REACTION OF THIOLO AND SELENOLO ESTERS OF PHOSPHORUS-ACIDS WITH HALOGENS .3. INTERACTION OF O, O,S-TRIALKYL PHOSPHOROTHIOATES AND O,S-DIALKYL TERT-BUTYLPHOSPHONOTHIOATES WITH SULFURYL CHLORIDE AND HALOGENS

The reaction of the title phosphono- and phosphoro-thiolates with sulphuryl chloride and halogens involves in every case the formation of intermediates containing two phosphorus atoms > P+(SR)OP(O) < X- (X = SO2Cl or halogen). The formation of the latter in the course of chlorinolysis of phosphorus thiolesters is suggested to be responsible for the occurrence of a mechanism involving retention of configuration. The effect of the structure of the reactants and the nature of solvent on the reaction stereochemistry is discussed.