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An NMR and Quantum-Mechanical Investigation of Tetrahydrofuran Solvent Effects on the Conformational Equilibria of 1,4-Butanedioic Acid and Its Salts

Kent, D. R., IV and Petterson, Krag A. and Gregoire, Françoise and Snyder-Frey, Ethan and Hanely, Linda J. and Muller, Richard P. and Goddard, William A., III and Roberts, John D. (2002) An NMR and Quantum-Mechanical Investigation of Tetrahydrofuran Solvent Effects on the Conformational Equilibria of 1,4-Butanedioic Acid and Its Salts. Journal of the American Chemical Society, 124 (16). pp. 4481-4486. ISSN 0002-7863. doi:10.1021/ja012016a.

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Vicinal proton−proton NMR couplings have been used to compare the influences of water and tetrahydrofuran (THF) as solvents on the conformational equilibria of 1,4-butanedioic (succinic) acid and its mono- and dianionic salts. An earlier NMR investigation (Lit, E. S.; Mallon, F. K.; Tsai, H. Y.; Roberts, J. D. J. Am Chem. Soc. 1993, 115, 9563−9567) showed that, in water, the conformational preferences for the gauche conformations for butanedioic acid and its monoanion and dianion were, respectively, ∼84%, 66%, and 43%, essentially independent of the nature of the cation or concentration. We now report the corresponding gauche percentages calculated in the same way for 0.05 M solutions in THF to be 66%, 90−100%, and 46−64%. Substantial evidence was adduced for the rotational angle between the substituents in the monoanion being ∼70°. The positions of conformational equilibria of the salts in THF, particularly of the dianion, were found to be rather insensitive to concentration and temperature, but more sensitive to the amount of water present. Ab initio quantum-mechanical calculations for 1,4-butanedioate dianion indicate that, as expected for the gas phase, the trans conformation of the dianion should be heavily favored over the gauche, but, in both THF and water, the gauche conformation is calculated to predominate with rotational angles substantially less than 60°. This conclusion is, in fact, generally consistent with the experimental vicinal proton couplings, which are wholly inconsistent with the trans conformation.

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Goddard, William A., III0000-0003-0097-5716
Additional Information: © 2002 American Chemical Society. Received November 6, 2000. Revised Manuscript Received January 30, 2002. Publication Date (Web): March 23, 2002. Acknowledgment is made to the donors of the Petroleum Research Fund administered by the American Chemical Society, for support of this research. We are also deeply indebted to the Summer Undergraduate Research Fellowship Program (SURF), the Beckman Institute of the California Institute of Technology, the E. I. Du Pont Company, and Dr. and Mrs. Chester M. McCloskey and the Camille and Henry Dreyfus Foundation for their helpful financial assistance. D.R.K. is grateful for support of part of this research by a graduate fellowship from the Fannie and John Hertz Foundation.The quantum chemistry calculations reported here were funded by DOE-BCTR (DE-FG36-93CH105 81, David Boron). The facilities of the MSC are also supported by grants from NSF (CHE 95-22179 and ASC 92-100368), Chevron Petroleum Technology Co., Saudi Aramco, Asahi Chemical, Owens-Corning, Exxon, Chevron Chemical Co., Chevron Research and Technology Co., Avery-Dennison, Hercules, BP Chemical, and the Beckman Institute.
Funding AgencyGrant Number
American Chemical Society Petroleum Research FundUNSPECIFIED
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
E. I. Du Pont CompanyUNSPECIFIED
Dr. and Mrs. Chester M. McCloskeyUNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
Fannie and John Hertz FoundationUNSPECIFIED
Department of Energy (DOE)DE-FG36-93CH10581
NSFCHE 95-22179
NSFASC 92-100368
Chevron Petroleum Technology Co.UNSPECIFIED
Chevron Chemical CoUNSPECIFIED
Chevron Research and Technology Co.UNSPECIFIED
Issue or Number:16
Record Number:CaltechAUTHORS:20151001-101403571
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Official Citation:An NMR and Quantum-Mechanical Investigation of Tetrahydrofuran Solvent Effects on the Conformational Equilibria of 1,4-Butanedioic Acid and Its Salts David R. Kent IV, Krag A. Petterson, Françoise Gregoire, Ethan Snyder-Frey,Linda J. Hanely, Richard P. Muller, William A. Goddard III, and John D. Roberts Journal of the American Chemical Society 2002 124 (16), 4481-4486 DOI: 10.1021/ja012016a
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:60655
Deposited By: Ruth Sustaita
Deposited On:02 Oct 2015 19:16
Last Modified:10 Nov 2021 22:37

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