Synthetic and Mechanistic Studies in Fluorine Chemistry. New Developments in Organonitrogen Fluorine Chemistry.

The reaction chemistry of the novel oxaziridine 2-trifluoromethyl-3,3-difluorooxaziridine, CF3NCF2O, acronym PFAPO-pentafluoroazapropene oxide is described, PFAPO shows many similarities to HFPO-hexafluoropropene oxide, CF3CFCF2O, a commercially important monome for polymer synthesis. PFAPO undergoes ring opening by many nucleophiles leading to polymers or compounds of the type CF3NNuCOF. The latter can be converted to amines CF3NNUH by reaction with H2O3NaF and to imines CF3NNu by reaction with KF. PFAPO also exhibits chemistry unique from that in that it undergoes novel cycloadditions with olefins and ketones, with itself in the presence of SbF5 and possibly with nitriles. These reactions re very unusual from a mechanistic standpoint and provide novel heterocycles and polymers with potentially useful properties. New chemistry of perfluoroimines is examplified by perfluoromethanimine, CF2NF. A novel chlorofluorination of ClCN, followed by dechorination with Hg in TFAA provides an excellent high-yield synthesis. This imine exhibits a rich chemistry in the presence of fluoride ion, which generates the perfluororeactions leading to novel examples of organonitrogen fluorine compounds. Perfluoromethanimes can also be cationically polymerized to form a unique N-F polymer CF2NF sub n.