Synthesis and properties of new dichlorophoshinothioyl-derivatives of amines

Abstract

Dichlorophosphinothioyl-derivatives of amines, [Cl₂P(S)]₂NR and Cl₂PS·NR·PCl₂(R = Me, Et, or Ph), have been prepared by reactions of the bis(dichlorophosphino)-amines, (Cl₂P)₂NR (R = Me, Et, or Ph), with elemental sulphur in the presence of anhydrous aluminium chloride. The compounds Cl₂P(S)·NR·PCl₂ eliminate PCl₃ when heated leaving cyclodiphosphazanes, [R·NP(S)Cl]₂. Dichlorophosphinothioyl(dichlorophosphinyl)amines, Cl₂P(S)·NR·P(O)Cl₂(R = Me, Ph) and bis(dichlorophosphinothioyl)amines, [Cl₂P(S)]₂NR (R = Me, Ph), have been prepared by the condensation of Cl₂P(S)·NHR with P(O) Cl₃ or P(S) Cl₃ respectively in the presence of triethylamine. All the above compounds were unreactive to anhydrous hydrogen chloride at atmospheric pressure. The ¹H and ³¹P n.m.r. and i.r. spectra of these compounds are discussed.