STUDIES ON CHIRAL THIOPHOSPHORIC ACIDS AND THEIR DERIVATIVES [ⅤⅢ]——THE STEREOCHEMISTRY OF SOME REACTIONS OF THE MIXED ANHYDRIDE OF O-ETHYL PHENYLPHOSPHONOTHIOIC AND O-ETHYL O-PHENYL PHOSPHOROTHIOIC ACIDS

In this paper, （1） alkaline methanolysis, （2） acid methanolysis, （3） alkaline hydro-lysis, （4） aminolysis of （+）-（R）-（R）-mixed anhydride 1 of O-ethyl phenylphosphonothioic:and O-ethyl O-phenylphosphorothioic acid, （5） its reactions with KSH and （6） with PClhave been studied. The cleavage of P-O-P bonds in all the reactions studied has beenfound. In reactions （1）-（4）, attacks of nucleophiles occur to the phosphorus atoms of phos-phonyl groups forming the products with inversion of configuration, while the configurationof the phosphorus atoms of phosphoryl groups which are not attacked is retained. Inreaction （5）, the uncleophile -SH attacks the phosphorus atom of the phosphonyl group,but a racemic product results because of the formation of ph（EtO）P（S）which loseschirality; the configuration of the phosphorus atom of the phosphoryl group which is notattacked is still retained. In reaction （6）, both the phosphonyl and phosphoryl groups arechlorinated giving as products （-）-（R）-thiophophonyl chloride 1