1582-13-4Relevant articles and documents
NOVEL REACTIONS INVOLVING 0-NITROSOBIS(TRIFLUOROMETHYL)HYDROXYLAMINE WITH M(CF3)3 (M=P, As AND Sb) AND SOME OLEFINS
Ang, H. G.,So, K. K.
, p. 95 - 98 (1983)
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, 3Sb and 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.
Nitroxide Chemistry. Part 13. Reaction of NN-Bis(trifluoromethyl)amino-oxyl with Hexafluoroisopropylideneimine and Related Compounds
Fisher, Raymond,Haszeldine, Robert N.,Tipping, Anthony E.
, p. 406 - 409 (2007/10/02)
The initial product from reaction of the oxyl (CF3)2N-O. with hexafluoroisopropylideneimine is the substituted imine (CF3)2C=N-O-N(CF3)2 (isolated in 81percent yield) which, via further oxyl attack at carbon, gives the compounds (CF3)2CO, (CF3)2N-NO, (CF3)2N-O-N(CF3)2, and (CF3)2N-O-C(CF3)2N+(O-)=N-C(CF3)2-O-N(CF3)2.Oxyl attack on hexafluoroacetone oxime affords as major products (CF3)2CO, (CF3)2NH, and (CF3)2N-O-NO.The oxyl reacts with hexafluoroacetone anil to yield a hexaoxyl adduct, with hexafluoroacetone hydrazone to afford the diazoalkane (CF3)2CN2 (100percent), and with hexafluoroacetone azine to give the bis-1:4-adduct (CF3)2N-O-C(CF3)2-N=N-C(CF3)2-O-N(CF3)2 (100percent).Thus, initial radical attack of the oxyl invariably takes place at carbon in the series of imines studied.
