PERFLUOROALKYL DERIVATIVES OF NITROGEN .28. REACTION OF TRIFLUORONITROSOMETHANE WITH TRIFLUOROACRYLOYL FLUORIDE - A ROUTE TO PERFLUORO-(3-AZABUT-2-ENOYL) FLUORIDE AND HENCE TRIFLUOROMETHYL ISOCYANIDE

Trifluoronitrosomethane combines with trifluoroacryloyl fluoride to yield a 1:1 alternating copolymer, mainly with structure [-N(CF3) ·O·CF2·CF(COF)-]n, and a small amount of material believed to be perfluoro-(4-fluoro-carbonyl-2-methyl-1, 2-oxazetidine), CF3·N·O·CF(COF)·CF 2. Pyrolysis of the copolymer gives, inter alia, perfluoro-(3-azabut- 2-enoyl) fluoride, which is hydrolysed to oxalic acid by aqueous base. Pyrolysis of the butenoyl fluoride over potassium fluoride causes α-elimination of carbonyl fluoride, to give trifluoromethyl isocyanide. The isocyanide isomerises to trifluoromethyl cyanide when heated, reacts with mercuric oxide to yield trifluoromethyl isocyanate, and readily yields a polymer that possibly has the structure [-C(:N·CF3)·C(:N·CF 3)-]n.