The conformations of tartaric acids in aqueous solution studied by 'H and 13Cnuclear magnetic resonance

Centro de Qubnicn Estrlrtural, Institute Superior TE'olico, Lisboc~, Portugrrl

C o ~ t r o Qui~nictr Coin~brn de de clnd Department of Chi~~nistry, Uniuc,rsity of Aueiro, Portrcgcrl Received October 24, 1979

Can. J. Chem. Downloaded from by on 08/12/11 For personal use only.

JOSEASCENSO VICTOR S. GIL.Can. J. Chem. 58, 1376 (1980). and M. Vicinal H-H and C-H coupling constants are reported for (+)-tartaric acid and rtleso-tartaric acid at various pH values and used in a discussion of the conformation of these molecules. This is found not to change much with pH. For the nlesu form, in particular, the most favoured conformer is determined not so much by the possibility of internal OH...OOC hydrogen bonding but, at least in part, by stabilization of polar conformations in a solvent (H,O) of high dielectric constant. JOSEA s c ~ ~ et o s VICTOR S. GIL. Can. J. Chem. 58, 1376 (1980). M. On rapporte les constantes de couplage vicinal H-H et C-H des acides (+)-tartarique et n16so-tartarique Bdifferents pH; on les utilise pour discuter de la conformation d e ces molecules et on a trouve que celles-ci ne varient pas appreciablement avec lepH. Dans le cas de la forme tnPso en particulier. le conformere le plus favorise est determine non pas tant par la possibilite d'une liaison hydrogene intramoleculaire OH ....OOC mais du moins en partie par la stabilisation des conformations polaires par H,O un solvant de forte constante dielectrique. [Traduit par le journal]

Introduction During an nmr study of rotational isomerism and metal complexation of simple carboxylic acids in aqueous solutions, the need was felt to know the conformations of active and meso-tartaric acids as free ligands at various pH values. Such conformations are known for the solid state (1,2). Regarding solutions, the work of Hargreaves and Richardson (3) on the changes of the rotatory power of (+)-tartaric acid presents an interpretation partly based on conformational changes with temperature, solvent, and concentration, it being assumed that the most stable conformation in solution is essentially the same as that of the crystal. For the optically inactive meso-tartaric acid in solution, no report of any conformation study was found. In solution and at room temperature, there is rotation of the molecules around the rapid HC-CH bond. A n approximate way of approaching rotational isomerism often used is to regard t h e mean molecular conformation as an weighted average of the conformations of the three staggered rotational isomers. F~~(+)-tartaric acid, these are as follows:

whereas for meso-tartaric acid they are:
H$ o; z c





(b~) and being enantiomers. since +inal IH-IH (3JHH)and 1 3 ~ - I H (3JCH) spin coupling constants depend on the dihedral angles, we have obtained those coupling constants for various p~ values and related them to the conformation ofthe tartaric acids in a manner similar to that previously used in related systems.
The spectra were run on JEOL PS-100, Varian XL-100, and Varian HA-100 spectrometers, at the temperature of the probes (-30°C) except when otherwise specified. D,O solutions were used throughout: for [ H and I3C studies the concentration was, resoectivek. 0 . 5 ' and 2 M. The DH was adiusted with NaOD ~ and (CH,)&OH. The pH+ values quoted are the direct pHmeter readings. Gated irradiation of protons was used to observe nOe in I3C spectra without decoupling.



H o z c ~ o H

w c o z H $ :

Since, because of symmetry, the normal (C)-'H Results and Discussion spectra of both tartaric and meso-tartaric acids consist of just one line, use had to be made of the (13C)-'H satellites to get 3JHH. values are The shown in Table 1.

~4 H



0008-4042/80/13 137604$01.OO/O @I980 National Research Council of CanadaIConseil national de recherches du Canada

