Some oxidation reactions of aminocyclodiphosph(III)azanes

Abstract

The reactions of cis and trans isomers of the aminocyclodiphosph(III)azane, Me₂[graphic omitted]Bu^t with t-butyl hydroperoxide, sulphur, selenium, tellurium, and methyl iodide give the oxidation products, Me₂N(Z)-[graphic omitted]Bu^t(Z = S, Se, Te, or MeI) and Me₂N(Z)[graphic omitted]Bu^t(Z = O, S, or Se), cis and trans isomers being isolated in each case (except where Z = Te). No reaction occurs with dimethyl sulphoxide. A series of sulphides and selenides of R₂N[graphic omitted]R¹(R₂= Et₂ or C₅H₁₀, R¹= Bu^t; and R₂= Me₂, R¹= Ph), Me[graphic omitted]H₂)₂, and Cl[graphic omitted]Bu^t have also been obtained by analogous routes. trans Isomers of Me₂N[graphic omitted]Bu^t are more reactive than the analogous cis isomers, and it has been established that the oxidation of both isomers by sulphur or selenium occurs with retention of configuration at phosphorus. Exchange of selenium and of tellurium between phosphorus atoms has been observed in some derivatives, and in one case indentification of the products of exchange enabled structural assignments to be made.

The chlorocyclodiphosph(V)azanes Cl(Y)[graphic omitted]R (R = Bu^t; Y = Z = O or S) react very slowly with dimethylamine even under forcing conditions. However, the latter compounds (R = Me, Y = lone pair, Z = O or S) are readily aminolysed by dimethylamine at the P^III atom. Selected ¹H and ³¹P n.m.r. and i.r. data are reported and their relevance to structural assignments discussed.