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

Abstract

Phosphorus trichloride and thiophosphoryl chloride derivatives of alkylene dithiophosphates of the type PCl_{3 − n} () _n and P(S)Cl_{3− n} () _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 (¹H and ³¹P). On the basis of above studies the formation of P-S-P and S = P–S–P(S) chemical linkages have been established. ²³¹P NMR studies provide convincing evidence regarding the chemical bonding mode in these derivatives.

Keywords:

• Ammonium alkylene dithiophosphate
• phosphorus trichloride
• thiophosphoryl chloride

Acknowledgments

*This paper is dedicated to (late) Prof. R.C. Mehrotra.

The authors are highly thankful to the Coordinator special assistance programme (late) Prof. R.C. Mehrotra for providing financial assistance under the above scheme. Department of Chemistry, University of Rajasthan, Jaipur.