The observed decrease of J H H consistent with the exis pectation. stabilized by intermolecular rather than intramolecular hydrogen bonds (2). if it were (c) where such orientation is trans. which is approximately the conformation in the solid state (I). As the X-combination lines are clearly detected and easily assigned on intensity grounds. the least repulsion of the carboxylic groups and a possibility of intramolecular by 200. see also below).9) and meso-tartaric acid (pH* = 0.nrcresearchpress. is obthis served but the effect is small. However.H-H appreciably different. the analysis of the X spectra gives the values of the vicinal and geminal '3C02H-1H coupling constants as pairs (it is not possible to distinguish between JAX JArX). The I3C nmr signal for the carboxylic groups of both acids is the X part of an AA'X spectrum. and by recognizing that 2J for tartaric and meso-tartaric acids should be about the same.32. It is clear that even when the C 0 2 H groups are fully (and the O H partially) ionized. The ionization of the acid should increase the weight of (a') leading now to an increase of 3JHH.ASCENSO AND GIL TABLE 'JHH 1.201. 5. This is in accordance with the reasonable assumption that (a).9). It is noted that these are the conformations in any of the crystal forms of meso-tartaric acid. in fact. Figure FIG. It is thus found that the vicinal 13C02H-'H coupling constant in (+)-tartaric acid. the asare signments are made by comparison with similar related systems (5) as far as 2Jis concerned. simultaneously.18 on 08/12/11 For personal use only. the J values for tartaric acid are typical of an essentially gauche coupling constant. this arrangement provides. This shows that between conformations (a) and (c). the 3Jvalue should be of the order of 7 H z (ref. the geminal being almost certainly the negative one.Co. However. Downloaded from www.1. pH* = 0. see also below). for any pH. Carboxylic 13Csignal for ( a )L(+) tartaric acid and (b) meso-tartaric acid ( 2 M solutions in D. a possible contribution of (c) cannot be ruled out.O. is typical of a gauche orientation of the coupled nuclei (5). The various coupling constants are shown in Table 2. for less (a) than for (c) (ref. 4. This shows that the conformations are essentially (6') and (c'). the 3JHH values presented in Table 1 are again typical of gauche coupling. J. Irrespective of the degree of ionization. values ( H z ) for tartaric acids 1 L(+) Tartaric pH* J Meso-Tartaric pH* J Can. . The analysis immediately and shows that these coupling constants have opposite signs. due to the orientation depenthe dence of substituent effects on 3JHH.groups). is the most stable conformer in solution. Whenever the magnitudes of 2J~~C02H-H and 3Jj.-C02Hhydrogen bonds (3).9). where A and A' are the C H hydrogen atoms. Chem.. (6') and (c') are much more stable than (a '). The weight of (a) is expected to increase upon ionization of the C 0 2 H groups (due to stronger repulsion of the C 0 2 . The arguments of least repulsion of carboxylic groups and establishment of intramolecular hydrogen bonds would lead one to expect (a') to be the most favoured conformation for meso-tartaric acid in solution. OH and C 0 2 H (or C02-) groups should make 3JH. 1 shows such signals for tartaric acid (pH* = 0. (a) is by far the more stable.

