Polyfluoroalkyl derivatives of nitrogen. Part XXXI. Reaction of N-chloro- and N-lodo-bistrifluoromethylamine with hexafluoropropene, trifluoroethylene, and vinyl fluoride under radical conditions

Abstract

Thermal reaction of N-chlorobistrifluoromethylamine with hexafluoropropene gives the 1 : 1 adducts 2-chlorohexafluoro-NN-bistrifluoromethylpropylamine and 2-chloro-1-trifluoromethyl-1,2,2-trifluoro-NN-bistrifluoromethylethylamine in the ratio 96 : 4. Photochemical reaction of the N-iodo-amine with hexafluoropropene affords the expected major 1 : 1 adduct 2-iodohexafluoro-NN-bistrifluoromethylpropylamine in low yield. Thermal reaction of the N-chloro-amine with trifluoroethylene gives 2-chloro-1,2,2-trifluoro-NN-bistrifluoromethylethylamine and 2-chloro-1,1,2-trifluoro-NN-bistrifluoromethylethylamine in high yield in the ratio 78 : 22. Reaction of the N-iodo-amine with trifluoroethylene in daylight or under photochemical conditions affords the corresponding 2-iodo-adducts in a similar ratio, whereas photochemical reaction of the N-chloro-amine gives the 2-chloro-adducts in the ratio 87 : 13. Photochemical reaction of the N-chloro-or N-iodo-amine with vinyl fluoride gives 2-halogeno-2-fluoro- and 2-halogeno-1-fluoro-NN-bistrifluoromethylethylamine in the ratio 95 : 5 and 93 : 7, respectively, whereas reaction of the N-iodo-amine in daylight gives the 1 : 1 adducts in the ratio 65 : 35 by competing ionic and radical mechanisms.