Interaction of N,N-dimethylperfluoroarylamines with nitric and nitrous acids

N,N-Dimethylpentafluoroaniline enters easily into reactions with a mixture of nitric and sulphuric acids or nitric acid with conversion of the side chain. In the reactions with mixtures of HNO3 and H2SO4, the formation of N-nitroso-N-methyl and N-nitro-N-methylpentafluoroanilines is observed. The ratio of these products was found to depend on the ratio of the acids: the formation of N-nitro-N-methylpentafluoroaniline increases with the quantity of sulphuric acid; N-nitroso-N-methylpentafluoroaniline is obtained when only nitric acid is employed. N,N-Dimethylperfluoro-p-toluidine, N,N-dimethylperfluoro-2,4-xylidine, N,N-dimethylperfluoro-5-aminoindane undergo similar transformations. N-Nitroso derivatives were converted by a mixture of HNO3 and H2SO4, HNO3 or NO2BF4 into the corresponding N-nitro derivatives. Formation of the corresponding N-nitroso-N-methyl derivatives occurs when N,N-dimethylpentafluoroaniline, N,N-dimethylperfluoro-p-toluidine are treated with HNO2.