Intermediates in the decomposition of aliphatic diazo-compounds. Part V. The effects of hydroxylic compounds on the decomposition of 4,4′-dichlorodiphenyldiazomethane catalysed by perchloric and toluene-p-sulphonic acids in acetonitrile

Abstract

The influence of low concentrations of alcohols on the rate of decomposition of 4,4′-dichlorodiphenyldiazomethane in acetonitrile catalysed by perchloric and toluene-p-sulphonic acids and on the partitioning of the intermediate carbonium ion forming tetra-arylethylene and 4,4′-dichlorodiphenylmethyl alkyl ether has been studied. The results have been used to estimate the relative acidities, basicities, and nucleophilic activities of the alcohols in acetonitrile. The abilities of the alcohols to act as hydrogen-bond donors and to accept protons appear to be controlled largely by electronic influences. However, the reactivity of the alcohols towards the 4,4′-dichloro-diphenylmethyl cation seems to be largely determined by steric factors.