123.3 172.8 8 7 18.3 12 7 Eremophil-7(ll)-en-l2,8a-oIide, 6~-angeloyloxy-3~,8~-dihydroxy 1854 ('2011806 2 1 6 28.7 71.8 33 4 42.8 70.7 154.3 105.6 39.8 36.3 a a 8.9 1 9 6 13 5 1855 ( .24//.i20E Eremophil-'l(l I)-en-12,8a-olide, u f 3 - a n ~ e l o ) . l o x y - 3 ~ , 8 ~ - ~ i a ~ ~ t r ~ x y 2 1 7 2 4 7 73.4 32.2 42.0 7 0 7 a 104.0 38.3 35.2 130.1 170.8 9.1 18.6 124
c
455
c
169
c
160
c
425
c
1
c
509
P
622
P
622
1848 ('liH200-I
('15117204 2 9 0 20 7 1857 ( ' / 6 / / 2 4 0 4 ? X 7b 18 9
1x56
23 2
lstanbulin A
Eremophil-7(lI)-en-l2,8~-olide, Lf3.8u-dihydroxy 31.9 46.1 6 9 6 163.5 a 40 2 36 5 a 173 0 Eremophil-7(1 I)-en-l2,8~-olide, 6B-hydroxy-8u-methoxy 28.9b 31.8 46.0 69.6 160.9 107 3 38 5 36.2 126.5 172 0
29.0
9.2
18 9
15 8
P
622
9.3
15 X
I4 3
P
622
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
433
Table 30.-continued Mol. formula Name / Chemical shifis C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-LO C-11 C-12 C-13 (2-14 C-15 1858 C19H2606 Eremophil-7(1l)~n-l2,8p~lide,6~,8cc-diaeetoxy 284 204 290 3 2 5 445 7 1 3 1 5 4 8 1 0 5 3 372 3 6 3 1 2 6 3 1 7 1 0 8 7 193 I 5 7
No
Sol Ref
P
622
Other carbons: 1840 Ang: 167.2 128 I 138.1 15.8 20.6; 1849 Ang: 167.4 128.1 138.0 15 8 2 0 6 . 1XSlI .4ng. 168.8 127.6 139 5 15.9 206; 1852 Ang: 167.1 127.5 138.8 15.6 20.8; 1854 Ang I660 127 I1 )1'; 7 I 6 0 20.8; 1855 2xAc: 169.0 21.0 170.1 21.4 Ang: 166.5 127.7 139.4 16.0 20.6, I857 O.l/e W X . IX5X 2 x 4 ~ 1684 20.4 170.0 21.8 u
H
co
co
1831
bCO
1832
1834
1833
...'SO,
1835
R =
R = a-OH
1838
R =
1841
1846
H
1836 1837
';3,. 1840
1839
@-OH
1842
1847
R = H
1848
R = OH
1843
R = a-OH
1844
R = 8-OH
1845
1849
HO
co
co
RO
R
OAng 1851
R = H
1852
R = OAng
1853
1854
R = ti
1855
R = Ac
R'
R'
1856
H
ti
1857
ti
CH,
1858
Ac
AC
434
M. BUDESINSKY AND D.
SAMAN
Table 30.-continued No
Mol formula
C-2 ClSH2204 260 20 3 C16H2404 25 9 202 C19H2606 256 199 C 15H2204 348 220 C-1
1859 1860 1861 1862
1863 C16H2404 34 I 218 1864 C21H2608 604 42 5 1865 C”H2808 604 42 5 1866 C16H240T 3 5 8 220 1867 (’I 7H2605 3 4 1 21 8 1868 C20H2806 278 295 1869 C24H3208 25 5 269 1870 (‘20H2807 24 9 266 1871 C21H3006 340 21 9 1872 C2IH3007 338 21 7 1873 (’OH2807 210 246 1874 CljH2005 62 5 244 1875 C19H2107 633 250 1876 C19H2407 61 7 237 1877 C23H2809 63 3 25 2 1878 C17H2007 556 486 1879 CISHI804 I444 324 1880 C71SH1804 1444 323
Name / Chemicalshifts C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-12 Eremophil-7(ll)-en-l2,8a-olide,6p,8p-dihydroxy 31 0 294 437 702 1576 1054 399 34 5 123 7 172 1 Eremoyhil-7(ll)-en-l2,8adlide, 6p-hydroxy-8p-methoxy 31 0 292 43 7 693 1565 I082 392 343 1268 171 5 Eremophil-7(11)-en-12,8a-olide, 6p.Sp-diacetoxy 305 289 41 9 708 1502 104 1 386 350 1294 1707
C-3 C-4
C-I3 C-14 C-I5
Sol Ref
8 4 166b 164b
P
622
8 7 167b 166b
P
622
8 9 16 3b 15 9b
P
622
C
425
Eremophilenolide, BpJOp-dihydroxy
295 334 461 30315881027 427 7451225
a
83
147 162
Eremophilenolide, lOp-hydroxy-8p-methoxy
294 332 463 30415591055 424 73212541710 8 3 146 161 C 42> Eremophil-7(1l)-en-12,8a-olide, 3 ~ - a c e t o x y - l ~ , l O ~ - e p o x y - 8 ~ - h y d r o x y - 6 P - m c t h ~ c r ~ l o ~ l o ~ ~ 680 338 445 724 1381 101 2 249 609 1244 1710 7 8 151 9 4 C 701 Eremoyhil-7(ll)-en-l2,8a-olide. 3~-acetoxyd~-angeloyloxy-l~,1O~-cpox)-8~-h~drox~ c 704 676 338 445 72413811013 250 60912441710 7 9 1 5 1 9 4 Eremophilenolide, 6p,lOg-dihydroxy-8~-methoxy
8.8 105 16 1
C
425
29.7 33.3 47.9 80.9 152.7 106.0 41.5 74.1 129.9 a 8 8 107 1 4 5 Eremophil-7(1l)-en-l2,8~-olide, 6p-angeloyloxy-3p.8a-dihydroxy 67.5 39.9 46.6 71.8 158.0 105.2 39.0 36.0 128.0 171.8 8.1 202 81 Eremophil-7(11)-en-l2,S~-olide, 6~-angeloyloxy-3~,8a-diacetoxy 70.3 35.1b 45.9 71.7 154.1 105.1 36.3 35.9b127.1171.0 8.4‘ 198 8 5 ‘
C
3
29.6 33.4 47.3 71.4 154.1 106.2 43.2 75.9 127.6 170 8 Eremophilenolide, 6a,8P-dimethoxy-IO~-hydroxy
P 622 P
622
8 4 205
C
469
71.6 42.4 44.9 34.7 156.2 105.1 47.3 73.3 127.3 170.5 8.2 19 1 10 1 Eremophilenolide, 3~-angeloyloxy-6~,10~-dihydroxy-8a-methoxy 71.6 34 6 51.1 69.6 157.0 103.9 46.7 73.0 127.3 171.6 8.7 127 9 7
C
425
Eremophilenolide, epi, 3~,6~-diacetoxy-8a-methoxy
71.5 34.9 45.8 71.0 154.8 106.6 37.8 35.2 126.3 1707
8.2
Eremophilenolide, 3~-angeoyloxy-1O~-hydroxy-8a-methoxy
C 425
Eremophilenolide, 3~,6~-diacetoxy-8~-methoxy 73.2 32.1 42.0 70.7 150.0 106.6 38.0 34.5 130.8 170.2
c 169 8.9 123 180 Eremophil-’l(lI)-en-l2,8a-olide, 6~,8~-dihydroxy-l~,lO~-epoxy 21.0 32.2 44.8 72.3 160.1 101.9 44.3 61.9 124.5 172.3 8.7 16.3 13 9 A 363,364 Eremophil-7(ll)-en-12,8u-olide, 1~,10~-epoxy-6~-(4’-hydroxymethacryloyloxy)-8~-hydroxy 21 0 32.2 44.8 73.9 151.4 102.9 44.0 61.5 126.6 169.9 8.8 16.9 15 9 C 363 Eremophil-7(ll)-en-12,8a-o1ide, 6~,8~-diacetoxy-l~,lO~-epoxy 21.4 32.3 43.0 72.5 152.4 101.8 41.7 60.1 125.9 170.2 8.4 15.4 14 5 C 364 Eremophil-7(ll)-en-12,8a-olide, 8~-acetoxy-l~,lO~-epoxy-6~-(4’-acetoxymethacrylo~loxy) C 36i 21.6 32.6 44.7 74.5 153.7 103.4 43.2 61.7 127.6 169.4 8.3 17.2 16 4 Eremophil-7(11)-en-l2,8a-~lide, 6~-acetoxy-l~.10~;2~,3~;7a,8a-triepoxy c 101 48.8 31.3 10.2 69.6 58.5 85.7 29.8 64.7 40.0 1696 10.8 15.1 12.0 Serratifolide A C 1x2 24.3 36.0 40.7 25.3 158.8 98.1 172 8 134.8 128.3 171 7 12.4 15 7 21 6 Serratifolide
B
24.3 35.8 40.6 25.3 158.8 97.9 172.7 134.6 128.3 171.6 12.4 15.7 21.5 1881 Cl6H2205 no name (2 epimers) a 141 8 324 23.8 35.7 40.9 25.3 158.6 98.1 168.2 135.6 128.2 170.8 12 5 15.6 21.5 b 141 7 323 23.8 35.5 40.8 25.3 158.6 98.0168.0 135.2 128.2 170.8 12.5 156 21 5 1882 C16H220S no name 1444 31 8 24.3 35.2 40.8 25.3 157.1 103 4 172.4 135.0 129 1 171 7 12.5 15.7 21 3 no name (2epimers) 1883 CI 7H2405 a 1416 317 23.9 35.0 41.0 25.3 157.1 103.4 167.7 135.7 129.1 172.4 12.4 15.7 21 3 b 141.4 31.8 23.9 34.9 40.9 25.3 157.0 103.5 167.7 135.7 129.0 172.3 12.6 15 7 21 3
C
182
c C
1x2 I82
c
182
c
I82 182
C
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
435
Table 30.--continued Other carbons: 1860 OMe. 51.1; 1861 2ulc: 169.1 20.4 169.7 21.6; 1863 OMe: 49.9; 1861 . \ h c 166 9 136 3 125.6 18 2 :lc: a 20.5: 1865 .4ng: 167.0 127.8 138.1 15 7 20 5 .4c. a 20.5: 1866 O.\k il 0. 1867 2xOMe: 60.0 51.3; 1868 Ang. 167.1 127.1 140.7 16.0 20.6; 1869 2xAc. 168.3 21.0 169 8 21 8 - I / % 1660 1264 140.9 16.0 20.6; 1870 2xAc. 170.2 19.2 170.3 21.2 OMe: 50.3; 1871 OMe- 50.1 A 7 . g 167 6 1280 1382 15 7 20.5; 1872 OMe. 49.9 Ang. 168.0 127.6 139.1 15.8 204; 1873 2xAc- 170.4 20 7 170 4 21.3 OMe: 50.5, 1875 Mac-COH- 165.2 136.4 121.0 65.5, 1876 2ulc: 169.3 20.5 167.6 20 3: 1877 .\lac-.l-O;lc. 165.4 136.0 121.8 63 8 170.3 20.1 Ac. 170.2 20.2; 1878Ac. 174 7 20.6; 1881a O.\k i l 4. I881b OMe. 51.4; 1882 OMe: 55.8; 1883a 2xOAk: 51 3 55.8; 1883b ZxOAte: 51.3 56.2
mo
g&
OH
OR
CO
AcO
H
R'
R2
1862
R =
1859
H
H
1863
R = CH,
1860
H
CH,
1861
Ac
Ac
R = Mac
1866
R = 8-OH
1865
R = Ang
1867
R = a-CH,
co
c0 R'O
1864
AngO
co
co ,
AcO
OR2
OAc
R'
R'
R'
1871
R =
1868
H
Ang
ti
1872
R =
1869
Ac
Ang
1870
Ac
Ac
H OH
OR' R'
R'
1874
H
H
Ac
1875
MOc-4-OH
ti
CH,
1876
Ac
Ac
1877
Mac-4-OAc
Ac
1873
R 2 0 0 C OR'
M
0
R'
R'
1881
H
CH,
1882
CH,
H
1883
CH,
CH, (2
1879. 1880 1878
(2 epimers)
(2 epimers) epimers)
436
M. BUDESINSKY AND D. SAMAN
4.3.7. Lactones of other structure types Carbon-13 NMR data of nearly 150 sesquiterpene lactones of less common structure types are collected in Table 31. They can be derived from more than 40 different sesquiterpene skeletons some of which are shown together with carbon numbering in Fig. 25. 1D-NMR methods - APT or DEFT - were typically used to distinguish between C, CH, CH2 and CH3 carbons (e.g. refs 11, 155,211, 294,295, 307, 506, 523, 530, 559, 560). Recently, 2D-NMR techniques - HETCOR and COLOC - have been applied for carbon assignment in: arteannuin [1897]," vernojalcanolide derivative "3991 ,420 compounds 1933,'11 7a-hydroxy-8Pacetoxymarasman-5,13-lactone [ 19351,155 compound 1945,506 aquatolide [ 19551,s60 illicinolide A [1963],*11 majucin, neomajucin and their derivatives [1973, 1972, 1974, 1968, 1964-1967, 1969, 1970],381-386,685 anisatin [ 19751,68s bakkenolide A [ 19871,3 isohyenachin [ 19901,489 picrodendrin C and D [ 1991, 19921,489 manshurolide [2000],542 compound 2008,602 and confertifoline derivatives 2018, 2023.271 HETCOR and COLOC spectra of alliacolide [1930] and lahydroxyalliacolide [1931] led to the reassignment of some carbon signals of previously described structurally related compound^.^^ Biosynthetically 13C-enriched samples allowed to run 2D-INADEQUATE spectrum to establish C-C connectivities and 1D-INADEQUATE spectrum to obtain one-bond J(C,C) constants in both 1930 and 1931. The Y b ( f ~ d induced )~ 13C NMR shifts were helpful in the assignment of C-1, C-7 and C-14, C-15 carbons of arteannuin B [1897]. Relative shift values clearly demonstrated the preferred binding of LSR with the lactone carbonyl rather than the epoxy oxygen in this bifunctional compound. l 1 X-ray structure analysis is described together with carbon-13 NMR data for following lactones: (-)-a-desmotroposantonin acetate [I8851,324 compound 1923,l4' asteriscanolide [ 19281,559 la-hydroxyalliacolide [ 19311,45 di-p-brombenzoate of illicinolide [ 19631,211 neomajucin [19721,383 pseudomajucin [ 19831,384 isohyenanchin [ 19901 ,489 alpinolide peroxide [19951,33x and compound [2010].29s
4.3.8. Lactone dimers Carbon-13 NMR data of 41 lactone dimers containing two sesquiterpene units are summarized in Table 32. Data on skeleton carbons are given in two lines corresponding to two C-15 units (carbon numbers C-16 to C-30 are always reserved for a second C-15 unit - for skeleton numbering in some complex cases the original literature has to be consulted). Unfortunately, for some dimeric compounds, carbon signals were not assigned [2031, 20361 and/or uncomplete data sets were published [2033, 2039, 2040, 2044-20471. Heteronuclear (C-H) 2D-COSY spectrum had been used for the assign-
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
437
ment of carbon signals in pungiolide A [2051].” The authors assume the formation of dimer by Diels-Alder cyclization reaction with participation of ll(13)-double bond of one xanthanolide molecule with 1(5),2-diene part of a second xanthanolide. Pungiolide B [2052] having a lp,Sp-epoxy group in a second unit was assigned by comparison with 2051.15 HETCOR and COLOC experiments on shizukaol A [2049] allowed the complete assignment of carbon signals in this natural dimeric lindenane and its acetylation product 2050.373The structure 2049 was derived by detailed ‘H NMR and HRMS study, which showed easy dissociation of dimer into its two components. Carbon signals in dimeric pseudoguaianolide maritimolide [2048] were assigned using HETCOR and comparison with spectra of corresponding monomer units.3s9 X-ray structure analysis was described together with carbon-13 NMR data for mexicanin F [2056].s33
438
M. BUDESINSKY AND D. SAMAN
13
3 \
13
11
15
15
12
EMMOTIN
12
14
CACALOL
15 13
Q 7 l 4
12
11
A 13
15
12
COPAAN
VERNOMARGOLIDE
Ix)
1s 1
a 4 12 3
4
ASTERISCANE
15
11
12
CYCLOBUTANE TYPE
12
ALLIACANE
i"
13
6 LACTARANE
14
15
Wl3 15
10
PICROTOXAN
12
SPIROVETIVANE
Fig. 25. Structures, names and carbon-numbering of sesquiterpene skeletons of some less common lactones occurring in Table 31.
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
1
&J
3
~
15
15
I4
12
A 13
CADINANE
FURODY SlNlN
15
: - l
8
12
12
CYCLOPENTANE TYPE
DAUCANE
5
h
1
154
13
15
* 13
14
12
ANISATIN TYPE
p+ 10
15
SPIROPINGUISANE
14
15
13
BAKKENOLIDE
01
14
12
BOURBONANE
MARASMANE
4
’
13
14
DRIMANE
439
440
M. BUDESINSKY AND D. SAMAN
Table 31. Carbon-13 chemical shifts of other types of sesquiterpene lactones. Name I Chemical shifts %,I Itel. C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-I0 C - l l C-12 C-I3 C-14 C-I5 C15H1602 Eudesman-1,3,5(10),11(13)-tetraen-l2,~~-nlide, 10-desmethyl-1-methyl 131 8 128.1 1282 132.1 134.2 30.1 37.4 76.9 29.8 133.6 139.2 170.2 122.5 1 9 4 I9 2 C 357 (-1 7H2004 Santonin, (+)-p-desmotropo, acetate 12X 9 1240 147.2 134.6b1306 75.1 39.4 19.2 25.6 134.8' 40.4 178.5 9.4 19.5 11 7 c 324 C17H2004 Santonin, (+)-a-desrptropo, acetate 12!, 123.8 147.4 131.3' 134.Xb 75.4 41.6 23.4 24.0 1340' 40.4 179.3 14.5 19.5 12.1 c 324 il I24 2 148 I il ii 75.6 42.1 23.Xb 244b a 40.8 179 4 I 4 6 19.5 12 1 C 4s') C17112004 Santonin, desmotropo, acetate c 459 a 124.4148.1 a a 75.5 40.0 19.7 25.9 a 4071787 9 5 11.9 20.X C / Yfl22O6 Santonin, (+)-a-desmotropo, diacetdte 3 124 0 148.4 a a 79.6 53.0 7 0 7 35.5 a 40.5 178.3 14.1b 13.hb 20 7 c 459 CIitIIXO4 Adenostylide ( 2 epimers) 23 0 16.3 29.5 2 8 6 135 3 74.3 138.4 137.2 138.3 126.8 124.7 178.4 12.5 24.0 20.8 c 3xx 23 2 16.4 29.6 28.6 135 6 74.6 138.4 137.1 138.3 126.9 124.8 178.4 12.5 24.3 20.8 c 38X CIYH2206 Adenostylide, acetyl (2 epimers) 22 2 16 0 29.3 28 7 130.6 76.4 138.2 142.3 131.7 129.8 123.5 173.3 12.8 23.4 20 7 c 78% 22 2 16 I 29 3 28 7 130.6 77.2 1382 142.3 131.7 129.X 123.5 173.3 12.8 23.6 20 7 c 3xx C'ICIIZOO.1 Furudysinin lactnne I74 R 115 3 169 X I04 9 41.2 30.4 123.5 134.5 31.0 18 6 47.3 38.5 23.0 25 3' Zh X' c 256 ('Il i 1 1 2 2 0 Furodysinin lactone. 0-methyl 171 9 I242 1315 106.9 40.6 30.5 117.9 1292 3 1 0 18.5 4 7 6 38.2 23.3 2 5 0 2 5 6 13 1341 C17112403 Tuphahutenolide i 7 2 4 l l 7 . 6 1 6 8 . 8 1 0 7 . 0 41.0 30.5124.2133.9 31.3 18.7 47.8 38.5 23.3 25.1 259 c 2% Arteannuin 8, deoxy 26.2 142.4 116.7 84.3 5 2 6 22.1 34.4 30.7 140.0 1707 118.9 19.8 2 0 0 c 6* Artrdnnuin R 24 2 5 8 4 58.5 80.9 52.6 21.5 33 7 3 0 4 138.6 169.7 117 2 18.3 22.5 C' II ~lR*,4H*,5R*,6H*,XS*,10RL)-Cadin-7(11)-en-12.6-olide, 5,13-diacetoxy-1,4-dih~drox)-X-tigloyloxy c' 71 33.3 75 8* 72 7 90.8 163.0 69.3 27.8 31 4 122.3 170.5 55 3 13 I 27 0 Vernnjalcannlide, 13-O-methyl, X-methacrylate C 420 359 89.1 73.2 77.1 157.1 6 6 3 3 4 4 84.4 130.1 I693 j3.2 19.6 23 4 ?? 35.3 72.7 75.7 77.0 157 7 6 6 0 33 9 84.2 129.4 169.1 62.7 19 2 -_ c' 124 Vernnjalcanolide, 13-0-ethy1, I-methrcrylate c' 420 35 9 88.9 73.2 76.5 157.2 6 2 34.3 84.3 1306 169.1 61.5 19 7 23 5 c' I24 35 9 73.2 76.4 77.0 157.1 6 6 2 34.2 84.2 130.5 169.1 61.4 19.7 23 4 Veroojalcanolide, 13-O-mcthyl, 8-acetate c' 755 3 5 9 73.3 76.1 76.9 157.1 64.9 34.1 84.4 129.7 168.9 63.1 1'4.1 23 4 Vernojalcanolide, 13-0-methy1, 4,s-diacetdte c' 3 7 5 32.5 84 I 73.1 75.9 156.8 64.6 33.9 8 4 4 130.6 168.6 63.0 19.6 I X 7 Vernomargnlide, lia-tiglayluxy C' 746 31 I 73.4 7 8 6 74.9 40.6 7 0 5 3 9 9 85.5 133 6 160 7 125 4 2 7 0 ?h 7 Vcrnomargolide, 2-epi-l,4-cyclnsemiacetal, Xa-tiglnyluxy C' 346 35.9 71.6 87.4 80.3 50.6 70.7 35.4 8 3 9 1 3 7 . 3 1 6 X 5 I 2 6 . 1 2 2 9 22 2 Vernomargolide, Z-epi-l,4-~emiacetal, 8a-methacrylnylux~ c 530 35.9 82.8 79.2 87.3 50.4 70.1 35.2 69.8 137.X 168.5 126.0 24.0 21 x Vcrnomargelide, 2-cpi-1,4-semiacetal, 10-acetyl-8a-methacryloyIoxy c' 5 3 0 3 6 5 83.5 79.9 88.2 50.7 70.4 30.8 81.0 137.Xb168.5 125.0 22.7 22 0 Vernomargolide, 2-cpi-1,4-semiacetal, 5-acetyl-Xa-methacrylnyloxy C i31) 36.4 82.7 80.5 83.8 50.9 70.3 35.3 70.6 137.1b168.1 125.h' 23.7 21 9 Vernomargnlide, 2-epi-1,4-semiacetal, 5.10-diacetyl-Xa-methacryluyl c' i 3 0 76.5 X 3 0 R03 84.2 50.8 70.0 31.0 81 5 I36.Xb I67 7 125.5' 2 2 6 21 '1 C~1pa-7(11~-en-12,~-olide, 2~-acet11~~-4a-h)dr1~xy-l3-mcth11x)-X~-methacr11~l~1~~ 47.X 72 2 5') I X3 3 165.1 69.4 40 I 36.6 123.9 170X 64 2 21 3 3 7 0 t' 3 i O Fastieiolide _4_3 . 1 40.1 27.2 160.6 53.5 77.6 126.2 136.9 3 0 2 38.6 119.6 1668 12.6 I 6 7 2% h C '10 Mol. formula
No
C-l
18x4 1885 1x86 a
h 18x7 1x88 IXXY
IXYO lXYl IXYZ 1XY3 IXY4 1x95
C-2
<,
441
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 31.-continued
__
~-
~
Mol. formula Name / Chemical shifts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-I0 C-lI C-12 C-13 C-14 C-I5 1911 C23H2606 Fercolide 5 9 2 217.0 37.4 45.8 93.1 34.9 29.7 147.2 1190 76.1 38.4 177.4 11.0 26.1 186
No.
