Polyfluoroalkyl derivatives of nitrogen. Part XXXVII. Reaction of N-bromobistrifluoromethylamine with propene under ionic and free-radical conditions

Abstract

Photochemical reaction of N-bromobistrifluoromethylamine with propene in the vapour phase gives the 1:1 adducts 2-bromo-NN-bistrifluoromethylpropylamine and 2-bromo-1-methyl-NN-bistrifluoromethylethylamine in the ratio 91:9; N-chlorobistrifluoromethylamine gives the corresponding chloro-adducts in the ratio 90:10. Reaction of the N-bromo-amine in the liquid phase in the dark at –78 and at –140° gives the same adducts in the ratio 40:60 and 55:45, respectively; the presence of acetone as solvent, air, or hydroquinone has no effect on the isomer ratio at –78°. 2-Bromo-NN-bistrifluoromethylpropylamine dehydrobrominates readily to afford a mixture of cis- and trans-NN-bistrifluoromethylprop-1-enylamine in high yield and 2-bromo-1-methyl-NN-bistrifluoromethylethylamine gives 2-(NN-bistrifluoromethylamino)propene. Reaction of the N-bromo-amine with isobutene at –78 or –140° gives mainly bistrifluoromethylamine and brominated material.