【摘要】 <正> 我们在工作中发现亚硫酸钾水溶液与1的正常反应产物是2,但加二氧六环于上述反应体系后发生了一个不同的反应,得到另一个产物3,即:3是熔点286℃的无色结晶,IR:1010cm^-1;¹⁹FNMR:δ_CFCl3为82.0,133.4ppm,这两个核磁共振吸收峰均为单峰并强度相等。元素分析与氧化还原滴定也符合3的结构。这一反应条件温和,产率及选择率都高达90％。因为这种反应未见文献报道,我们建议称之为“脱碘亚磺化反应”,它具有自由基反应的性质。除二氧六环外,其它醚类溶剂如二乙二醇二甲醚及四氢呋喃等亦有相同的作用,而更多还原

【Abstract】 The normal reaction product of 3-oxa-5-iodoperfluoropentanesulfonyl fluoride （1） with potassium sulfite in aqueous solution was the corresponding potassium sulfinate 2, but when the reaction was carried out in aqueous dioxane, potassium 3-oxa-1, 5-perfluoropentane disulfinate（3）, was formed instead of 2. The optimal condition for the preparation of 3 （90% yield） was stirring at 70～80℃ for several hours with a molar ratio of the reducing agent to the substrate of≥3:1. 3-Oxa-7-iodoperfluoroheptanesulfonyl fluoride （5） and 1, 4-diiodoperfluorobutane （6） were similarly converted into the corresponding disulfinate 7 and 8 respectively. We suggest the name deiodosulfination for this radical reaction which can also be carried out in diglyme or THF but not in DMF, pyridine or triethylamine.Reaction of 3 with HI in glacial acetic acid gave a mixture of 3-oxa-5-iodoperfluoropentanoic acid （9, in 38% yield）, 3-oxa-1, 5-diiodoperfluoropentane （10）, 3-oxaperfluoroglutaric acid （11） and 3-oxa-5-H-perfluoropentanoic acid （12）. Similarly, 3 and HBr furnished 3-oxa-5-bromoperfluoropentanoic acid （13）as the major product accompanied by 11 and 12. The formation of 9, 10 and 13 was explained through the reaction of the sulfinate group in 3 with the free halogen formed from the interaction of the CF₂SO₂K moiety with HX[equations （a） and （b） of the Chinese text], and was confirmed by the finding that reaction of 2 or 3 with iodine in glacial acetic acid gave 10 in moderate yield.The discovery of deiodosulfination reaction coupled with the known process of oxidizing sulfinic acid and derivatives constitutes a novel and convenient method for the synthesis of perfiuorosulfonic acid and related compounds.更多还原