Nitroxide chemistry. Part III. Photolysis of bistrifluoromethyl nitroxide and some reactions of the major product, perfluoro-(2,4-dimethyl-3-oxa-2,4-diazapentane)

Abstract

U.v. irradiation of bistrifluoromethyl nitroxide yields perfluoro-(2,4-dimethyl-3-oxa-2,4-diazapentane) together with oxygen, carbonyl fluoride, trifluoronitrosomethane, trifluoronitromethane, O-nitroso-NN-bistrifluoromethylhydroxylamine, and tristrifluoromethylhydroxylamine. Perfluoro-(2,4-dimethyl-3-oxa-2,4-diazapentane) decomposes thermally to bistrifluoromethyl nitroxide and tetrakistrifluoromethylhydrazine and reacts (i) with hydrogen iodide to yield equimolar amounts of NN-bistrifluoromethylhydroxylamine and bistrifluoromethylamine, (ii) with nitric oxide to give equimolar amounts of O-nitroso-NN-bistrifluoromethylhydroxylamine and bistrifluoromethylnitrosamine, and (iii) with fluoro-olefins to yield 1 : 1 adducts of the type (CF₃)₂N·O·CFX·CFY·N(CF₃)₂[for CF₂:CF₂, X = Y = F; for CF₂:CFCl, X = Cl, Y = F; for CF₂:CF·CF₃, X = CF₃, Y = F (major product) and X = F, Y = CF₃(minor); for CF₂:CHF, X = F, Y = H (80%) and X = H, Y = F (20%)] and, in the cases of tetrafluoroethylene and chlorotrifluoroethylene, polymeric material.