Unsaturated nitrogen compounds containing fluorine. Part 13. Reaction of 2--1,1,1,3,3,3-hexafluoropropan-2-ide with compounds containing N=O or N-O bonds

Article abstract of DOI:10.1016/0022-1139(93)02915-2

Reaction of the title azomethinimine (1) with nitrogen dioxide gives nitric oxide, hexafluoroacetone and 3,3-dimethyl-5,5-bis(trifluoromethyl)-1-pyrazoline (2) in high yield, while with the perfluoronitrosoalkanes R_FNO (R_F = CF3 and CF2CF2CF3) the products are hexafluoroacetone and the azimines 8a and 8b, respectively.The reactions involve initial <3+2> cycloaddition involving the N=O bonds, followed by elimination of hexafluoroacetone and niric oxide to give 2 or of hexafluoroacetone to give 8.From reaction of 1 with nitrosyl chloride the major products are nitric oxide, 7-chloro-8,8,8-trifluoro-2-methyl-4,4,7-tris(trifluoromethyl) -5,6-diazaocta-1,5-diene (13) and 5,5-dimethyl-3,3-bis(trifluoromethyl)-1-<2,2,2-trifluoro-1-(trifluoromethyl)ethyl>pyrazolidine (14) formed via decomposition of the 1:1 adduct containing C-chloro and N-nitroso substituents.The oxyl (CF3)2NO^. attacks azomethinimine 1 at carbon and the resulting 1:1 adduct decomposes to give hexafluoroacetone, the pyrazoline 2 and (CF3)2N^. radicals which are trapped by the oxyl to afford the oxadiazapentane (CF3)2NON(CF3)2 (19).Secondary reaction then takes place involving attack of the oxygen atom of the oxadiazapentane on 1 at carbon to give hexafluoroacetone, N,N-bis(trifluoromethyl)amine and 3-methyl-5,5-bis(trifluoromethyl)-3--1-pyrazoline (21).This is confirmed by treatment of 1 with the oxadiazapentane 19.