可控的硫醇与乙烯基醚反马氏和马氏加成反应合成烷氧基硫醚 .pdf

2010 年第68 卷 化 学 学 报 Vol. 68, 2010 第12 期, 1223～1228 ACTA CHIMICA SINICA No. 12, 1223～1228 ·研究论文· 可控的硫醇与乙烯基醚反马氏和马氏加成反应合成烷氧基硫醚 娄凤文a 周建峰*,a 林贤福b a ( 淮阴师范学院化学化工学院 江苏省低维材料化学重点建设实验室 淮安 223300) (b 浙江大学化学系 杭州 310027) 摘要 报道了在无溶剂、无催化剂也不加任何助剂的条件下, 硫醇与乙烯醚之间的加成反应. 考察了物料比、温度、 底物结构等因素对加成反应的影响. 通过改变物料比实现了反马氏(1 ∶1.2)和马氏(1 ∶8)加成反应的位置选择性调控, 合成了12 种2-烷氧基取代的硫醚和6 种1-烷氧基取代的硫醚. 反应过程中避免使用任何有机溶剂, 过量的乙烯基醚通 过减压蒸馏回收并且可以循环利用, 是简单易行的合成烷氧基硫醚的绿色新方法, 具有潜在的应用价值. 关键词 硫醇; 烷氧基硫醚; 无溶剂; 无催化剂; 选择性调控 Controllable Anti-Markovnikov and Markovnikov Addition of Thiols to Vinyl Ethers for the Synthesis of Alkyloxy Thioethers Lou, Fengwena Zhou, Jianfeng*,a Lin, Xianfub a ( School of Chemistry Chemical Engineering, Huaiyin Normal University, Jiangsu Province Key Laboratory for Chemistry of Low Dimensional Materials, Huaian 223300) (b Department of Chemistry, Zhejiang University, Hangzhou 310027) Abstract An efficient protocol for the addition reaction of thiols to vinyl ethers has been developed under solvent- and catalyst-free conditions. The influence factors of the structure of thiol and vinyl ether, tempera- ture, molar ratio were investigated. The regioselectivity of the addition reaction can be controlled by the molar ratio of material so that both the anti-Markovnikov (1 ∶1.2) and the Markovnikov products (1 ∶8) are now easily accessible in excellent selectivities. The work synthesized 18 kinds of