Substituent Effects on the Stabilities of Phenoxyl Radicals and the Acidities of Phenoxyl Radical Cations

Journal of the American Chemical Society

Volumn 113, Issue 5, 1991, Pages 1736-1743

  Bordwell, Frederick G ^a   Cheng, Jin Pei ^a  

^a NORTHWESTERN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000161895     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00005a042     Document Type: Article

References (52)

1. McMillen, D. F.; Golden, D. M. Annu. Rev. Phys. Chem. 1982, 33, 493–532.
2. Holmes, J. L.; Lossing, F. P.; Terlouw, J. K. J. Am. Chem. Soc. 1986, 108, 1086, 1087.
3. Bordwell, F. G.; Bausch, M. J. J. Am. Chem. Soc. 1986, 108, 1979–1985.
4. Bordwell, F. G.; Chen, J.-P.; Seyedrezai, S. E.; Wilson, C. A. J. Am. Chem. Soc. 1988, 110, 8178–8183.
5. Bordwell, F. G.; Harrelson, J. A. Jr. Can. J. Chem. 1990, 68, 1714–1718.
6. Bordwell, F. G.; Lynch, T.-Y. J. Am. Chem. Soc. 1989, 111, 7558–7562.
7. Pryor, W. A. Free Radicals; McGraw-Hill: New York, 1986; pp 170–177.
8. Dust, J. M.; Arnold, D. R. J. Am. Chem. Soc. 1983, 105, 1221–1227.
9. Wayner, D. D. M.; Arnold, D. R. Can. J. Chem. 1984, 62, 1164–1168.
10. Creary, X.; Mehrsheikh-Mohammadi, M. E. J. Org. Chem. 1986, 51, 1110–1114 and references cited therein.
11. Bordwell, F. G.; Cheng, J.-P.; Bausch, M. J.; Bares, J. E. J. Phys. Org. Chem. 1988, 1, 209–223.
12. Bordwell, F. G.; Bausch, M. J.; Branca, J. C.; Harrelson, J. A., Jr. J. Phys. Org. Chem. 1988, 224–241.
13. Bordwell, F. G.; Cheng, J. P.; Harrelson, J. A., Jr. J. Am. Chem. Soc. 1988, 110, 1229–1231.
14. Janousek, B. K.; Reed, K. T.; Brauman, J. I. J. Am. Chem. Soc. 1980, 102, 3125–3129.
15. Janousek, B. K.; Brauman, J. I. In Gas Phase Ion Chemistry; Bowers, W. A., Ed.; Academic Press: New York, 1979; p 53.
16. Brauman, J. I. In Frontiers of Free Radical Chemistry; Pryor, W. A., Ed.; Academic Press: New York, 1980; p 23.
17. Friedrich, L. E. J. Org. Chem. 1983, 48, 3851, 3852.
18. Lind, J.; Shen, X.; Eriksen, T. E.; Merényi, G. J. Am. Chem. Soc. 1990, 112, 479–482.
19. Tilset, M.; Parker, V. D. J. Am. Chem. Soc. 1989, 111, 6711–6717.
20. Mulder, P.; Saastad, O. W.; Griller, D, J. Am. Chem. Soc. 1988, 110, 4090, 4091.
21. Arnett, E. M.; Amarnnath, K.; Harvey, N. C.; Cheng, J.-P. J. Am. Chem. Soc. 1990, 112, 344–355.
22. Arnett, E. M.; Amarnnath, K.; Harvey, N. C.; Venimadhaven, S. J. Am. Chem. Soc. 1990, 112, 344–355.
23. Bordwell, F. G.; Branca, J. C.; Hughes, D. L.; Olmstead, W. N. J. Org. Chem. 1980, 45, 3305–3313.
24. Bordwell, F. G.; McCallum, R. J.; Olmstead, W. N. J. Org. Chem. 1984, 49, 1424–1427.
25. Rüchardt, C. Angew. Chem., Int. Ed. Engl. 1970, 9, 830–843.
26. Burkey, T. J.; Castelhano, A. L.; Griller, D.; Lossing, F. P. J. Am. Chem. Soc. 1983, 105, 4701–4703.
