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化学学报
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化学学报 ›› 1989, Vol. 47 ›› Issue (8): 788-791. 上一篇    下一篇

研究论文

全氟卤代烷在氯磺酸中的电化学反应

杜学梅;杨冰华;胡昌明;钱道荪;沈天憬;唐瑞平   

  1. 中国科学院上海有机化学研究所;上海交通大学应用化学系
  • 发布日期:1989-08-15

The anodic chlorosulfonation of perfluoroalkyl iodide

DU XUEMEI;YANG BINGHUA;HU CHANGMING;QIAN DAOSUN;SHEN TIANJING;TANG RUIPING   

  • Published:1989-08-15

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本文报道了以氯磺酸钾为电解质, 铂为电极, 进行氯磺酸的阳极氧化, 产生过氧二磺酰氯, 并和阳极池内α,ω-氯磺含氟烷进行反应, 生成相应的氯磺酸酯, 反应主要副产物为α,ω-二氯全氟烷, 在阳极有大量氢气逸出, 并得到碘。

关键词: 铂, 水, 钾化合物, 电解质, 自由基反应, 电化学反应, 阳极氧化, 氯磺酸, 全氟代烃, 电极反应

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

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