NOVEL REACTIONS INVOLVING 0-NITROSOBIS(TRIFLUOROMETHYL)HYDROXYLAMINE WITH M(CF3)3 (M=P, As AND Sb) AND SOME OLEFINS

Article abstract of DOI:10.1016/S0022-1139(00)81494-3

O-nitrosobis(trifluoromethyl)hydroxylamine gives novel reactions with tris(trifluoromethyl)phosphine, -arsine and -stibine to afford mainly the corresponding bis(trifluoromethyl)nitroxy derivatives.Tris(trifluoromethyl)phosphine affords (CF3)2NOP(O)(CF3)2 and (CF3)2NNO.Tris(trifluoromethyl)arsine also gives (CF3)2NNO in high yield, together with smaller amounts of (CF3)2NOAs(CF3)2, CF3N=CF2, COF2 and a polymeric white solid.With tris(trifluoromethyl)stibine, no oxidation nor addition reactions occured.Instead, <(CF3)2NO>3Sb and <(CF3)NO>SbCF3 were obtained in high yields.The stoichiometry of the reactions suggests that the additional amounts of bis(trifluoromethyl)nitroxy groups bonded to antimony are derived from the trifluoromethyl groups bonded to antimony.However, O-nitrosobis(trifluoromethyl)hydroxylamine gives addition products at room temperature with 1,1-difluoro-2,2-dichloroethylene and 1,1-difluoro-2-fluoro-2-bromoethylene.Mechanism to rationalise the above reactions involving Group V compounds are proposed.