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A description of unimolecular phenoxyl radical generation appeared subsequent to our early9,10 reports, using a strategy based on the Barton reaction. Cf. Togo, Y.; Nakamura, N.; Iwamura, H. Chem. Lett. 1991, 1201. See also a recent method based upon photolysis of bist(aryloxy)phosphine azides. in Kalgutkar, R.; Ionkin, A.; Quin. L. D.; Lahti, P. M. Tetrahedron Lett. 1994, 3889.
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A description of unimolecular phenoxyl radical generation appeared subsequent to our early9,10 reports, using a strategy based on the Barton reaction. Cf. Togo, Y.; Nakamura, N.; Iwamura, H. Chem. Lett. 1991, 1201. See also a recent method based upon photolysis of bist(aryloxy)phosphine azides. in Kalgutkar, R.; Ionkin, A.; Quin. L. D.; Lahti, P. M. Tetrahedron Lett. 1994, 3889.
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o = 48.0 kcal/mol, for phenoxyl 11.6 kcal/mol, from DeFrees, D. J.; McIver, R. T., Jr.; Hehre, W. J. J. Am. Chem. Soc. 1980, 102, 3334.
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2 and CO of -21.6, -94.1, and -26.4 kcal/mol, respectively, production of phenoxyl from 9 is endothermic by about 9 kcal/mol, production of benzyl radical from tert-butyl phenylperacetate by about 12 kcal/mol
-
2 and CO of -21.6, -94.1, and -26.4 kcal/mol, respectively, production of phenoxyl from 9 is endothermic by about 9 kcal/mol, production of benzyl radical from tert-butyl phenylperacetate by about 12 kcal/mol.
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o of about 2 kcal/mol, comparable to the overall enthalpy change for formation of phenoxyl radical. Since this pathway is not observed, the reaction is apparently controlled by preferential breaking of the weakest bonds in 9. rather than purely thermodynamic factors
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o of about 2 kcal/mol, comparable to the overall enthalpy change for formation of phenoxyl radical. Since this pathway is not observed, the reaction is apparently controlled by preferential breaking of the weakest bonds in 9. rather than purely thermodynamic factors.
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