全氟卤代烷在氯磺酸中的电化学反应  

The Anodic Chlorosulfonation of Perfluoroalkyl Iodide

作　　者：杜学梅[1] 杨冰华 胡昌明[1] 钱道荪[2] 沈天憬 唐瑞平[2] 

机构地区：[1]中国科学院上海有机化学研究所 [2]上海交通大学应用化学系

出　　处：《化学学报》1989年第8期788-791,共4页Acta Chimica Sinica

摘　　要：过氧二磺酰氟的制备、性质及其应用，近年来已有报道。但过氧二磺酰氯的制备及反应则不然。本文报道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（1）。并和阳极池内α，ω－氯磺全氟烷进行反应，生成相应的氯磺酸酯2，反应主要副产物为α，ω－二氯全氟烷3。在阴极有大量氢气逸出，并得到碘，上述反应可用自由基机理解释。Anodic oxidation of potassium chlorosulfonate in chlorosulfonic acid under mild condition gave peroxydisulfuryl dichloride, S_2O_6Cl_2, which reacted with a, ω-ehlo- roiodoperfluoroalkane to give ω-chloroperfluoroalkylchlorosulfate (2) and Cl(CF_2), Cl (3). In the reaction of Cl(CF_2)_6I, hexachlorobenzene was formed as a byproduct. The effcet of current density, quantity of electricity on product yield were studied. It was found that the reaefion occured only when certain amount of S_2O_6Ol_2 has been accumulated in the reaction system. The reactions of 2(n=6) with nucleophiles, such as (C_2H_5)NH, HCF_2CF_2CH_2O^- , F^- and water were studied. The order of nucleophilicity was found to be: Et_2NH> HCF_2CF_2CH_2O^-?F^-> H_2O.

关 键 词：全氟卤代烷 氯磺酸 电化学反应 过氧二磺酰氯 氯磺酸酯 

分 类 号：O623.84[理学—有机化学]