The Wolff Rearrangement. I. Kinetic Studies of the Decomposition of α-Diazoacetophenone

Kinetic studies of the Wolff rearrangement of α-diazoacetophenone were performed in t-butyl alcohol, by the volumetric measurement of the evolved nitrogen, using a solution of silver benzoate in triethylamine as a catalyst. A pseudo-first-order rate constant was obtained accompanying the induction period. The effects of the concentrations of silver benzoate and triethylamine on the reaction rate were studied. The concentration of silver ions was determined by the gravimetric measurement of silver chloride in the course of the reaction. The silver ions were found to be consumed only in the initial stage of the reaction. On the basis of these results, a novel reaction mechanism, in which the active entity of the catalyst was thought to be a silver ion-triethylamine complex, was proposed.