Some Novel Reactions of N-Chlorodifluoromethanimine

Article abstract of DOI:10.1021/jo00193a027

Some reactions of N-chlorodifluoromethanimine, CF2=NCl, have been studied and are compared to related reactions of perfluoromethanimine, CF2=NF.Fluoride promoted reactions of CF2=NCl result in evidence for the CF3NCl^- anion, which is thermally less stable and less reactive than CF3NF^-.Oxidation of CF3NCl^-, formed in situ by reaction of CF2=NCl with KF or CsF, with Cl2 forms CF3NCl2.With Br2, CF3NBrCl is formed along with CF3NBr2.The latter arises from a novel fluoride-catalyzed conversion of CF3NBrCl to CF3NBr2 by Br2, and the same products can be obtained starting with CF3NCl2, Br2, and MF.Extension of this reaction to C2F5NCl2 and C3F7NCl2 is also discussed.Addition of XOSO2F (X=Cl, Br) to CF2=NCl forms the novel diazene FSO2OCF2N=NCF2OSO2F, presumably via the intermediate FSO2OCF2NClX addition products.Competitive reaction of CF2=NF and CF2=NCl with fluoride ion results in the preferential formation of CF3NF^-.Nucleophilic attack of the latter on CF2=NCl forms the novel diaziridine , which can be reduced by Hg in trifluoroacetic acid to .The mechanism for the formation of the diaziridines is discussed.