Dimethylamino- and methoxy-derivatives of dichlorophosphino(dichlorophosphinyl)methylamine, Cl2P·NMe·P(O)Cl2

Abstract

Dimethylaminolysis and methoxylation of dichlorophosphino(dichlorophosphinyl)methylamine, Cl2P·NMe·P(O) Cl2 by dimethylaminotrimethylsilane and methoxytrimethylsilane respectively initially occurs at the tervalent phosphorus atom. The mono-dimethylamino-derivative Cl(Me2N)P·NMe·P(O)Cl2, rearranges to its isomer, Cl2P·NMe·P(O)ClNMe2 at ambient temperatures. Further dimethylaminolysis gives the bisdimethylaminoderivative, Cl2P·NMe·P(O)(NMe2)2 which may also be formed by rearrangement of its isomer, Cl(Me2N)P·NMe·P(O)Cl(NMe2). The mono-methoxy-derivative, Cl2P·NMe·P(O)Cl(OMe) was obtained by cleavage of the silicon–nitrogen bond in the methoxy-derivative, Cl(MeO)P(O)·NMe·SiMe3 by phosphorus(III) trichloride, and the bis- and tris-methoxy-derivatives, Cl2P·NMe·P(O)(OMe)2, and, Cl(MeO)P·NMe·P(O)(OMe)2, were prepared by the condensation of dimethoxy(methylamino)phosphine oxide, (MeO)2(MeNH)PO, with phosphorus(III) trichloride and methoxyphosphorus(III) dichloride respectively in the presence of triethylamine. The results of the foregoing dimethylaminolysis and methoxylation experiments have been compared with the positions the equilibria observed when dimethylamino- and methoxy- groups are scrambled between phosphorus(III) trichloride and phosphoryl(V) chloride. The 1H and 31P n.m.r. spectra of these derivatives are reported.