以亚磺酸盐或单质硫为硫源的C-S键生成反应研究

发布时间：2018-06-10 18:56

本文选题：含硫有机分子 + 环境友好　；参考：《湘潭大学》2017年硕士论文

【摘要】：含硫有机化合物广泛存在于农药、药物、染料和功能材料等领域,发展简单高效绿色构筑C-S键的方法具有重要的研究意义。从可持续发展的远景来看,寻找更加稳定而且储量丰富的硫源变得更加的迫切;从绿色化学发展的远景来看,寻找无毒无害及可再生资源的原料,无毒无害的催化剂以及无毒无害的溶剂变得更加的迫切。通过活化C-H键直接构建C-S可以有效增强反应步骤经济性、提高合成转化的原子经济性,甚至可能实现常规方法难以完成的化学合成。亚磺酸盐或单质硫相对其它有机硫化试剂存在性质稳定、无特殊气味、价格便宜、原料易得等诸多优点。本论文以“环境友好的C-S键生成反应”作为研究核心,以亚磺酸盐或单质硫为硫源,开展一系列构建C-S键的研究工作,具体内容如下:1、以亚磺酸盐和2-甲基喹啉类化合物为原料发展了一类合成2-砜基甲基喹啉类化合物的新方法。该反应以亚磺酸盐为磺酰化试剂,无需添加任何过渡金属催化剂,通过碘化钾作为添加剂实现了高效、绿色的2-砜基甲基喹啉类化合物的合成。2、水相条件下亚磺酸盐与酚类化合物化学选择性的偶联反应。该反应以稳定易得的亚磺酸盐作为硫化试剂,水作为反应介质,反应体系中不需要添加任何过渡金属催化剂,通过控制反应的酸碱性可以化学选择性的得到芳基硫醚或砜类化合物。3、铜催化水相条件下三组分(单质硫、碘代烃和芳烃)“一锅法”反应合成芳基硫醚类化合物。该反应以水作为反应的唯一绿色溶剂,储量丰富的单质硫作为硫源,合成了出了一系列的芳基硫醚类化合物,反应具有非常好的官能团容忍度。该反应为绿色、高效的合成芳基硫醚类化合物提供了一条新途径。
[Abstract]:Sulfur organic compounds are widely used in pesticides, drugs, dyes and functional materials. It is of great significance to develop simple and efficient green C-S bond construction methods. From the perspective of sustainable development, the search for more stable and abundant sources of sulfur becomes more urgent; from the perspective of green chemical development, the search for non-toxic, harmless and renewable sources of raw materials, Non-toxic and harmless catalysts and non-toxic and harmless solvents become more urgent. The direct construction of C-S by activation of C-H bond can effectively enhance the economy of reaction steps, improve the atom economy of synthesis and transformation, and even realize the chemical synthesis which is difficult to be completed by conventional methods. Compared with other organic sulphide reagents, sulfite or elemental sulfur has many advantages, such as stable properties, no special smell, low price and easy to obtain raw materials. In this thesis, a series of studies on the formation of C-S bond have been carried out, with "environmentally friendly C-S bond formation reaction" as the core and sulfinite or sulfur as the sulfur source. The main contents are as follows: 1. A new method for the synthesis of 2-sulfone methyl quinoline compounds has been developed by using sulfonate and 2-methylquinoline compounds as raw materials. In this reaction, sulfonate was used as sulfonylation reagent and no transition metal catalyst was added in the reaction, and potassium iodide was used as additive to achieve high efficiency. Synthesis of Green 2-sulfone Methyl Quinoline compounds. 2. Chemical selective Coupling reaction between Sulfonate and Phenolic compounds in Aqueous Phase. In this reaction, stable and easily available sulfides were used as sulphide reagents, and water was used as the reaction medium. No transition metal catalyst was needed in the reaction system. Aryl sulfides can be chemically selectively synthesized by controlling the acidity and alkalinity of the reaction. Aryl sulfides can be synthesized by "one pot" reaction of three components (simple sulfur, iodinated hydrocarbons and aromatic hydrocarbons) in aqueous phase catalyzed by copper. A series of aryl sulfide compounds were synthesized by using water as the only green solvent and abundant sulfur as the sulfur source. The reaction has a very good tolerance of functional groups. The reaction provides a new way for the green and efficient synthesis of aryl sulfide compounds.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.1

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