Some Novel Reactions of N-Chlorodifluoromethanimine,
CLEMSON UNIV SC DEPT OF CHEMISTRY
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Some reactions of N-chlorodifluoromethanimine, CF2 double bond NCl, have been studied and are compared to related reactions of perfluoromethanimine, CF2 double bond NF. Fluoride promoted reactions of CF2 double bond NCl result in evidence for the CF3NCl- anion, which is thermally less stable and less reactive than CF3NF-. Oxidation of CF3NC- formed in situ by reaction of CF2 double bond 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 double bond NCl forms the novel diazene FSO2OCF2N double bond NCF2OSO2F, presumably via the intermediate FSO2OCF2NCIX addition products. Competitive reaction of CF2 double bond NF and CF2 double bond NCl with fluoride ion results in the preferential formation of CF3NF-. Nucleophilic attack of the latter on CF2 double bond NCl forms the novel diaziridine CF3NCF2NCl, which can be reduced by Hg in trifluoracetic acid to CF3NCF2NH. The mechanism for the formation of the daziridines is discussed.
- Organic Chemistry