SA-l<sl c'
445
Othercarbans: 1885 Ac: 169.6 20.8; 1886a Ac: 169.6 20.8; 1886b Ac: 169.6 20 7: 1887 Ac 3 . I X X X 2 i A 169.7 19.8 170.9 21.1: 1891 2xAc: 167.7 19.8 168.8 20.1; 1892 2xAc: 167.7 19 8 168.8 20.1. l X Y 4 OMr49.9: 1895 OEt: 58.4 14.9; 1898 2xAc: 170.0 20.3 169.6 19.8 77g: 166.0 127.9 139.0 14 4 12.0: IXYYa 21Ac: 170.4 23.5 171.6 20.3 MOC: 167.8 136.4 125.6 18.2 OMe: 58.5. 1899b Z\Ac. 171 6 22 X 171 I I'JO Mac: 167.5 135.9 125.4 17.7 OMe: 58.0; 1900a ZxAc: 171.3 23.4 171.7 20.4 Mac 167 6 1364 125 7 18.2 OEf. 66.4 15.1; 1900b ZxAc: 171.7 23.4 171.3 20.4 Muc: 167.6 136 3 125 8 I X 2 O E l ' 6 6 4 I T I 1901 .?.lAc: 171.3 22.9 171.1 21.1 170.4 20.4 OMe: 58.5; 1902 4xAc: 170.7 22 J I706 22 I 169 4 21 I 168.9 20.1 OMe: 58.5; 1903: Tig: 166.8 127.5 139.9 14.7 11.9; 1904 7fg. 165 7 12X I 139 0 I4 X 1 2 1905 Mac: 165.6 135.8 124.8 17.8; 1906 Mac: 165.5 136.1b 125.4' 18.2 Ac: I6O.R I9 0. 1907 Moic I6 136.1' 126.1' 18.2 Ac: 169.8 20.7; 1908 Mac: 165.5 136.4b 126.0' 18.3 2xAc; 1699 19 : 169.9 2 0 7 . ]!JOY Ac: 171 4 21.2 OMe: 51.9 Muc: 165.9 135.7 126.6 18.3; 1911 Bz-4'-OMe: 164 7 122.3 131 4 I 1 4 0 163 7 1140 131.4 55.5
hco 1884
R'
R'
R'
R'
1886
H
u-CH,
iaag
H
U-OH
1887
H
8-CH,
lago
H
p-oti
1888
OAc
a-CH,
1891
Ac
cr-OAc
1892
AC
B-OA~
1885
1893
R = H
1894
R = CH,
1895
R = CH2CH,
1899
R
=
Me
1901
R = H
1900
R
=
Et
1902
R = Ac
1896
1897
1903
1898
R'
R'
R'
'1
Tig
ti
1905
H
Mac
H
1906
H
Mac
Ac
1907
Ac
Mac H
1908
Ac
Mac A C
R = OTig
1904
p-30OBz-4'-OMe
I
ili
co-0
1909
1910
1911
442
M. BUDESINSKY AND D . SAMAN
Table 31.--continued hlol. formula Name / Chemical shifts C-I C-2 C-3 C-4 C-5 C-6 C-7 1912 CZOH2605 Feruginin No
C-8
C-9
C-10 C-lI C-12 C-13 C-14 C-15
59.1217.0 34.6 45.4 93.0 29.6 3 7 5 146.7119.0 75.7 38.3 11.0 177.3 26.0 1 8 6 1913 C15H2203 Parvinolide, epoxy 47.7 21.6 24.2 58.8 64.1 28.6 38.4 143.0 88.8 180.4 43 6 18 I b 17 3b 22.Xb 123.5 Crocinervolide 1914 CI2H1803 1 11.9 144.9 72.5 45.1 135.7 125.4 85 4 34.1 29.0 176.7 ---- 26.6 27 3 1Y15 C14H1804 Santolinidilactone A, nor -1720 119.4 167.5 87.3 91.0 43.5 21.6 38.7 41.7 51.3 1809 13.4 24.5 1 6 9 1Y16 C23H.34011 no name 69.3 27.9' 27.1b 47.4 215.5 63.2 46.5 81.6 47.7 82.2 138.0 171.4 124.0 26.5 I4.X IY17 CI6H220S Santolinifolide A, methylester 173.1 32.9 28.6 144.7 204.1 96.0 42.9 20.1 38.5 52.5 50.6 180.8 13.2 .26.0 125.X 1Y18 C16H2205 Santolinifolide B, methylester 173.1 33.0 28.7 144.8 204.0 88.9 38.6 17.0 38.1 52.6 56.4 181.4 8.6 25.9 1260 1919 C16H2205 Santolinifolide C, methylester 166.5 122.0 144.8 46.7 210.6 89.9 42.9 20.5 34.4 54.3 51 7 180 7 13.3 23 0 17 6 a-Isocedren-14B,15-olide, 9~-acetoxy-14a-hydroxy-3a-senecioyluxy 1920 C22H2807 43.9 53.9 74.6 135.3 136.0 51.0 42.8 39.6 74.5 69.1 43.9 29 7 31 9 96.8 164 4 1Y21 C2UH280S Lasiolaenolide-9-01 50 I 34.1 124.9 143.9b 47.7' 81.3 47 5' 71.0 70 8 42.5 144 Ob 167 4 1200 18 8 16 8 1922 CISH2204 no name 79.4 40.3 203.2 49.9 51.8 78.9 54.4 23.2 37.7 48.1 40.9 179 1 12.8 18 4 14.6 1Y23 C19H2206 no name 55.3 46.1 204.6 133.1 165.7 74.9 54.1 63.2 43.3 204.6 138.2 167.6 122.3 23.2 8.8 1Y24 CI5H220S no name 79.8 21.9 35.2 81.5 205.2 83.3 51.9 22.7 28.2 40.1 42.1 177.3 12.5 13.4 54.5 1925 CISH2206 Tehranolide 80.9 24.6 33.8 93.8 105.6 84.7 50.5 29.6 37.7 50.1 43.1 175 Y 12.2 12 6 50 1 1926 CISH2203 Artedouglasiolide 177.7 85.6 138.9 126.9 73.1 48.2 41.6 20.0 34.7 40.1 54.9 27 2 25.6 22.2* 21 6b 1927 CISH2204 Versicolactone C 73.3 35.3b 29.0b 56.8 80.1 87.2 49.2 21 7' 21Sb 48.1 146.7 21 5 I l l 2 14.9 179 7 1Y28 CI5H2203 Asteriscanolide 90.9 45.7 43.1 22.5 22.9 27.9 45.7 213.8 50.1 38.5 40.8 177.9 13.2 24.5 23.0 1Y2Y CI5H2004 Alliacol A 39.3 26.4 31.6 95.0 76.7 38.7 41.8 67.2 69.5 19.4 143.0 124.7 168.8- 24.2 24 5 1930 CI5H2204 Alliacolide 31.5 25.3 28.2 76.8 92.5 41.0 38.5 68.3 68.5 17.3 45 1 7.5 176.0 24.0b 24.3' I931 CISH2205 Alliacolide, la-hydroxy 70.0 34.9 29.4 76.7 92.0 41.6 38.4 68.1 6 7 0 22.9 45.9 7 2 175.0 23.gh 24 2* no name 1Y32 C19H2807 660 34.3 74.3 70.4' 176.4 72.0 36.8 6 9 4 53.4 71.6' 49.6 175.9 10.9 24.9 12 9 1933 C23H3209 no name 53 5 32.4 76.4 69.0b 98.5 73.8 48.9 65 7 50.4 72.4' 39.3 170.0 10.5 24.4 11.2 1Y34 C17H2405 Marasm-5-oic acid y-lactone, Xa-acetoxy-7a,l3-dihydroxy 44.3b 36.8 31.8' 24.2 176.2 34.9 74.9 75.0 45.8 41.7b 36.6 17.2 79.6 32.2' 32 (IJ 1935 C17H2405 Marasman-5,13-lactone, 7a-hydroxy-8p-acetoxy 49.0 40.5 27.6 26.6176.7 32.6 77.9 74.3 43.2 46.1 37.5 17.1 74.4 26.3 2 9 0 1936 CISH2002 Marasm-7(8)-en-5-oic acid ylactone, 13-hydroxy 47.@ 38.4 32.8' 30.6 177.5 27.4'133.2 118.0 42.5 43.hb 37.0 16.F 68.9 31 7d 31 X ' 1937 C2OH240.5 Bourbon-11(13)-en-l2,6-nlide, 8a-tigloyloxy-l~,5~H-4a,7a-epoxy 42.6 24.1 43.5 95.7 55.9 100.1 100.9 7 9 2 40.7 45.6 140.1 168.0 1280 22.5 2 4 7 1Y3X C22H2809 Bourhonen-12,6a-olide, 2a,l3-diacetoxy4a-hydroxy-8a-methacryloyloxy 5 1 0 7 7 2 4 9 2 8 0 6 5 9 5 9 2 0 1690 7 0 8 4 5 2 4 7 8 1235 1703 5 5 3 2 2 6 2 3 %
Sill Ref
c
230
C
467
c
4'IX
c
361
c
2x4
C
361
C
361
c
361
c
697
c
92
c
54
C
140
c
547
c
547
,c
xx
C
703
c
550
c
3901
.
c
45
C
45
c.
111
c
Ill
C
153
C
I55
c
151
c
91
c
WI
443
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 3L-continued Other carbons: 1912 Ang: 165.8 126.6 139.6 15.7 20.6; 1916 Glc-6-Ac: 102.6 73.8' 76.5 70.2 73.5' h3.X 170.4 20.9; 1917 OMe: 51.6; 1918 OMe: 51.6; 1919 OMe: 51.3; 1920 Ac: 170.1 21.7 Serl: 165.7 115.7 158.2 20.3 27.5; 1921 Ang: a ; 1923 iBul: 175.5 34.0 18.9 18.9; 1932 iBuf: 176.4 49.8 19.0 19.0; 1Y33 illrrl: 176.0 34.3 19.1 19.1 ZxAct 170.6 21.2 170.6 21.3; 1934 Ac: 170.6 28.8(?); 1935 Ac: 169.9 21.2; 1Y37 7;s. 167.5 128.3 137.9 14.4 12.1; 1938 ZxAc: 170.2 21.2 170.1 20.5 Muc: 166.2 135.1 127.3 18.2
0
'K-
0-co
O
1913
RO o?,+
1916
1914
1915
0
R = Glc-6-AC
R
1918
R
& : H
1920
1917
--
0-co
oe
1919
a-CH,
8-CH,
O iBut
i
0-co
0.
1921
1922
co
1923
0
H?
HQcc Ho
0"O,,
Q
o'
f
HO 1924
1926
1925
1927
Jrlt - R'
R'O
,,, 018ut
0,CO
1928
1929
1930
R = H
1931
R = OH
R'
R2
1932
H
0
1933
Ac
a-OAc.
8-H
Ac? "8
1936 1934
R = a-OAc
1935
R = P-OAC
1937
1938
OMai
444
M. BUDESINSKY AND D.
SAMAN
Table 31.--continued No.
Mol. formula C-l C-2
1939 C17H1806 50.8 72.6 1940 CISH2005 8 4 8 29.0 1941 C1YH2407 84.6 27.7 1942 C17H220S 44.8 23.7 1943 C17H2305CI 50.1 20.9 1944 C17H2205 125.3 23.8 1Y45 CISH2204 a 43.1 17.7 h 43 0 17.8 1946 CISH2003 44.9 53.7 1947 ClSH2204 45.5' 49.1' 1Y48 ClSH2205 a 45.8 50.3' h 45 X 50 6t 1Y4Y C17H260S 45 8 b 4') i' 45 X I 4') J' 1950 ClSl122flS a 46 I * 50.7' h 46 I 50.5' 1Y51 ('I 7112605 a
h
Name I Chemical shifts C-3
C-4
C-5 C-6
C-7
C-X
C-9
C-10 C - l l C-I2 C-13 C-14 C-15
77.3
45.1
71.1
33.4
40.2'135.1 169.2 122.5 181.6 20.2
82.3
51.1 24.8 121.3 140.2142.1 169.5 118.3 33.2
Sol Ref
no name 43.7
42.2b 53.9
C
294
23.1
P
36
32.5
22.5
c
36
Crispnlide 31.5
41.5
72.4
Crispnlide, diacetyl 30.3
39.6
72.0
79.0
49.6
24.8 122.6 138.5 139.2 168.4 119.5
83.4
79.1
45.5
70.8
41.5 142.6 136.4 168.3 123.2 116.5
14.5
C
680
83.2 17.8 44.1
69.4
43.6
13.7
C
680
80.2
69.7
35.0 141.5 135.4 168.8 123.3
18.4
18.1
c
6x0
51.4 51.0
16.2 16 2
c A
506 506
22.1 173.9 28.6
26.6
c
62
29.2d 26.4'
c
160
31.2 97.3 29.4' 26.9' 31.2 1000 29.4' 269'
A A
160 I60
45.6b 37.1 24.9 9 7 3 29.6d 27.2d 25.4 100.2 29.6' 27.26
A
A
160 I60
46.1b 37.3 46.1 37.3
31.7 172.1 29.3' 26.6d 31.7 172.1 29.3' 2 6 6 '
A A
160 160
45Xb 37.1 45.Sb 37.1
25.6 172.0 29.4' 26.7' 25.5 172.0 29.4' 26.7'
A A
160 I60
46.3' 39 3b 425
29.9
70.5' 72.2'
26.3
M
154
85.6
no name 33.0
43.7
no name 32.8
45.1
69.8 134.5 168.5 124.0 32.7
no name 30.8
47.3
79.1
44.8
no name 30.7 31.1
43.0 43.0
85.5 85.1
83.4 48.0 26.6 39.4 57.4 83.0 47.5 26.3 39.6 56.9 Lactaroscrohiculide B 70.4 50.1 72.4 152.5 122.6 111.0 151.8 43.2
44.2 176.5 43.9 175.8 36.8
12.9 12.8
Lactarorunn A 75.1
34.8 175.6 123.3 160.1 67.4 46.2' 45.3b 36.9
31.3
71.8
Lactarolide A, (2 epimers) 35.3 172.3 126.5 159.4 66.5 47.Ib 35.8 172.4 126.5 158.3 67.6 47.4b Lactarolide A, 3-0-ethyl (2 epimers) 81.1 29.X 172.7 125.1 160.4 66.5 47.3' 81.1 29 8 172 7 125.1 160.4 67.6 47.8' Lactarolidc B (2 epimers) 74.5 38.4 98.9 159.4 130.1 65.5 47.1' 7 4 4 38.0 98 1 159.2 129.9 65.5 47.1b Lactarolide B, 3-0-ethyl (2 epimers) X I 0 33 2 98 5 157.0 131.4 65.5 47.6' X I 0 32 3 97 6 156.9 131.2 65.5 47.5'
74.9 74.5
a 46.3h 49 2' h 46 3' 49 2' IY52 ( ' 1 i 1 1 2 2 0 Lactarorufin R 40 s 5 3 4 73 2 35.2 177.4 166.1 123.9 a 1Y53 CISHI604 Lactarotropone, 2,Y-epoxy 41 0 76.3 128.4 118.5 172.4 146.3 148.6 191.3 1954 C14111602 Lactaranelactone, 8-nor 45 2 124.4 135.5 124.2 171.7 136.6 140.5 -1Y55 C15111803 Aquatolide 8 4 1 54.5 62.8 22.1 28.5 130.9 135.1 211.6 1Y56 CISH2005 Artemisitene 46 2 33.7 35.9 105.4 93.5 79.4 50.2 31.6 1YS7 C15H2005 Artimisitene, is0 47 6 30.6 36.4 104.8 93.0 77.2 148.1 22.9' I Y S X CISH2205 Artemisinin 45 I 36.0 37.6 105.4 03 7 79.5 33.7 24.9 1959 CI5H2205 Artcmisinin, 1I-epi 45 5 35 9 34.0 10.5 3 94.1 110.7 37 6 3 1 1 1Y60 C I S I I 2 I O S U r Artemisinin, brimo 50.4 35 7 33.7 105.6 94.5 80.0 52.0 26.6 1961 Cl5H2IOSBr Artemisinin, 1 I-epi, hromo 5 0 2 39.5 34.5 105.4 94.4 81.9 51.0 32.3 lY62 CISH2205 Artemisinin G 4 6 6 34.9 69.1 168.3 92.9 79.3 34.6 27.6 IYh3 C1611240X Illicinolide A 36.5 78.2 83.8 79.0 46.3 70.2 105.0 66.0
45.8 45.8
37.3 37.3
45.6b 37 1
45.4
32.2
24.7
69.0
31.2
32 2
C
117
150.0 46.8
40.4
19.2
68.7
29.2
27.2
c
I17
54.4
62.6 41.7 177.3 22.0
22.7
225
c
519
24.6
37.8 135.0 162.7 130.3
24.6
25.4
c
4
22.3b 29.5 126.1 163.4
12.9
19.2
26.0
c
5*
23 5
327
50.2 172.0
12.0
19.8
25 2
C'
1
24 7
39.7
50.5 172.6
205
19 9
25 5
c
i'
24.9
37.3
51.3 168.8
30.2
15.8
25 2
c
5*
24.0
34.8
62.2 168.9 37.4
19.8
25.5
c
5'
24.2
30.8
54.8 171.5
12.4 20.3
21 I
C
671
45.6
82.8
36.2 59.7 179.4
18 I
I'
2
8.2
445
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 31.-continued -~ ~
No. Mol. formula C-l C-2 1964 C I S H I 6 0 7 53.4 206.1 1965 C I S H I 6 0 7 50.7 208.1 1966 C I S H J 6 0 7 49.1 208.6 1967 C I S H I 8 0 7 48.8 74.2
Name I C-3 C-4 Majucin, 134.5 171.9 Majucin, 134.1 172.8 Majucin, 133.6 176.2 Majucin, 135.4 146.0
Chemical shifts C-5 C-6 C-7 C-8 C-Y C-I0 C-11 neo, 3.4-dehydroxy-2-0x0 43.8 79.4 78.8 30.0 49.7 69.6 173 6 neo, (lR)-2-0~0-3,4-dehydroxy 44.6 80.0 79.1 27.7 50.4 72.5 1743 neo, (1R,lOS)-2-0~0-3,4-dehydroxy 44.8 79.4 79.8 22.7 51 4 73.6 I706 neo, (2R)-hydroxy-3,4-dehydroxy 42.8 78.5 79.8 30.8 50.2 68.5 173.3
C-12 C-I3 C-14 C-I5
~~~
Sol I
177.2 22.8
73.8
8.8
I’
3x2
1770 22.7
73.2
123
I’
3x2
177 0
71 7
13 2
I’
3x2
177.9 22.7 74 7
9.2
I’
3x2
21 I
Othercarbons: 1939 Ac: 170.5 21.0: 1941 2xAc: 167.8 20.4 171.2 17.7; 1942 Ar: 169.9 20.8; 1943 A < 10‘1 (7 20.7; 1944 Ac: 170.5 21.1; 1Y49a OEf: 57.4 15.7; 1Y49h OEI: 57.4 15.7; 1951a OEt: 57.6 15.7; l Y S l h 0I:r 57.4 15.7: 1963 OMe: 55.0
:g-&
0-co :
H
b
Z
R’
R2
1940
H
H
1941
Ac
AC
1939
& 1944
1943
1942
.OR’
& o
1946
1945
R’
R2
1947
H
H
1948
OH OH
H
1949
1950
R = H
1951
R = CH,CH,
1955
1952
H i
0
0
1956
1963
CH,CH,
1954
1953
b i t
0 1962
b-co
HO
,,+OH
b-cO
HO
bFC0
HO
0-co
’.=;.
1957
R‘
R2
1964
a-t!
a-H
1965
8-H
a-H
1966
8-H
8-H
1958
7 = a-H
1959
R =
1960
R = a-Br
1961
r)
6-H
= p-Br
1967
446
M. BUDESINSKY AND D. SAMAN
Table 31.--continued No
Irld l o m u l a
c-I
c-2
Name / Chemical shifts
C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-11 C-I2 C-I3 I968 CI.ifllXO7 Maiucin. . neo, 2.3-dehydro 4‘9 ’I I 4 0 4 130.5 07.0 4 8 6 78.5 71.8 29.2 53.7 73.2176.6177.9 179 1YOY ( ‘ I 511 I X O R Majucin, neo, 2-ox0 4 9 6 215 2 45.1 79.0 46.3 79.4 7 9 7 26.5 50.8 7 0 0 174.0 177 5 21 6 I9711 C ~ I 5 l l I O O K Majucin, neo, (tS)-hydroxy GO 0 79 0 42.8 83.1 4 7 2 79.5 80.5 27.4 52.6 70.1 1749 1776 21.6 1971 CI.itllXO7 Anisatin, neo, 6-dehydroxy-2-0x0 4X.8 214 5 46.2 77.6 66.4 35.2 78.9 31.2 50.5 69.8174.6 1 2 8 1 7 1 . 5 I972 ClSfl7007 Majucin, neu 3 9 4 31 4 31.6 84.1 47.5 7 9 6 80.5 27.5 51.0 70.7 174.8 177.2 21.4 1973 CISH2008 Majucin 3 x 0 4 2 9 72.7 82.8 47.5 79.9 80.6 27.1 51.5 70.3 174.7 177.6 20.9 1914 C15112007 Majucin, 6-deoxy 38 I 4 2 7 72.4 82.1 45.1 54.1 75.3 29.5 51.5 70.2 175.8 175.3 25 5 1915 CISH2008 Anisatin 3 7 4 41.9 71.1 85.4 26.0 74.8 81.5 27.5 50.6 70.0 174.6 22.0 16X 6 1976 C15112008 Anisatin, neu, Za-hydroxy 4 x 9 7 x 5 43.3 84 3 669 75.0 81.8 2 7 6 5 2 5 69 7 175.0 22 7 1692 IYJJ CISIl2205 Anisatin, pseudo, 6-deoxy 4 0 X 43 3 78.5 83.1 47.9 48.8 2G9 5 47.1 48.1 35.2 174 2 I X 0 X 2 1978 CIS112206 Anisatin, pseudo 40 2 43.1 78 2 84.7 47.7 79.3 206.5 43.8 4X.8 35.2 174 3 18.4 13 8 1979 CIS112406 Anisatin, pseudo, 7-deoxy-7p-hydroxy 3x 2 41.5 75.7 88.0 50.3 77.3 83.7 28.4 45.9 36.2 172.0 22 7 16.2 i w o ~ 2 2 ~ 2 8 0 6 Dunnianin, 6-deoxy 40 0 42 0 81.1 81.3 46.6 41.7 72.3 367‘ 45.6 36Xb 171 I 21 X 150 19x1 C22112807 Ihnnianin 4 0 0 4I.X 81.1 8 2 7 4 8 3 78.4 7 7 1 32.3 463 36.31714 2.10 1551 I982 C19H2607 no name 5 1 2 76.6 40.8 96.9 50.4 4 5 . 0 2 0 8 3 47.1 49.8 42.1 1754 8.7 1 9 6 ~
..
19x3 CISMZZOS 55.0 73.6 19x4 C2l~132010 25 I 73.6 1985 CISH2207 45 1 39 I 19x6 C3IH4201S 52.9 77 3 19x7 ClSH2202 23 3 20.9 1988 CISH2201 21.5 30.0 1989 C20H2804 21.4 26.7 1990 C15112007 46.3 73.1 1991 CISH2007 45.5 75.4 1992 CISH2006 4 0 8 76.2 1993 CI.iH2006 53.6 72.3 I994 CISH2006 50.8 83.5
C-3
C - I 4 C-I5
Sol Ket
74.1
13.5
P
3x3
72 2
X5
I’
3x2
72.5
123
1’
3x2
64.1
XO
C
6x4
72.6
14.31’JX?.3Yi.6JX
72.4
14.11’382.3R3.648
74.3
14 2
65 2
13 7
65.8
I1 X
c
3x6
69 5
13 ‘J
P
3x5
696
17 9
P
385
63.7
15 2
c
3x6
67.X
I? 7
I’
3x5
668
14‘1
I’
3x5
64.4
‘12
I’
3x4
P
3x1
I) 1 X i . h X S
Majucin, pseudo 51.1 43.7 106.9 54.6 Majucin, pseudo, glucoside
43.8 100.3 43.8
99.9
48.8
4 1 6 176.8
90
I44
71.1
10.0
1’
3x4
14.0
72.2
100
P
3x4
13 9b
I’
3x4
51.0
44.5 109.5
52.3
48.9
41.5 176.7
8.8
52.8
78.0 106.9 47.8
48.6
41.2 176.6
19.0
41.0 175.8
84
no name 77.3 102.2
124b 72.2
Majucin, pseudo, glucoside pentaacetate 40.3
99.4
50.9
13 6
72 4
96
I’
3x4
46.1 150.3
70.3 182.5 105 7
16.3
I9 I
c
3
41.4 149.6
70.4 182.4 106.2
11.6 20.6
C
I26
44.3 109 4
52.3
49.0
48.5
42 3 49.0
Bakkenolide A 30.8
33.8
43.9
49.8
Bakkenolide A, 3a-hydroxy 73.1
45.4
45.8
42.2
49.9
Bakkenolide A, 3a-angcloyloxy 75.3
43.3
48.9
49.9
42.2
38.8 149.9
70.4 182.1 106.1
11.8
206
c
348
77.3
21.4
68.4
28 5
30.5
61.1 60.3
67.0
52.2 175.6
P
4x9
78.5
21.8
30.9
15.4
18.3 61.8
61.0
66.9
52.41764
I)
489
51 5
45 2
27.7
29 6
15.3
16.5
57.2
608 67.3 52 0 177 6
I’
4x9
54.3
87.5
221
26.7
20.1
20.5
42.9
61.0
74.5
52.2
47.4
25.8
28.9
16.1
16.9
30.4
38.1
85.8 178.8 178 4
46.1
Hyenanchin, is0 84.8
54.5
50.2
Picrodendrin C 90.0
82.0
58.3
Picrodendrin D X9.4
80.9
Amoenin 85.1
53.6
64.7 176.5
I’
1521
Amotin ~~. ~
84.2
81.7
P 15?*
447
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 31.--continued No. 1995 1996 1997 1998
Mol. formula C-1 C-2 CISH2004 45.1 31.0 C15H2203 55.4 32.3 ClSH2203 51.2 34.1 ClSH2204 55.0 34.5
Name / Chemical shifts C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 Alpinolide peroxide 25.9 37.6 39.6 109.8 170.6 119.6 174.5 100.8 Alpinolide, epi 27.3 37.7 46.0 82.6173.4114.3180.7210.5 Alpinolide 26.7 35.1 43.4 83.3 173.3 114.6 178.8 210.2 Alpinolide, 6-hydroxy 29.1 35.1 53.2 109.9 170.9 116.2 177.5 213.9
C-I1 C-12 C-13 C-I4 C-15
SIII Ref
27.6 21.6 21.7
15.7 24.2
C
338
28.3 20.5
22.3
16.1 30.0
C
337
20.2 22.1
16.2 29.9
28.1
Ci;8..33Y
27.6 21.3 21.3 22.7 29 I
C
Orhercarbons: 1980 Bz: 166.8 131.7 130.1 (2) 128.8 (2) 133.0; 1981 Bz: 166.6 131.3 129.9 (2) 12X.X 17) 113.1. 1982 2xAc: 169.7 20.6 170.2 20.9; 1984 Glc: 98.8 75.4 78.8 71.8 78.4 62.9: 1986 Glc-2.3.4.fi-A< 95.8 71.7 73.3 69.4 72.3 62.7 170.3 20.5 170.3 20.5 170.2 20.7 169.9 20.7 Ac: 169.6 20.9: I Y X Y / l w 167.8 128.3 136.9 15.6 20.5
1968
1969
1970
1971
R'
R'
R'
R'
1977
R = H
1972
H
OH
1975
H
OH
1978
R = OH
1973
OH
OH
1976
OH
H
1974
OH
H
1982
H OGlc
1984
OH
H
1985
H
OHOHOH
1986
OAc H
R'
R1
1979
d
OH
1980
Bz
H
1981
3r
CH
R'
H
1987
R =
1988
R R = OAng
Ri
H
OGlc-2.3.4.6-Ac
1989
$>
-~
~
1990
nn
k i
,-ti
1991
f'&+
OH
H
1992
ti
C
H
n 1993
1994
?'
