Reactions of Ammonium Alkylene Dithiophosphates with Phosphorus Trichloride and Thiophosphoryl Chloride*

Phosphorus trichloride and thiophosphoryl chloride derivatives of alkylene dithiophosphates of the type PCl3-n(S(2)POGO)(n) and P(S)Cl3-n(S(2)POGO)(n) (where G = CH2CH2CHMe-, -CMe2CMe2-, -CH2CH2CH2CH2- and -CMe2CH2 CHMe-, n = 1, 2, 3) have been synthesized for the first time by reacting the ammonium salt of alkylene dithiophosphoric acid with phosphorus trichloride and thiophosphoryl chloride in different stoichiometric ratios under anhydrous reaction conditions. The newly synthesized derivatives are either colorless liquids or viscous semisolids, hygroscopic in nature and are soluble in common organic solvents. These are characterized by elemental analysis, molecular weight determinations and physicochemical studies IR, NMR (H-1 and P-31). On the basis of above studies the formation of P-S-P and S=P-S-P(S) chemical linkages have been established. P-231 NMR studies provide convincing evidence regarding the chemical bonding mode in these derivatives.