Fluorocarbon Derivatives of Nitrogen. Part 5. Replacement of Imidoyl Halogen by the Bistrifluoromethylamino-oxy Group : Reactions of Perfluoro-2-azapropene and Related Compounds with Bis(bistrifluoromethylamino-oxy)mercury(II) or NN-Bistrifluoromethylhydroxylamine-Caesium Fluoride

Article abstract of DOI:10.1039/P19810001443

Treatment of perfluoro-2-azapropene with bis(bistrifluoromethylamino-oxy)mercury(II) yields the new mercurial <<(CF3)2NOCF2>(CF3)N>2Hg (11), chlorinolysis of which provides the N-chloroamine CF3NClCF2ON(CF3)2 (16); pyrolysis of the mercurial (11) gives a complex mixture containing the imine CF3N=CFON(CF3)2 (12) and material tentatively identified as >2O.The N-chloro-compound (16) reacts with hydrogen chloride and silver cyanide to provide the corresponding amine CF3NHCF2ON(CF3)2 and the related imine (12).The latter product, together with the di-substituted analogue (CF3)2NCF2N=CFON(CF3)2, can also be procured by treating perfluoro-2-azapropene with a caesium fluoride-NN-bistrifluoromethylhydroxylamine adduct.This reagent also attacks perfluoro-1-azacyclohexene to yield perfluoro-<2-(dimethylamino-oxy)-1-azacyclohexene> and perfluoro-<2,6-bis(dimethylamino-oxy)-1-azacyclohexene>, and similarly effects nucleophilic substitution in pentafluoropyridine to provide 4-(bistrifluoromethylamino-oxy)-2,3,5,6-tetrafluoropyridine.The mercurial <(CF3)2NO>2Hg attacks the alkyliminocarbonyl chloride Me3CN=CCl2 to give the bistrifluoromethylamino-oxy-derivatives Me3CN=CCl and Me3CN=C2.