MECHANISTIC AND SYNTHETIC ASPECTS OF RADICAL CHEMISTRY OF α-AZOCARBINOLS

Abstract

<p>α-Phenylazodimethylcarbinol, a new compound in the series of α-azocarbinols prepared in our laboratory, was synthesized by air oxidation of acetone phenylhydrazone to give the hydroperoxide which is subsequently reduced to the α-azocarbinol by the action of triphenylphosphine. The kinetics of thermolysis of this new compound, along with those of α-phenylazodiphenylcarbinol, α-azoethers, and α-azoacetates, were studied under several reaction conditions in an attempt to further elucidate the decomposition mechanism of these new azo compounds.</p> <p>Radical intermediates are involved in the chemistry of these α-azocarbinols. The evidence presented reinforces the claim that α-azocarbinols decompose by an induced radical chain mechanism. Such a radical chain process permits the application of these α-azocarbinols, which generate a variety of radicals R (R is phenyl in this research), to the hydroalkylation (hydrophenylation) of several unsaturated compounds.</p>