Mechanism of the thermal rearrangement of N-aroyl-O-(NN-dimethylthiocarbamoyl)-N-methylhydroxylamines

Abstract

Mechanistic investigations on the thermolysis of N-aroyl-O-(NN-dimethylthiocarbamoyl)-N-methylhydroxylamines lead to the conclusion that the thiono–thiolo rearrangement proceeds, at least in part, by a radical cage process. This is accompanied by a reaction, due to escaped amidyl radicals, leading to the corresponding amide in a hydrogen abstraction process. The proposed mechanisms are supported by CIDNP effects, kinetic studies with diphenyl-picrylhydrazyl, and measurement of the activation parameters of the observed unimolecular reaction.