Kinetic studies on nitroalkane anomaly of phenylnitromethanes(2).

Abstract

Anomalous relation between rates and equilibria for the acid-base reactions of nitroalkanes is known as nitroalkane anomaly. This anomaly has been confirmed in the deprotonation of phenylnitromethane with hydroxide ion. We have carried out to clarify the cause of the anomaly the kinetic analysis of the proton-transfer reactions of phenylnitromethanes. The substituent effect of the protonation of nitronate anion under basic conditions was examined by means of the H-D exchange reaction in 50% D2O-50% CD3OD (v/v). The results of the protonation reactions will be discussed together with the previously reported results of the deprotonation reactions.