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

Abstract

The reactions of a selection of secondary and tertiary amines with carbon tetrachloride catalysed by copper(II) acetate have been investigated. The mechanisms of these reactions are interpreted as proceeding by an initial radical-chain reaction followed by further ionic processes. Oxygen has a pronounced effect on the course of the reaction. It is suggested that oxygen not only intercepts the trichloromethyl radical in the chain reaction, giving phosgene, but is also involved in the oxidation of intermediates in the secondary ionic processes. Kinetic studies in a variety of different solvents show that these reactions are favoured by solvents of high dielectric constant.