R2
1996
8-H
H
1997
a-H
H
1998
a-H
OH
1995
448
M. BUDESINSKY AND D. SAMAN
Table 31.--continued No
Mol formula Name / Chemical shifts C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C - l l C-12 C-13 C-14 C-I5 Sol. Rcl. C15112203 no name S69 31.7 25.5 38.5 42.9 146.6 121.1 31.6 175.8 207.7 25.2 21.5 22.2 16.1 29.2 C 33X ClSH2002 Manshurolide 1736 128.6 150.5 80.0 40.8 133.1b 130.2 25.4 39.2 135.5D125.1 24.6 25.8 19.1 15 I C 542 C20M2606 (4~6~7S,llR,10S)-Jujuyensa-l,ll(l3)-dien-l2,6-olide, 3-oxo-8-SarrdcenyloXy C 236 1412 116.1 215.1 35.9 40.3 75.7 49.0 70.1 40.0 54.0 135.7 168.5 122.8 22.2 19.8 C22H2809 Trichosalviolide, 9~-acetoxy-5~-hydroxy-8B-(2-methyl-2,3~~xybutyryloxy) (2 epirners) C 106 129.3 30.9 38.5 50.7108.7 86.1 83.6 77.3 76.1130.7140.2168.4127.6 19.1 13.2 C lo6 129.6 30.9 38.5 47.9 105.4 84.2 87.7 76.4 76.5 130.7 138.9 168.4 128.0 19.1 13.6 CiSH2005 no name C 107 44.2 150.7 38.9' 38.0b143.3 129.2 41.3 75.7 59.2 31.0 34.0 116.2 30.0 21.7 170.6 CISH1803 Xanthipungolide n 15 52.8 127 9 141.4 69.2 82.9 29.5 50.1 80.7 30.9 29.5 49.0 178.2 43.4 20.9 12.4 CI 71f2403 Penlanhutenolide R 257 a 143.3 a 101.4 31.4 143.3 129.8 a 28.8 23.3 42.9 29.0 18.0 21.4 110.5 ( ' 1 7112403 Penlanbutcnolide, 4-epi 13 257 i~ 142 7 a 101.5 31.4 142.7 129.8 a 28.8 23.3 42.8 29.0 17.9 20.7 110.4 CIS112402 3b,4,4,7a-tetramethyl-lH-decahydrni~eno[l,2-c~furan-3-one C 602 36.1* 18.6 36.gb 35.7' 47.8' 51.0 38.6 49.3 52.3' 22.7d 24.5" 30.6& I4.Yd178.3 73 2 CISH2004 no name s I26 162.2 134.8 209.7 45.1 58.7 81.3 46.0 22.8 37.1 74.5 40.5 178.5 12.3 25.3 1 1 4 C15H2003 (4S,SS,7R,8R)-Ratibida-ll(13)-en-12,8-olide, lOa,l4-epoxy C 2'15 32.0 22.3 40.0 44.2 46.2 34.1 37.2 75.5 35.1 58.7 139.0 170.2 121.X 50.0 I S 9 C1SH2002 (4S,5S,7~8R)-Ratibida-l0(14),11(13)-dien-~2,8-olide C 295 32.4 22.4 33.9 44.7 49.7 41.4 37.2 77 7 38.8 148.4 139.4 170.4 122.2 113.7 14 8 C20H2606 Vetispiranolide, 14-angeloyloxy-2~,3a-dihydroxy C 604 127.8 73.6 75.1 44.6 53.3 42.3 45.9 84.8 40.2 140.0 139.2 169.9 122.2 63.2 1 1 6 ClSH1802 Spiroeuryolide c 265 34.4 24.5 377 47.9 142.8 117.1 146.5 153.8 116.4 56.0 112.2 172.8 8.1 13.7 2 3 2 ClSH22OS Spiropinguisanin (not assigned) I' 6% 10.3 12.1 17.0 21.3 4 5 8 47.7 48.9 515 59.3 63.1 77.4 78.6 92.1 102.5 1762
___. C:1
1999 ZOOU
LO01 2002
2003 2004 2005
2006 2lM7 ZOOX ZOOY
2010 2011 2012 2013 2014
2015 CISl12202 Drimenin, iso 35.1 1R.6 41.9 33.2 52.3 18.3 25.2 159.9 150.9 34.8 2016 C l S H 2 2 0 3 Drimenin, iso, 6p-hydroxy 37.5 19.0 43.6 34.1 54.9 63 9 36 3 157 2 157.2 35.3 2017 CISH2204 Confertifoline, 6p,7a-dihydroxy 3R 3 18.6 4 2 9 33.3 49.0 71 3 66.5 123.0 173.8 37 2 2018 CIY112606 Confcrtifoline, 6p,7a-dihydroxy, diacetate 384 I 8 2 42.9 333 49.6 69.0 63.7119.8175.4 37.1 2019 C2911.1006 Confcrtifoline, 6pJa-dihydroxy, dibenzuate 38 7 I 8 5 43.1 33.6 50.5 70.2 64.7 120.2 175.8 37.2 2O20 ClijI2103C1 Confertifoline. 7a-chloro-li~-hydrcxy 3 x 6 18.5 42.6 33.4 48 3 71.8 52.5 121.6 174.3 37 3 2021 ('17/i2.<04CI Confertifoline, 6p-acetoxy-7a-chloro 3R 6 18.4 42.6 33.3 47.5 72.0 49.0 121 7 173.1 37.4 2022 C15112003 Fragrolide 35 7 17.9 42.5 32.5 62 7 205.7 37.7 121.8 172.4 40.0 2023 ('ISH1903CI Confertifoline, 7a-chlnro-6-oxo 3 S 4 18.0 41.8 32.2 49.9 2007 57.1 122.5 173.9 41.8 LO24 C151I200.7 Confertifoline, 6p,7p-epoxy 37 7 18.5 43.1 33.6 50.5 70.2 64.7 120.2 175 8 37.2 2025 C26H100.5 Astellolide A 31.6 17.9 37.0 37.7 539 66.6 29.0 122.5 165.6 40.5 2026 ~ ' 2 / , 1 / 1 O O Y Astellolide Ii 117 I 7 9 3 7 0 377 5 4 1 6 6 0 2 9 1 1228 1656 405
172.4 70.X
20.1
21.4
134
c
610
71 0
33 9
23 5
20 X
I'
630
6 8 2 1698
21 X
23 2
33 I
A
271
68.31718
22.2
22.7
32')
C
271
68.4 171.7 23.0
23 0
33 7
C
271
687 172.9 22.6
23.5
37 2
i'
211
68.3 171.5 22.6
23.0
32 9
i'
271
68 2 170 I
21.6
21.X
32 4
C.
271
67 9 169.8
21 6
22.3
31 6
c'
271
68.4 171 7
23.0
23.0
33 2
c
271
66.9 71 3
c
252
671
I
252
172 5
65.9 173.0 27.7 6f101734
278
714
449
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 31.--continued ~~
Othercartens: 2001 Tig-5-OH: 166.1 131.6 142.5 14.3 56.7: 2002,2003 AC: a Q i u q ; a , 2006 0 ) I 15.1. 2007 OEr: 65.4 15.1; 2012 Ang: 167.3 127.4 1389 15.8 20.6; 2018 2xAr: 16X 4 2 0 6 1 6 X X 2 1 I 2019 2xBz: 169.4 128.4(2) 128.8(2) 131 1 a 165.3 128.6(2) 129.9(2) 133.3 a : 2026 ZxA( 171 I 2 1 0 170.3 20.6 Bz-l'-OH: 165.6 120.6 131.3(2) 115.6(2) 161.3
'
0,do
> r O
co
6
J
Epmg
0-co
2000
1999
2004
2005
2002. 2003
2001
2006
R = a-OEt
2007
R = 8-OEt
2008
CrilOAnq
Hoow 2010
2009
2014
2013
7
2012
2011
2015
R = H
2016
R = OH
0
2022
R = H
2025
R = Ez
2023
R = GI
2026
R = Ez-4'-OH
R'
R2
2017
Oh
OH
2018
Obc
OAc
2019
OEz
OH2
2020
on
CI
2021
OA
C1
450
M. BUDESINSKY AND D. SAMAN
Table 31.-continued ~-
~
___
h l d lomula N.we / Chemical shifts C-I C-2 C-4 C-4 C-5 C-6 C-7 C-8 C-9 C-I0 C - l l C-12 C-13 C-14 C-15 2027 CISH2203 Cinnamolide, ’)a-hydraxy 41.6 17.9 31.3 32.7 41.7 25.3 141.1 130.0 77.3 38.5 74.3 169.3 17.0 21.5 33.3 202X C17112h03 Cinnamolide, 11-ethoxy 393 18.5 42.3 33.1 49.7 25.1 136.0 128.2 57.6 34.1 104.3 1678 21.4 33.2 1 5 3 202Y CISH2402 Confertifolin, dihydro 40.4 18.1 42.0 32.9 51.4 18.4 22.4 37.4 49.9 35.4 67.6 179.1 14 5 22.0 31 5 2030 C241f3207 Pebrolide 82.4 27.4 35.1 36.8 46.4 67.6 28.0 35.9 48.1 39.3 70.1 178.4 117 IY.6 7 2 0
Nu
Sol. I
17X
C
210
(.
432
C
412
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 31.--continued Other carbons: 2028 OEr: 6 6 4
R'
R'
2027
ti
OH
2028
OEt
H
14.7: 2030 Ac: 170 8 27
2029
3(?):
Bz: a 130.3 128.5(?) 129 7(2) a
2030
45 1
452
M. BUDES~NSKYAND D.
SAMAN
Table 32. Carbon-13 chemical shifts of dimeric sesquiterpene lactones. Name I Chernlcal shlfts C-l C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-I0 C-lI C-12 C-I3 C-I4 C-15 - C-16 C-I7 C-I8 C-19 C-20 C-21 C-22 C-23 C-24 C-25 C-26 C-27 C-28 C-29 C-30 2031 CW114006 Mikaguyanolide (not assigned) 17K.7 144.3 135.9 132.5 130.5 126.9 79.6 75.9 52.5 38.8 37.0 35 9 262 18.1 16.8 170 7 138.4 135.5 131 3 129.8 123.0 79.5 71.2 44.0 37.2 36.1 35.5 25.2 17.7 15.4 2032 C W I 4 ~ 0 6 N (-)-Bisparthenolidine I25 3 24.2* 36.Sb 61.6 66.1 82.3 49.0 30.2* 40.9 134.3 45.5 176.7 46.2 17.2 16.8 125 3 24.2 3 6 5 61.6 66.1 82.3 49.0 30.2 40.9 134.3 45.5 176.7 46.2 17.2 16.8 2033 C4Xll6d014N2 no name (not assigned) 178 3 177.6 165.9 144.6 142.5 133.0 129.8 129.2 124.1 77.4 74.1 69.5 61.2 60.8 52.9 4'9 h 49 4 41.0 35.0 32.1 26.5 20.1 19.0 16.9 Othercarbons: not given 2 0 w ( ~ ~ 0 1 1 ~ 4 0 7 Encelin, hydroxy-his-dihydro 158 3 126.4 202.1 76.1 49.5 24.2 40.6 76.0 41.4 36.1 140.8 170.0 121.4 20.5 28.9 157 Y 122.8 200.0 41.6 45.9 18.2 39.5 75.8 38.2 34.6 1407 169.9 121.3 18.5 21 7 2032 C101140OX Artenolide 153 6 128.9 79 7 87 5 60.6 82.3 43.2 21.5 39.4 69.4 60.0 180.5 35 I 27 5 17.3 I47 9 52 I 53.3 56.7 143.5 83.9 50.2 25.5 39.3 71.7 42.6 178.7 13.0 30.5 1 1 3 2036 C I Z I M O R Artanomaloide (not assigned) 145 2 0 0 2 0 3 21.7 299 23.7 34.9 36.7 43.6119.4 43.4 50.3 56.6 66.2 6 6 4 79 2 79.5 113.9 136.2 142.9 57.3 59.9 63.1 72.7 134.3 140.7 143.4 170.1 I704 170.2 2037 C30tIMO6 Artesieversin 42.2 24.3 64.0 66.3 50.7 81.4 54.6 28.9 33.1143.1 54.5183.3 38.5113.5 18.4 71 2 45.6 45 7 135.4 147.4 83.7 46.8 28.1 42.7 76.4 42.2 178.6 12.5 32.1 14.2 21nx C.WI14406 Ahsinthin, tetrahydro 71.3 45.6 122.4 146.6 64.0 82.7 46.3 27.5 43.6 73.9 42.2 179.3 13.0 29.4 1 3 6 57.0 46.5 58.8 135 4 147.8 R1.5 49.2 23 6 42.4 71.6 42.0 179.8 12.1 32 2 I X 3 203') C10114006 Absinthin, is0 71 I 46 8 121.5 139.9 65 I X26 46.6 C-8 to C-15. notglven 5'J 7 43 6 60 3 133 4 148 2 8 0 9 46.8 C-23 toC-30: not given 204ll C.(Ii1/4OOt, Ahsinthin a 71 3 45 6 122 4 146.6 64.0 R27 46 3 C-8 toe-15: not glven 57 0 46 5 5X.8 135 4 147.8 81.5 49.2 C-23 toC-30: not given h 71 4 45.7 122.1 148.5 64.2 82.7 46.7 27.5 42.5 71.9 42.0 178.4 13.1 32.3 13 7 57 I 46.5 5 8 9 134.9 147.5 81.4 49.4 23.6 43.7 74.1 42.3 178.8 12.2 29.4 I X 3 21-11 C.?01/4006 Ahsinthin, 11-epi 7 1 5 4 5 6 122.1 148.4 644 8 2 7 39.9 23.7 42.3 71.X 40.5 178.8 11.0 32.2 I 3 7 57 I 46.7 58.9 135.0 147 6 81.4 49.4 23 6 43.7 74.1 42.3 179.9 12.2 29 4 I X 4 2042 C W 1 4 0 0 6 Ahsinthin, lO',ll'-epi 71 3 45 3 122.4 148.1 64 2 82 9 46.6 27.5 42.5 72.0 42.1 178.6 13 0 32.3 13 7 5 x 4 4 7 2 59.1 135.2 145.6 80.4 4 4 0 22.4 45.3 75.7 40.1 1791 '1.2 22.7 179 2043 ( ' ~ ~ V l J O O 6 A hsinlhin, 11,10', I 1'-epi 71 1 4 5 4 1223 148.2 6 4 5 82.8 40.0 238 4 2 4 71.9 40.7 I797 11.0 322 l i X 58 4 47.2 59 1 135 3 145.7 80.4 4 4 0 22 5 45.2 75.7 40.1 180.0 9.2 22 7 I X o 2114.4 < ~ < i l f l < X O 5 Anahsinthin, dehydro (2 epirners) 62 5 10.3 35.3 8 9 0 62.7 82.4 48.1 C-8 to C-IS: notg!ven 13X.I 47 7 50.8 124.9 145.8 80.7 49.4 C-23 to C-30: not given 2045 63 ? 39 7 35.3 88.6 62.1 82.3 49.2 C-8 toC-15: not given 137 1 47.5 50.8 129.1 1489 78.1 45.2 C-23 toC-30: notglven 2046 ~ ~ ~ f l l l 4 f l O 6 Anahsinthin (2 epirners) 6 2 9 41 3 3 4 7 88 3 62 I 82.4 49.4 C-8 toC-15: notglven 56 7 43.2 52.5 132.5 148.0 81.0 49.2 C-23 toC-30: not given 2047 62 6 41 I 35.2 88.3 62 6 82 4 47.0 C-8 to C-15: not given 59 7 41 I 53.7 131.2 I404 80.7 49.3 C-23 toC-30: not given 204x ('W114007 hlaritimnlide 4 4 1 24.1 3 7 5 2 1 7 5 5 2 7 85.1 162.5 2 3 3 3 2 6 331 1271 1741 179 17.4 1 1 3 4 6 0 23X 364 220.9 5 4 9 81.0 5 1 2 174 35.1 34.8 16.0 178.2 35.5 16.3 I S ? 204Y c'.?III1JIlCj Shizukaol A ?i 7 15 8 24.9 142.2 132 I 41 0 132.0 200.1 79.7 51.2 146.8 170.9 20.1 15.3 2 5 6 2 7 7 1 6 s 22.9 1 4 9 0 59.8 23.1 165.2 93.0 54.5 41.9 124.4 173.5 8.6 2 5 0 107 2 21110 ( ' 1 111 (5'17 Shizukaol 4. acetate 25 3 1 5 0 24.9 143.0 133 2 40.9 131.5 1940 78.4 50.4 145.5 170.8 19.7 16.2 25 7 13 7 I6 5 22.8 148.6 60.1 22.9 165 3 92.9 54.4 41.7 124.3 173.5 8.6 25.0 107 3 Yi,
Mol fimnula
()lliei ~ . i i h o n ~2036 Cj/.C32
176 2 194.7: 204Y OMe. 52 6 : 2050 OMe. 52 5 A,,
170.5 20 7
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
453
Table 32.--continued
2032
2031
2033
R = Moc-4-OH
oq3+o HO
2036
2035
2034
2038
2037
R'
RZ
1.'
@-CH,
a-CH,
a-OH
2041
8-CH,
@-CH,
a-OH
2042
a-CH,
a-CH,
@-OH
2043
a-CH,
fl-CH,
@-OF
2039
2044
R = a- H
2046
2045
R = 8-H
2047
R = a-H
~
2040
R = 0-H OR
0.
co
2048
2049
R = H
2050
R = Pc
454
M. BUDESINSKY AND D. SAMAN
Table 32.-continued No
2051 2052 2053 2054 2055 2056 2057 205X 2059 2060 2061 2062 2063 2064 2065
2066 2067 2068 2069 2070 2071
Mol. formula Name / Chemical shifts C-I C-2 C-3 C-4 C-5 C-6 C-7 C-8 C-9 C-10 C-I1 C-12 C-13 C-14 C-I5 C-16 C-17 C-18 C-19 C-20 C-21 C-22 C-23 C-24 C-25 C-26 C-27 C-28 C-29 C-30 Pungiolide A C.?OH3607 142.4 146.1 125.5 198.2 135.7 23.3 44.0 78.8 36.2 31.9 47.3 181.0 35.3 21 1 29 4 68.7 146.3 138.7 198.6 34.7 29.4 41.3 80.9 34.7 40.0 139.2 169.9 122.5 16.9 27.8 CZOH3608 Pungiolide B 62.2 146.0 130.0 197.6 65.8 26.4 41.9 80.4 32.6 41.5 47.9 180.0 34.9 17.4 26 I 68.9 146.7 138.6 199.2 32.9 29.6 41.5 80.7 34.7 40.0 140.4 169 7 122.7 17.0 27 Y CZOH4207 Biennin C 38.2' 32.1 90.8 102.2 38.0b a 42.1 77.0 36.0' 26.1 61.5 180.6 20.0 1 7 7 205 41.7 179.0 9.8 20.5 15.0 59.4 35.8' 55.3 138.0 143.2 34.9' 45.0 80.4 35.2' a C34H4609 Biennin C. diacetate 38.0 31.0 89.8 100.2 36.8 42.2 42.0 76.3 35.8 31.8 61.0 179 5 20.7 20 3 20 I 59.0 34.5 54.4 136.7 144.3 33.5 45.1 80.0 34.3 25.5 41.5 178.6 10.0 17.6 15 2 C34H4609 Biennin C, diacetate, 3,4-diepi 39.3 29.5 91.6 91.7 38.6 41.8 40.8 75.7 35.9 30.6 61.4 1799 20.1 2 0 9 17.4 9.7 15.1 13 6 58.0 35.1 55.6 137.1 144.4 31.7 44.6 80.3 34.8 25.4 41.6 179 2 C28H3206 Mexicanin F 50.3 166.3 133.0 211.0 57.9 28.4b 37.6 78.4' 36.7 26.3' 56.2 178 I 34 2 21 j. 47.9 43.3 38.9 213.3 59.0 26.0b 54.3 76.0' 36.3 26.0'139.2 169.3 123.3 21 I' Mexicanin F, tetrahydro C28H3606 49.0 20.3 37.0 221.5 57.7 27.4b 38.5 78.8' 37.2 28.5' 55.6 178.2 34.5 21.3' 4 8 7 44.3 38.8 213.6 59.0 24.4b 51.2 77.2' 36.7 26.6' 38.8 178.0 10.6 21.2' C30H3806 Gnchnatiolide A, 10-desnxy 169.3 142.2 193.7 141.9 51.0 82.7 43.7 25.3 31.2 33.3 138.7 169.6 120.8 26 I 120 i 40.0 45.1 220.2 51.0 49.4 84.0 43.5 32.0 39.5 150.6 139.4 1708 121.4 I13 '1 27 7 CZ0113007 Gnchnatiolide A, 10-desoxy-Sp-hydroxy 169.5 141.5 193.5 141.7 5 1 4 78.6 50.7 70.5 4 4 0 2 9 4 1379 1697 1215 262 121 2 39.9 45.0 220.4 50.9 49.5 84.0 43.5 31.9 39.5 150.5 1386 170.8 1227 113.9 2 7 9 C30H3008 Gnchnatiolide A. SO-hvdroxv 169.1 142.8 193.8 141.2 48.4 79.2 52.9 70.7 46.2 71.8 138.0 169.3 121.7 38.4 122.6 399 44.8 219.5 50.9 49.2 84.5 43.5 32.0 39.4 150.1 138.9 170.8 122.8 114 2 27 9 C30H3007 Gochnatiolide A, 10-epi, 10-desnxy-8'p-hydroxy 168.9 142.5 192.7 140.9 51.3 82.2 52.6 28.8 30.6 40.1 138.7 169.5 1192 27.9 1213 41.0 45.0 220.7 49.9 49.4 75.7 48.0 66.5 47.9 145.6 136.1 171.5 121.8 116.9 310 C30H3007 Gnchnatiolide A, 10-epi, 10-desnxy 169.5 142.6 192.8 140.9 49.9 82.2 52.5 28.8 31.1 40.1 138.7 169.5 119.2 27.9 121 2 40.9 45.1 220.8 51.1 49.8 83.9 43.5 31.9 39.5 150.5 138.6 171.2 121.4 1140 3 0 6 C30H3008 Gnchnatiolide A, 10-epi, IO-desnxy-8p,8p '-dihydroxy 168.8 142.5 192.7 140.9 51.0 76.5 57.3 63.2 40.1 32.0 135.6 169.4 120.3 28.6 121 0 39.6 45.1 220.8 50.4 49.6 84.0 43.6 31.2 39.4 150.4 138.6 171 4 121.4 114.1 3 0 9 C3OH3207 Lactucin, 8-0-hypnglabrate 133.1 194.4 124.7 171.7 53.3 81.0 55.0 69.6 44.4 165.3 133.1 168.0 121.8 18.6 62 5 39.2 207.3 133.7 145.7 37.4 28.3 48.6 23.5 27.1 37.4 136.4 176.3 126.3 21 5 17 6 3-Hydroxyambrosin damsinate C30H3806 46.2 22.5 35.8 220.5 51.0 38.1 37.0b 34.1 30.8 35.7b 146.8 163.6 124.7 21.0 17.2 42.8 143.8 145.9 201.8 55.2 79.9 44.4 24.7 29.9 33.8 138.5 170.1 119.4 17.3' 17 2' ~ 3 0 ~ 4 2 0 7 Arrivacin A 45.3 73.7 78.2 209.6 52.6 81.4 43.9 25.7 34.7 35.0 139.4 169.6 120.7 17 4 17 2 54.8 43.4 20.2 41.0 34.7 27.3 40.8 26.5 44.4 72.5 145.0 166 3 123.7 22 9 18 7 Arrivacin B C30H4006 43.0 143.3 144.4 202.2 55.3 79.9 44.5 24.8 29.9 34.0 138 2 170.2 119.9 17.2 17 2 55.2 43.4 20.1 41.0 34.6 26.5 4 0 7 27.2 44.5 72.0 147.0 164.1 125.3 2 2 6 18.7 Picrioside A, aglycone C30H3208 137.3b196.3 133.4' 172.9 48.8' 31.0' 44.1 32.W 36.4 154.1 144.7 165.8 124.7 61.0 I6 3 133.5' 194.5 134.0 175.0 49.3' 81.3 54.9 70.2 44.1 146.0 137.7b168.3 120.7 21.0 62 5 C36H42013 Picrioside A 137.4*196.5 133.6'173.2 48.7' 30.9' 44.0 32.W 36.3 154.2 145.38165.8 125.1 60.8 I 6 4 133.7' 194.6 135.0 169.5' 49.3* 81.3 54.7 70.1 44.0 146.P 137.6' 168.5' 121.0 21.1 6X.8 ~ 4 6 ~ 5 2 0 1 6 Picrioside A. acetate 139.8 195.7 133.3b173.5 48.9' 30.7' 43.8 31.7' 35.7 150.7 145.7' 165.7 125.2 62 5 I 6 4 133.Sh 194.1 134.4 168.2' 49.1' 81.1 54.7 70.0 44.2 145.9'137.5 168.3'121.2 21.1 68.8 Picrinside B C36H44013 137.4 196.3 133.4b173.1 48.8' 30.9' 44.0 32.0' 3 6 4 154.2 145.7' 165.8 1249 60.7 164 134.8 169.7 49.3' 80.9 58.5 71.3 44.5 146.1' 41.1 176.8 15.3 21 1 6 8 9 133.6b194.6
, . .
