Perfluoro- and polyfluoro-sulphonic acids. Part 22. Polyfluorophenyl pentafluorobenzenesulphonates and their electron transfer reaction with sodium iodide

Abstract

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 poly-fluorodiphenyl 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.