Some reactions of fluorinated azaalkenes, R fNCF 2

Abstract

More facile routes to fluorinated azaalkenes encourage further studies of the reactions of these compounds. Reactions of (CF 3) 2NCF 2NCF 2 with lithiated polyfluoroalkoxides give (CF 3) 2NCF 2NCF 2−x (OR f) x [X=1 or 2; R fCF 3CH 2, (CF 3) 2CH or (CF 3) 2C(CH 3)]. Chlorine fluoride can be added to the nitrogen-carbon double bond of these mono- and bis-alkoxides with retention of the molecular backbone to give (CF 3) 2NCF 2N(Cl)CF 3−x (OR f) x [X=1 or 2; R fCF 3CH 2, (CF 3) 2CH or (CF 3) 2C(CH 3)]. Photolysis of neat NF 2CXFCF 2NCl 2, which results from chlorofluorination of F 2NCXFCN (X=Cl or F), gives diazencs [F 2NCXFCF 2N] 2. Thermolysis of F 2NCF 2CF 2NCl 2 in a 1:1 ratio with CF 2CClF results in F 2NCF 2CF 2N(Cl)CF 2CCI 2F. Upon photolysis of the latter, a new azaalkene, F 2NCF 2CF 2NCF 2 results. Following chlorofluorination of F 2NCF 2CF 2NCF 2, insertion of ClCN or F 2NCF 2CN into the resulting nitrogen-chlorine bond gives imines F 2NCF 2CF 2N(CF 3)NCCl 2 and F 2NCF 2CF 2N(CF 3)NC(Cl)CF 2NF 2. Successive chlorofluorination of the latter compound with intramolecular elimination of chlorine, followed by photolysis, gives rise to a stable, non-volatile tetrazane (70%) that contains eight nitrogen atoms, F 2NCF 2CF 2N(CF 3)N(CF 2CF 2NF 2)N(CF 2CF 2NF 2)N(CF 3)CF 2CF 2NF 2.