.
455
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
Table 32.--continued
2052
2051
a*
2056
0
0
O 2064
R'
8-OH
a-OH
2054 2055
B-OAc
a-OAc
a-OAc
8-3Ac
2058 2059 2060 2061 2062 2063
R'
R2
R3
H
n-H
H
H
a-H
OH
ti
a-OH
OH
OH
6-H
ti
H
8-H
H
OH
8-ti
OH
pQ
0-co
2065
G*+* 0
O
2066
R'
2053
0
co
O
0-co 2067
RJ
0.
co
2068 2069
R'
R2
R3
H
H
CH2
H
Glc
CH2
2070 Ac
Glc-2.3.4.6-Ac
2071
Glc
ti
CH, a-CH,.
I
456
M. BUDESINSKY AND D . SAMAN
REFERENCES 1. M. Abdel-Mogib, J. Jakupovic, A. M. Dawidar, M. A. Metwally and M. Abou-Elzahab, Phytochemistry, 1989, 28, 3528. 2. B. Abegaz, F. Camps, J. Colt, M. Feliz, U. Jacobson, C. Miravitlles, E. Molins and J. Torrarnilans, Tetrahedron, 1986, 42, 6003. 3. P. Aclinou, A. Benkouider, G . Massiot and L. Le Men-Olivier, Phytochemistry, 1991, 30, 2083. 4 . N. Acton and D . L. Klayman, Planta Medica, 1985, 49, 441. 5. N. Acton and D. L. Klayman, Planta Medica, 1987, 51, 266. 6. N. Acton and R. J. Roth, Phytochemistry, 1989, 28, 3530. 7. S. Adegawa, T. Miyase and S . Fukushima, Chem. Pharm. Bull., 1986, 34, 3769. 8. S . Adegawa, T. Miyase and A. Ueno, Chem. Pharm. Bull., 1987, 35, 1479. 9. S. Adegawa, T. Miyase, A. Veno, T. Noro, M. Kuroyanagi and S . Fukushima, Chem. Pharm. Bull., 1985, 33, 4906. 10. S . M. Adekenov, M. BudCSinsky, M. A . Abdikalikov, C. M. Turdybekov, D. Saman, E . Bloszyk, B. Drozd and M. Holub, Collect. Czech. Chem. Commun., 1990, 55, 1568. 11. P. K. Agrawal, R. A. Vishwakarma, D. C. Jain and R. Roy, Phytochemistry, 1991, 30, 3469. 12. V. U. Ahmad, A. Amber, K. Fizza and A. Karnal, 2. Naturforsch.. 1990, 45b, 1100. 13. V. U . Ahrnad, T. Zarnir, N. M. Hasan and K. Albert, J . Chem. SOC., 1986, 8, 425. 14. A. A. Ahmed, M. A. El-Eta, J. Jakupovic, A. A. S. El-Din and M. El-Ghazouly, Phytochemistry, 1990, 29, 3946. 15. A. A. Ahmed, J. Jakupovic, F. Bohlrnann, H. A. Regaila and A. M. Ahrned, Phytochemistry, 1990, 29, 2211. 16. A. A. Ahrned, A. T. Whitternore and T. J. Mabry, Phytochemistry, 1985, 24, 605. 17. A. A. Ahmed, A. T. Whitternore and T. J. Mabry, J . Nut. Prod., 1986, 49, 363. 18. M. Ahmed, J. Jakupovic, F. Bohlrnann and M. G . Mungai, Phyfochemistry, 1991, 30, 2807. 19. M. A. Al-Yahya, A. M. El-Sayed, J. S. Mossa, J. F. Kozlowski, M. D. Antoun, M. Ferin, W. M. Baird and J. M. Cassady, J . Nat. Prod., 1988, 51, 621. 20. M. S. At-Said, S. 1. Khalifa, F. S. El-Feraly and C. D. Hufford, Phytochemistry, 1989, 28, 107. 21. A. A. Alfatafta and C . A. Mullin, Phytochemistry, 1992, 31. 4109. 22. A. A. Ah, 0. M. Abdallah and W. Steglish, Pharmazie, 1989, 44,800. 23. I. Aljancic-Solaja, S. Milosavljevic, M. Djerrnanovic, M. Stefanovic and S. Macura, Mag. Reson. Chem., 1988, 26, 725. 24. M. Alonso-Lopez, J. Borges-del-Castillo, J. C. Rodriguez-Ubis and P. Vazquez-Bueno, J . Chern. SOC. Perkin I . , 1986, 2017. 25. L. Alvarez and G . Delgado. J . Org. Chem.. 1988, 53. 5527. 26. L. Alvarez, R. Mata, G . Delgado and A. Rorno de Vivar, Phytochemistry, 1985, 24, 2973. 27. Y . Amate, J . L. Breton, A. Garcia-Granados, A. Martinez, E. Onorato and A. Saenz de Buruaga, Tetrahedron, 1990, 46, 6939. 28. Y . Arnate, A. Garcia-Granados, A. Martinez, A. Saenz de Buruaga, J. L. Breton, M. E. Onorato and J. M. Arias, Tetrahedron, 1991, 47, 5811. 29. M. Ando, H. Kusaka, H . Ohara, K. Takase, H. Yamaoka and Y. Yanagi, J . Org. Chern., 1989, 54, 1952. 30. M. Ando, T. Wada and K. Isogai, J . Org. Chem., 1991. 56, 6235. 31. G. Appendino and P. Gariboldi, Phytochemistry, 1982, 21, 2555. 32. G . Appendino and P. Gariboldi, J . Chem. SOC.Perkin I , 1983, 2017. 33. G. Appendino and P. Gariboldi, Unpublished results, 1987. 34. G. Appendino, P. Gariboldi and F. Belliardo, Phytochemistry, 1986, 25, 2163.
CARBON-13 NMR SPECTRA O F SESQUITERPENE LACTONES
457
35. G. Appendino, P. Gariboldi, M. Calleri, G . Chiari and D. Viterho, J. Chem. SOC. Perkin I, 1983, 2705. 36. G. Appendino, P. Gariboldi and G . M. Nano, Phytochemistry, 1982, 21, 1099. 37. G. Appendino, P. Gariboldi and G . M. Nano, Phytochemistry, 1983, 22, 2767. 38. G. Appendino, P. Tettamanzi and P. Gariboldi, Phytochernistry, 1991, 30, 1319. 39. G. Appendino, M. G. Valle, R. Caniato and E. M. Cappelletti, Phytochemistry, 1986, 25, 1747. 40. H. Asada, T. Miyase and S. Fukushima, Chem. Pharm. Bull., 1984, 32, 3403. 41. H. Asada, T. Miyase and S. Fukushima, Chem. Pharm. Bull., 1984, 32, 3036. 42. H . Asada, T. Miyase and S. Fukushima, Chem. Pharm. Bull., 1984, 32, 1724. 43. Y. Asakawa, M. Toyota, Z. Taira and T. Takemoto, J. Chem. SOC. Chem. Commun., 1980, 1232. 44. Y. Asakawa, M. Toyota and T. Takemoto, Phytochemistry, 1981, 20, 257. 45. A. G. Avent, J. R. Hanson, P. B. Hitchcock and B. L. Yeoh, J. Chem. SOC.Perkin I , 1985, 2749. 46. F. Balza and G. H. N. Towers, Phytochernistry, 1988, 27, 1421. 47. C. Banh-Nhu, E. Gacs-Baitz, L. Radics, J. Tamas, K. Ujszaszy and G. Verzar-Petri, Phytochemistry, 1979, 18, 331. 48. P. Barbetti, G. Fardella, I. Chiappini, V. Scarcia and A . Furlani Candiani, Eur. J Med. Chem., 1989, 24, 299. 49. A. Bardon, C. A. N. Catalan, A. B. Gutierrez and W. Herz, Phytochemistry, 1988, 27, 2691. 50. A. Bardon, C. A. N. Catalan, A. B. Gutierrez and W. Herz, Phytochernistry, 1990, 29, 313. 51. A. Bardon, N. I. Kamiya, C. A. P. De Leon, C. A. N. Catalan, J. G . Diaz and W. Herz, Phytochemistry, 1992, 31, 609. 52. A. F. Barrero, M. M. Herrador and P. Arteaga, Phytochemistry, 1992, 31, 203. 53. A . F. Barrero, J. F. Sanchez and E. Arana, Phytochemistry, 1988, 27, 3969. 54. A. F. Barrero, J. F. Sanchez, A. Barron and A. Ramirez, Phytochemistry, 1992, 31, 332. 55. A. F. Barrero, J. F. Sanchez, J. Molina, A. Barron and M. Del Mar Salas, Phytochemistry, 1990, 29, 3575. 56. A. F. Barrero, J. F. Sanchez and I. Rodriguez, Phytochemistry, 1989, 28, 1975. 57. A. F. Barrero, J. F. Sanchez, M. J. Zafra, A. Barron and A. San Feliciano, Phytochemistry, 1987, 26, 1531. 58. S. Bartel and F. Bohlmann, Tetrahedron Lett., 1989, 30, 685. 59. N. C. Baruah, R. P. Sharma, K. P. Madhusudanan and G . Thyagarajan, J. Org. Chem., 1979. 44, 1831. 60. R. N. Baruah, R. P. Sharma, K. P. Madhusudanan, G . Thyagarajan, W. Herz and R. Murrari, Phytochemistry. 1979, 18, 991. 61. R. N. Baruah, R . P. Sharma, G . Thyagarajan, W. Herz, S. V. Govindan and J. F. Blount, J . Org. Chem., 1980, 45, 4838. 62. R . Battaglia. M. De Bernandi, G . Fronza, G. Mellerio, G . Vidari and P. Vita Finzi, 1. Nut. Prod.. 1980, 43, 319. 63. A. Bax, R. Freeman and 7’.Frenkiel, J. Am. Chem. SOC., 1981, 103, 2102. 64. A. Bax, R. Freeman and S. P. Kempsell, J . Am. Chem. SOC., 1980, 102, 4851. 65. A. Bax and G. A. Morris, J. Magn. Reson., 1981, 42, 501. 66. J. Beauhaire and J.-L. Fourrey, J. Chem. SOC. Perkin I , 1982, 861. 67. J. Beauhaire, J.-L. Fourrey, J. Y. Lallemand and M. Vuilhorgve, Tetrahedron Lett., 1981, 22, 2269. 68. J. Beauhaire, J.-L. Fourrey, M. Vuilhorgne and J. Y. Lallemand, Tetrahedron Lett., 1980, 21. 3191. 69. A . F. Beecham, Tetrahedron, 1972, 28, 5543.
458
M. BUDESINSKY AND D. SAMAN
70. M. J. Begley, L. Crombie, W. M. L. Crombie, A. K. Gatuma and A. Maradufu, J. Chem. SOC. Perkin I , 1984, 819. 71. M. J. Begley, M. J. Hewlett and D . W. Knight, Phytochemktry, 1989, 28, 940. 71a.H. Beierbeck, J. K. Saunders and J. W. ApSimon, Can. J. Chem. 1977, 55, 2813. 72. I. S. Bellido, M. Medarde, E. Caballero, A. R. Feijoo and M. Gordaliza, Planta Medica, 1988, 52, 180. 73. C. A. Bevelle, G. A. Handy, R. A. Segal, G. A. Cordel and N. F. Farnsworth, Phytochemistry, 1981, 20, 1605. 74. N. S. Bhacca, F. W. Wehrli and N. H. Fischer, J . Org. Chem., 1973, 38, 3618. 75. N. S. Bhacca, R. A. Willey, N. H. Fischer and F. W. Wehrli, J. Chem. SOC. Chem. Commun., 1973, 614. 75a.P. Bhandari and R. P. Rastogi, Ind. J. Chem., 1983, 22B, 286. 76. M. Bittner, J. Jakupovic, F. Bohlmann and M. Silva, Phytochemistry, 1989, 28, 271. 77. G. Blay, L. Cardona, B. Garcia and J. R. Pedro, Tetrahedron Lett., 1992, 33, 5253. 78. G . Blay, I. Fernandez, B. Garcia and J. R. Pedro, Tetrahedron, 1989, 45, 5925. 79. G. Blay, M. L. Cardona, B. Garcia and J . R. Pedro, J. Org. Chem., 1991, 56, 6172. 80. E. Bloszyk, M. BudeSinskf, W. M. Daniewski, E. PeSkova, B. Drozdz and M. Holub, Collect. Czech. Chern. Commun., 1990, 55, 1562. 81. E. Bloszyk, A. Dudek, 2. Kosturkiewicz, U. Rychlewska, W. M. Daniewski, M. Gumulka, J. Nawrot, M. BudBSinskg, S. VaSitkova and M. Holub, Collect. Czech. Chem. Commun., 1989, 54, 1903. 82. E. Bloszyk, U. Rychlewska, B. Szcepanska, M. BudEinsky, B. Drozdz and M. Holub, Collect. Czech. Chem. Commun., 1992, 57, 1092. 83. Bodenhausen, R. Freeman and D . L. Turner, J. Chem. Phys., 1976, 65, 839. 84. R. Boeker, J. Jakupovic, F. Bohlmann and G. Schmeda-Hirschmann, Planta Medica, 1987, 51, 105. 85. F. Bohlmann, A. Adler, J. Jakupovic, R. M. King and H. Robinson, Phytochemistry, 1982, 21, 1349. 86. F. Bohlmann, W. Ang, C. Trinks, J. Jakupovic and S. Huneck, Phytochemistry, 1985, 24, 1009. 87. F. Bohlmann, G . Brindopke and R . C. Rastogi, Phytochemistry, 1978, 17, 475. 88. F. Bohlmann, N. Goren, J. Jakupovic, R. M. King and H. Robinson, Phytochemistry, 1982, 21, 2691. 89. F. Bohlmann, J. Jakupovic, W.-R. Abraham and C. Zdero, Phytochemistry, 1981, 20, 2371. 90. F. Bohlmann, J. Jakupovic, N. Goren, A. Schuster, J. Pickardt, R. M. King and H. Robinson, Liebigs Ann. Chem., 1983, 962. 91. F. Bohlmann, J. Jakupovic, R. K. Gupta, R. M. King and H. Robinson, Phytochemistry, 1981, 20, 473. 92. F. Bohlmann, J. Jakupovic, R. M. King and H. Robinson, Phytochemistry, 1981, 20, 1613. 93. F. Bohlmann, J. Jakupovic and A. Schuster, Phytochemistry, 1985, 24, 495. 94. F. Bohlmann and K.-H. Knoll, Phytochemistry, 1979, 18, 995. 95. F. Bohlmann, W. Kramp, R. K. Gupta, R. M. King and H. Robinson, Phytochemistry, 1981, 20, 2375. 96. F. Bohlmann, G.-W. Ludwig, J. Jakupovic, R. M. King and H. Robinson, Phytochemisfry, 1983, 22, 983. 97. F. Bohlmann, L. N. Misra and J. Jakupovic, Phytochemistry, 1985, 24, 1021. 98. F. Bohlmann, G . Schmeda-Hirschmann, J. Jakupovic, R. M. King and H. Robinson, Phytochemistry, 1984, 23, 1989. 99. F. Bohlmann, K. Umemoto and J. Jakupovic, Phytochemistry, 1985, 24, 1017. 100. F. Bohlmann, M. Wallmeyer and J. Jakupovic, Phytochemistry, 1982, 21, 1445.
CARBON-13 NMR SPECTRA O F SESQUITERPENE LACTONES
459
101. F. Bohlmann, C. Zdero, J. Jakupovic, M. Grenz, V. Castro, R. M. King, H. Robinson and L. P. D. Vincent, Phytochemistry, 1986, 25, 1151. 102. F. Bohlmann, C. Zdero, J. Jakupovic and J. P. Rourke, Liebigs Ann. Chem., 1985,2342. 103. F. Bohlmann, C. Zdero, R. M. King and H. Robinson, Phytochemlstry, 1981, 20, 1069. 104. F. Bohlmann, C. Zdero, R. M. King and H. Robinson, Phytochemistry, 1982, 21, 695. 105. F. Bohlmann, C. Zdero, R. M. King and H. Robinson, Liebigs Ann. Chem., 1986, 799. 106. F. Bohlmann, C. Zdero, J. Pickard, H. Robinson and R. M. King, Phytochemistry, 1981, 20. 1323. 107. F. Bohlmann, C. Zdero, H. Robinson and R. M. King, Phytochemlstry, 1980, 19, 2381. 108. F. Bohlmann, C. Zdero and M. Ahmed, Phytochemistry, 1982, 21, 1679. 109. F. Bohlmann, C. Zdero, G. Schmeda-Hirschmann, J. Jakupovic, X. A . Dominguez, R. M. King and H. Robinson, Phytochemistry, 1986, 25, 1175. 110. F. Bohlmann, C. Zdero and B. L. Turner, Phytochemistry, 1985, 24, 1263. I l l . M. Bordoloi, J. C. Sarmah and R. P. Sharma, Tetrahedron, 1989, 45, 289. 112. J. C. Borella, J. L. Callegarilopes, H. F. L. Filho, J. Semir, J. G. Diaz and W. Herz, Phytochemistry, 1992, 31, 692. 113. J. Borges-del-Castillo, M. T. Manresa Ferrero, F. Rodriguez Luis, P. Vazquez Bueno and P. Joseph Nathan, Org. Magn. Res., 1981, 17, 232. 114. J. Borges-del-Castillo, M. T. Manresa Ferrero, F. Rodriguez Luis, P. Vazquez Bueno, N. Genoves Lenor and S. Castillo Arevalo, J . Nat. Prod., 1981, 44,348. 115. J. Borges-del-Castillo, M. T. Manresa Ferrero, F. Rodriguez Luis, J. C. Rodriguez Ubis and P. Vazquez Bueno, Rev. Latinoamer. Quim.,1984, 15, 96. 116. A. K. Bose and P. R. Srinivasan, Tetrahedron, 1975, 31, 3025. 117. A . Bosetti, G. Fronza, G . Vidari and P. Vita-Finzi, Phytochemistry, 1989, 28, 1427. 118. E. Breitmaier and W. Voelter, Carbon-I3 NMR Spectroscopy, 3rd edn, VCH Publishers, Weinheim, 1989. 119. J. L. Breton, F. Camps, J. Coll, L. Eguren, J. A. Gavin, A. G . Gonzales, X. Martorell, C. Miravitlles, E. Molins and J. Torramilans, Tetrahedron, 1985, 41, 3141. 120. M. Bruno, J. G. Diaz and W. Herz, Phytochemistry, 1991, 30,4165. 121. M. Bruno, J. G. Diaz and W. Herz, Phytochemistry, 1991, 30, 3458. 122. M. Bruno and W. Herz, Phytochemistry, 1988, 27, 1873. 123. M. BudtSinsky, H. Grabarczyk, W. M. Daniewski, A. Wawrzun, M. Gumulka, D. Saman, B. Drozdz and M. Holub, Collect. Czech. Chem. Commun., 1989, 54, 1919. 124. M. BudBSinsk9, N. Perez Souto and M. Holub, Collect. Czech. Chem. Commun., 1994, 59. 913. 125. M. BudCSinsky, L. V. N. Phuong, N. P. Souto, W. M. Daniewski, A. Wawrzun, M. Gumulka, S. VaSiEkova, D. Saman, B. Drozdz, H. Grabarczyk, U. Rychlewska and M. Holub, Collect. Czech. Chem. Commun., 1989, 54, 473. 126. M. BudBSinsky and D. +man, Unpublished results. 127. M. BudtSinsky and D. Saman, Collect. Czech. Chem. Commun., 1987, 52, 453. 128. M. BudtSinsky, D. Saman, J. Pelnai, S. VaSiEkovA, B. Drozdz, H. Grabarczyk, L. V. N. Phuong and M. Holub, Collect. Czech. Chem. Commun., 1989, 54, 166. 129. Cambridge Crystallographic Data Centre, Lensfield Road, Cambridge CB2 1EW, England. 130. M. Carda, J. F. Sanz and J. A. Marco, J . Org. Chem., 1992, 57, 804. 131. M. L. Cardona, I. Fernandez, B. Garcia and J. R. Pedro, J . Nat. Prod., 1990, 53, 1042. 132. M. L. Cardona, I. Fernandez, J. R. Pedro and B. Perez, Phytochemistry, 1991, 30, 2331. 133. M. L. Cardona, B. Garcia, J. R. Pedro and J. F. Sinisterra, Phytochemistry, 1989, 28, 1264. 134. B. Carte, M. R. Kernan, E . B. Barrabee and D. J. Faulkner, J . Org. Chem., 1986, 51, 3528. 135. C. G. Casinovi, G. Fardella and C. Rossi, Planta Medica, 1982, 46, 186.