58. by OH. then.5 3. b' = c ' = 0. According to the values above for the three rotamers and those in Tables 1 and 2.3 - 1.nrcresearchpress. coupled with the assumption that. 3JHH(b)= 1. 0 2 . Within experimental error (less than f0. trans situation) than in meso-tartaric acid (mainly conformations (b') and (c').3 f 3. An important difference between (a') and (b') is that the former has no electric dipole moment whereas (b') and (c') will have an appreciable di- Can. since the effect of an individual substituent is reduced when another similar substituent is present. fratzs = 6.9 0. 3JCH'a'= By ' 1. 0. By then using 3JHH(a')=and 3JCHca') 13.1 M solutions obtained the JHH of tartaric and meso-tartaric acids as well as for solutions at 80°C.4 acid (7). values are concerned. 1980 T A B L ~ 3 J ~ 3 . It is expected should increase if the substituent is trans that 'JCH to IH and decrease if it is gauche (6). as is likely. We have 2.5 3. (b). CHEM.04. 3.0 12.7 f 0.0.5 we obtain. Chem. 3JCH'b'). . from Table 1. although this is the molecular conformation of meso-tartaric acid in the solid state (2). As already mentioned.08. J. However. + 5 + .3 3. 3JHH(n) and from Table 2. b' = c ' = 0.5 f 1.2 3.7.4 - 0.65 1.5 It is clear that in view of the values shown in Tables 1 and 2.16 T 0.6 and 2 X 3.42 f 0. (c').5. b = 0. the presence of a second C 0 . the finding that conformation (b') (or (c')) is much more stable than (a') is somewhat surprising. using 3JHH'b'= 3JHH(C'= 3JcH'b'= 13.0 5 3JHH(b')= 5 3JHH(C' 2. c = 0.1 1. (b'). the total effect of the 4 substituents is in between +and i of the sum of the individual effects. The various J-values would then be as follows: 3JHH'a) f = 1.3 L ( + ) Tartaric Meso-Tartaric 4. 3JHH'')= 0.7 . 3JCH(a') f 0.8 5. 2JCfl should be larger in tartaric acid (mainly conformation (a) by 200. Downloaded from www. in accordance with the dominant contributions of conformations (b ') and (c ').91.0 10. (c) and (a '). we can obtain the approximate weight of the conformations (a).7.6f = 13. This is observed if. We thus have the following tentative values: 3JCH'a'1.Tartaric 'J pH* 'J pH* 3J 2J The vicinal 13C02H--1Hcoupling constant in meso-tartaric acid.6: a = 0. and in spite of the limitations of the method.1 6.7 I JCH(b')(gauche) 3JcH'")(tran~) I 3.05. we will proceed with the following calculations.7 3.4 3.5 3Jo'c) 6. because of degeneracy of or values alone enable (b') and (c'). we base our estimates on the work of Feeney and co-workers (5) on the conformation of amino acids and allowing for the replacement of NH. In Table 3 the magnitudes of the geminal I3CH-C'H coupling constant are also recorded. and a ' = 0.7 = 2.5.9): a ' = 0.32.9 3. ~ 0. . with respect to IH.9 1.5. Accordingly. T o find out whether self-association through intermolecular hydrogen bonding is sufficiently important in aqueous solution to explain the preference for conformation (b') instead of (a').9.3 - 0. the uncertainties quoted above can lead to appreciable errors.Cvalues (Hz) for tartaric 3. 3 J ~ H ( C ' ) = 2.9 8.7. H group and the deon pendence of 3JcH the orientation of the substituents (6). we attribute reasonable values to the vicinal H-H and C-H coupling constants of the staggered conformers. we have values for 5 M and 0. -~11 acids L(+) Tartaric Meso.02. an equal mixture of trans and gauche arrangements).3 k 1. As far as the 3JH. This must be attributed mainly to the dependence of the I3CH-CIH coupling constant on the orientation of the substituent OH group bonded to I3C. 3JCH'b) k 0. Regarding the vicinal C-H coupling constants.5.0 f 0. 1 Hz) no changes were detected. 3JHH(a 13. 3JHH'"" f 0.48 f 0.7 1. ~H acids pH * 0.03 T 0. For meso-tartaric acid.5 = 1.6 and 15 3JcH(c) we obtain the following weights for = 6.3 = 2. . If it is assumed that the tartrate ion exists almost exclusively in conformation (a). the JHH the JcH the calculation of the various weights. = 2.1378 CAN.201.~ and 2 J ~ ~ . the values for tneso-tartaric acid are negative. is intermediate between gauche and trans values. J. we take essentially the approach previously used for malic TABLE Z J ~ 3 C H . VOL.5 3 J C ~ ' c " g a ~ = h e f 0.5. If.5 tartaric acid at pH* = 1.2 2.0. = = 1.18 on 08/12/11 For personal use only. 0 2 1 1 values (Hz) for tartaric 2.3. separately (for pH* = 0.5 3.5. for any pH.6.4 2. The difference observed for both acids is noteworthy.

and J and references therein. 177. 854 (1948). 1. ABRAHAM G. K. G .G. 7.Chem. MARIA NO^^^ V. V.S. BEEVERS F. However. STERN. 522 (1967). HUGHES. Vol. . V. B. HARGREAVES P. FEENEY. Phys. 3. G. Chem. 961 (1969). M. Soc. It is a joint contribution of the Centro de Investiga~ao Quimica de Coimbra and Centro de Quimica Estrutural de Lisboa supported by the Instituto Nacional de Investiga~ao Cientifica. J . K.nrcresearchpress. A. E W I N GIt2 Annu. studies in other solvents are needed. and references therein. Rep.. C. GIL. R. P.ASCENSO A N D GIL 1379 pole moment. BEEVERS W. Feeney and A. J . Xavier and Professor Gillard for helpful discussions. A. F. D. 5.201. R. and J. London for the use of a Varian XL-100 spectrometer.O molecules. A. S. 6A. 2260 (1957). 4. 1975. C. C. These will be the object of a future paper. 17. 251 (1941). New York. 162.Mol. 6. In a solvent of high dielectric constant such as water.. Downloaded from www.249 (1975). . and Acta Crystallogr. Thanks are also due to Drs. J. A. J and J Reson. S. Acknowledgements Part of this work was presented at the 1978 Meeting of the Portuguese Chemical Society. C.M. 22. and Nature. In tartaric acid the lowest energy conformation (a) is also that corresponding most likely to a higher dipole by 200. Editedby E . J. in order to assess the importance of this effect as well as specific hydrogen bonding to the H. NMR Spectrosc. HANSEN. E .18 on 08/12/11 For personal use only. ROBERTS. Can. RICHARDSON. Chem. M. . Soc. these latter conformations will therefore be more stabilized. Mooney. thanks the National Institute for Medical Research. Sect. J . BOOTSMA J . 2. SCHOONE. GATTI. Academic Press. Soc. Magn.313 (1969). F. and Proc.32. 17.

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