Conformational studies in the cyclohexane series. 2. Phenylcyclohexane and 1-methyl-1-phenylcyclohexane

Journal of Organic Chemistry

Volumn 65, Issue 4, 2000, Pages 1181-1187

  Wiberg, Kenneth B ^a   Castejon, Henry ^a,d   Bailey, William F ^b   Ochterski, Joseph ^c  

^a YALE UNIVERSITY   (United States)

^b UNIVERSITY OF CONNECTICUT   (United States)

^c GAUSSIAN INC   (United States)

^d UNIVERSITY OF NOTRE DAME   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOHEXANE DERIVATIVE;

ARTICLE; CONFORMATION; ENTHALPY; ENTROPY; MOLECULAR DYNAMICS;

EID: 0034712312     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9917386     Document Type: Article

References (25)

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2. Eliel, E. L.; Manoharan, M. J. Org. Chem. 1981, 46, 1959.
3. For early experimental estimates of the conformational energy of phenylcyclohexane, see: (a) Eliel, E. L.; Rerick, M. J. Am. Chem. Soc. 1960, 82, 1367. (b) Allinger, N. L.; Allinger, J.; DaRooge, M. A.; Greenberg, S. J. Org. Chem. 1962, 27, 4603. (c) Garbisch, E. W.; Jr.; Patteson, D. B. J. Am. Chem. Soc. 1963, 85, 3228.
4. For early experimental estimates of the conformational energy of phenylcyclohexane, see: (a) Eliel, E. L.; Rerick, M. J. Am. Chem. Soc. 1960, 82, 1367. (b) Allinger, N. L.; Allinger, J.; DaRooge, M. A.; Greenberg, S. J. Org. Chem. 1962, 27, 4603. (c) Garbisch, E. W.; Jr.; Patteson, D. B. J. Am. Chem. Soc. 1963, 85, 3228.
5. For early experimental estimates of the conformational energy of phenylcyclohexane, see: (a) Eliel, E. L.; Rerick, M. J. Am. Chem. Soc. 1960, 82, 1367. (b) Allinger, N. L.; Allinger, J.; DaRooge, M. A.; Greenberg, S. J. Org. Chem. 1962, 27, 4603. (c) Garbisch, E. W.; Jr.; Patteson, D. B. J. Am. Chem. Soc. 1963, 85, 3228.
6. Eliel, E. L.; Wilen, S. H. Stereochemistry of Organic Compounds; Wiley: New York, 1994; pp 665-834.
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8. 1H NMR study of 1-methyl-1-phenyl-4,4-dimethoxycyclohexane indicated a 0.34 kcal/mol preference for the conformation having axial phenyl. See: De Beule, H.; Tavernier, D.; Anteunis, M. Tetrahedron 1974, 30, 3573.
9. Allinger, N. L.; Tribble, M. T. Tetrahedron Lett. 1971, 3259.
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12. Previous ab initio studies of monosubstituted cyclohexanes have been reviewed and the difficulties attending such calculations have been discussed: see, Cremer, D.; Szabo, K. J. In Conformational Behavior of Six-Membered Rings; Juaristi, E., Ed.; VCH Publishers: New York, 1995; pp 59-135.
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16. For example, the barrier to rotation in toluene is a mere 13 cal/mol (Kreiner, W. A.; Rudolph, H. D.; Tan, B. T. J. Mol. Spectrosc. 1973, 48, 86) while the barrier in nitromethane is less than 6 cal/mol (Rohart, F. J. Mol. Spectrosc. 1975, 57, 301).
17. For example, the barrier to rotation in toluene is a mere 13 cal/mol (Kreiner, W. A.; Rudolph, H. D.; Tan, B. T. J. Mol. Spectrosc. 1973, 48, 86) while the barrier in nitromethane is less than 6 cal/mol (Rohart, F. J. Mol. Spectrosc. 1975, 57, 301).
18. Details of the thermal corrections are given in the Supporting Information.
19. Murcko, M. A.; Castejon, H.; Wiberg, K. B. J. Phys. Chem. 1996, 100, 16162.
20. Eliel has also noted (ref 3) that the conformational enthalpy reported by Garbisch and co-workers (ref 4c) for the 2a → 2e equilibrium (ΔS° = 2.09 ± 0.45 eu) is most likely too large.
21. Wiberg, K. B.; Murcko, M. A. J. Comput. Chem. 1987, 8, 1124.
22. Allinger, N. L.; Yuh, Y. H.; Lii, J.-H. J. Am. Chem. Soc. 1989, 111, 8551.
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