460
M. BUDESINSKY AND D. SAMAN
136. C. G. Casinovi, L. Tomassini and M. Nicoletti, Gaz. Chim. Ztal., 1989, 119, 563. 137. V. Castro, J. Jakupovic and F. Bohlmann, Phytochemistry, 1986, 25, 1750. 138. P. Ceccherelli, M. Curini, M. C. Marcotullio and 0. Rosati, Tetrahedron Lett., 1990, 31, 307 1. 139. Y. Chen, M. F. Bean, C. Chambers, T. Francis, M. J. Huddleston, P. Offen, J. W. Westley and B. K. Carte, Tetrahedron, 1991, 47, 4869. 140. P. K. Chowdhury, N. C. Barua, R. P. Sharma, J. N. Barua, W. Herz, K. Watanabe and J. F. Blount, J . Org. Chem., 1983, 48, 732. 141. S. B. Christensen, I. K. Larsen and U. Rasmussen, J. Org. Chem., 1982, 47, 649. 142. S. B. Christensen, E. Norup, U. Rasmussen and J. 0. Madsen, Phytochemistry, 1984, 23, 1659. 143. S. B. Christensen and K. Schaumburg, J. Org. Chem., 1983, 48, 396. 144. J. C. Christofides and D. B. Davies, J . A m . Chem. Soc., 1983, 105, 5099. 145. D. L. J. Clive and A. C. Joussef, J. Org. Chem., 1990, 55, 1096. 146. J. D. Connolly and R. A. Hill (eds), Dictionary of Terpenoids, Vol. 1, Chapman & Hall, London, 1991. 147. P. L. Cowall, J. M. Cassady, C.-J. Chang and J. F. Kozlowski, J. Org. Chem., 1981, 46, 1108. 148. P. J. Cox, Tetrahedron Lett., 1979, 3569. 149. M. D. R. Cuenca, A. Bardon, C. A. N. Catalan and W. C. M. C. Kokke, J. Nat. Prod., 1988, 51, 625. 150. M. R. Cuenca and C. A. N. Catalan, J. Nat. Prod., 1990, 53, 686. 151. A. J. R. Da Silva, M. Garcia, P. M. Baker and J. A. Rabi, Org. Magn. Reson., 1981, 16, 230. 152. J. Dahmen and K. Leander, Phytochemistry, 1978, 17, 1949. 153. W. M. Daniewski, M. Gumulka, K. Ptaszynska, P. Skibicki, J. Krajewski and P. Gluzinski, Phytochemistry, 1992, 31, 913. 154. W. M. Daniewski, M. Gumulka and P. Skibicki, Phytochemistry, 1990, 29, 527. 155. W. M. Daniewski, M. Gumulka, P. Skibicki, U. Jacobson and T. Norin, Bull. Pol. Acad. Sci., 1987, 35, 251. 156. W. M. Daniewski, W. Kroszczynski, E. Bloszyk, B. Drozdz, J. Nawrot, U. Rychlewska, M. BudCSinsky and M. Holub, Collect. Czech. Chem. Commun., 1986, 51, 1710. 157. W. M. Daniewski, G. Nowak, E. Routsi, U. Rychlewska, B. Szcepanska and P. Skibicki, Phytochemistry, 1992, 31, 2891. 158. S. Das, R. N. Baruah, R. P. Sharma, J. N. Baruah, P. Kulanthaivel and W. Herz, Phytochemistry, 1983, 22, 1989. 159. M. T. Davies-Coleman, R. B. English and D. E. A. Rivett, Phytochemistry, 1992, 31, 2165. 160. M. De Bernardi, G. Fronza, G. Mellerio, G. Vidari and P. Vita-Finzi, Phytochemistry, 1979, 18, 293. 161. A. N. De Gutierrez, E. E. Sigstad, C. A. N. Catalan, A. B. Gutierrez and W. Herz, Phytochemistry, 1990, 29, 1219. 162. C. S. De Heluani, M. P. De Lampasona, C. A. N. Catalan, V. L. Goedken, A. B. Gutierrez and W. Herz, Phytochemistry, 1989, 28, 1931. 163. D. H. De Luengo, M. Miski, D. A. Gage and T. J. Mabry, Phytochemistry, 1986, 25, 1917. 164. J. De Pascual Teresa, J. Anaya, E. Caballero and M. C. Caballero, Phytochemistry, 1988, 27, 855 165. J. De Pascual Teresa, E. Caballero, J. Anaya, C. Caballero and M. S. Gonzalez, Phytochemistry, 1986, 25, 1365. 166. G. Delgado, L. Alvarez, E. Huerta and A. Romo de Vivar, Mag. Res. Chem., 1987, 25, 201.
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
461
167. G. Delgado, L. Alvarez and A . Romo de Vivar, Phytochemistry, 1984, 23, 675. 168. G. Delgado, H. Cardenas, G. Pelaez and A. Romo de Vivar, J . Nat Prod., 1984, 47, 1042. 169. G. Delgado, P. E. Garcia, R. A. Bye and E . Linares, Phytochernistry, 1991, 30, 1716. 170. G. Delgado, S. Guzman and A. Romo de Vivar, Phytochemistry, 1987, 26, 755. 171. G. Delgado, H. Hernandez and A. Romo de Vivar, J . Org. Chem., 1984, 49, 2994. 172. G. Delgado, A. Romo de Vivar and W. Herz, Phytochernistry, 1982, 21, 1305. 173. R. Di Benedetto, F. Menichini, E. Gacs-Baitz and F. Delle Monache, Phytochernistry, 1991. 30, 3657. 174. A. E. Derome, Nat. Prod. Rep., 1989, 5, 111. 175. E. Diaz, G. G. Dominguez, A. Mannino, G. Negron and K. Jankowski. Magn. Reson. Chem., 1985, 23, 494. 176. J. G. Diaz, V. L. Goedken and W. Herz, Phytochemistry, 1992, 31, 597. 177. C. Djerassi et al. (eds), Dictionary of Natural Products, Chapman & Hall, London, 1992. 178. D. M. Doddrell, D. T. Pegg and M. R. Bendall, J . Magn. Reson., 1982, 48, 323. 179. R. W. Doskotch, F. S. El-Feraly, E. H. Fairchild and C.-T. Huang, J . Org. Chem., 1977, 42. 3614. 180. R. W. Doskotch, E. H. Fairchild, C.-T. Huang, J. H. Wilton, M. A. Beno and G. G. Christoph, J . Org. Chem., 1980, 45, 1441. 181. R. W. Doskotch, J. M. Wilton, F. M. Harraz, E. H. Fairchild, C.-T. Huang and F. S. El-Feraly, J . Nat. Prod., 1983, 46, 923. 182. S. Dupre, M. Grenz, J. Jakupovic, F. Bohlmann and H. M. Niemeyer, Phytochemistry, 1991, 30, 1211. 183. M. A. El-Ela, J. Jakupovic, F. Bohlmann, A. A. Ahmed, S. A. El-Din, S. Khafagi. N. Sabri and M. El-Ghazouly, Phytochernistry, 1990, 29, 2704. 184. S . El. Dahmy, T. Sarg, S. A. Salem, J. Jakupovic and F. Bohlmann, Planta Medica, 1986, 50, 365. 185. M. A. El Sohly. J . Nat. Prod., 1984, 47, 533. 186. M. A. El Sohly, A. S. Sharma and C. E. Turner, J . Nat. Prod., 1981, 44, 617. 187. F. S. El-Feraly, Phytochernistry, 1983, 22, 2239. 188. F. S. El-Feraly, Phytochernistry, 1984, 23, 2372. 189. F. S . El-Feraly, D. A. Benigni and A. T. McPhail, J . Chem. SOC. Perkin I , 1983, 355. 190. F. S . El-Feraly, Y.-M. Chan, G. A. Capiton, R. W. Doskotch and E. H. Fairchild, J . Org. Chem., 1979, 44, 3952. 191. S. El-Masry, A. H. A. Abou-Donia, F. A. Darwish, M. A. Abou-Karam, M. Grenz and F. Bohlmann, Phytochemistry, 1984, 23, 2953. 192. N . H. El-Sayed, M. Miski, A. T. Whittemore and T. J. Mabry, Phytochemistry, 1988, 27, 3312. lY3. E. Ellmauerer, V. P. Pathak, J. Jakupovic. F. Bohlmann, X. A. Dominguez, R. M. King and H. Robinson, Phytochernistry, 1987. 26, 159. 194. W. W. Epstein and E. E. U. Jenkins, J . Nat. Prod., 1979, 42, 279. 195. R. R. Ernst, J . Chem. Phys., 1966, 45, 3854. 196. G . Falsone, H. Haddad and D. Wendisch, Arch. Pharm., 1986, 319, 372. 197. N. Fang, D. H. De Luengo and T. J. Mabry, Phytochemistry, 1986, 25, 2665. 198. N. Fang, D. A. Gage and T. J. Mabry, Phytochernistry, 1988, 27, 203. 199. N. Fang and T. J. Mabry, Phytochemistry, 1988, 27, 283. 200. N. Fang, S. Yu, T. J. Mabry, K. A. Abboud and S. H. Simonsen, Phytochemistry, 1988, 27. 3187. 201. I . Fernandez, B. Garcia, F. J. Grancha and J. R. Pedro, Phytochemistry, 1987, 26, 2403. 202. I. Fernandez, B. Garcia, F. J. Grancha and J. R. Pedro, Phytochernistry, 1989, 28, 2405. 203. 2 . S. Ferreira, N. F. Roque, 0. R. Gottlieb, F. Oliveira and H. E. Gottlieb, Phytochernistry, 1980, 19, 1481.
462
M. BUDESINSKY AND D. SAMAN
204. N. H. Fischer, I.-Y. Lee and F. R. Fronczek, J . Nut. Prod., 1984, 47, 419. 205. N. H. Fischer, E. J. Olivier and H. D. Fischer, Fortschrifte d . Chern. org. Nufursf.,1979, 38. 47. 206. R. Freeman and H. D. W. Hill, J . Chern. Phys., 1969, 51, 3140. 207. F. R. Fronczek, D. Vargas and N. H. Fischer, J . Nut. Prod., 1984, 47, 1036. 208. Y. Fujimoto, T. Kinoshita, N. Ikekawa and J. Mungarulire, Phytochernistry, 1987, 26. 2593. 209. Y . Fujimoto, A. Soemartono and M. Sumatra, Phytochernistry, 1988, 27, 1109. 210. Y. Fukuyama, T. Sato, I. Miura and Y. Asakawa, Phytochernistry, 1985, 24, 1521. 211. Y. Fukuyama, N. Shida, M. Kodama, M. Kido and M. Nagasawa, Tetrahedron Left., 1990, 31, 5621. 212. C. A. Fyfe, Solid Sfate N M R for Chemists, C.F.C. Press, Guelph, 1983. 213. I. Ganjian, I. Kubo and P. Fludzinski, Phytochernistry, 1983, 22, 2525. 214. U. Ganzer and J. Jakupovic, Phytochernistry, 1990, 29, 535. 215. F. Gao and T. J. Mabry, Phytochernistry, 1986, 25, 137. 216. F. Gao, M. Miski and T. J. Mabry, Phytochernistry, 1986, 25, 1231. 217. F. Gao, B. L. Turner and T. J. Mabry, Phytochernistry, 1988, 27, 2685. 218. F. Gao, H. Wang and T. J. Mabry, Phytochernistry, 1987, 26, 779. 219. F. Gao, H. Wang and T. J. Mabry, J . Nut. Prod., 1987, 50, 23. 220. F. Gao, H. Wang and T. J. Mabry, Phytochernistry, 1990, 29, 1601. 221. F. Gao, H. Wang and T. J. Mabry, Phytochernistry, 1990, 29, 2273. 222. F. Gao, H. Wang and T. J. Mabry, Phytochernistry, 1990, 29, 3875. 223. F. Gao, H. Wang, T. J. Mabry, K. A . Abboud and S . H. Simonsen, Phytochernistry, 1989, 28, 2409. 224. F. Gao, H. Wang, T. J. Mabry and M. W. Bierner, Phytochernistry, 1990, 29, 895. 225. F. Gao, H. Wang, T. J. Mabry and J . Jakupovic, Phyfochernistry, 1991, 30, 553. 226. F. Gao, H. Wang, T . J. Mabry and A. D. Kinghorn, Phytochernistry, 1990, 29, 2865. 227. F. Gao, H. Wang, T. J. Mabry, W. H. Watson and R. P. Kashyap, Phytochernistry, 1990, 29, 551. 228. E. E. Garcia and E. Guerreiro, Phytochernistry, 1988, 27, 288. 229. M. Garcia, A. J. R. Da Silva, P. M. Baker, B. Gilbert and J. A. Rabi, Phytochernisfry, 1976, 15, 331. 230. S. N. Garg, L. N. Misra, S. K. Aganval, V. P. Mahajan and S. N. Rastogi, Phytochernistry, 1987, 26, 449. 231. J. Gershenzon, Y.-L. Liu, T. J. Mabry, J. D. Korp and I. Bernal, Phytochemisrry, 1984, 23. 1281. 232. J. Gershenzon and T. J. Mabry, Phytochernistry, 1984, 23, 1959. 233. J. Gershenzon and T. J. Mabry, Phytochernisfry, 1984, 23, 2557. 234. J. Gershenzon, T. J. Mabry, J. D. Korp and I. Bernal, Phytochernisfry, 1984, 23, 2561. 235. J. Gershenzon, R. M. Pfeil, Y. L. Liu, T. J. Mabry and B. L. Turner, Phytochernistry, 1984, 23, 777. 236. R. R . Gil, A. D. V. Pacciaroni, J . C. Oberti, J. G . Diaz and W. Herz, Phytochernistry, 1992, 31, 593. 237. R. R . Gil, J . C. Oberti, A. B. Gutierrez and W. Herz, Phyfochernistry, 1990, 29, 3881. 238. R. R. Gil, J. C. Oberti, V. E. Sosa and W. Herz, Phytochernistry, 1987, 26, 1459. 239. R. R. Gil, J. A . Pastoriza, J. C. Oberti, A. B. Gutierrez and W. Herz, Phytochernistry, 1989, 28, 2841. 240. 0. S. Giordano. M. J. Pestchanker, E. Guerreiro, J. R. Saad, R. D . Enriz, A. M. Rodriguez, E. A. Jauregui, J. Guzman, A . 0. M. Maria and G . H. Wendel, J . Med. Chern., 1992, 35, 2452. 241. V. W. Goodlet, Anal. Chern., 196.5, 37, 431. 242. A . G. Gonzales, J. Bermejo, H. Mansilla, A. Galindo, J. M. Arnaro and G . M. Massanet, J . Chern. Soc. Perkin I , 1978, 1243.
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
463
243. A. G . Gonzales, A. Galindo, M. M. Afonso, H. Mansilla and M. Lopez, Tetrahedron, 1988, 44,4585. 244. A. G. Gonzales, A. Galindo, M. M. Afonso, H. Mansilla, J. A . Palenzuela, M. A. G. Rodriguez and M. Martinez-Ripoll, Tetrahedron, 1988, 44,4575. 245. A. G. Gonzales, A. Galindo, H. Mansilla and A. Gutierrez, Phytochernistry, 1981, 20, 2367. 246. A. G. Gonzales, A. Galindo, H. Mansilla, V. H. Kesternich, J. A. Palenzuela and M. Lopez, Tetrahedron, 1988, 44,6750. 247. A. G . Gonzales, A. Galindo, H. Mansilla, V. H. Kesternich, J. A. Palenzuela and M. L. Rodriguez, J. Nat. Prod., 1990, 53, 462. 248. A. G. Gonzales, T. A. Grillo, J. G . Luis, J. T. Vazquez, M. L. Rodriguez, J. L. Ravelo, J. Calle and A. Rivera, fhytochemistry, 1990, 29, 3581. 249. N. Goren, C. Bozok-Johansson, J. Jakupovic, L.-J. Lin, H.-L. Shieh, G . A. Cordell and N. Celik, Phytochemistry, 1992, 31, 101. 250. N. Goren, A. Ulubelen, J. Jakupovic, F. Bohlmann and M. Grenz, Phytochemistry, 1984, 23. 2281. 251. A. C. Goswani, R. N. Baruah, R. P. Sharma, J. N. Baruah, P. Kulanthaivel and W. Herz, Phytochemisrry, 1984, 23, 367. 252. R. 0. Gould, T. J. Simpson and M. D. Walkinshaw, Tetrahedron Lett., 1981, 1047. 253. G. Grandolini, C. G. Casinovi, P. Betto, G . Fardella, F. Menichini, R. Gabriele, P. Barbetti, M. Kajtar-Peredy and L. Radics, Phytochernistry, 1988, 27, 3670. 254. N. A. B. Gray, Progr. NMR Spectrosc., 1982, 15, 201. 255. A. E. Greene and M. T. Edgar, J . Org. Chem., 1989, 54, 1468. 256. S. H. Grode and J. H. Cardellina 11, J . Nut. Prod., 1984, 47, 76. 257. G. Guella, A. Guerriero and F. Pietra, Helv. Chim. Acta, 1985, 68, 39. 258. G . Guella, I. Mancini, A. Guerriero and F. Pietra, Helv. Chem. Acta, 1985, 68, 1276. 259. E. Guerreiro, fhytochemistry, 1986, 25, 748. 260. E. Guerreiro and P. Joseph-Nathan, Rev. Latinoamer. Quim., 1985, 16, 110. 261. F. H. Guidugli, M. J. Pestchanker, M. S. A . De Salmeron and 0. S. Giordano, Phytochemistry, 1986, 25, 1923. 262. A. B. Gutierrez and W. Herz, Phytochemistry, 1988, 27, 2225. 263. A. B. Gutierrez, J. C. Oberti, V. E. Sosa and W. Herz, Phytochemistry, 1987, 26, 2315. 264. A. B. Guttierez and W. Herz, Planfa Medica, 1990, 56, 295. 265. S. Hafez, J. Jakupovic, F. Bohlmann, T. M. Sarg and A. A. Omar, Phytochemistry, 1989, 28, 843. 266. R. Hansel, M. Kartarahardja, J.-T. Huang and F. Bohlmann, fhytochemistry. 1980, 19, 857. 267. P. E. Hansen, Prog. NMR Spectrosc., 1981, 14, 175. 268. F. M. Harraz, F. F. Kassem, M. Grenz, J. Jakupovic and F. Bohlmann, Phytochemistry, 1988, 27, 1866. 269. M. Haruna, M. Kato, K. Ito, T. Nikai, H. Sugihara and H. Murata, Phytochemistry. 1981, 20, 2583. 270. C. Hasbun, M. A. Calvo, L. J. Poveda, A. Malcolm, T. J. Delord, S. F. Watkins, F. R. Fronczek and N. H. Fischer, J . Nut. Prod., 1982, 45, 749. 271. T. Hashimoto, M. Tori and Y . Asakawa, Phytochemistry, 1989, 28, 3377. 272. N. A. R. Hatam, N. J. Yousif, A. Porzel and K. Seifert, Phytochemistry, 1992, 31, 2160. 273. T. Hayashi, J. Koyama, A. T. McPhail and K.-H. Lee, fhytochernistry, 1987, 26, 1065. 274. W. Herz and M. Bruno, fhytochemistry, 1987, 26, 457. 275. W. Herz and M. Bruno, Phytochemistry, 1987, 26, 201. 276. W. Herz, R. De Groote and R. Murari, J . Org. Chem., 1978, 43. 3559. 277. W. Herz, R. De Groote, R. Murari and N. Kumar, J . Org. Chem., 1979, 44, 2784. 278. W. Herz, D. Gage and N. Kumar, Phytochernistry, 1981, 20, 1601. 279. W. Herz and S. V. Govindan, Phytochemistry, 1980, 19, 1234.
464 280. 281. 282. 283. 284. 285. 286. 287. 288. 289. 290. 291. 292. 293. 294. 295. 296. 297. 298. 299. 300. 301. 302. 303. 304. 305. 306. 307. 308. 309. 310. 311. 312. 313. 314. 315. 316. 317. 318. 319. 320. 321. 322. 323. 324. 325.
M. BUDESINSKY AND D. SAMAN W. Herz and S. V. Govindan, Phytochemistry, 1981, 20, 1740. W. Herz and S. V. Govindan, Phytochemistry, 1981, 20, 2229. W. Herz, S. V. Govindan, M. W. Biener and J. F. Blount, J . Org. Chem., 1989, 45, 493. W. Herz, S. V. Govindan and J. F. Blount, J . Org. Chem., 1980, 45, 1113. W. Herz, S. V. Govindan, J. F. Blount, J . Org. Chem., 1980, 45, 3163. W. Herz, S. V. Govindan and J . F. Blount, J . Org. Chem., 1981, 46, 761. W. Herz, S. V. Govindan and N. Kumar, Phytochemistry, 1981, 20, 1343. W. Herz and P. S. Kalyanaraman, J . Org. Chem., 1975, 40,3486. W. Herz, P. S. Kalyanaraman, G . Ramakrishnan and J . F. Blount, J . Org. Chem., 1977, 42. 2264. W. Herz and P. Kulanthaivel, Phytochemistry, 1982, 21, 2475. W. Herz and P. Kulanthaivel, Phytochemisfry, 1983, 22, 513. W. Herz and P. Kulanthaivel, Phytochemistry, 1983, 22, 715. W. Herz and P. Kulanthaivel, Phytochemisfry, 1984, 23, 2271. W. Herz and P. Kulanthaivel, Phytochemistry, 1984, 23, 1453. W. Herz and P. Kulanthaivel, Phytochemistry, 1985, 24, 1761. W. Herz, P. Kulanthaivel and V. L. Goedken, J . Org. Chem., 1985, 50, 610. W. Herz and N. Kumar, Phytochemistry, 1979, 18, 1743. W. Herz and N. Kumar, Phytochemistry, 1980, 19, 593. W. Herz and N. Kumar, J . Org. Chem., 1980, 45, 489. W. Herz and N. Kumar, Phyfochemistry, 1980, 19, 2387. W. Herz and N. Kumar, Phyfochernistry, 1981, 20, 99. W. Herz and N. Kumar, Phyfochemistry, 1981, 20, 93. W. Herz and N. Kumar, Phytochemistry, 1981, 20, 13391. W. Herz, N. Kumar and J . F. Blount J . Org. Chem., 1979, 44, 4437. W. Herz, N. Kumar and J. F. Blount, J . Org. Chem., 1981, 46,1356. W. Herz, N. Kumar, W. Vichnewski and J. F. Blount, J. Org. Chem., 1980, 45, 2503. W. Herz, R. Murari and S. V. Govindan, Phytochernistry, 1979, 18, 1337. W. Herz, K. D. Pethtel and D. Raulais, Phytochemistry, 1991, 30, 1273. W. Herz, J. S. Prasad and J. F. Blount, J . Org. Chem., 1982, 47, 3991. W. Herz and R. P. Sharma, J . Org. Chem., 1975, 40, 392. W. Herz and R. P. Sharma, J . Org. Chem., 1975, 40, 2557. W. Herz and R. P. Sharma, J . Org. Chem., 1975, 40, 3118. W. Herz and R. P. Sharma, J . Org. Chem., 1976, 41, 1248. W. Herz and R. P. Sharma, J . Org. Chem., 1976, 41, 1015. W. Herz and V. E. Sosa, Phytochemistry, 1986, 25, 1481. W. Herz and V. E. Sosa, Phytochemistry, 1988, 27, 155. W. Herz, P. S. Subramaniam, R. Murari, N. Dennis and J . F. Blount, J . Org. Chem., 1977, 42, 1720. W. Herz, 1. Wahlberg, C. S. Stevens and P. S. Kalyanaraman, Phytochemistry, 1975, 14, 1803. W. Herz, K. Watanabe and J . F. Blount, Phytochemistry, 1984, 23, 373. W. Herz, K. Watanabe, R. K. Godfrey and J. F. Blount, Phytochemistry, 1984, 23. 599. A. Hisham, L. Pieters, M. Claeys, R. Dommisse, D. Van den Berghe and A. Vlietinck, Planta Medica, 1992, 58, 474. M. Holub, M. BudiSinskL, 2. Smitalova, D. Saman and U. Rychlewska, Collect. Czech. Chem. Cornrnun., 1985, 50, 1878. M. Holub, M. BudiSinsky. 2. Smitalova, D. Saman and U. Rychlewska, Collect. Czech. Chem. Cornrnun., 1986, 51, 903. T. D. Hubert, A. L. Okunade and D. F. Wiemer, Phytochemistry, 1987, 26, 1751. J . W. Huffman, W. T. Pennington and D. W. Bearden, J . Nut. Prod., 1992, 55, 1087. T. Iida and K. Ito, Phytochemisfry, 1982, 21, 701.
CARBON-13 NMR SPECTRA O F SESQUITERPENE LACTONES
465
326. S. Inayama, K. Harimaya, T. Ohkura and T. Kawamata, Heterocycles, 1982, 17, 219. 327. N. Ishihara, T. Miyase and A. Ueno, Chem. Pharm. Bull., 1987, 35, 3905. 328. G. M. Iskander, B. M. Modawi, H. E. Ahmed, E. 0. Schlemper and H. Duddeck, J . Prakt. Chem., 1988, 330, 182. 329. K. Ito and T. Iida, Phytochemistry, 1981, 20, 271. 330. K. Ito, T. Iida and T. Kobayashi, Phytochernisfry, 1984, 23 188. 331. K. Ito, Y . Sakakibara and M. Haruna, Chern. Lett., 1979, 1503. 332. K. Ito, Y. Sakakibara and M. Haruna, Chem. Len., 1979, 1473. 333. K. Ito, Y. Sakakibara and M. Haruna, Phytochernisfry, 1982, 21, 715. 334. K. Ito, Y . Sakakibara, M. Haruna and K.-H. Lee, Chem. Lett., 1979, 1469. 335. M. Itoigawa, N. Kumagai, H . Sekiya, K . Ito and H. Furukawa, J . Pharm. SOC.Jpn., 1981, 101, 605. 336. H. Itokawa, H . Matsumoto, K. Mizuno, K. Watanabe, H. Morita and Y. Iitaka, Chem. Pharm. Bull., 1986, 34, 4682. 337. H . Itokawa, H. Morita, T. Kobayashi, K. Watanabe and Y. Iitaka, Chem. Pharm. Bull., 1987. 35, 2860. 338. H . Itokawa, H. Morita, K. Osawa, K. Watanabe and Y . Iitaka, Chem. Pharm. Bull., 1987, 35, 2849. 339. H . Itokawa, H . Morita, K. Watanabe, A. Takase and Y. Iitaka, Chem. Lett., 1984, 1687. 340. J. Jakupovic, S. Banerjee, V. Castro, F. Bohlmann, A. Schuster, J. D. Msonthi and S. Keeley, Phytochernistry, 1986, 25, 1359. 341. J. Jakupovic, R . N. Baruah, F. Bohlmann, R. M. King and H. Robinson, Plunta Medica, 1986, 50, 204. 342. J. Jakupovic, R. Boeker, M. Grenz, L. Paredes, F. Bohlmann and A. S. El-Din, Phytochemistry, 1988, 27, 1135. 343. J. Jakupovic, R. Boeker, A Schuster, F. Bohlmann and S. B. Jones, Phytochemistry, 1987, 26, 1069. 344. J . Jakupovic, V. Castro and F. Bohlmann, Phyfochemistry, 1987, 26, 2011. 345. J. Jakupovic, Z.-L. Chen and F. Bohlmann, Phytochernistry, 1987, 26, 2777. 346. J. Jakupovic, D . A. Gage, F. Bohlmann and T. J. Mabry, Phytochemistry, 1986,25, 1179. 347. J. Jakupovic, U. Ganzer, P. Pritschow, L. Lehmann, F. Bohlmann and R . M. King, Phytochemistry, 1992, 31, 863. 348. J. Jakupovic, M. Grenz and F. Bohlmann, Planta Medica, 1989, 53, 571. 349. J. Jakupovic, M. Grenz, F. Bohlmann and G . M. Mungai, Phytochemistry, 1990,29, 1213. 350. J. Jakupovic, M. Grenz, F. Bohlmann, D. C. Wasshausen and R. M. King, Phyfochemistry. 1989, 28, 1937. 351. J. Jakupovic, S. Hafez, F. Bohlmann and X. A. Dominguez, Phytochemistry, 1988, 27, 3881. 352. J . Jakupovic, Y. Jia, C. Zdero, U. Warning, F. Bohlmann and S. B. Jones, Phytochemistry, 1987, 26, 1467. 353. J . Jakupovic, H. Klemeyer, F. Bohlmann and E. H . Graven, Phytochemistry, 1988, 27, 1120. 354. J. Jakupovic, V. P. Pathak, F. Bohlmann, R. M. King and H . Robinson, Planfa Medica, 1986. 50, 331. 355. J . Jakupovic, G. Schmeda-Hirschmann, A. Schuster, C. Zdero, F. Bohlmann, R. M. King, H. Robinson and J. Pickardt, Phytochernistry, 1986, 25, 145. 356. J. Jakupovic, A. Schuster, F. Bohlmann and M. D. Dillon, Phytochernistry, 1988, 27, 1771. 357. J . Jakupovic, A. Schuster, F. Bohlmann and M. 0. Dillon, Phytochemistry, 1988, 27, 1113. 358. J . Jakupovic, A. Schuster, T. V. Chau-Thi, F. Bohlmann and X. A. Dominguez, Phytochernistry, 1988, 27, 2235.
