Polyfluoroalkyl derivatives of nitrogen. Part XXVII. Some reactions of NN-bistrifluoromethylvinylamine

Abstract

NN-Bistrifluoromethylvinylamine, prepared in high yield by the dehydrohalogenation of 2-iodo- or 2-bromo-NN-bistrifluoromethylethylamine, reacts with hydrogen bromide or with N-bromobistrifluoromethylamine in the dark to give 1-bromo-NN-bistrifluoromethylethylamine or 1,1-di(bistrifluoromethylamino)-2-bromoethane, respectively, which indicates that the olefin is polarised in the sense (CF₃)₂N·[graphic omitted]. The products from the same reactants under conditions conducive to the formation of free-radical intermediates are 2-bromo-NN-bistrifluoromethylethylamine and 1,2-di(bistrifluoromethylamino)-1-bromoethane, respectively. Dehydrobromination of the isomeric 1 : 1 adducts [(CF₃)₂N]₂CH·CH₂Br and (CF₃)₂N·CHBr·CH₂·N(CF₃)₂ gives the corresponding olefins in good yield. Hydrogen bromide reacted with 1,1-di(bistrifluoromethylamino)ethylene when exposed to u.v. light, but not in the presence of aluminium bromide. N-Bromobistrifluoromethylamine reacts with cyclopropane to give bromocyclopropane and bistrifluoromethylamine, and not 3-bromo-NN-bistrifluoromethylpropylamine.