ESR Studies on the Radical Cation Mechanism of the Ring Opening of Cyclopropylamines

Journal of the American Chemical Society

Volumn 109, Issue 2, 1987, Pages 595-597

  Qin, Xue zhi ^a   Williams, Ffrancon ^a  

^a UNIVERSITY OF TENNESSEE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001568210     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00236a055     Document Type: Article

References (12)

1. Tullman. R. H.; Hanzlik. R. P. Drue Metabolism Rev. 1984. 15. 1163.
2. (a) Silverman, R. B. J. Biol. Chem. 1983, 258, 14766. (b) Silverman, R. B.; Yamasaki, R. B. Biochemistry 1984, 23, 1322. Silverman, R. B.; Zieske, P. A. Biochemistry 1985, 24, 2128.
3. For experimental details, see, e.g.: Snow, L. D.; Williams, F. Faraday Discuss. Chem. Soc. 1984. 78. 57.
4. is a distonic radical cation. For other examples, see: (a) Yates, B. F.; Bouma, W. J.; Radom, L. J. Am. Chem. Soc. 1984, 106, 5805. (b) Sack, T. M.; Cerny, R. L.; Gross, M. L. J. Am. Chem. Soc. 1985, 107, 4562.
5. Maeda. Y.: Ingold. K. U. J. Am. Chem. Soc. 1980. 102. 328.
6. Kimura, K.; Katsumata, S.; Achiba, Y.; Yamazaki, T.; Iwata, S. Handbook of He I Photoelectron Spectra of Fundamental Organic Molecules; Halsted: New York, 1981; pp 118, 119.
7. Qin, X. Z. ; Williams, F. J. Phys. Chem. 1986, 90, 2292.
8. Qin, X. Z. ; Williams, F. Tetrahedron, in press.
9. Danen, W. C.; West, C. T. J. Am. Chem. Soc. 1974, 96, 2447.
10. Neale and Walsh13e have criticized our earlier brief consideration14 of the Hofmann-Loffler reaction by stating that contrary to our thesis, the basicity of Bu2N may be greater than that of the parent amine Bu2NH, since there is evidence that the basicity of the anilino radical C6H5NH exceeds that of aniline (Land, E. J.; Porter, G. J. Chem. Soc. 1961, 3540). We believe that this comparison is inappropriate and emphasize that our considerations are not applicable to delocalized radicals. Curiously, Neale and Walsh also seem to doubt the validity of this comparison in footnote 13 of their paper. More recently, it has been shown that the basicity of Me2NH exceeds that of Me2N (Fessenden, R. W.; Neta, P. J. Phys. Chem. 1972, 76, 2857), and this is in fact the general rule for localized nitrogen-centered radicals.13h,
11. The Hofmann-Loffler reaction has an extensive bibliography. Some leading references to the history, mechanism, and synthetic utility of this reaction are: (a) Wolff, M. E. Chem. Rev. 1963, 63, 55. (b) Wawzonek, S.; Thelen, P. H. J. Am. Chem. Soc. 1950, 72, 2118. (c) Wawzonek, S.; Nelson, Jr., M. F.; Thelen, P. J. J. Am. Chem. Soc. 1951, 73, 2806. (d) Corey, E. J.; Hertler, W. R. J. Am. Chem. Soc. 1960, 82, 1657. (e) Neale, R. S.; Walsh, M. R. J. Am. Chem. Soc. 1965, 87, 1255. (f) Neale, R. S. Synthesis 1971, 1. (g) Deno, N. C. In Methods in Free Radical Chemistry; Huyser, E. S., Ed.; Marcel Dekker: New York, 1972; Vol. 3, Chapter 3, pp 135–154. (h) Chow, Y. L.; Danen, W. C.; Nelsen, S. F.; Rosenblatt, D. H. Chem. Rev. 1978, 78, 243–274. (i) Green, M. M.; Moldowan, J. M.; Armstrong, M. W.; Thompson, T. L.; Sprague, K. J.; Hass, A. J.; Artus, J. J. J. Am. Chem. Soc. 1976, 98, 849.
12. Williams, F. J. Am. Chem. Soc. 1962, 84, 2895.