Enolization Enthalpies for Aliphatic Carbonyl and Thiocarbonyl Compounds

Journal of Organic Chemistry

Volumn 63, Issue 16, 1998, Pages 5314-5317

  Zhang, Xian Man ^a   Malick, David ^a   Petersson, George A ^a  

^a WESLEYAN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000756845     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo972157o     Document Type: Article

References (32)

1. (a) Lowry, T. H.; Richardson, K. S. Mechanism and Theory in Organic Chemistry, 3rd ed.; Harper and Row: New York, 1987; Chapter 8.
2. (b) Toullec, J. In The Chemistry of Enols; Rappoport, E., Ed.; Wiley: Chichester, 1990; Chapter 6, pp 323-398.
3. (a) Keeffe, J. R.; Kresge, A. J.; Schepp, N. P. J. Am. Chem. Soc. 1990, 112, 4862-4868.
4. (b) Chiang, Y.; Kresge, A. J. Science 1991, 253, 395.
5. (a) Ohno, A. In Organic Chemistry of Sulfur; Oae, S., Ed.; Plenum Press: New York, 1977; Chapter 5.
6. (b) Paquer, D.; Vialle, J. Bull. Soc. Chim. Fr. 1969, 3327.
7. (c) Paquer, D.; Vialle, J. Bull. Soc. Chim. Fr. 1969, 3595.
8. (d) Fraser, P. S.; Robbins, L. V.; Chilton, W. S. J. Org. Chem. 1974, 39, 2509.
9. (e) Selzer, T.; Rappoport, Z. J. Org. Chem. 1996, 61, 5462.
10. (f) Fabian, J.; Mayer, R. Spectrochim. Acta 1964, 20, 299.
11. (g) Morgenstern, J.; Mayer, R. J. Prakt. Chem. 1966, 34, 116.
12. Bruno, A. E.; Steer, R. P.; Mazey, P. G. J. Comput. Chem. 1983, 4, 104.
13. (a) Ochterski, J. W.; Petersson, G. A.; Montgomery, J. A., Jr. J. Chem. Phys. 1996, 104, 2598.
14. (b) Ochterski, J. W.; Petersson, G. A.; Wiberg, K. B. J. Am. Chem. Soc. 1995, 117, 11299.
15. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A., Jr.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. GAUSSIAN94; Gaussian, Inc.; Pittsburgh, PA, 1995.
16. (a) Zhang, X.-M. J. Org. Chem. 1998, 63, 1872.
17. (b) Zhang, X.-M. J. Org. Chem. 1998, 63, 3590.
18. Schleyer, P. R.; Kost, D. J. Am. Chem. Soc. 1988, 110, 2105.
19. The calculated enolization enthalpies (Schemes 2 and 3) are expected to equal the corresponding enolization free energies within ±1 kcal/mol since the enolization entropies of the keto and enol tautomers are similar. For example, the calculated enolization free energies of acetone and cyclopropanone are 12.1 and 23. 3 kcal/mol at 298 K, whereas the corresponding enolization enthalpies are 11.4 and 24.1 kcal/mol (Table 2) at 298 K, respectively.
20. Pollack, S. K.; Hehre, W. J. J. Am. Chem. Soc. 1977, 99, 4845.
21. Chiang, Y.; Kresge, A. J.; Schepp, N. P. J. Am. Chem. Soc. 1989, 111, 3977.
22. Zhang, X.-M., submitted for publication.
23. Isaacs, N. Physical Organic Chemistry, 2nd ed.; Longman: UK, 1995; p 44.
24. Harnisch, J.; Baumgartel, O.; Szeimies, G.; van Meerssche, M.; Germain, G.; Declercq, J. J. Am. Chem. Soc. 1979, 101, 3370.
25. 11 suggesting that the aqueous solution enolization enthalpy of acetone is only about 1 kcal/mol higher than the corresponding enolization free energy.
26. Bordwell, F. G.; Harrelson, J. A.; Lynch, T.-Y. J. Org. Chem. 1990, 55, 3337.
27. (a) Campaigne, E.; Edwards, B. E. J. Org. Chem. 1962, 27, 3760.
28. (b) Campaigne, E. The Chemistry of the Carbonyl Group; Patai, S., Ed.; Interscience Publishers: New York, 1966; Chapter 17.
29. (c) Pedersen, B. S.; Scheibye, S.; Nilsson, N. H.; Lawesson, S.-O. Bull. Soc. Chim. Belg. 1978, 87, 223.
30. (a) Mayer, R.; Fabian, J. Angew Chem., Int. Engl. Ed. 1964, 3, 272.
31. (b) Campaigne, E. Chem. Rev. 1946, 39, 1.
32. Wiberg, K. B.; Caringi, J. J.; Matturro, M. G. J. Am. Chem. Soc. 1990, 112, 5854.