Intermediates in the decomposition of aliphatic diazo-compounds. Part VI. Reactivity of alcohols towards 4,4′-dichlorodiphenylmethylene

Abstract

The thermal decomposition of 4,4′-dichlorodiphenyldiazomethane at 85° in acetonitrile containing methyl, isopropyl, isobutyl, t-butyl, 2,2,2-trifluoroethyl, and benzyl alcohols has been investigated. Kinetic arguments lead to the conclusion that 4,4′-dichlorodiphenylmethylene is formed as an intermediate which by attack on the alcohol yields the corresponding diarylmethyl ether as the principal product. The relative reactivities of the alcohols, obtained from competition experiments, appear to increase with increasing acidity of the alcohol. The implications of this finding with regard to the mechanism of the reaction between carbenes and alcohols are discussed.