The formation of phosphorus-containing nitroxyl radicals in the photolysis of 2-methyl-2-nitrosopropane in esters of unsaturated phosphonic acid
In the photolysis of 2-methyl-2-nitrosopropane in esters ofα-alkenylphosphonic acids, nitroxyl radicals are formed with a phosphonealkyl group at the nitrogen atom on account of the addition of radical chain carriers to the nitroso compound during the radical polymerization of the phosphonates.
The constants of hyperfine interaction with the31p nucleus in the ESR spectra of the nitroxyls studied depend on the degree of polymerization of the radical to be trapped. The mechanism of this interaction is not associated to any appreciable degree with p-d overlapping and may include as the principal element the hyperconjugation of the orbital of the unpaired electron with the P-C bond.
KeywordsEster Nitrogen Atom Photolysis Phosphonates Radical Polymerization
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- 1.E. G. Janzen, Accounts Chem. Res.,4, 31 (1971).Google Scholar
- 2.C. Lagercrantz, J. Phys. Chem.,75, 3466 (1971).Google Scholar
- 3.A. L. Buchachenko and A. M. Vasserman, Stable Radicals [in Russian], Khimiya (1973).Google Scholar
- 4.G. R. Chalfont, M. J. Perkins, and A. Horsfield, J. Amer. Chem. Soc.,90, 7141 (1968).Google Scholar
- 5.T. Kunitake and S. Murakami, Polymer J.,3, 249 (1972).Google Scholar
- 6.T. A. J. W. Wajer, A. Mackor, T. J. de Boer, and J. D. W. Van Voorst, Tetrahedron,23, 4021 (1967).Google Scholar
- 7.H. Karlsson and C. Lagercrantz, Acta Chem. Scand.,24, 3411 (1970).Google Scholar
- 8.N. S. Garif'yanov, A. V. Il'yasov, and Yu. V. Yablokov, Dokl. Akad. Nauk SSSR,149, 876 (1963).Google Scholar
- 9.P. Atkins and M. Symons, ESR Spectra and Structure of Inorganic Radicals [Russian tanslation], Mir (1970) p. 33.Google Scholar
- 10.A. R. Lyons and M. C. R. Symons, J. Chem. Soc., Faraday Trans., 622 (1972).Google Scholar
- 11.A. G. Davies, D. Griller, and B. P. Roberts, J. Amer. Chem. Soc.,94, 1782 (1972).Google Scholar
- 12.W. Damerau, G. Lassman, and K. Lohs, J. Magnetic Resonance,5, 408 (1971).Google Scholar