Conformational studies in the cyclohexane series. 2. Phenylcyclohexane and 1-methyl-1-phenylcyclohexane
The structures and relative energies of the conformers of phenylcyclohexane, and 1-methyl-1-phenylcyclohexane have been calculated at theoretical levels including HF/6-31G, B3LYP/6-311G, MP2/6-311G, MP2/6-311(2df,p), QCISD/6-311G, and QCISD/6-311G(2df,p). The latter gives conformational enthalpy (DeltaH degrees ), entropy (DeltaS degrees ), and free energy (DeltaG degrees ) values for phenylcyclohexane that are in excellent agreement with the experimental data. The calculations for 1-methyl-1-phenylcyclohexane find a free energy difference of 1.0 kcal/mol at -100 degrees C, favoring the conformation having an axial phenyl group, that is in only modest agreement with the experimental value of 0.32 +/- 0.04 kcal/mol. The origin of the phenyl rotational profiles for the conformers of phenylcyclohexane and 1-methyl-1-phenylcyclohexane is discussed.
Wiberg
KB
Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107, Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269-3060, and Gaussian, Inc., 140 Washington Avenue, North Haven, Connecticut 06473, USA.
Castejon
H
Bailey
WF
Ochterski
J