铜催化芳基丙炔酸与磺酰肼的脱羧偶联反应

发布时间：2018-03-07 02:09

本文选题：铜催化　切入点：芳基丙炔酸　出处：《郑州大学》2016年硕士论文　论文类型：学位论文

【摘要】：本论文主要研究了铜催化下芳基丙炔酸与磺酰肼类化合物的脱羧加氢磺酰化反应。主要研究结果如下:1.以芳基丙炔酸和磺酰肼类为底物,空气中的氧气作为氧化剂,一价铜为催化剂,得到一系列具有医药活性和生物活性的烯砜类衍生物。该课题的关键是催化剂和溶剂的选择,相对于非质子性溶剂,质子性溶剂更有利于反应。该方法使用芳基丙炔酸作为新的烯源,以空气中的氧气作为氧化剂,并且使用了较为便宜低毒的铜催化剂,反应条件温和、操作简单、环境友好、不需要加入添加剂和碱,得到单一E型烯砜类产物。此外,该催化体系还可兼容脂肪族磺酰肼。2.在芳基丙炔酸与磺酰肼脱羧偶联基础上,反应体系还可适用于末端炔烃与磺酰肼类化合物的反应。3.为阐明反应机理,设计以下对比试验:当苯丙炔酸和对甲苯磺酰肼的反应在氮气保护下,几乎没有发现烯砜类产物;在无铜催化剂存在条件下,反应几乎不能发生。以上实验表明,铜催化剂和氧气的参与是反应的必需条件。反应体系中加入自由基抑制剂TEMPO时,同样没有得到烯砜类化合物,证明此反应机制是一个自由基历程。
[Abstract]:This paper mainly studies the decarboxylation reaction of hydrogenation of sulfonated copper catalyzed aryl propargyl acid and sulfonyl hydrazine compounds. The main results are as follows: 1. with aryl propionic acid and sulfonyl hydrazine as substrate, the oxygen in the air as the oxidant, copper as catalyst, a with pharmaceutical activity and biological activity of allyl sulfone derivatives. The key issue is the choice of solvent and catalyst, compared with aprotic solvents, protonic solvent reaction. This method is more conducive to the use of aryl propionic acid as a new vinyl source, uses oxygen in the air as the oxidant, and the use of the catalyst copper is relatively cheap and low toxicity, mild reaction conditions, simple operation, friendly environment, without adding additives and alkali, a single E type sulfones products. In addition, the catalytic system can be compatible with aliphatic sulfonyl hydrazide.2. decarboxylation in propiolic acid with aryl sulfonyl hydrazide Based on the coupling reaction of.3., the reaction system can be applied to terminal alkynes and sulfonyl hydrazine compounds in order to elucidate the reaction mechanism, the design of the following tests: when phenylpropiolic acid and ptsh reaction under the protection of nitrogen, hardly found sulfones products; in the presence of copper catalyst the reaction, almost cannot occur. These results indicate that the copper catalyst and oxygen is necessary for participating in the reaction. The addition of a free radical inhibitor TEMPO in the reaction system, the same has not been vinyl sulfone compounds, the reaction mechanism is a free radical process.

【学位授予单位】：郑州大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

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