Intrinsic barriers for the reactions of an oxocarbenium ion in water

Journal of the American Chemical Society

Volumn 121, Issue 36, 1999, Pages 8403-8404

  Richard, John P ^a   Williams, Kathleen B ^a   Amyes, Tina L ^a  

^a UNIVERSITY AT BUFFALO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACETOPHENONE;

ANALYTIC METHOD; ARTICLE; CATALYSIS; CHEMICAL REACTION; HYBRIDIZATION; PROTON TRANSPORT; REACTION ANALYSIS; THERMODYNAMICS;

EID: 0033568228     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9915293     Document Type: Article

References (25)

1. Richard, J. P. Tetrahedron 1995, 51, 1535-1573.
2. McClelland, R. A. Tetrahedron 1996, 52, 6823-6858.
3. Bernasconi, C. F. Tetrahedron 1985, 41, 3219-3234.
4. Bernasconi, C. F. Acc. Chem. Res. 1987, 20, 301-308.
5. Bernasconi, C. F. Acc. Chem. Res. 1992, 25, 9-16.
6. Amyes, T. L.; Jencks, W. P. J. Am. Chem. Soc. 1989, 111, 7888-7900.
7. Young, P. R.; Jencks, W. P. J. Am. Chem. Soc. 1977, 99, 8238-8248.
8. +.
9. (a) Fox, J. P.; Jencks, W. P. J. Am. Chem. Soc. 1974, 96, 1436-1449.
10. (b) Funderburk, L. H.; Aldwin, L.; Jencks, W. P. J. Am. Chem. Soc. 1978, 100, 5444-5459.
11. (c) Bonvicini, P.; Levi, A.; Lucchini, V.; Modena, G.; Scorrano, G. J. Am. Chem. Soc. 1973, 95, 5960-5964.
12. Eigen, M. Angew. Chem., Int. Ed. Engl. 1964, 3, 1-72.
13. Cordes, E. H.; Bull, H. G. Chem. Rev. 1974, 74, 581-603.
14. The reactions of 2 were monitored by following the appearance of acetophenone by UV spectroscopy. The protonation of 2 is rate-limiting for its conversion to acetophenone [Loudon, G. M.; Berke, C. J. Am. Chem. Soc. 1974, 96, 4508-4517].
15. -1) determined from the ratio of product yields were reproducible to better than ±10%.
16. 22
17. + in the reverse direction. This suggests that catalysis of the addition of water, whose basicity is similar to that of methanol, is negligible.
18. oxo = 33 M reported here also shows a similar agreement with the value of 65 M determined by a different indirect method in this earlier study.
19. Marcus, R. A. J. Phys. Chem. 1968, 72, 891-899.
20. o is discussed in the Supporting Information.
21. McClelland, R. A.; Kanagasabapathy, V. M.; Banait, N. S.; Steenken, S. J. Am. Chem. Soc. 1991, 113, 1009-1014.
22. Kresge, A. J. Can. J. Chem. 1974, 52, 1897-1903.
23. Bernasconi, C. F.; Wenzel, P. J. J. Am. Chem. Soc. 1994, 116, 5405-5413.
24. (a) Ta-Shma, R.; Jencks, W. P. J. Am. Chem. Soc. 1986, 108, 8040-8050. Richard, J. P.; Jencks, W. P. J. Am. Chem. Soc. 1984, 106, 1396- 1401.
25. (a) Ta-Shma, R.; Jencks, W. P. J. Am. Chem. Soc. 1986, 108, 8040- 8050. Richard, J. P.; Jencks, W. P. J. Am. Chem. Soc. 1984, 106, 1396-1401.