Reactions of bis(trifluoromethyl)nitroxyl with CF 3PX 2 (where X = F, Cl, Br, I and CN) and P(CN) 3

Abstract

The reactions between bis(trifluoromethyl)nitroxyl and CF 3PX 2 (where X = F, Cl, Br and CN) in 2:1 molar ratio give addition products, [(CF 3) 2NO] 2P(CF 3)X 2. The bromo and cyano products are unstable. The former decomposes at room temperature to give bromine and perfluoro-2-azapropene, and the latter yields predominantly (CF 3) 2NOCF 3. With CF 3PI 2, iodine displacement occurs to afford [(CF 3) 2NO] 2PCF 3. On the other hand, P(CN) 3 affords [(CF 3) 2NO] 3PO, (CF 3) 2NON(CF 3) 2 and paracyanogen. Mechanisms for these reactions are proposed.