以复合材料为支持电解质的电化学诱导C-H键活化官能团化研究

发布时间：2018-04-21 10:29

本文选题：离子液体聚合物复合材料 + 电氧化氧化　；参考：《北京工业大学》2016年硕士论文

【摘要】：有机电化学合成作为一种“绿色化学”合成手段受到了越来越多的关注。在有机电化学合成过程中,往往要加入大量的支持电解质以保证离子电导率和电荷有效移动,导致反应后处理步骤繁多,同时浪费大量资源;因此,对支持电解质的回收利用研究具有很重要的意义,是有机电化学合成中的一个重要研究领域。本实验组的合作伙伴——UCSB的Little课题组,采用离子液体聚合物与超级碳黑制备可回收的复合材料,并将其作为支持电解质进行研究和测试。发现该离子液体聚合物复合材料作为支持电解质时不仅具有很好的电化学稳定性和很宽的电化学窗口,而且可以通过简单的方法进行回收利用。在此基础上,本课题进行了以下研究:(1)使用可回收离子液体聚合物复合材料作为支持电解质进行一系列的电化学氧化反应。首先,在双室电解池中,进行了恒电位条件下查尔酮的环氧开环/傅-克烷基化反应,同时,考察可回收离子液体聚合物复合材料的重复利用性和回收率;随后,进行了单室电解池恒电位条件下的苄醚的羰基化反应研究;最后,进行了单室电解池恒电流条件下的苯并VA唑衍生物的氧化胺化反应研究。通过实验发现该离子液体聚合物复合材料可以广泛的应用于电化学氧化中,并且在多次回收利用后,依然保持较高的电化学性能。(2)电化学原位生成的TBPA阳离子自由基诱导富电子芳香族化合物与烯酰胺间的阳离子链式反应研究。在此过程中,首先,考察了一锅法和预制备TBPA+。法这两种不同的反应方式、底物比例以及催化剂量对反应的影响,并进一步考察了该反应的普适性;随后,在可回收的离子液体聚合物复合材料作为支持电解质的体系中对该反应进行考察;最后,结合循环伏安法、控制实验等手段探讨并提出了可能的反应机理。
[Abstract]:As a method of green chemistry synthesis, electromechanical synthesis has attracted more and more attention. In the process of electrochemistry synthesis, a large number of supporting electrolytes are often added to ensure the effective movement of ionic conductivity and charge, resulting in numerous steps of post-reaction processing and a large waste of resources; therefore, It is of great significance to study the recycling of supporting electrolytes and is an important research field in electrochemistry synthesis. The Little group of UCSB, a partner of the experimental group, prepared recoverable composite materials with ionic liquid polymer and super carbon black, and used them as supporting electrolytes for research and test. It is found that the ionic liquid polymer composites not only have good electrochemical stability and wide electrochemical window, but also can be recycled by simple methods. On this basis, a series of electrochemical oxidation reactions using recoverable ionic liquid polymer composites as supporting electrolytes were studied as follows: 1. Firstly, the epoxide ring opening / Friede-g alkylation of chalcone was carried out in a two-chamber electrolytic cell, and the reusability and recovery of recoverable ionic liquid polymer composites were investigated. The carbonylation of benzyl ether at constant potential in a single cell electrolytic cell was studied. Finally, the oxidation amination of benzovasazole derivatives at constant current in a single cell electrolytic cell was studied. It is found that the ionic liquid polymer composites can be widely used in electrochemical oxidation and can be reused for many times. TBPA cationic radical induces cationic chain reaction between electron-rich aromatic compounds and alkenamide. In this process, first of all, the one pot method and pre-preparation of TBPA were investigated. The effect of the ratio of substrate and catalyst on the reaction was investigated, and the universality of the reaction was further investigated. The reaction was investigated in the system of recoverable ionic liquid polymer composites as supporting electrolytes. Finally, the possible reaction mechanism was discussed and proposed by means of cyclic voltammetry and control experiments.
【学位授予单位】：北京工业大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.25;O646

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