PERFLUORO-SULFONIC AND POLYFLUORO-SULFONIC ACIDS .22. POLYFLUOROPHENYL PENTAFLUOROBENZENESULPHONATES AND THEIR ELECTRON-TRANSFER REACTION WITH SODIUM-IODIDE

Polyfluorophenyl pentafluorobenzenesulphonates (1) have been synthesized in excellent yields by the reaction of pentafluorobenzenesulphonyl chloride with polyfluorophenoxides. Nucleophilic attack on 1 resulted in the breakage of the S-O bond accompanied by displacement of o- and/or p-fluorine. Reaction of 1 with sodium iodide (8) in a mole ratio of 1:3 (1:8) yielded polyfluorodiphenyl ethers 9 and 10 as the main products. However, p-C6F5OC6F4SO3C6F5 (12) was isolated as the major product in addition to 9 and 10 when the reactant ratio was 1:1 or 1:0.25. Reaction of 12 with sodium iodide also gave 9 and 10 when the reactant ratio was 1:3 (12:8). The reaction of 1 (or 12) with Nal is supposed to be an electron-transfer process.