27. Taft, R. W.; Topsom, R. D. Prog. Phys. Org. Chem. 1987, 16, 1–83 (Table I, p 16).
28. The traditional view that resonance in the phenoxide ion is the major factor in making phenol a stronger acid than cyclohexanol has been challenged by the calculations of Siggel and Thomas, which focus on electrostatic effects and the high energy of the phenol ground state.23a,c The traditional view has been supported by Exner,23b and more recently by Taft, Koppel, Topsom, and Anvia, who find (from an analysis of substituent effects on gas-phase acidities using a three-parameter equation, which takes into account polarizability, field/inductive, and resonance factors) that derealization in the phenoxide ion is indeed the major factor contributing to the 1017,6 greater acidity of phenol than cyclohexanol.23d
29. Siggel, M. R.; Thomas, T. D. J. Am. Chem. Soc. 1986, 108, 4360–4362.
30. Exner, O. J. Org. Chem. 1988, 53, 1810–1812.
31. Thomas, T. D.; Carroll, T. X.; Siggel, M. R. F. J. Org. Chem. 1988, 53, 1812–1815.
32. Taft, R. W.; Koppel, I. A.; Topsom, R. D.; Anvia, F. J. Am. Chem. Soc. 1990, 112, 2047–2052.
33. Howard, J. A.; Ingold, K. U. Can. J. Chem. 1963, 41, 1744–1751.
34. Bartlett, P. D.; Rüchardt, C. J. Am. Chem. Soc. 1960, 82, 1756–1762.
35. Parker, V. D. Electrochim. Acta 1973, 18, 519–524.
36. Bordwell, F. G.; Bausch, M. J. J. Am. Chem. Soc. 1986, 108, 2473, 2474.
37. Bordwell, F. G.; Cheng, J.-P.; Bausch, M. J. J. Am. Chem. Soc. 1988, 110, 2869–2872.
38. Bordwell, F. G.; Cheng, J.-P.; Bausch, M. J. J. Am. Chem. Soc. 1988, 110, 2872–2877.
39. Bordwell, F. G.; Cheng, J.-P.; Bausch, M. J. Phys. Org. Chem. 1988, 1, 209–223.
40. Bordwell, F. G.; Bausch, M. J.; Branca, J. C.; Harrelson, J. A., Jr. J. Phys. Org. Chem. 1988, 1, 225–241.
41. Bordwell, F. G.; Algrim, D. J.; Harrelson, J. A., Jr. J. Am. Chem. Soc. 1988, 110, 5904–5906.
42. Bordwell, F. G.; Cheng, J.-P.; Seyedrezai, S. E.; Wilson, C. A. J. Am. Chem. Soc. 1988, 110, 8178–8183.
43. Bordwell, F. G.; Cheng, J.-P. J. Am. Chem. Soc. 1989, 111, 1793–1795.
44. Gusanov, B. R.; Strodyn, Ya.P J. Gen Chem. USSR (Engl. Transi.) 1976, 46, 2469.
45. Hammerich, O.; Parker, V. D.; Ronlán, A. Acta Chem. Scan. B 1976, B30, 89, 90.
46. Hammerich, O.; Parker, V. D. Acta Chem. Scand., Ser. B 1982, B36, 63, 64.
47. Hawley, M. D.; Adam, R. N. J. Electroanal. Chem. 1965, 10, 317–386.
48. Marcus, M. F.; Hawley, M. D. J. Electroanal. Chem. 1968, 18, 175–183.
49. Richards, J. A.; Whitson, P. E.; Evans, D. H. J. Electroanal. Chem. 1975, 63, 311–317.
50. Dixon, W. T.; Murphy, P. J. Chem. Soc., Faraday Trans. 2 1976, 72, 1221–1230.
51. Dixon, W. T.; Murphy, P. J. Chem. Soc., Faraday Trans. 2 1978, 74, 432–439.
52. Holton, D. M.; Murphy, D. J. Chem. Soc., Faraday Trans. 2 1979, 75, 1637–1642.