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(bistrifluoro-methylamino-oxy)mercury(II) or NN-bistrifluoromethylhydroxylamine–caesium fluoride

Abstract

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 CF₃NCICF₂ON(CF₃)₂(16); pyrolysis of the mercurial (11) gives a complex mixture containing the imine CF₃NCFON(CF₃)₂(12) and material tentatively identified as {CF₃NC[ON(CF₃)₂]}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)₂NCF₂NCFON(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 pentafluoro-pyridine to provide 4-(bistrifluoromethylamino-oxy)-2,3,5,6-tetrafluoropyridine. The mercurial [(CF₃)₂NO]₂Hg attacks the alkyliminocarbonyl chloride Me₃CNCCl₂ to give the bistrifluoromethylamino-oxy-derivatives Me₃CNCCl[ON(CF₃)₂] and Me₃CNC[ON(CF₃)₂]₂.