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Conformational Studies in the Cyclohexane Series. 1. Experimental and Computational Investigation of Methyl, Ethyl, Isopropyl, and tert-Butylcyclohexanes

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Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269-3060, and Department of Chemistry, College of the Holy Cross, Worcester, Massachusetts 01610
Cite this: J. Org. Chem. 1999, 64, 6, 2085–2095
Publication Date (Web):March 4, 1999
https://doi.org/10.1021/jo990056f
Copyright © 1999 American Chemical Society
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Abstract

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The conformational enthalpy (ΔH°), entropy (ΔS°), and free energy (−ΔG°) of methyl- (1), ethyl- (2), and isopropylcyclohexane (3) have been reinvestigated both experimentally and computationally. A novel experimental approach to evaluation of highly biased conformational equilibria is described that obviates the need to measure large axial/equatorial isomer ratios directly in order to determine the equilibrium constant:  the natural abundance 13C signal for the C(2,6) resonance in the equatorial isomer of an alkylcyclohexane may be used as an internal reference, and the ratio of this band area to that of an enriched 13C nucleus in the axial isomer gives K following correction for statistical differences and the differing 13C-content of the signals being monitored. The experimental conformational enthalpies (ΔH°), determined at 157 K in independent studies at two laboratories, were found to be (kcal/mol) 1.76 ± 0.10 (Me), 1.54 ± 0.12 (Et), and 1.40 ± 0.15 (i-Pr); the corresponding conformational entropies (ΔS°, eu) were 0.2 ± 0.2 (Me), 1.3 ± 0.8 (Et), and 3.5 ± 0.9 (i-Pr). Computational studies at the QCISD level gave satisfactory agreement with the experimental results, but B3LYP gave energy differences that were too large, whereas MP2 gave differences that were too small. The computed structural data indicates that an axial alkyl substituent leads to local flattening of the cyclohexane ring but there was no evidence of a 1,3-synaxial interaction with the axial hydrogens at C(3,5).

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Summary of the calculations, including additional theoretical levels and details of the thermal corrections to 298 K, and calibration of the 2-chlorobutane thermometer. This material is available free of charge via the Internet at http://pubs.acs.org.

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