Kinetics and Mechanism of The Benzylaminolysis of O,O-Dimethyl S-Aryl Phosphorothioate in Dimethyl Sulfoxide

초록

The interpretation of mechanism with the experimental database of physical behavior of bioactive organophosphorus compounds are interesting and important in the field of physical organic chemistry. In the incessant of the progress of experimental physical chemistry the kinetics and its mechanism are usually concern to the physical factors of the relevant compound in the nature. Recently we are studying the mechanistic criteria of benzylaminolysis of O,O-Dimethyl S-Aryl Phosphorothioate in Dimethyl Sulfoxide at 85.0 °C . Usually a biphasic Hammette plot indicates the mechanistic alteration during the change in X or Z-substituents variation of nucleophiles or substrate while acting in the reaction stream or linear correlation for straight forward SN1 or SN2 type of mechanistic interpretation. The deuterium kinetic isotope effect is the strong tool for mechanistic interpretation, although respective activation parameters and obtained cross-interaction constants are the main basic information for interpreting mechanism of the system. Where, we are especially endeavored to introduce the frontal and backward attack of nucleophiles through the usual SN1 or SN2 nucleophilic substitution reaction. In the present work, It was intended to speculate and provoke the mechanistic criteria and change with the sharp deviation into break of the Hammett and Brönsted linear correlations in the course of reactions mentioned above.