The reaction of elemental phosphorus with alkanethiolates in the presence of tetrachloromethane

Abstract

White phosphorus in a finely divided form reacts with sodium alkanethiolates in the presence of the corresponding thiol and an excess of tetrachloromethane to give high yields of the trithioite, (RS)3P, and trichloromethane. When a stoicheiometric quantity of sodium ethanethiolate was used, triethyl phosphorotrithioite together with diethyl phosphorochloridodithioite and diethyl trichloromethylphosphonodithioite were isolated as major products. A minor side reaction between thiolate ions and tetrachloromethane leads to the formation of dialkyl disulphide and trialkyl trithio-orthoformate. A reaction scheme for the formation of these products is suggested.