- EXCHANGE REACTIONS BETWEEN O-NITROSOBIS(TRIFLUOROMETHYL)HYDROXYLAMINE AND M(CF3)3 (M=P, As and Sb)
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O-Nitrosobis(trifluoromethyl)hydroxylamine gives novel reactions with tris(trifluoromethyl)-phosphine, -arsine and -stibine to afford mainly the corresponding bis(trifluoromethyl)nitroxyl 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 occurred.Instead, 3Sb and 2SbCF3 were obtained in high yields.The stoichiometry of the reactions suggests that the additional amounts of bis(trifluoromethyl)nitroxyl groups bonded to antimony are derived from the trifluoromethyl groups bonded to antimony.Mechanisms to rationalise these reactions are proposed.
- ANG, H. G.,SO, K. K.
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- NOVEL REACTIONS INVOLVING 0-NITROSOBIS(TRIFLUOROMETHYL)HYDROXYLAMINE WITH M(CF3)3 (M=P, As AND Sb) AND SOME OLEFINS
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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.
- Ang, H. G.,So, K. K.
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