Kinetics and mechanism of the anilinolysis of aryl N,N-dimethyl phosphoroamidochloridates in acetonitrile

Abstract

The nucleophilic substitution reactions of Y-aryl N,N-dimethyl phosphoroamidochloridates with substituted anilines and deuterated anilines are kinetically investigated in acetonitrile at 65.0 °C. A stepwise mechanism with a rate-limiting leaving group departure from the intermediate is proposed based on the positive pXY value. The deuterium kinetic isotope effects involving deuterated anilines show secondary inverse with all the nucleophiles, rationalized by a dominant backside nucleophilic attack.