The reaction between amines and polyhalogenoalkanes. Part I. Reaction of primary amines with carbon tetrachloride in the presence of copper(II) acetate

Abstract

The copper(II) acetate-catalysed reaction between carbon tetrachloride and primary amines proceeds by a combination of radical and ionic steps. Evidence is provided that, in the absence of oxygen, an initial radical chain process gives chloroform, amine hydrochloride, and N-chloroamine. Oxygen has a profound effect on the reaction for it alters not only the rate but also the course of the reaction. These changes can be interpreted by assuming that oxygen intercepts the trichloromethyl radical chain-carrier to produce carbonyl chloride followed by the reaction of carbonyl chloride with amine. A reaction scheme that explains these observations is described. Evidence from simple kinetic studies are in agreement with the suggested scheme.