The reaction of perfluoroalkyl bromide and a,w-perfluoralkylene dibromide in sulfinatodehalogenation system with olefins and the differences in behavior between perfluoroalkyl bromides and their corresponding iodides are reported. The secondary perfluoroalkyl bromide CF3CFBrOCF2CF(CF3)O(CF2)2SO2F was synthesized and reacted with olefins to give 1:1 adducts. However, the sulfonate CF3CFBrOCF2CF(CF3)O(CF2)2SO3Na reacted with sodium dithionite to give only the hydrodebromination product. The polyfluoroalkyl bromides CF3CBr2R (R = F, Cl, Br) reacted normally to give the corresponding sodium sulfinate CF3CBrRSO2Na. The reaction intermediate polyfluoroalkyl radical can also be trapped by olefins to give good yields of 1:1 adducts.

Key words: ALKENE, BROMOHYDROCARBON, ALKANE P, FREE RADICAL REACTION, DEHALOGENATION REACTION, PERFLUORO-HYDROCARBON, SULFINATION