58022-53-0Relevant academic research and scientific papers
Conformational studies in the cyclohexane series. 1. Experimental and computational investigation of methyl, ethyl, isopropyl, and tert- butylcyclohexanes
Wiberg, Kenneth B.,Hammer, Jack D.,Castejon, Henry,Bailey, William F.,DeLeon, Eric L.,Jarret, Ronald M.
, p. 2085 - 2095 (1999)
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).
The Experimental Determination of the Conformational Free Energy, Enthalpy, and Enthropy Differences for Alkyl Groups in Alkylcyclohexanes by Low Temperature Carbon-13 Magnetic Resonance Spectroscopy
Booth, Harold,Everett, Jeremy R.
, p. 255 - 259 (2007/10/02)
13C N.m.r. studies at low temperatures of solutions in CFCl3-CDCl3 of methylcyclohexane, -isopropylcyclohexane, cis-1-ethyl-4-methylcyclohexane, cis-1-isoprpyl-4-methylcyclohexane, and cis-1-ethyl-4-isopropylcyclohexane have yielded conformational enthalpy differences and conformational enthropy differences for methyl, ethyl, and isopropyl groups in alkylcyclohexanes.For -ΔH0, the averaged values obtained, in kcal mol-1, were 1.75 (Me), 1.60 Et), and 1.52 (Pri); for ΔS0, the averaged values, in cal mol -1 K-1, were -0.03 (Me), 0.64 (Et), and 2.31 (Pri).The determined values are in good agreement with those calculated by the Allinger group for the gas phase, using a method based on classical mechanics.As a result of the opposing trends for -ΔH0 and ΔS0 values, the sequence of -ΔG0 values at 300 K, namely PriEtMe, is reversed at temperatures below ca. 40 K.