466
M. BUDESiNSKY AND D . SAMAN
359. J. Jakupovic, H. Sun, S. Geerts and F. Bohlmann, Planta Medica, 1987, 51, 49. 360. J. Jakupovic, R. X . Tan, F. Bohlmann, P. E. Boldt and Z. J. Jia, Phytochemistry, 1991, 30, 1573. 361. J. Jakupovic, R. X. Tan, F. Bohlmann, Z. J. Jia and S . Huneck, Phytochemistry, 1991, 30, 1941. 362. J. Jakupovic, C. Zdero, R. Boeker, U. Warning, F. Bohlmann and S. B. Jones, Liebigs Ann. Chem., 1987, 111. 363. Z. Jia, Y. Zhao and R. X. Tan, Planta Medica, 1992, 58, 365. 364. Z. J. Jia, Y. Zhao, R. X. Tan and Y. Li, Phytochemistry, 1992, 31, 199. 365. H. Jin, J . Pharm. Soc. Jpn., 1982, 102, 911. 366. S. D. Jolad, J. J. Hoffmann, R. B. Bates, S. Calders and S. P. McLaughlin, Phytochemistry, 1990, 29, 3024. 367. S. D. Jolad, J. J. Hoffmann, B. N. Timmermann, R. B. Bates, F. A. Camou and S. P. McLaughlin, Phytochernistry, 1990, 29, 649. 368. H. 0. Kalinowski, S. Berger and S . Braun, "C-NMR-Spektroskopie, G . Thieme Verlag, Stuttgart, 1984. 369. T. Kanayama and M. Tada, Bull. Chem. SOC.J p n . , 1988, 61, 2971. 370. A. Karube and M. Maruyama, Nippon Kagaku Zaishi, 1990, 53. 371. R. Kasai, T. Shungu, R.-Y. Wu, I. H. Hall and K.-H. Lee, J . Nut. Prod., 1982, 45, 317. 372. U. Kastner, J. Jurenitsch, S. Glasl, A. Baumann, W. Rohien and W. Kubelka, Phytochemistry, 1992, 31, 4361. 373. J. Kawabata, Y. Fukushi, S. Tahara and J. Mizutani, Phytochemistry, 1990, 29, 2332. 374. J. Kawabata and J. Mizutani, Agric. Biol. Chem., 1989, 53, 203. 375. P. K. Kelly and T. B. H. McMurry, Mag. Reson. Chem., 1986, 24, 553. 376. S. M. Khafagy, A. A. S. El-Din, J. Jakupovic, C. Zdero and F. Bohlmann, Phytochemzstry, 1988, 27, 1125. 377. A. Kijjoa, L. M. M. Vieira, J. M. Cardoso and W. Herz, Phytochemistry, 1992,31, 3635. 378. D. Kioy, A. I. Gray and P. G. Waterman, J . Nut. Prod., 1989, 52, 174. 379. M. Koreeda, S. Matsueda, T. Satomi, K. Hirotsu and J. Clardy, Chem. Lett., 1979, 81. 380. M. Koreeda, M. Nagaki, K.-I. Hayami and S . Matsueda, J . Pharm. SOC. Jpn., 1988, 108, 434. 381. I. Kouno, T. Akiyama and N. Kawano, Chem. Pharm. Bull., 1988, 36, 2990. 382. I. Kouno, N. Baba, M. Hashimoto, N. Kawano, M. Takahashi, H. Kaneto and C.-S. Yang, Chem. Pharm. Bull., 1990, 38, 422. 383. I. Kouno, N. Baba, M. Hashimoto, N. Kawano, M. Takahashi, H. Kaneto, C . 3 . Yang and S. Sato, Chem. Pharm. Bull., 1989, 37, 2448. 384. I. Kouno, N. Baba, M. Hashimoto, N. Kawano, C.-S. Yang and S . Sato, Chem. Pharm. Bull., 1989, 37, 2427. 385. I . Kouno, N. Kawano and C.-S. Yang, J . Chem. SOC. Perkzn I , 1988, 1537. 386. I. Kouno, K. Mori, T. Akiyama and M. Hashimoto, Phytochemistry, 1991, 30, 351. 387. W. Kiibler, 0. Petrov, E . Winterfeldt, L. Ernst and D. Schomburg, Tetrahedron, 1988, 44,4371. 388. M. Kuroyanagi, H . Naito, T. Noro, A. Ueno and S. Fukushima, Chem. Pharm. Bull., 1985, 33, 4792. 389. G. L. Lange and P. Galatsis, J . Org. Chem., 1984, 49, 178. 389a.G. L. Lange and M. Lee, Mag. Reson. Chem., 1986, 24, 656. 390. P. T. Lansbury and B.-X. Zhi, Tetrahedron Lett., 1988, 29, 5735. 391. R . Lanzetta, G . Lama, G . Mauriello, M. Parrilli, R. Racioppi and G . Sodano, Phytochemistry, 1991, 30, 1121. 392. K.-H. Lee, T. Kimura, M. Okamoto and C. M. Cowherd, Tetrahedron Lett., 1976, 1051. 393. W. S. Li, J . Nut. Prod., 1992, 55, 1614. 394. Y. Li and Z.-J. Jia, Phytochemistry, 1989, 28, 3395.
CARBON-13 NMR SPECTRA O F SESQUITERPENE LACTONES
467
395. Y.-L. Liu, J. Gershenzon and T. J. Mabry, Phytochemistry, 1984, 23, 1967. 396. Y.-L. Liu and T. J. Mabry, J. Nat. Prod., 1981, 44,722. 397. G. Lonergan, E. Routsi, T. Georgiadis, G. Agelis, J. Hondrelis, J. Matsoukas, L. K. Larsen and F. R. Caplan, J. Nat. Prod., 1992, 55, 225. 398. F. A. Macias and N. H. Fischer, Phytochemistry, 1992, 31, 2747. 399. A. J. Malcolm, J. F. Carpenter, F. R. Fronczek and N. H. Fischer, Phytochemistry, 1983, 22, 2759. 400. A. J. Malcolm and N. H. Fischer, J. Nat. Prod., 1987, 50, 167. 401. P. S. Manchand and J. F. Blount. J. Org. Chem., 1978, 43, 4352. 402. P. S. Manchand, L. J. Todaro, G . A. Cordell and D. D. Soejarto, J. Org. Chem., 1983, 48, 4388. 403. C. Marcinek-Hupen-Bestendonk, G . Willuhn, A. Steigel, D. Wendisch, B. Middelhauve, M. Wiebcke and D. Mootz, Planta Medica, 1990, 56, 104. 404. J. A. Marco, Phytochemistry, 1989, 28, 3121. 405. J. A. Marco, 0. Barbera, J. Lex, P. De Clercq and A. De Bruyn, J. Nat. Prod., 1989,52, 547. 406. J. A. Marco, 0. Barbera, V. Martinez, D. Strack and B. Meurer, Planta Medica, 1988, 52, 460. 407. J. A. Marco and M. Carda, Tetrahedron, 1987, 43, 2523. 408. J. A. Marco and M. Carda, Mag. Reson. Chem., 1987, 25, 1087. 409. J. A. Marco and M. Carda, Mag. Reson. Chem., 1987, 25, 628. 410. J. A. Marco, J. F. Sanz and M. Carda, Phytochemistry, 1989, 28, 2505. 411. J. A. Marco, J. F. Sanz and M. Carda, Phytochemistry, 1992, 31, 2163. 412. J. A. Marco, J. F. Sanz, E. Falco, J. Jakupovic and J. Lex, Tetrahedron, 1990, 46, 7941. 413. J. A. Marco, J. F. Sanz, J. Jakupovic and S. Huneck, Tetrahedron, 1990, 46, 6931. 414. J. A. Marco, J. F. Sanz, F. Sancenon, A. Susanna, A. Rustaiyan and M. Saberi, Phytochemistry, 1992, 31, 3527. 415. J. A. Marco, J. F. Sanz, A. Yuste, M. Carda and J. Jakupovic, Phytochemistry, 1991, 30, 3661. 416. J. A. Marco, J. F. Sanz, A. Yuste and J. Jakupovic, Tetrahedron Lett., 1991, 32, 5193. 417. J. L. Marshall, Carbon-Carbon and Carbon-Proton NMR Couplings: Applications to Organic Stereochemistry and Conformational Analysis, Verlag Chemie Int., Deerfield Beach, 1983. 418. M. V. Martinez and A. Munoz-Zamora, J . Nat. Prod., 1988, 51, 221. 419. M. Martinez-Vazquez, R. E. Gallegos and P. Joseph-Nathan, Phytochemistry, 1990, 29, 1689. 420. M. Martinez-Vazquez, S. Sepulveda, M. A. Belmont, M. Rubio and P. Joseph-Nathan. J . Nat Prod., 1992, 55, 884. 421. M. Maruyama, Phytochemistry, 1990, 29, 547. 422. M. Maruyama and S. Omura, Phytochemistry, 1977, 16, 782. 423. M. Maruyama, A. Karube and K. Sato, Phytochemistry, 1983, 22, 2773. 424. G. Massiot, A.-M. Morfaux, L. Le Men-Olivier, J. Bouquant, A. Madaci, A. Mahamoud, M. Chopova and P. Aclinou, Phytochernistry, 1986, 25, 258. 425. G. Massiot, J.-M. Nuzillard, L. Le Men-Olivier, P. Aclinou, A. Benkouider and A. Khelifa, Phytochemistry, 1990, 29, 2207. 426. R . Mata, G. Delgado and A. Romo de Vivar, Phytochemistry, 1984, 23, 1665. 427. R. Mata, G. Delgado and A. Romo de Vivar, Phytochernistry, 1985, 24, 1515. 428. R. Mata, A. Rojas, M. Soriano, R. Villena, R. Bye and E. Linares, Heterocycles, 1990, 31. 1111. 429. S. Matsueda and M. Nagaki, J. Pharm. SOC. Jpn., 1984, 104, 753. 430. S. Matsueda, M. Nagaki and M. Koreeda, J. Pharm. SOC. Jpn., 1980, 100, 615. 431. R . Mayer and G. Rucker, Arch. Pharm. (Weinheim), 1987, 320, 318.
468
M. BUD6SINSKY AND D. SAMAN
432. N. J. McCorkindale, C. H. Calzadilla, S. A. Hutchinson, D. H. Kitson, G. Ferguson and I. M. Campbell, Tetrahedron, 1981, 37, 649. 433. F. R. Melek, A. A. Ahmed, J. Gershenzon and T . J. Mabry, Phytochernistry, 1984, 23, 2573. 434. F. R. Melek, D. A. Gage, J. Gershenzon and T . J. Mabry, Phytochemistry, 198.5, 24, 1537. 435. F. R. Melek, J. Gershenzon, E. Lee and T. J. Mabry, Phytochemistry, 1984, 23, 2277. 436. N. Mengi, S. C. Taneja, V. P. Mahajan and C. S. Mathela, Phytochemistry, 1991, 30, 2329. 437. A. H. Mericli, J. Jakupovic, F. Bohlmann, B. Damadyan, N. Ozhatay and B. Cubukcu, Planta Medica, 1988, 52, 447. 438. M. A. Metwally, J. Jakupovic, M. I. Youns and F. Bohlmann, Phytochemistry, 1985, 24, 1103. 439. B. Meurer, F. C. Seaman and T. J. Mabry, Phytochemistry, 1987, 26, 1743. 440. S. Milosavljevic, I. Aljancic, S. Macura, D. Milinkovic and M. Stefanovic, Phytochemistry, 1991, 30,3464. 441. C. W. Ming, R. Mayer, H. Zimmermann and G. Rucker, Phytochemistry, 1989, 28, 3233. 442. M. Miski, D. H . De Luengo and T . J. Mabry, Phytochemistry, 1987, 26, 199. 443. M. Miski, D. A. Gage and T. J. Mabry, Phytochemistry, 1987, 26, 2753. 444. M. Miski, D. A. Gage and T. J. Mabry, Phytochemistry, 1987, 26, 3277. 445. M. Miski and T. J. Mabry, Phytochemistry, 1986, 25, 1673. 446. T. Miyase and S. Fukushima, Chem. Pharm. Bull., 1984,32, 3043. 447. T. Miyase and S. Fukushima, Chem. Pharm. Bull., 1987, 35, 2869. 448. T. Miyase, M. Kuroyanagi, T. Noro, A. Ueno and S. Fukushima, Chem. Pharm. Bull., 1985, 33, 4445. 449. T. Miyase, A. Ueno, T. Noro, M. Kuroyanagi and S. Fukushima, Chem. Pharm. Bull., 1985, 33, 4451. 450. T. Miyase, M. Yamada and S. Fukushima, Chem. Pharm. Bull., 1987, 35. 1969. 451. T. Miyase, K. Yamaki and S. Fukushima. Chem. Pharm. Bull., 1984, 32, 3912. 452. K. Mladenova, E. Tsankova and D. Van Hung, Planta Medica, 1988, 52, 553. 453. B. Mompon, G. Massiot and R. Toubiana, C.R. Acud. Sci Paris, Ser. C , 1974. 279, 907. 454. K. Monde, T. Oya, A. Shirata and M. Takasugi, Phytochemistry, 1990, 29, 3449. 455. B. G. Morales, R. J. Borquez, P. A. Mancilla, T. S. Pendreros and M. L. A. Loyola, Phytochernistry, 1986, 25, 2412. 456. H. Morimoto and H. Oshio, J. Nat. Prod., 1981, 44,748. 4.57. T. C. Morrill (ed.), Lanthanide Shifr Reagents in Stereochemical Analysis, VCH Publishers, Deerfield, 1986. 458. G. A. Morris and R. Freeman, J. A m . Chem. SOC., 1979, 101, 760. 459. G. P. Moss, P. S. Pregosin and E. W. Randall, J. Chem. SOC. Perkin I , 1974, 1525. 460. L. Muller, A. Kumar and R. R. Ernst, J. Chem. Phys., 1975, 63, 5940. 461. M. Nagaki, Phytochemistry, 1984, 23, 462. 462. M. Nagaki and S. Matsueda, Phytochemistry, 1989, 28, 2731. 463. B. A. Nagasampagi, U. G. Bhat, F. Bohlmann and C. Zdero, Phytochemistry, 1981, 20, 2031. 464. S. Nagumo, K. Izawa, K. Higashiyama and M. Nagai, J. Pharm. SOC.J p n . , 1980, 100, 427. 465. S. Nagumo, K.-I. Kawai, H. Nagase, T . Inoue and M. Nagai, J. Pharm. SOC. Jpn., 1984, 104, 1223. 466. S. Nagumo, M. Nagai and T. Inoue, Chem. Pharm. Bull., 1983, 31, 2302. 467. B. Nanda, S. A. Patwardhan and A. S. Gupta, Phytochemistry, 1985, 24, 2735. 468. J. J. Navarro, M. C. Caballero, J. R. Moran, M. Medarde, M. Grande and J. Anaya, J. Nut. Prod., 1990, 53, 573.
CARBON-13 NMR SPECTRA O F SESQUITERPENE LACTONES
469
469. K. Naya, M. Shirnizu, H. Nishio, M. Takeda, S. Oka and K. Hirota, Bull. Chem. Soc. J p n . , 1991, 64,1071. 470. P. Nelson and R. 0. Asplund, Phytochemistry, 1983, 22, 2755. 471. D. Neuhaus and M. P. Williamson, The Nuclear Overhauser Effect in Structural and Conformational Analysis, VCH Publishers, New York, 1989. 472. K. Nishimura, T. Miyase, A. Ueno, T. Noro, M. Kuroyanagi and S . Fukushirna, Chem. Pharm. Bull., 1985, 33, 3361. 473. K. Nishimura, T. Miyase, A. Ueno, T. Noro, M. Kuroyanagi and S . Fukushirna, Phytochemistry, 1986, 25, 2375. 474. K. Nishirnura, T. Miyase, A . Ueno, T. Noro, M. Kuroyanagi and S. Fukushirna, Chem. Pharm. Bull., 1986, 34,2518. 475. E. Norup, U. W. Smitt and S. B. Christensen, Planta Medica, 1986, 50, 251. 476. H. Nozaki, M. Hiroi. D. Takaoka and M. Nakayama, J . Chem. Soc. Chem. Commun., 1983, 1107. 477. A. G . Ober and N. H. Fischer, Phytochemistry, 1987, 26, 848. 478. A. G . Ober, F. R. Fronczek and N. H. Fischer, J . Nat. Prod., 1985, 48, 302. 479. A . G. Ober, F. R. Fronczek and N. H. Fischer, J. Naf. Prod., 1987, 50, 604. 480. A. G . Ober, L. Quijano, L. E. Urbatsch and N. H. Fischer, Phytochemistry, 1984. 23, 910. 481. A. G . Ober, L. Quijano, L. E. Urbatsch and N. H. Fischer, Phytochemistry, 1984. 23, 1289. 482. A. G . Ober, L. E. Urbatsch and N. H. Fischer, Phytochemistry, 1985, 24, 795. 483. A. G . Ober, L. E. Urbatsch and N. H. Fischer, Phytochemistry, 1986, 25, 467. 484. A. G. Ober, L. E. Urbatsch and N. H. Fischer, Phytochemistry, 1987, 26, 1204. 485. J. C. Oberti, R. R. Gil, V. E. Sosa and W. H e n , Phytochemistry, 1986, 25, 1479. 486. J. C. Oberti, G . L. Silva, V. E . Sosa, P. Kulanthaivel and W. Herz, Phytochemistry, 1986, 25, 1355. 487. J . C. Oberti, V. E. Sosa, W. Herz, J. S. Prasad and V. L. Goedken, J . Org. Chem., 1983, 48, 4038. 488. C. Ochir, M. BudESinsky and 0. Motl, Phytochemistry, 1991. 30, 4163. 489, T. Ohmoto, K. Koike, H. Fukuda, K. Mitsunaga, K. Ogata and K. Kagei. Chem. Pharm. Bull., 1989, 37, 2988. 490. K. Ohmura, T. Miyase and A. Ueno, Phytochemistry, 1989, 28, 1919. 491. N. Ohno, J. Gershenzon, P. Neurnan and T. J . Mabry, Phytochemistry, 1981, 20, 2393. 492. N. Ohno, J . Gershenzon, C . Roane and T. J. Mabry, Phytochemistry, 1980, 19. 103. 493. N. Ohno and T. J. Mabry, Phytochemistry, 1979, 18, 1003. 494. N. Ohno and T. J . Mabry, Phytochemistry, 1980, 19, 609. 495. S. Oksiiz, Phytochemistry, 1990, 29, 887. 496. S . Oksiiz and G . Topcu, Phytochemistry. 1992, 31, 195. 497. A. L. Okunade and D. F. Wierner, Phytochemisfry, 1985, 24, 1199. 498. R. Ortega, J. D. C . Lopez and E. Maldonado, Phytochemisfry, 1989, 28, 2735. 499. A. Ortega and E. Maldonado, Phytochemistry, 1986, 25, 699. 500. Y. Oshima, S.-M. Wong, C. Konno, G . A. Cordell, D. P. Waller, D. D. Soejarto and H. H . S . Fong, J . Nat. Prod., 1986, 49, 313. 501. A. Ovezdurdyev, N. D. Abdulaev, M. I. Yusunov and S . 2. Kasymov, Khim. Prirod. Soed., 1988, 667. 502. P. Pachaly, A. Lansing and K. S . Sin, Planta Medica, 1989, 55, 59. 503. U. C. Pandey, R. P. Sharma, K. Kulanthaivel and W. H e n , Phytochemistry, 1985, 24, 1509. 504. F. J. Parodi and N. H. Fischer, Phytochemistry, 1988, 27. 2987. 505. F. J . Parodi, F. R. Fronczek and N. H. Fischer, J . Nat. Prod., 1989, 52, 554. 506. S. L. Patt and J. N. Shoolery, J . Magn. Reson., 1982, 46, 535.
470
M. BUDESINSKY AND D.
SAMAN
507. J. Pearce, J . Geszhenzon and T . J. Mabry, Phytochemistry, 1986, 25, 159. 508. A,-L. Perez, A. Ortega and A . Romo de Vivar, Phytochemistry, 1988, 27, 3897. 509. A,-L. Perez, P. Vidales, J. Cardenas and A. Romo de Vivar, Phytochemistry, 1991, 30, 905. 510. A.-L. Perez, J . S. Mendoza and A. Romo de Vivar, Phytochemistry, 1984, 23, 2911. 511. C. A. L. Perez, 0. M. Lara and A. Romo de Vivar, Phytochemistry, 1992, 31, 4227. 512. C. A. L. Perez, M. L. Nava and A. Romo de Vivar, Phytochemistry, 1987, 26, 765. 513. D. L. Perry, D. M. Desiderio and N. H. Fischer, Urg. Muss. Spectr., 1978, 13, 325. 514. D. L. Perry and N. H. Fischer, J . Org. Chem., 1975, 40,3480. 515. E. Petenatti, M. J. Pestchanker, M. Guo and E. Guerreiro, Phytochemistry, 1990, 29, 3669. 516. G. R. Pettit, C. L. Herald, D. Gust, D. L. Herald and L. D. Vanell, J. Org. Chem., 1978, 43, 1092. 517. G. R. Pettit, D. L. Herald, G. M. Cragg, J. A. Rideout and P. Brown, J . Nut. Prod., 1990, 53, 382. 518. P. E. Pfeffer, K. M. Valentine and F. W. Parrish, J . Am. Chem. SOC., 1979, 101, 1265. 519. R. M. Pfeil, D. A. Gage, E. F. Lee, M. Miski, T. J. Mabry and A . M. Powell, Phytochernistry, 1987, 26, 195. 520. A . K. Picman, Biochem. System. Ecol., 1986, 14, 255. 521. P. S. Pregosin, E. W. Randall and T. B. H. McMurry, J . Chem. SOC. Perkin I , 1972, 299. 522. L. Quijano and N. H. Fischer, J . Nut. Prod., 1981, 44,266. 523. L. Quijano, F. Gomez-Garibay, R. I. Trejo-B. and T. Rios, Phytochemistry, 1991, 30, 3293. 524. G. Quinkert, H.-G. Schmalz, E. Walzer, S. Gross, T. Kowalczyk-Przewloka, C. Schierloh, G. Diirner, J. W. Bats and H. Kessler, Liebigs Ann. Chem., 1988, 283. 525. L. V. Reis, M. R. Tavares, F. M. S. B. Palma and M. J. Marcelo-Curto, Phytochemistry, 1992, 31, 1285. 526. W. F. Reynolds, R. G. Enriquez, M. A. Chavez, A. L. Silva and M. A. Martinez, Can. J . Chem. 1985, 63, 849. 527. E. Rodriguez, G . H. N. Towers and J. C. Mitchell, Phytochemistry, 1976, 15, 1573. 528. L. Rodriguez Hahn, M. Oliveros, M. Jimenez and E. Diaz, Rev. Latinoamer. Quim., 1981. 12, 73. 529. G. Rodriguez, L. J. Pestchanker, M. J. Pestchanker and 0. S. Giordano, Phytochemistry, 1990, 29, 3028. 530. L. Rodriguez-Hahn, J. Cardenas, E. Maldonado, A. Ortega, M. Martinez, M. S. Garcia and A. Toscano, J . Org. Chern., 1988, 53, 2965. 531. S. R . Rojatkar and B. A . Nagasampagi, Phytochemistry, 1992, 31, 3270. 532. A. Romo de Vivar, E. Bratoeff, E. Ontiveros, D. C. Lankin and N. S. Bhacca, Phytochemistry, 1980, 19, 1795. 533. A. Romo de Vivar and G . Delgado, Tetrahedron Lett., 1985, 26, 579. 534. A . Romo de Vivar, C. A. L. Perez and R. Saucedo, Phytochemistry, 1982, 21, 375. 535. C. Rossi, A . Evidente and A. Menghini, Phytochemistry, 1985, 24, 603. 536. N. Ruangrungsi, S. Kasiwong, K. Likhitwitayawuid, G . L. Lange and C. P. Decicco, J . Nat. Prod., 1989, 52, 130. 537. N. Ruangrungsi, K. Likhitwitayawuid, S. Kasiwong, G . L. Lange and C. P. Decicco, J . Nut Prod., 1988, 51, 1220. 538. N. Ruangrungsi, A. Rivepiboon, G. L. Lange and C. P. Decicco, J . Nat. Prod., 1988, 51, 163. 539. N. Ruangrungsi, A. Rivepiboon, G . L. Lange, M. Lee, C. P. Decicco, P. Picha and K. Preechanukool, J . Nut. Prod., 1987, 50, 891. 540. G . Riicker, A. Kiefer and J . Breuer, PIantu Medicu, 1992, 58, 293. 541. G. Riicker, D. Manns and J. Breuer. Arch. Pharm. (Weinheim), 1991, 324. 979.
