Novel chemistry of trifluoromethylenimine

Abstract

The reaction chemistry of CF 2NF has been examined and a variety of novel N-fluoro compounds were found. Reaction with AsF 5 in HF yields an ammonium salt, CF 3NFH 2 +AsF 6 − . The salt is a solid with a dissociation pressure of 7 torr at 22°C. Electrophilic reaqents(XOSO 2F, X=Br,Cl,OSO 2F) add across the carbon-nitroqen double bond to form the corresponding N-halo-N-fluoroamines. Reactions with metal fluorides (KF or CsF) at ambient temperature generated the perfluoromethanamine ion, CF 3NF −. This ion undergoes nucleophilic substitution reactions with CF 2NF, R fCOF (R f = F,CF 3, C 2F 5) and it is oxidized by halogens to CF 3NXF (X=Br,Cl). Higher molecular weight polymers of CF 2NF can be generated by reaction with strong acids. With SbF 5, an air-sensitive polymer film is formed in a glass reactor. With CF 3SO 3H, a water-resistant viscous liquid is formed. Preliminary evidence indicates a structure -(CF 2NF) n-. Reaction of CF 3NBrF with olefins (CF 2CF 2, CF 2CFCl, CF 2CBr 2, CF 2CH 2 and CH 2CH 2) at elevated temperature cleaves the NBr bond and results in addition to the olefin. The reaction mechanism is believed to be free radical and only a single regioisomer is observed with the unsymmetrical olefins.