Synthesis of dichlorophosphinyl and dichlorophosphinothioyl derivatives of methylamine

Abstract

Bis(dichlorophosphinyl)methylamine, [Cl₂P(:O)]₂NMe, has been prepared by the reaction of phosphoryl(V) chloride with dichlorophosphinylmethylamine, Cl₂P(:O)·NHMe, and with heptamethyldisilazane, (Me₃Si)₂NMe. The former reaction has been extended to prepare the analogous monophenyl derivative, Cl₂P(:O)·NMe·P(:O)ClPh, and reactions involving heptamethyldisilazane were adapted to give the dichlorophosphinyl derivatives, Cl₂P(:O)·NMe·SiMe₃ and Cl₂P(:O)·NMe·PCl₂. The dichlorophosphinothioyl derivatives, Cl₂P(:S)·NMe·SiMe₃, Cl₂P(:S)·NMe·PCl₂, and Cl₂P(:O)·NMe·P(:S)Cl₂ were prepared by related routes. These derivatives were characterised by elemental analyses, and by i.r., mass, ¹H and -¹P n.m.r. spectroscopy. The n.m.r. results are discussed in detail.