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
471
542. G. Riicker, C. W. Ming, R. Mayer, G . Will and A. Giillmann, Phytochemistry, 1990, 29, 983. 543. G. Riicker, G. Paulini, H. Sakulas, B. Lawong and F. Goeltenboth, Planta Medica, 1991, 57, 278. 544. A. Rustaiyan, A. Bamonieri, M. Raffatrad, J. Jakupovic and F. Bohlmann, Phytochemistry, 1987, 26, 2307. 545. A. Rustaiyan, 2. Habibi, M. Saberi and J. Jakupovic, Phytochemisfry, 1991,30,2405. 546. A. Rustaiyan, L. Nazarians and F. Bohlmann, Phytochemistry, 1980, 19, 1230. 547. A. Rustaiyan, H. Sigari, J. Jakupovic and M. Grenz, Phytochemistry, 1989, 28, 2723. 548. U. Rychlewska, M. BudbSinsky, B. Szczepanska, E. Bloszyk and M. Holub, Collect. Czech. Chem. Commun., 1994 (in press). 549. U. Rychlewska, D. J. Hodgson, H. Grabarczyk, B. Drozdz, W. M. Daniewski, W. Krozsczynski, M. BudCSinskL and M. Holub, Collect. Czech. Chem. Commun., 1986, 51, 1698. 550. U. Rychlewska, D. J. Hodgson, M. Holub, M. BudCSinsky and Z. Smitalova, Collect. Czech. Chem. Commun., 1985, 50, 2607. 551. U . Rychlewska, M. Holub, M. BudCSinskL and Z. Smitalovi, Collect. Czech. Chem. Commun., 1984, 49, 2790. 552. U. Rychlewska, B. Szczepanska, M. BudCPinsky, D. Saman, S. VaSiEkovB, B. Drozdz, H. Grabarczyk and M. Holub, Collect. Czech. Chem. Commun., 1993, 58, 909. 553. I. H. Sadler, Natural Product Reports, 1988, 5, 101. 554. A. A. Saleh, G. A. Cordell and N. R. Farnsworth, J. Chem. Soc. Perkin I , 1980, 1090. 555. 2. Samek, 11th Int. Symposium on Chemistry of Natural Products, Symp. Papers, Vol. 4, part 1, p. 390. 556. 2. Samek, Tetrahedon Lett., 1970, 671. 557. 2. Samek, Collect. Czech. Chem. Commun., 1978, 43, 3210. 558. Z. Samek and M. BudCSinsky, Collect. Czech. Chem. Commun., 1979, 44,558. 558a.F. SBnchez-Ferrando, Mag. Reson. Chem., 1985, 23, 185. 559. A. San Feliciano, A. F. Barrero, M. Medarde, J. M. Miguel del Corral and A . Aramburu, Tetrahedron Lett., 1985, 30, 2369. 560. A. San Feliciano, M. Medarde, J. M. Miguel del Corral, A. Aramburu, M. Gordaliza and A. F. Barrero, Tetrahedron Lett., 1989, 2851. 561. A. San Feliciano, M. Medarde, M. T. Poza and J. M. Miguel del Corral, Phytochemistry, 1986, 25, 1757. 562. S. M. B. P. Santos, F. M. S. Brito Palma, J. G. Urones and M. Grande, Phytochemistry, 1988, 27, 3672. 563. J. F. Sam, 0. Barber0 and J. A. Marco, Phytochemistry, 1989, 28, 2163. 564. J . F. Sanz, G. Castellano and J. A. Marco, Phytochemistry, 1990, 29, 541. 565. J . F. Sanz, E. Falco and J. A. Marco, J. Nut. Prod., 1990, 53, 940. 566. J. F. Sanz, C. Ferrando and J. A. Marco, Phytochernistry, 1991, 30, 3653. 567. J. F. Sanz and J. A. Marco, Liebigs Ann. Chem., 1990, 541. 568. J. F. Sanz and J. A . Marco, Planta Medica, 1990, 56, 236. 569. J. F. Sanz and J. A. Marco, Phytochernistry, 1990, 29, 2913. 570. J. F. Sanz and J. A. Marco, Planta Medica, 1991, 57, 74. 571. J. F. Sanz and J. A. Marco, J. Nut. Prod., 1991, 54, 591. 572. J. F. Sanz, A. Rustaiyan and J. A . Marco, Phytochemistry, 1990, 29, 2919. 573. J. C. Sarma and R. P. Sharma, Ind. J. Chem., 1988, 27B, 324. 574. Y . Sashida, H. Nakata, H. Shimomura and M. Kagaya, Phytochemistry, 1983, 22, 1219. 575. G. Savona and M. Bruno, J. Nat. Prod., 1983, 46, 277. 576. G. Schmeda-Hirschmann, R. Boeker, J. Jakupovic and F. Bohlmann, Phytochemistry, 1986, 25, 1753. 577. G . Schmeda-Hirschmann, J. Jakupovic, V. P. Pathak and F. Bohlmann, Phytochemistry, 1986. 25, 2167.
472
M. BUDESINSKY AND D. SAMAN
578. G. Schmeda-Hirschmann, C. Zdero, R. N. Baruah and F. Bohlmann, Phytochemistry, 1985, 24, 2019. 579. A. Schuster, V. Castro, L. Poveda, F. Papastergiou and J. Jakupovic, Phyfochemisfry, 1992, 31, 3143. 580. A. Schuster, S. Stokes, F. Papastergiou, V. Castro, L. Poveda and J. Jakupovic, Phytochemistry, 1992, 31, 3139. 581. F. C. Seaman, The Botanical Review, 1982, 48, 121. 582. F. C. Seaman and N. H. Fischer, Phyfochemistry, 1978, 17, 2131. 583. F. C. Seaman, N. H. Fischer and T. J. Mabry, Phyfochemisfry, 1986, 25, 2663. 584. R. Segal, A. Dor, H. Duddeck, G. Snatzke, D. Rosenbaum and M. Kajtar, Tetrahedron, 1987, 43, 4125. 585. R. Segal, L. Eden, A. Danin, M. Kaiser and H. Duddeck, Phyfochemistry, 1984, 23, 2954. 586. R. Segal, L. Eden, A. Danin, M. Kaiser and H . Duddeck, Phytochemisfry, 1985, 24, 1381. 587. R. Segal, I. Feuerstein, H. Duddeck, M. Kaiser and A. Danin, Phytochemisfry, 1982, 22, 129. 588. S. V. Serkerov and A. N. Aleskerova, Khim. Prirod. Soedin., 1986, 787. 589. V. K. Sethi, S. K. Koul, S. C. Taneja and K. L. Dhar, Phyfochemistry, 1987, 26, 3359. 590. M. Seto, T. Miyase and S. Fukushima, Chem. Pharm. Bull., 1986, 34, 4170. 591. M. Seto, T. Miyase, K. Umehara, A. Ueno, Y. Hirano and N. Otani, Chem. Pharrn. Bull., 1988, 36, 2423. 592. M. S. Shekhani, P. M. Shah, K. M. Khan and Atta-ur-Rahman, J. Nut. Prod., 1991, 54, 882. 593. S. Shimizu, N. Ishihara, K. Umehara, T. Miyase and A. Ueno, Chem. Pharm. Bull., 1988, 36, 2466. 594. S. Shimizu, T. Miyase, A. Ueno and K. Usmanghani, Phytochemisfry, 1989, 28, 3399. 595. R. E. Sievers, ed., Nuclear Magnetic Resonance Shiff Reagents, Academic Press, New York, 1973. 596. E. E. Sigstad, C. A. N. Catalan, A. B. Gutierrez, J. G. Diaz, V. L. Goedken and W. Herz, Phytochemisfry, 1991, 30, 1933. 597. G . L. Silva, J. C. Oberti and W. Herz, Phytochemistry, 1992, 31, 859. 598. G . L. Silva, A. del V. Pacciaroni, J. C. Oberti, L. A. Espinar, J. G. Diaz and W. Herz, Phytochernistry, 1992, 31, 1621. 599. 2. Smitalova, M. BudBSinsky, D. Saman and M. Holub, Collect. Czech. Chem. Comrnun., 1986, 51, 1323. 600. U. W. Smitt and S. B. Christensen, Planta Medica, 1991, 57, 196. 601. U. W. Smitt, C. Comett, A. Andersen, S. B. Christensen and P. Avato, J. Nar. Prod., 1990, 53, 1479. 602. U. W. Smitt, C. Comett, E. Norup and S. B. Christensen, Phyfochemistry, 1990, 29, 873. 603. J . S. Sohoni, B. A. Nagasampagi, J. Ziesche, R. K. Gupta and F. Bohlmann, Phytochemistry, 1984, 23, 1181. 604. J. S. Sohoni, S. R. Rojatkar, M. M. Kulkami, N. N. Dhaneshwar, S. S. Tavale, T. N. Gururow and B. A. Nagasampagi, J. Chem. SOC. Perkin I , 1988, 157. 605. F. Sorm, Fortschritfe d. Chem. org. Nafurst., 1961, 19, 1. 606. V. E. Sosa, J. C. Oberti, R. R. Gil, E. A. Ruveda, V. L. Goedken, A. B. Gutierrez and W. Herz, Phyfochemisrry, 1989, 28, 1925. 607. 0. Spring, K. Albert and W. Gradmann, Phytochernistry, 1981, 20, 1883. 608. 0. Spring, K. Albert and A. Hager, Phytochemistry, 1982, 21, 2551. 609. 0. Spring, T. Benz and M. Ilg, Phytochemistry, 1989, 28, 745. 610. M. Stefanovic, I. Aljancic-Solaja and S. Milosavljevic, Phytochemistry, 1987, 26, 850. 611. M. Stefanovic, V. Djermanovic, M. Gorunvic, M. Djermanovic, S. Macura and S. Milosavljevic, Phytochernistry, 1989, 28, 1765.
CARBON-13 NMR SPECTRA O F SESQUITERPENE LACTONES 612. 613. 614. 615. 616. 617. 618. 619. 620. 621. 622. 623. 624. 625. 626. 627. 628. 629. 630. 631. 632. 633. 634. 635. 636. 637. 638. 639. 640. 641. 642. 643. 644. 645. 646. 647. 648. 649. 650. 651. 652.
473
K. L. Stevens, Phytochemistry, 1982, 21, 1093. K. L. Stevens, R. J. Riopelle and R. Y. Wong, J. Nut. Prod., 1990, 53, 218. K. L. Stevens and R. Y. Wong, J. Nat. Prod., 1986, 49, 833. E. Stewart and T. J. Mabry, Phytochemistry, 1985, 24, 2733. E. Stewart and T. J. Mabry, Phytochemistry, 1985, 24, 2731. D. B. Stierle, Phytochemistry, 1986, 25, 743. R. D. Stipanovic, R. B. Miller and H. Hope, Phytochemistry, 1985, 24, 358. W. Stocklin, T. G. Waddell and T. A. Geissman, Tetrahedron, 1970, 26, 2397. S. Stokes, V. Castro, L. Poveda, F. Papastergiou and J. Jakupovic, Phytochernistry, 1992, 31, 2894. H. Stuppner, H. Stuppner and E. Rodriguez, Phytochemistry, 1988, 27, 2681. K. Sugama, K. Hayashi and H. Mitsuhashi, Phytochemistry, 1985, 24, 1531. M. F. Summers, L. G. Marzili and A. Bax, J. Am. Chem. SOC., 1986, 108, 4285. M. Tada and A. Kanamori, Chem. Lett., 1989, 1085. M. Takasugi, S. Okinaka, N. Katsui, T. Masamune, A. Shirata and M. Ohuchi, J. Chem. SOC. Chem. Comrnun., 1985,621. R. Takeda, Y. Ohta and Y. Hirose, Chem. Len., 1980, 1461. R. Takeda, Y. Ohta and Y. Hirose, Bull. Chem. SOC. Jpn., 1983, 56, 1120. R. Tan and 2. Jia, Planta Medica, 1992, 58, 370. R. X. Tan, 2. J. Jia, J. Jakupovic, F. Bohlmann and S. Huneck, Phytochemistry, 1991, 30,3033. N. Tanaka, T. Kimura, T. Muramaki, Y. Saiki and C.-M. Chen, Chem. Pharm. Bull., 1980, 28, 2185. N. Tanrisever and G. H. N. Towers, Phytochemistry, 1988, 27, 3893. M. Todorova and I. Ognyanov, Planta Medica, 1985, 49, 174. G. Topcu, G. A. Cordell, N. R. Farnsworth and H. H. S. Fong, J. Pharm. Sci., 1988,77, 553. G. Topcu and S. Oksiiz, Phytochemistry, 1990,29, 3666. K. Ton, I. Horibe, Y. Tamura, K. Kuriyama, H. Tada and K. Takeda, Tetrahedron Lett., 1976, 387. K. Ton, M. Ueyama, I. Horibe, Y. Tamura and K. Takeda, Tetrahedron Lett., 1975, 4583. M. Toyota, Y. Asakawa and J.-P. Frahm, Phytochernistry, 1990, 29, 2334. M. Toyota, F. Nagashima and Y. Asakawa, Phytochernistry, 1989, 28, 3383. M. Toyota, A. Ueda and Y. Asakawa, Phytochemistry, 1991, 30, 567. E. Tsankova, U. J. Kempe, T. Norin and I. Ognyanov, Phytochemistry, 1981, 20, 1436. F. Tsichritzis, K. Siems, J. Jakupovic, F. Bohlmann and G. M. Mungai, Phytochernistry, 1991, 30, 3808. F. Tsichritzis, J. Jakupovic and F. Bohlmann, Phytochernistry, 1990, 29, 195. L. E. Tully, M. S. Carson and T. B. H. McMurry, Tetrahedron Lett., 1987, 28, 5925. M. Uchida, Y. Koike, G. Kusano, Y. Kondo, S. Nozoe, C. Kabuto and T. Takemoto, Chem. Pharm. Bull., 1980, 28, 92. T. Uchiyama, T. Miyase, A. Ueno and K. Usmanghani, Phytochemistry, 1989, 28, 3369. T. Uchiyama, N. Nishimura, T. Miyase and A. Ueno, Phytuchemistry, 1990, 29, 2947. A. Ulubelen and H. Abdolmaleky, Phytochernistry, 1982, 21, 2128. A. Ulubelen, N. Goren, F. Bohlmann, J. Jakupovic, M. Grenz and N. Tanker, Phytochemistry, 1985, 24, 1305. J. G. Urones, D. Diez Martin and J. M. Cruz Morais, Fitoterapia, 1989, 60, 178. V. Vajs, D. Jeremic, S. Milosavljevic and S. Macura, Phytochemistry, 1989, 28, 1763. M. Vasquez, F. A. Macias, L. E. Urbatsch and N. H. Fischer, Phytochemistry, 1988, 27, 2195. M. Vasquez, L. Quijano, F. R. Fronczek, F. A. Macias, L. E. Urbatsch, P. B. Cox and N. H. Fischer, Phytochernistry, 1990, 29, 561.
474
M. BUDESINSKY AND D. SAMAN
653. M. Vasquez, L. Quijano, L. E. Urbatsch and N. H. Fischer, Phytochemistry, 1992, 31, 2051. 654. W. Vichnewski, E. G . Goulart and W. Herz, Phytochemistry, 1982, 21, 464. 655. W. Vichnewski, W. Herz and N. Kumar, J . Org. Chem., 1979, 44, 2575. 656. W. Vichnewski, P. Kulanthaivel, V. L. Goedken and W. Herz, Phytochemistry, 1985, 24, 291. 657. W. Vichnewski, S. J. Sarti, B. Gilbert and W. Herz, Phytochemistry, 1976, 15, 191. 658. W. Vichnewski, I. K. Shuhama, R. C. Rosanske and W. Herz, Phytochemistry, 1976, 15, 1531. 659. W. Vichnewski, A. M. Takahashi, A. M. T. Nasi, D. C. R. G . Goncalves, D. A. Dias, J. N. C . Lopes, V. L. Goedken, A . B. Gutierrez and W. Herz, Phytochemistry, 1989, 28, 1441. 660. A. Villar, M. C. Zafra-Polo, M. Nicoletti and C. Galeffi, Phytochernistry, 1983, 22, 777. 661. R. L. Vold, J. S. Waugh, M. P. Klein and D. E. Phelps, J . Chem. Phys., 1968, 48, 3831. 662. T. G. Waddell, W. Stocklin and T. A . Geissman, Tetrahedron Lett., 1969, 1313. 663. H. Wagner, B. Fessler, H . Lotter and V. Wray, Planta Medica, 1988, 52, 171. 664. G. R. Waller (ed.), Biochemic Applications of Mass Spectrometry, Wiley-Interscience, New York, 1972. 665. T. Warashina, M. Ishino, T . Miyase and A. Ueno, Phytochemistry, 1990, 29, 3217. 666. U. Warning, J. Jakupovic, F. Bohlmann and S. B. Jones, Liebigs Ann. Chem., 1987, 467. 667. K. Watanabe, N. Ohno and T . J. Mabry, Phytochemistry, 1986, 25, 141. 668. K. Watanabe, N. Ohno, H. Yoshioka, J . Gershenzon and T. J. Mabry, Phytochemistry, 1982, 21, 709. 669. M. Watanabe and A. Yoshikoshi, J . Chem. SOC.Perkin I , 1990, 257. 670. S. F. Watkins, J. D . Korp, I. Bernal, D. L. Perry, N. S. Bhacca and N. H. Fischer, J . Chem. SOC. Perkin 11, 1978, 599. 671. Z.-X. Wei, J.-P. Pan and Y. Li, Planta Medica, 1992, 58, 300. 672. F. W. Wehrli and T. Nishida, Fortschritte d . Chem. org. Naturst., 1979, 36, 2. 673. F. W. Wehrli and T. Wirthlin, Interpretation of Carbon-I3 NMR Spectra, Heyden, London, 1976. 674. T. J. Wenzel (ed.), NMR Shift Reagents, CRC Press, Boca Raton, 1987. 675. T. J. Wenzel, A. C . Ruggles and D. L. Lalonde, Mag. Reson. Chem., 1985, 23, 778. 676. A. T. Whittemore, J. Gershenzon and T. J. Mabry, Phytochemistry, 1985, 24, 783. 677. G. Willuhn, J. Kresken and W. Leven, Planta Medica, 1990, 56, 111. 678. G. Willuhn, J. Kresken and D. Wendisch, Planta Medica, 1983, 47, 157. 679. G. Willuhn, G. Pretzsch and D. Wendisch, Tetrahedron, 1981, 37, 773. 680. J. H. Wilton and R. W. Doskotch, J . Org. Chem., 1983, 48, 4251. 681. J.-B. Wu, Y.-T. Chun, Y. Ebizuka and U. Sankawa, Chem. Pharm. Bull., 1985,33,4091. 682. S.-L. Wu and W.-S. Li, Phytochemistry, 1991, 30, 4160. 683. H. Yamazaki, M. Miyakado and T. J. Mabry, J . Nut. Prod., 1982, 45, 508. 684. C . 3 . Yang, M. Hashimoto, N. Baba, M. Takahashi, H. Kaneto, N. Kawano and I. Kouno, Chem. Pharm. Bull., 1990, 38, 291. 685. C.-S. Yang, I. Kouno, N. Kawano and S. Sato, Tetrahedron Lett., 1988, 29, 1165. 686. M. I. Ybarra, C. A. N. Catalan, E. Guerreiro, A. B. Gutierrez and W. Herz, Phytochemistry, 1990, 29, 2020. 687. H. Yoshioka, T. J. Mabry and B. N. Timmermann, Sesquiterpene Lacfones, Chemistry, NMR and Plant Distribution, University of Tokyo Press, Tokyo, 1973. 688. S. Yu, N. Fang, T . J. Mabry, K. A. Abhoud and S. H. Simonsen, Phytochernistry, 1988, 27, 2887. 689. C. Zdero and F. Bohlmann, Phytochemistry, 1987, 26, 2597. 690. C. Zdero and F. Bohlmann, Phytochemistry, 1989, 28, 3105. 691. C. Zdero and F. Bohlmann, Phytochemistry, 1989, 28, 1155. 692. C. Zdero and F. Bohlmann, Phytochemisfry, 1989, 28, 1949.
CARBON-13 NMR SPECTRA OF SESQUITERPENE LACTONES
475
C. Zdero and F. Bohlmann, Phyrochemistry, 1989, 28, 1433. C. Zdero and F. Bohlmann, Phytochemistry, 1989, 28, 3101. C. Zdero and F. Bohlmann, Phytochemistry, 1990, 29, 183. C. Zdero, F. Bohlmann, L. Haegi and R. M. King, Phytochemistry, 1988, 27, 865. C. Zdero, F. Bohlmann, R. M. King and H. Robinson, Phytochernistry, 1986, 25, 2873. C. Zdero, F. Bohlmann, R. M. King and H. Robinson, Phyrochemistry, 1988, 27, 2835. C. Zdero, F. Bohlmann, R. M. King and H. Robinson, Phytochernistry, 1989, 28, 517. C. Zdero, F. Bohlmann and M. Miiller, Phyrochemistry, 1987, 26, 2763. C. Zdero, F. Bohlmann and R. Scott. Phytochemistry, 1987, 26, 1999. C. Zdero, F. Bohlmann, D. C. Wasshausen and M. G . Mungai, Phytochemistry, 1991, 30, 4025. 703. J. Zhang and L.-X. He, Acta Pharm. Sinica, 1986, 21, 273. 704. Y. Zhao, Z. J . Jia, R. X. Tan and L. Yang, Phytochemistry, 1992, 31, 2785. 705. K. Zitterl-Eglseer, J. Jurenitsch, S. Korhammer, E. Haslinger, S. Sosa, R. Della Loggia, W. Kubelka and C. Franz, Planta Medica, 1991, 57, 444.
693. 694. 695. 696. 697. 698. 699. 700. 701. 702.
