Anodic oxidation of chlorosulfonic acid under mild conditions gave peroxydisulfuryl dichloride, S2O6Cl2, which reacted with a,w-chloroiodoperfluoroalkane to give w-chloroperfluoroalkyl chlorosulfate (I) and Cl(CF2)nCl. In the reaction of Cl(CF2)3L, hexachlorobenzene was formed as a byproduct. The effects of c.d. and efficiency on the product yield were studied. The reaction occurred only when a certain amount of S2O6Cl2 was accumulated in the reaction system. The reactions of I (n = 6) with nucleophiles, such as Et2NH, HCF2CF2CH2O-, F-, and H2O were studied. The order of nucleophilicity was: Et2NH > HCF2CF2CH2O- x F- < H2O.

Key words: PLATINUM, WATER, POTASSIUM COMPOUNDS, ELECTROLYTE, FREE RADICAL REACTION, ELECTROCHEMICAL REACTION, ANODIC OXIDATION, CHLOROSULFONIC ACID, PERFLUORO-HYDROCARBON, ELECTRODE REACTION