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Borden, W.T.1
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For recent discussions of such rules, see: (a) (b) Klein, D. J.; Nelin, C. J.; Alexander, S.; Matsen, F. A. J. Chem. Phys. 1982, 77, 3101–3108 (c) Borden, W. T.; Davidson, E. R. J. Am. Chem. Soc. 1977, 99, 4587–4594. See, however: Dowd, P.; Chang, W.; Paik, Y. H. J. Am. Chem. Soc. 1986, 108, 7416-7417; 1987, 109, 5284-5285; Du, P.; Borden, W. T. J. Am. Chem. Soc. 1987, 109, 930–931.
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For recent discussions of such rules, see: (a) Ovchinnikov, A. A. Theor. Chim. Acta 1978, 47, 297–304. (b) Klein, D. J.; Nelin, C. J.; Alexander, S.; Matsen, F. A. J. Chem. Phys. 1982, 77, 3101–3108. (c) Borden, W. T.; Davidson, E. R. J. Am. Chem. Soc. 1977, 99, 4587–4594. See, however: Dowd, P.; Chang, W.; Paik, Y. H. J. Am. Chem. Soc. 1986, 108, 7416-7417; 1987, 109, 5284-5285; Du, P.; Borden, W. T. J. Am. Chem. Soc. 1987, 109, 930–931.
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5
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Although they are generally not hydrocarbons, localized biradicals derived from Norrish type I and Norrish type II photoreactions are clearly relevant. An overview of early work involving primarily CIDNP (type I) and laser flash photolysis (type II) studies, as well as the dehydrobenzenes, is provided in Borden, W. T., Ed.; Wiley: New York A list of more recent works follows, which is not intended to be exhaustive. Type II biradicals: Scaiano, J. C. Acc. Chem. Res. 1982, 15, 252–258. Caldwell, R. A.; Majima, T.; Pac, C. J. Am. Chem. Soc. 1982, 104, 629–630. Scaiano, J. C.; Wagner, P. J. J. Am. Chem. Soc. 1984, 106, 4626–4627. Johnston, L. J.; Scaiano, J. C.; Sheppard, J. W.; Bays, J. P. Chem. Phys. Lett. 1986, 124, 493–498. Akiyama, K.; Ikegami, Y.; Tero-Kubota, S. J. Am. Chem. Soc. 1987, 109, 2538–2539. Type I biradicals and the hydrocarbon biradicals derived by CO loss: Caldwell, R. A.; Sakuragi, H.; Majima, T. J. Am. Chem. Soc. 1984, 106, 2471–2473. Weir, D.; Scaiano, J. C. Chem. Phys. Lett. 1985, 118, 526–529. Zimmt, M. B.; Doubleday, C., Jr.; Gould, I. R.; Turro, N. J. J. Am. Chem. Soc. 1985, 107, 6724–6726. Zimmt, M. B.; Doubleday, C., Jr.; Turro, N. J. J. Am. Chem. Soc. 1985, 107, 6726-6727; 1986, 108, 3618–3620. Johnston, L. J.; Scaiano, J. C. J. Am. Chem. Soc. 1986, 108, 2349–2353. Closs, G. L.; Forbes, M. D. E. J. Am. Chem. Soc. 1987, 109, 6185–6187. See also: Mizuno, K.; Ichinose, N.; Otsuji, Y.; Caldwell, R. A. J. Am. Chem. Soc. 1985, 107, 5797–5798. Sugawara, T.; Bethell, D.; Iwamura, H. Tetrahedron Lett. 1984, 25, 2375–2378. Localized, triplet biradicals can be trapped by dioxygen. See, for example: Wilson, R. M.; Geiser, F. J. Am. Chem. Soc. 1978, 100, 2225–2226.
-
Although they are generally not hydrocarbons, localized biradicals derived from Norrish type I and Norrish type II photoreactions are clearly relevant. An overview of early work involving primarily CIDNP (type I) and laser flash photolysis (type II) studies, as well as the dehydrobenzenes, is provided in: Dervan, P. B.; Dougherty, D. A. In Diradicals; Borden, W. T., Ed.; Wiley: New York, 1982; pp 107–149. A list of more recent works follows, which is not intended to be exhaustive. Type II biradicals: Scaiano, J. C. Acc. Chem. Res. 1982, 15, 252–258. Caldwell, R. A.; Majima, T.; Pac, C. J. Am. Chem. Soc. 1982, 104, 629–630. Scaiano, J. C.; Wagner, P. J. J. Am. Chem. Soc. 1984, 106, 4626–4627. Johnston, L. J.; Scaiano, J. C.; Sheppard, J. W.; Bays, J. P. Chem. Phys. Lett. 1986, 124, 493–498. Akiyama, K.; Ikegami, Y.; Tero-Kubota, S. J. Am. Chem. Soc. 1987, 109, 2538–2539. Type I biradicals and the hydrocarbon biradicals derived by CO loss: Caldwell, R. A.; Sakuragi, H.; Majima, T. J. Am. Chem. Soc. 1984, 106, 2471–2473. Weir, D.; Scaiano, J. C. Chem. Phys. Lett. 1985, 118, 526–529. Zimmt, M. B.; Doubleday, C., Jr.; Gould, I. R.; Turro, N. J. J. Am. Chem. Soc. 1985, 107, 6724–6726. Zimmt, M. B.; Doubleday, C., Jr.; Turro, N. J. J. Am. Chem. Soc. 1985, 107, 6726-6727; 1986, 108, 3618–3620. Johnston, L. J.; Scaiano, J. C. J. Am. Chem. Soc. 1986, 108, 2349–2353. Closs, G. L.; Forbes, M. D. E. J. Am. Chem. Soc. 1987, 109, 6185–6187. See also: Mizuno, K.; Ichinose, N.; Otsuji, Y.; Caldwell, R. A. J. Am. Chem. Soc. 1985, 107, 5797–5798. Sugawara, T.; Bethell, D.; Iwamura, H. Tetrahedron Lett. 1984, 25, 2375–2378. Localized, triplet biradicals can be trapped by dioxygen. See, for example: Wilson, R. M.; Geiser, F. J. Am. Chem. Soc. 1978, 100, 2225–2226.
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We have found that 3-phenylcyclobutanone can be easily prepared in multigram quantities by reductive dechlorination of 2, 2-dichloro-3-phenylcyclobutanone (Krepski, L. R.; Hassner, A. J. Org. Chem. 1978, 43, 2879-2882) with zinc in refluxing acetic acid (Bak, D. A.; Brady, W. T. J. Org. Chem. 1979, 44, 107–110. Stewart, E. G., unpublished results).
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