“Spontaneous” Formation of Radicals from Nitroso Compounds. Inadvertent Photolysis vs. Molecule Assisted Homolysis

Journal of the American Chemical Society

Volumn 103, Issue 16, 1981, Pages 4833-4837

  Chatgilialoglu, C ^a   Ingold, K U ^a  

^a NATIONAL RESEARCH COUNCIL CANADA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0011154749     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00406a027     Document Type: Article

References (65)

1. Pryor, W. A.; Coco, J. H.; Daley, W. H.; Houk, K. N. J. Am. Chem. Soc. 1974, 96, 5591. Pryor, W. A. ACS Sym. Ser. No. 69 1978, 33.
2. The term “molecule induced radical formation”, MIRF, which has been used to describe all three processes, seems to have fallen into disuse
3. Hamony, J. A. K. Methods Free-Radical Chem. 1974, 5, 101.
4. Ginsburg, V. A.; Dubov, S. S.; Medvedev, A. N.; Martynova, L. L.; Tetel'baum, B. I.; Vasil'eva, H. N.; Yakubovich, A. Y. Doki. Akad. Nauk SSSR 1963, 152, 1104.
5. Ginsburg, V. A.; Medvedev, A. N.; Lebedeva, M. F.; Dubov, S. S.; Yakubovich, A. Ya. Zh. Obshch. Khim. 1965, 35, 1418.
6. Ginsburg, V. A.; Medvedev, A. N.; Martynova, L. L.; Vasil'eva, H. N.; Lebedeva, M. F.; Dubov, S. S.; Yakubovich, A. Y. Ya. Zh. Obshch. Khim. 1965, 35, 1924.
7. Ginsburg, V. A.; Medvedev, A. N.; Dubov, S. S.; Lebedeva, M. F. Ya. Zh. Obshch. Khim. 1967, 37, 601.
8. Ginsburg, V. A.; Mededev, A. N.; Lebedeva, M. F.; Vasil'eva, M. N.; Martynova, L. L. Ya. Zh. Obshch. Khim. 1967, 37, 611.
9. Ginsburg, V. A.; Medvedev, A. N.; Miszabekova, N. S.; Lebedeva, M. F. Ya. Zh. Obshch. Khim. 1967, 37, 620.
10. Medvedev, A. N.; Smirnov, K. N.; Dubov, S. S.; Ginsburg, V. A. Ya. Zh. Obshch. Khim. 1968, 38, 2462.
11. Ginsburg, V. A.; Medvedev, A. N.; Dubov, S. S.; Gitel', P. O.; Smolyanitskaya, V. V.; Nikolaenko, G. E. Ya. Zh. Obshch. Khim. 1969, 39, 282.
12. Ginsburg, V. A.; Smolyanitskaya, V. V.; Medvedev, A. N.; Faermark, V. S.; Tomilov, A. P. Ya. Zh. Obshch. Khim. 1971, 41, 2284.
13. Ginsburg, V. A.; Medvedev, A. N.; Martynova, L. L.; Gitel', P. O.; Nikolaenko, G. E. Zh. Org. Khim. 1972, 8, 486.
14. Ginsburg, V. A.; Medvedev, A. N.; Gitel', P. O.; Lagutina, Z. N.; Martynova, L. L.; Lebedeva, M. F.; Dubov, S. S. Zh. Org. Khim. 1972, 8, 500. (1) Ginsburg, V. A.; Medvedev, A. N.; Lebedev, M. F.; Martynova, L, L. Zh. Org. Khim. 1974,10, 1416, and other works by the same authors cited in the foregoing papers.
15. Booth, B. L.; Edge, D. J.; Haszeldine, R. N.; Holmes, R. G. J. Chem. Soc., Perkin Trans. 2 1977, 7.
16. Sullivan, A. B. J. Org. Chem. 1966, 31, 2811.
17. Thielacker, W.; Knop, A.; Uffmann, H. Angew. Chem. 1965, 77, 717.
18. Knight, G. T. Chem. Commun. 1970, 1016.
19. Layer, R. W. Tetrahedron. Lett. 1970, 4413.
20. Banks, R. E.; Haszeldine, R. N.; Miller, P. J. Tetrahedron Lett. 1970, 4417.
21. Filby, W. G.; Gunther, K. Z. Naturforsch., Teil B. 1977, 32, 693.
22. Bowman, D. F.; Brokenshire, J. L.; Gillan, T.; Ingold, K. U. J. Am. Chem. Soc. 1971, 93, 6551.
23. Wajer, T. A. J. W.; Mackor, A.; De Boer, T. J.; van Voorst, J. D. W. Tetrahedron 1967, 23, 4021.
24. Russell, G. A.; Geels, E. J.; Smentowski, F. J.; Chang, K.-Y.; Reynolds, J.; Kaupp, G. J. Am. Chem. Soc. 1967, 89, 3821.
25. Mulvey, D.; Waters, W. A. J. Chem. Soc., Perkin Trans. 2 1977, 1868.
26. Mulvey, D.; Waters, W. A. J. Chem. Soc., Perkin Trans. 2 1978, 1059.
27. Waters, W. A. J. Chem. Soc., Perkin Trans. 2 1979, 1079.
28. Camaggi, C. M.; Caser, M.; Placucci, G.; Guerra, M. J. Chem. Soc., Perkin Trans. 2 1979, 1675.
29. Fairhurst, S. A.; Sutcliffe, L. H. J. Chem. Soc., Faraday Trans. 1 1979, 75, 1521.
30. Aurich, H. G.; Heinrich, J.-M.; Wassmuth, G. J. Chem. Res. Suppl. 1980, 222, 224.
31. Wajer, T. A. J. W.; Mackor, A.; de Boer, T. J. Tetrahedron 1969, 25, 175.
