Studies in the reactions of N, N-Dimethyl chloramine and a variety of tri coordinate phospohorus compounds

Abstract

In this work the reactions "between various phosphorus (III) species and dimethyl chloramine have been studied. In all cases the phosphorous (III) species were oxidised to phosphorus (v), in most cases by ohloramination, that is by the addition of the dimethylamino group to the phosphorus producing a phosphonium cation with chloride as the anion. Me(_2)NCl + PX(_3) → Me(_2)NPX(_3)(^+)Cl(^-) This reaction occurred in the cases of Me(_2)NPCl(_2), (Me(_2)N)(_2)PCl, (C(_6)H(_5)O)(_5)P, Me(_2)N(C(_6)H(_5))PCl, (C(_6)H(_5))(_2)PCl and C(_6)H(_5)PCl(_2) although in the latter two cases the salt was too unstable to be isolated as the chloride but the systems could be stabalised as the tetrachloroborate or hexachloroantirnonatesalts. It is likely that dimethyichloramine chloraminated trimsthyl phosphite to give a similar species, but this decomposed quickly giving chlororethane and Me(_2)NP0(0Me)(_2). In the case of (Me(_2)N)(_2)P chlorination occurred giving (Me(_2)N)(_3)PCl(_2) and (Me(_2)N)(_2). Phosphorus trichloride seemed to be an intermediate case, as, in the presence of excess phosphorus trichloride the following reaction occurred:- 4PCl(_3) + 3Me(_2)NCl → Me(_2)NPCl(_4) + Me(_2)NPCl(_3)PCl(_6) + Me(_2)NPCl(_2)