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Nuclear Magnetic Resonance Spectroscopy. Conformational Properties of Substituted 1,1-Difluorocyclohexanes

Spassov, Stefan L. and Griffith, Dean L. and Glazer, Edward S. and Nagarajan, Kuppswamy and Roberts, John D. (1967) Nuclear Magnetic Resonance Spectroscopy. Conformational Properties of Substituted 1,1-Difluorocyclohexanes. Journal of the American Chemical Society, 89 (1). pp. 88-94. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20151014-144942097

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Abstract

Rates of ring inversion and conformational equilibria of gem-fluorocyclohexanes carrying various substituents were determined by fluorine magnetic resonance spectroscopy. For 1 ,l-dilluorocyclohexane, 1,1,2,2-tetrafluorocyclohexane, 4-methyl-4-ethyl-l,l-difluorocyclohexan4e,,4 -dimethyl-l,l-difluorocyclohexanea,n d 4-chloro-1,l-difluorocyclohexane, the activation energies (E,) for ring inversion were found to fall between 8.0 and 11.2 kcal/mole. For 4-chloro-1 ,l-difluorocyclohexane, the difference in free energy for the conformation with chlorine equatorial and the conformation with chlorine axial was found to be -0.32 and -0.17 kcal/mole for solutions in propene and acetone, respectively, and practically independent of temperature. The corresponding free-energy difference for the conformations of 4-methyl-4-ethyl-1 ,l-difluorocyclohexane is - 0.10 kcal/mole. With 3-methyl-, 4-methyl-, and 4-t-butyl-substituted ll-difluorocyclohexanes the equilibria between the conformations is shifted so much in favor of one conformer that only qualitative conclusions could be drawn from the fluorine magnetic resonance spectra.


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http://dx.doi.org/10.1021/ja00977a018DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja00977a018PublisherArticle
Additional Information:© 1967 American Chemical Society. Received August 8, 1966. Supported in part by the National Science Foundation.
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Caltech Gates and Crellin Laboratories of Chemistry3405
Record Number:CaltechAUTHORS:20151014-144942097
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20151014-144942097
Official Citation:Nuclear Magnetic Resonance Spectroscopy. Conformational Properties of Substituted 1,1-Difluorocyclohexanes Stefan L. Spassov, Dean L. Griffith, Edward S. Glazer, Kuppswamy. Nagarajan, and John D. Roberts Journal of the American Chemical Society 1967 89 (1), 88-94 DOI: 10.1021/ja00977a018
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:61117
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:15 Oct 2015 17:05
Last Modified:15 Oct 2015 17:05

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