Kinetic Properties of Caged Ambident Radicals Formed in the Thermolyses of Nitrones

Article abstract of DOI:10.1021/jo00315a006

Thermal decompositions of N-benzhydryl-α,α-diphenylnitrone (1) and the para-tetradeuterated analogue 1-d₄ in several solvents are reported.Mass spectral analyses of recovered nitrones and/or O-benzhydryl ethers were performed.These data are combined with previously reported spectroscopic rate constants for the decomposition of 1 to evaluate the true carbon-nitrogen homolysis rate constant and the relative rate constants for (a) geminate radical recombination at the iminoxy nitrogen, (b) irreversible recombination at oxygen, and (c) diffusion of the solvent-caged radicals.