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Index ACESII programs, 14 Acetone, monoprotonated and nonprotonated, 183 Acetoxime, non-protonated, 183 Acetylenes 'J(CC) across triple bonds, 145 disubstituted, 138 FPT INDO-calculated values of onebond CC coupling constants, 136 influence of p substituents on 'J(CC) coupling constants, 146 one-bond CC coupling constants, 145 silyl-substituted, 139 Acetylisomontanolide, 263 Acyl groups identification of, 271-8 occurring in sesquiterpene lactones, 272-7 Adamantane, 143 Adsorbate-adsorbent systems, selfdiffusion measurements, 82 27A1CPIMAS spectra, 45,60, 70 27A1DOR NMR spectra, 46,60 27A1MAS NMR spectra, 57,66,70 27AlNMR spectra, 44-7, 70 Alditols, 203 AIdose oximes, 182 Aldoses, 202 Alicyclics, CC couplings, 133-6 Alkylallenes, 148 Alkyl-substituted furanoses, 204 Allenes, INDO FPT total 'J(CC) values, 137 Alliacane, 438 A1PO4 molecular sieves, 55-62 elements substituted into, 55 studies of, 5&61 Aluminas, 70-1 Aluminium Keggin ion, 64,66 Aluminium polyoxycations, 66 Aluminoarsenates, 62 Amino acids, random coil shifts of, 2 Amorpha fruticosa, 210 Anabaena, 218 Aniline, 183
Anisatin type sesquiterpene lactones, 439 Archangelolide, 255-9,265 Arctolide, 247, 252 Arthropsadiol A diacetate, 211 Arthropsis truncata, 210 Aspergillus oryzae, 210 Aspergillus variecolor, 217 Asteriscane, 438 Average electrical perturbation, 20 Azobenzenes, trans and cis, 160 Azotobacter vinelandii. 206 Bacillus aurantinus, 217 Bakkenolide, 439 Band-selective uniform-response pure phase (BURP) pulses, 215 Benzene, one-bond 13C-13C spin-spin coupling constants ,143 Benzene derivatives, one-bond 13C-13C spin-spin coupling constants, 153-7 Benzenes monosubstituted, 158 multisubstituted, 160 ortho and meta disubstituted, 158 para-substituted, 159 Benzoates, 269 Benzylidenaniline, 11 Beryllophosphates, 62 Biologically important compounds, 200 Bis(cyclopropylidene)methane, 140 Bis(tetramethylcyclopropy1idene)methane, 140 Bistrarnide A, 217, 218 Bond length, and chemical shielding, 19 Born-Oppenheimer approximation, 5 Bourbonane, 439 Bovine pancreatic trypsin inhibitor (BPm ring current shifts in, 3 structural shifts, 3 Breck's structure six (EMT), 41 Bronsted acid sites, 47-51, 70 Buckminsterfullerene, 58
478
INDEX
I3C CPIMAS NMR spectroscopy, 74 I3C isotropic chemical shieldings, 31 I3C MAS NMR spectroscopy, 72 13 C NMR spectroscopy, 58 C" proton chemical shifts, 3 Cacalol, 438 Cadinane, 439 Carbohydrates and their derivatives, 200 Carbon-monoxyheme proteins, CO in, 30-3 Catalysts, 73-4 Catalytic reactions in zeolites, 52-5 Cembrene, 180 Charge-balancing cations, 41 . Charged molecules, one-bond 13C-13C spin-spin coupling constants, 196-200 Chemical shielding, 2, 11, 21-6 accuracy of calculated, 18 and bond length, 19 and protein structure, 18-21 correlation with other molecular properties, 30 dynamical effects, 19-21 tensor, 4 Chemical shifts, 1, 2 ab initio approaches and basis sets, 10-18 in nucleic acids, 2 in proteins, 3 influence of external electrical perturbations, 12 of poly-L-alanine, 2 polymer blends, 111-13 torsion in, 18-19 ChloroJlexusaurantiacus, 221 Chorismate, 210, 211 Chorismic acid, 210, 211 CLOPPA (Contributions from Localized Orbitals within the Polarization Propagator Approach) method, 30, 186 Clostridium M P , 206 Cloverite, 62-3 CO in carbon-monoxyheme proteins, 30-3 Cobalt complexes, 194, 195 Colens forskohlii, 218 Copaan, 438 Correlation effects, 10 COSY, 42,43 Coulomb gauge, 8
Coupled-perturbed Hartree-Fock (CPHF), 10-12 CRAMPS, 68 7-Cyano-3-azaoctabisvalene, 171 Cyclobutane type sesquiterpene lactones, 438 Cycloheptatriene, 198 Cyclohexane, 72 one-bond I3C-l3C spin-spin coupling constants, 143 Cyclopentane type sesquiterpene lactones, 439 Cyclopropanes, 168 substituted, 166 Cyclopropenes, 168 silyl-substituted, 167 Datura stramonium, 210 Daucane, 439 Deoxyfuranoses, 204 DEPT-INADEQUATE, 214 Derivative Hartree-Fock (DHF) theory, 12 Desulfovibrio vulgaris, 206 [di-13C]Norborn-2-ylderivatives, 178 Diacetylene derivatives 'J(CC), 146 one-bond CC coupling constants, 146 Diacetylenes, INDO FPT total 'J(CC) values, 137 syn-3,7-Diazaoctabisvalene,171 DICPFeCp, 196 Dienes, 190 1,3-Dienes, 191 Diffusion coefficients, 82 Diffusion measurements in amorphous solids, 84 in zeolites, 82-4 on adsorbed species, 82 Diffusion quantum Monte Carlo (QMC), 20 Dimethyl l-acetyl-6-hydroxy-4,5indoledicarboxylate, 165 I-(Dimethylethenylidene) cyclopropane, 140 2,5-Dimethylpiperidine-4-ones, 175 7,9-Dimethyl-9aH-quinolizine, 179 Diorganotin dication, 188 Disaccharides, 207 Distributed origin gauge with origin at the nuclei (DOGON), 11 Dithieno[b,d]pyridines, 164 Double-rotation (DOR), 45-7, 52, 59
INDEX
Drimane, 435, Dunning contraction, 13 DZP, 14 Electric field gradient, 31 Electron correlation, 14 Electron density, 18 Elemanolides, 247,278,426,428-31 Emmotin, 438 Energy derivatives, 4-6 ab initio calculation, 7 Enynes, 192 ENZYMIX program, 20 Eremophilanolides, 247, 278, 426-7, 432-5 Escherichia coli, 20, 209, 210 Ethane, CC couplings, 133-6 Ethene, CC couplings, 133-6 Ethene derivatives, 192 Ethenes INDO FPT total 'J(CC) values, 137 monosubstituted, 148 trans- and cis-substituted, 149 Ethylenes, 191 monosubstituted, 147 variously substituted, 150 Ethyne, CC couplings, 133-6 Eudesmanolides, 246,278,332-64 Eudesman- 12,6-olides, 34@53 Eudesman-12,8-olides, 358-61 Eudesm-l1(13)-en-12,8-olides,354-7 Eudesm-11( 13)-en-12,6-olides, 334-9 Exchange NMR experiments, polymer blends, 106-8 "F NMR spectra, 63 FAB (fast atom bombardment) ionization, 237 Faujasite (FAU), 41 Five-membered heteroaromatic systems, 162 Five-membered ring compounds, 172 Flavin nucleotides, 206 Fluoroethenes, INDO FPT and FOPPA INDO/MCI one-bond CC couplings, 137 Four-membered ring compounds, 169 Free-induction decay (FID), 105 Frei-Bernstein relationship, 142 Fructofuranosides, 201 D-Furanosides, 205 Furodysinin, 439 Fusarium moniliforme, 218
479
'lGa MAS NMR spectroscopy, 63 7'Ga NMR spectroscopy, 63 Galactose binding protein (GBP), 20 Gallium in zeolites, 50 Galloarsenates, 62 Gallophosphates, 62 Gasoline, conversion of methanol to, 53 Gauge choice of, 9-10 dependence, 13 sensitivity, 13 Gauge-invariant atomic orbitals (GIAO), 9-18 5-Germaaspiro[4,4]nonatetraenes, 174 Germacranolides, 246,278-332 13Cchemical shifts, 330-31 Germacran-12,6-olides, 312-21 Germacr- 11(13)-en-12,6-olides1284311 Germacr- 11(13)-en-12,8-olides, 322-7 GIAO-MP2 method, 14,18 Gibbs free energy of mixing, 111 Glass transition, polymer blends, 122-4 Glycine, 207 Goldman-Shen spin-diffusion experiments, polymer blends, 105 Guaianolides, 246, 278, 365412 Guaian- 12,6-olides, 38&401 Guaian- 12,8-olides, 404-7 Guai-11(13)-en-12,8-olides,402-3 Guai-11(13)-en-12,6-olides, 368-87 'H CRAMPS spectra, 68 'H MAS NMR spectra, 48, 58, 62 'H NMR spectra, 63, 72 Hamiltonian parameters, 5 Heart mitochondria, 213 Helenalin 13C chemical shifts, 242, 264, 266 13CNMR spectrum, 242,243,24850, 251, 261 crystalline forms, 239, 240 'H chemical shift, 266 proton-carbon HMQC (A) and HMBC (C) spectrum, 261 Hellmann-Feynman theorem, 5 , 6 Heptafulvenes, 198 Heteroaromatic systems, one-bond 13C-'3C spin-spin coupling constants, 157-60 Heterocyclic systems, 160-80
480
INDEX
Heteronuclear cross-relaxation experiments, polymer blends, 108-9 Huzinaga primitive bases, 13 Hydrogen in zeolites, 52 Hydroxy compounds, 268 Hydroxyphenyl pyruvate, 210,211 Imines, 183 INADEQUATE method, 44, 131-2, 143,207,209,211-19,262 Independent gauge for localized orbitals (IGLO), 11, 12, 14 Interresidue interactions, 4 Iron complexes of siloles and spirobisiloles, 194 Isosilerolide, 254 'J(CC) computed values, 133 theoretical considerations, 132-9
Klebsiella pneumoniae, 209 Lactarane, 438 Lactococcw lactis, 209 Lactone dimers, 436-7 Large ring compounds, 176-80 Laserolide, 254 Lauernobiolide, 271 Lewis acid sites, 70 Local origin approximation (LORG), 11, 14 Localized molecular orbitals (LMOs), 186 Lone pair effect, 18M Long-range effects, 4 on NMR parameters, 21-30 Lyzosyme, structural shifts in, 2 Magic-angle spinning (MAS), 39, 110 Magnesium aluminophosphate, 62 Magnetic property operators, 7-9 MAGOPS program, 9 Marasmane, 439 MCM-41,72-3 Megasphaera elsdenii, 206 Mesoporous materials, 66-74 MCM-41,72 129XeNMR, 79-80 Metallacyclopropanes, 188 Metalloaluminophosphates (MeAPOs), 55, 62
Methanol, conversion to gasoline, 53 Methyl groups of valine and leucine, 208 9a-Methyl-9aH-quinolizine, 179 Microporous framework solids, 62-3 Microporous materials, 38-66 la ered, 63-6 Jxe NMR spectroscopy, 74-9 Molecular dynamics (MD) simulations, 3,4,20,21 Molecular motion, polymer blends, 114-15, 122 Molecular sieves. See AIP04 molecular sieves Molecular transport in porous solids, 81-5 Molecular wavefunction, calculation of, 8 Moment shielding, 28, 29 Montmorillonite clay, 80 Morphology NMR imaging, polymer blends. 115-16 "N MAS NMR spectroscopy, 70 NMR imaging applications, 84-5 morphology of polymer blends, 11516 pore size distributions, 84 NMR parameters long-range effects on, 21-30 theoretical approach, 4-18 Nuclear Overhauser effect (NOE), 1, 108,255 polymer blends, 112-14 Nuclear quadrupole coupling, 26-9 Nuclear quadrupole moment, 31 Nucleic acids, chemical shifts in, 2 Numerov-Cooley method, 30 1 7 0 isotropic chemical shieldings, 31 Olefins, conversion inside zeolites, 54 One-bond 13C-'3C spin-spin coupling constants, 131-230 across single bonds, 152-3 benzene derivatives, 1 5 S 7 biological studies, 200-11 experimental methods, 211-16 heteroaromatic systems, 157-61 hybridization effect, 140-1 in charged molecules and related compounds, 196-200
INDEX
in structural studies of complexes, 186-96 ring size effect, 140-1 subsituent effects across single, double and triple bonds, 144-51 theoretical considerations, 132-9 unsubstituted hydrocarbons, 140-5 1 One-electron current, 10 One-electron integrals, 9, 10 Organosilicate materials, porous, 73 Oximes, 180, 181 Oxiranes, 170 31PMAS NMR spectra, 56, 61 31PNMR spectra, 63 Penicillium paxilli, 218 Pentafulvenes, 198 (v-Pentamethylcyclopentadienyl) titanium-diene complexes, 188 Pentos-2-uloses, 204 Pentuloses, 204 D-Penturonic acids, 205 3-Phenyl- l-thia-2,3,4-triazol-3-ium-5ylmethanides, 220 .rr-complexes, 188 Picrotoxan, 438 Piperidones, variously substituted, 176 Platinum complexes, 195 P(OAMOMg)2, 62 P(OAl),(OMg), 62 Poly-L-alanine, chemical shifts of, 2 Polycondensed cyclic compounds, 17680 Polymer blends, 97-130 chemical shift, 111-13 exchange NMR experiments, 106-8 glass transition, 122-4 Goldman-Shen spin-diffusion experiments, 105 heteronuclear cross-relaxation experiments, 108-9 macroscopic properties, 101 microscopic heterogeneity, 122 miscibility, 101-11 molecular motion, 114-15, 122 distribution of correlation time, 125 effects of blending on local motion, 124-5 motional heterogeneity, 1 2 5 4 morphology lineshape, 116-18 NMR imaging, 115-16
481
NMR studies, 99-100 nuclear Overhauser effect (NOE), 113-14 relaxation decay curves, 120-2 spin-diffusion, 104-8, 118-19 spin-lattice relaxation, 102-4, 11G19 spin-lattice relaxation times, 102-4, 118-19 thermally induced morphological change, lineshapes, 119-20 '29XeNMR spectroscopy, 109-10 Polymer-polymer interaction, 110-15 Polymethyl substituted cyclopentadienes, 143, 144 Polysilsesquioxane xerogels, 73
Polystyrene/poIy(2,6-dimethyl-l,4-
phenylene oxide) (PS/PPO), 98 Polystyrenetpolystyrene-pol ybutadiene block copolymer (PS/PS-PB), 98 Polystyrene-poly(viny1methyl ether) (PS/PVME), 98 Pore size distribution, 71-2 NMR imaging, 84 Porous materials lz9XeNMR studies, 74-81 layered, 80 Porous solids, 37-95 molecular transport in, 81-5 Porous systems, water transport in, 84-5 Prephenate, 210,211 Protein structure, and chemical shielding, 18-21 Proteins, chemical shifts in, 3 Proton isotropic and anisotropic chemical shielding, 13 Pseudoguaianolides, 246, 278, 412-13, 424-5 Pseudoguaian- 12,6-olides, 4 14-5 Pseudoguaian-12,8-olides, 416-23 Pulsed field gradient (PFG) NMR, 52, 82-4 Pygmacopremna herbacea, 218 Quantum mechanical studies of dynamical effects on chemical shieldings, 20 Random coil protein structure, 2 Random coil shifts, amino acids, 2 Relaxation behaviour, polymer blends, 120-2
482
INDEX
Respiratory proteins property correlations, 30-3 structural NMR shifts, 1-36 Retinylidenebutylimime, 11 Rhenium complexes, 195 Ribonucleosides, 205 Ring current shifts in bovine pancreatic trypsin inhibitor (BPTI), 3 Rotational-echo double-resonance (REDOR), 58 SAPO molecular sieves, studies of, 61-2 Saponite, 64 Schrodinger equation, 5 , 6 SEDOR pulse sequence, 74 Self-consistent field (SCF), 10, 14 INDO values of one-bond CC couplings, 133 Self-diffusion measurements of adsorbate-adsorbent systems, 82 SELINQUATE, 214 Sesquiterpene globulol, 179 Sesquiterpene lactones, 231-475 acyl groups occurring in, 272-7 anisatin type, 439 I3C chemical shift data, 278437 I3CNMR spectra, 242437 carbon-carbon correlations, 258-62 carbon-proton correlations, 255-8 carbon-proton coupling constants, 247-53 CD spectra, 237 chemical correlation, 236 chemical shifts, 244-5 cyclobutane type, 438 cyclopentane type, 439 derivatization, 267-9 dimeric, 452-5 identification of acyl groups, 271-8 IR spectra, 237 isotope labelling, 267 less common structure types, 436 mass spectra, 237 miscellaneous types, 452-5 molecular dynamics, 269-70 NMR spectra, 238-9 nuclear Overhauser effect (NOE), 255 relaxation times, 253 shift reagents, 265 signal multiplicities, 245 skeletal types, 233
solvent effects, 262-5 spectral methods, 23742 structural assignment of signals, 24270 structure classification, 232-5 structure determination methods, 234-42 types of lactonic function, 234 UV spectra, 237 X-ray structure analysis, 239-42 Short-range effects, 4 *'Si CP/MAS NMR spectra, 66-8, 73 *'Si MAS NMR spectra, 39-42, 61, 63, 668 *'Si NMR spectra, 39-44 5-Silaaspiro[4,4]nonatetraenes,174 Silica-alumina catalyst supports, 71 Silicas, 66-9 Silicoaluminophosphates (SAPO), 55 Siloles, 194 Six-membered ring compounds, 172-5 Sodium in zeolites, 52 SOLO (second order LORG), 14 SOPPA (second order polarization propagator approximation), 14 Spin-diffusion, polymer blends, 104-8, 118-19 Spin-echo Fourier transform (SEFT) spectra of zeolites, 40 Spin-echo pulse sequences, 82 Spin-lattice relaxation, polymer blends, 102-4,118-19 Spin-spin coupling, 29-30 general theory, 132 Spirobisiloles, 194 Spiropinguisane, 439 Spirovetivane, 438 5-Stannaspiro[4,4]nonatetraenes,174 Sternheimer shielding factor, 26, 28 Structural shifts, 2 bovine pancreatic trypsin inhibitor (BPTI), 3 in lyzosyme, 2 in macromolecules, 2 Substituted aliphatic cyclic systems, 160-80 Terpenoids, nomenclature, 234-5
[1,4,8,11-Tetrakis(2-hydroxyethyl)1,4,8,11tetraazacyclotetradecane] cadmium (11), 193
INDEX
Tetramethyl 9aH-quinolizine-l,2,3,4tetracarboxylate, 177 TEXAS 90 program, 11 Thieno[c]isoquinolines, 163 Thieno[c]quinolines, 163 Three-membered ring compounds, 160-9 Titanium complexes, 195 Titanosilicates, 62, 63 Tolypocladium inflatum, 209 Torsion in chemical shifts, 1&19 Transferred-echo double-resonance (TEDOR), 58 Trichloroacetyl isocyanate (TAI), 269 Trilobolide, 254 N-( 1,2,5-Trimethylpiperidilidene4)aniline, 185 1,2,5-TrimethyIpiperidine-4-one, 183
2,3,3-Triphenylcyclopropene-l-
carboaldehyde, 167 Tropylium ion, 198 Tryptophan, 20 Tryptophane, 165 Two-electron integrals, 10 Unsubstituted hydrocarbons, one-bond 1 3 C - 1 3spin-spin ~ coupling constants, 140-51 Vernomargolide, 438 Vinylalkoxyallenes, 148 VPI-5, 56-9
483
Water transport in porous systems, 84-5 Williams-Landel-Ferry equation, 123 L29XeNMR spectroscopy mesoporous materials, 79-80 microporous materials, 74-9 miscellaneous porous materials, 8 G 1 polymer blends, 109-10 porous materials, 74-81 zeolites, 74-9 Zeolite molecular sieves, 3&55 Zeolite Y , 45 Zeolites adsorbates in, 52 27AlDOR NMR spectra, 46 27AlNMR spectra, 44-7 catalytic reactions in, 52-5 conversion of olefins, 54 diffusion measurements in, 8 2 4 allium in, 50 ‘€ MAS I NMR spectra, 48 hydrogen in, 52 oxygen in, 50 29SiMAS NMR spectra, 41-2 29SiNMR spectra, 39-44 sodium in, 52 spin-echo Fourier transform (SEFT) spectra of, 40 12’Xe NMR spectra, 74-9 Zirconium complexes, 195 Zirconium tetramer, 64 a-Zr(HP0&.H20, 64
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Cumulative index of topics covered in Volumes 21-30 of this series
Ab initio calculations of NMR chemical shielding, 29, 71 of the NMR chemical shift, 21, 51 Agrochemicals and pesticides, applications of NMR in the analysis of, 22, 139 Azo dyestuffs, multinuclear NMR of, 26, 247 Cancer pathology, the use of proton MR in, 27, 173 Ceramics, high-resolution solid-state NMR studies on, 28, 29 g, '@As, '69Tm, 183Wand 18'Os, 23, Cinderella nuclei, The, 57Fe, "Y, lo3Rh, lCnA 141 Coal research, applications of NMR methods in, 24, 331 Coals and coal products, NMR of, 23, 375 Complex organic resins, NMR characterization of, 29, 169 Cyclodextrins and their inclusion complexes, NMR studies of the structure and properties of, 27, 59 Diffusion of chain molecules in polymer matrices, pulsed-field-gradient NMR studies of, 27, 217 Electronic structures of macromolecules, NMR nuclear shielding and, 22, 205 Food science, applications of NMR to, 26, 1 Glasses and ceramics, application of NMR spectroscopy to the science and technology of, 28, 1 Graphics-aided NMR, 21, 1 199HgNMR parameters, 24, 267 Higher-order structures of solid polymers, NMR studies of, 28, 189 Inorganic and organometallic chemistry, dynamic NMR spectroscopy in, 27, 103 Interfacial phenomena, NMR studies of, 24, 181 Intracellular ions in living systems, NMR measurements of, 24, 219 Isolated spin pairs in the solid state, NMR studies of, 23, 1 Ligand-macromolecule interactions, NMR studies of, 22, 61 Living systems, application of 87Rb NMR to, 26, 211 Membrane transport, NMR studies of, 21, 99 Metal-ion NMR studies of ion binding, 22, 1 Multiple pulse NMR, recent developments of, 21, 162 Nitrogen NMR spectroscopy, 25, 1 Nuclear spin relaxation in diamagnetic fluids general aspects and organic applications, 22, 308 organic s stems and solutions of macromolecules, 23, 289 One-bond 'C-"C spin-spin coupling constants, 30, 131 Organic thin films, NMR studies of, 28, 277 Oxidation-state dependence of transition-metal shieldings, 23, 85 *07Pb-NMRparameters, 22, 249 Peptides and polypeptides in the solid state, structural studies by I5N NMR, 26, 55 Peptides and proteins in synthetic membrane environments, structural biology of, by solid-state Nh4R spectroscopy, 29, 123 Permutation symmetry in NMR relaxation and exchange, 23, 210 Polymer blends, miscibility, morphology and molecular motion in, 30, 97
486
CUMULATIVE INDEX
Polymer chemistry, application of high-resolution NMR spectroscopy to, 26, 100 Polyolefines and olefine copolymers, I3C NMR assignments of, based on the I3C NMR chemical shift calculations and 2D INADEQUATE NMR, 29, 325 Porous solids, NMR applications to, 30, 37 Respiratory proteins, calculation and prediction of structural NMR shifts in, 30, 1 Sensitivity-enhanced NMR techniques for the study of biomolecules, 27, 1 Sesquiterpene lactones, 13C NMR spectra of, 30, 231 Solid state NMR developments in, 24, 1 imaging, 24, 88 Spin-spin coupling constants, advances in theoretical and physical aspects of, 27, 255 Synthetic and biological macromolecules, high-resolution solid-state NMR studies of, 21,210 Synthetic polymers, applications of labelling and multidimensional NMR in the characterization of, 29, 287 Zeolites, NMR studies of, 28, 91
Cumulative index of authors who have contributed to Volumes 21-30
Allis, J. L., 26, 211 Ando, I., 21,210, 22, 205, 26, 55, 28, 189 Ando, S., 26, 55, 28, 189 Asakura, T., 29, 325 Augspurger, J. D., 30, 1
Jameson, C. J., 29, 1 Johansson, C., 22, 1
Barrie, P. J., 30, 37 Belton, P. S., 21, 99, 26, 1 Binsch, G., 23, 210 Blum, F. D., 28, 277 Bright, A. A. S., 22, 139 Brownlee, R . T. C., 21, 1 BudGinsky , M., 30, 231
Kitayama, T., 26, 160 Kowalewski, J., 22, 308, 23, 289 Kuroki, S., 26, 55 Kurosu, H., 22, 205, 28, 189
Cavanagh, J., 27, 1 Chesnut, D. B., 21,51,29,71 Chuang, I., 29, 169 Clayden, N. J., 24, 1 Colquhoun, I. J., 26, 1 Contreras, R., 24, 267, 27, 255 Cory, D. G., 24, 88 Craik, D. J., 21, 1,22, 61 Cross, T. A., 29, 123
Maciel, G. E., 29, 169 Mackinnon, W. B., 27, 173 Mann, B. E., 23, 141 Meiler, W., 23, 375, 24, 331 Meusinger, R., 23, 375, 24, 331 Moad, G., 29,287 Mountford, C. E., 27, 173
Demura, M., 29, 325 de Dios, A. C., 29, 1 Drakenberg, T., 22, 1 Dykstra, C. E., 30, 1
Orrell, K. G., 27, 103
Ernst, H., 28, 91 Facelli. J. C., 27, 255 Grandjean, J., 24, 181 Gupta, R. K., 24, 219 Hatada, K., 26, 100 Hayashi. S., 28, 29 Hayashi, T., 29,325 Higgins. K. A , , 22, 61 Hills, B. P., 21, 99, 26, 1 Horchler, K., 22, 249 Inoue, Y., 27,59
Kamienska-Trela. K., 30, 131 Kawazoe, H . , 28, 1 Kidd, R. G., 23, 85
Lean, C. L., 27, 173 LyCka, A , , 26, 247
Nose, T., 27, 217
Pfeifer, H . , 28, 91 Power, W. P., 23, 1 Rance, M., 27, 1 Ratcliffe, R. G., 22, 173 Russell, P., 27. 173 Saito, H., 21, 210 Saman, D., 30,231 Shoji, A , , 26, 55 Sik, V., 27, 103 Stefaniak, L., 25, 1 Szymanski, S., 23, 210 Takegoshi, K., 30, 97 Turner, D. L., 21. 162 Ute, 26, 100
488
AUTHOR INDEX
Veniero. J. C.. 24. 219
Witanowski, M . , 25, 1 Wrackmeyer, B . , 22, 249, 24,261
Wasylishen, R. E., 23. 1 Webb, G . A , , 22, 205, 25, 1, 26, 55
Yamanobe, T., 22,205 Yoshimizu, H., 28, 189