32. There have also been many studies of the products formed when nitroso compounds react with organic substrates. The potential involvement of free radicals in most of these reactions was not specifically investigated. See, e.g., Shemyakin, H. M.; Maimind, V. I.; Vaichunaite, B. K. Izv. Akad. Nauk, Otd, Khim. Nauk 1957, 1260. Banks, R. E.; Barlow, M. G.; Haszeldine, R. N. J. Chem. Soc. 1965, 4714. Ginsburg, V. A.; Privezentseva, N. F. Zh. Obshch. Khim. 1968, 38, 832. Ginsburg, V. A.; Martynova, L. L.; Privezentseva, N. F.; Buchek, Z. A. Tetrahedron. 1968, 38, 2505. Howe, R. K. J. Org. Chem. 1968, 33, 2848. Motherwell, W. B.; Roberts, J. S. J. Chem. Soc., Chem. Commun. 1972, 329. Boyer, J. H. In “The Chemistry of the Nitro and Nitroso Groups”, Feuer, H., Ed.; Interscience: New York, 1969; Part 1, Chapter 5. Houben-Weyl “Methoden der Organischen Chemie”, Georg Thieme Verlag: Stuttgart, 1971; Band X. Teil 1, Chapters 3-5.
33. Radicals can be formed from nitroso compounds by a nucleophilic attack on the nitroso group followed by oxidation of the resultant hydroxylamine anion by adventitious oxygen or an excess of the nitroso compound. See: Forrester, A. R.; Hepburn, S. P. J. Chem. Soc. C 1971, 701.
34. Perkins, M. J. Adv. Phys. Org. Chem. 1980,17, 1.
35. Mahoney, L. R.; Mendenhall, G. D.; Ingold, K. U. J. Am. Chem. Soc. 1973, 95, 8610; 1974, 96, 4067.
36. Caceres, T.; Lissi, E. A.; Sanhueza, E. Int. J. Chem. Kinet. 1978,10, 1167.
37. Benson, S. W.; Cruickshank, F. R.; Golden, D. M.; Haugen, G. R.; O'Neal, M. E.; Rodgers, A. S.; Shaw, R.; Walsh, R. Chem. Rev. 1969, 69, 279.
38. Griller, D.; Ingold, K. U. Acc. Chem. Res. 1976, 9, 13.
39. Mackor, A.; Wajer, T. A. J. W.; De Boer, T. J.; van Voorst, J. D. W. Tetrahedron Lett. 1966, 2115.
40. Morrison, H. A. In “The Chemistry of the Nitro and Nitroso Groups”, Interscience: New York, 1969; Part 1, Chapter 4.
41. Jander, J.; Haszeldine, R. N. J. Chem. Soc. 1954, 696.
42. Haszeldine, R. N.; Mattinson, B. J. H. J. Chem. Soc. 1957, 1741.
43. Roellig, M. P.; Houston, P. L. Chem. Phys. Lett. 1978, 57, 75.
44. Asscher, M.; Haas, Y.; Roellig, M. P.; Houston, P. L. J. Chem. Phys. 1980, 72, 768.
45. Ayscough, P. B.; Scaly, R. C.; Woods, D. E. J. Phys. Chem. 1971, 75, 3454.
46. Pak, K.; Testa, A. C. J. Phys. Chem. 1972, 76, 1087.
47. The claimed41 stability of certain sterically hindered nitrosoaromatics towards UV irradiation has been shown to be in error.42
48. Terabe, S.; Konaka, R. J. Chem. Soc., Perkin Trans. 2 1973, 369.
49. Terabe, S.; Kuruma, K.; Konaka, R. J. Chem. Soc., Perkin Trans. 1973, 1252.
50. Barclay, L. R. C.; Carson, D. L.; Gray, J. A.; Grossman, M.; Khazanie, P. G.; Milton, J. R.; Scott, C. E. Can. J. Chem. 1978, 56, 2665.
51. Choo, K. Y.; Mendenhall, G. D.; Golden, D. M.; Benson, S. W. Int. J. Chem. Kinet. 1974, 6, 813.
52. Rao, C. N. R.; Bhaskar, K. R. In ref 33, Chapter 3.
53. Roellig, M. P. Diss. Abstr. Int. B 1980, 41, 219.
54. Choo, K. Y.; Golden, D. M.; Benson, S. W. Int. J. Chem. Kinet. 1975, 7, 713.
55. It is therefore hardly surprising that nitrosobenzene does not exhibit “any photochemical activity with 730-nm excitation”.39
56. Ginsburg6* also observed this radical in the absence of hydrogencontaining organic compounds.
57. The N and F hfs's show a pronounced temperature dependence. Full EPR data for this and related radicals will be published elsewhere.51
58. Chatgilialoglu, C.; Ingold, K. U. Can. J. Chem. in press.
59. Resolved only at lower temperatures.51
60. Under similar, i.e., dark, conditions with ethanol or diethyl ether the blue color persists for weeks.
61. Hoffmann, H. M. R. Angew. Chem., Int. Ed. Engl. 1969, 8, 556.
62. Banks, R. E.; Barlow, M. G.; Haszeldine, R. N. J. Chem. Soc. 1965, 4714.
63. Suehiro, T.; Kamimori, M.; Tokumani, K.; Yoshida, M. Chem. Lett. 1976, 531.
64. Suehiro, T.; Kamimori, M.; Sakuragi, H.; Yoshida, M.; Tokumaru, K. Bull. Chem. Soc. Jpn. 1976, 49, 2594.
65. Barlow, M. G.; Haszeldine, R. N.; Murray, K. W. J. Chem. Soc., Perkin Trans. 1 1980, 1960.