SILICON-PHOSPHORUS ANALOGIES. NUCLEOPHILIC CATALYSIS IN THE ALCOHOLYSIS OF CHLOROPHOSPHORUS DERIVATIVES

Article abstract of DOI:10.1016/S0040-4020(01)80059-4

The mechanism of the alcoholysis of chlorophosphonates and chlorophosphates in presence of nucleophilic catalysts like hexamethylphosphotriamide, pyridine and N-methylimidazole is discussed on the basis of kinetic and stereochemical results.We have proposed a mechanism for the reaction, which is governed by entropy, involving reaction of the alcohol with a pentacoordinated intermediate.This accounts for the differences in the stereochemical outcome and the rate equation which can be derived for the reaction with a variety of substrates in addition to the absence of common ion + solvent effects observed.