Homolytic and heterolytic mechanisms of the rearrangement of some N-chloroanilides

Abstract

A quantitative estimation of the products of the rearrangement of N-chlorobenzanilide, catalysed by hydrogen chloride, has been carried out. The composition of the products, and the kinetics of the rearrangement of N-chlorobenzanilide and of N-chlorophenylacetanilide in acetic acid alone, have been studied, and possible mechanisms consistent with the rate equation have been suggested. The prescence of silver acetate greatly affected both the kinetics and composition of the product of the reactions in this solvent, and various reasons for this have been considered. The kinetics and products of the thermal and photolytic rearrangements of several N-chloroanilides, in non-polar solvents, both alone and in the presence of added anilides have been investigated. From these results, the various factors which are involved in theautocatalysis, exhibited by many of these reactions, have been determined and a mechanism which correlates all these data has been proposed. A similar study has been made of the reaction of several N-chloroanilide, in carbon tetrachloride, catalysed by benzoyl peroxide. Autocatalysis was again observed and its cause investigated. An attempt has been made to explain, in terms of the mechanism of the reaction, why the o:p ratio was considerably lower than for the corresponding photolytic reaction.