高价碘介导下碳碳键氧化偶联合成四氢咔唑酮化合物

发布时间：2018-06-05 12:11

本文选题：二三氟乙酸碘苯 + 四氢咔唑酮衍生物　；参考：《天津大学》2014年硕士论文

【摘要】：四氢咔唑酮类化合物，作为一类重要的含氮杂环化合物，近年来在医药化工领域被发现在诸多方面具有突出的生物活性，包括抗菌、抗艾滋病病毒、抗人类乳头状瘤病毒、抗朊病毒、抗癌等。正因如此，越来越多的研究人员将精力投入到对此类化合物的合成研究中来，迄今已经开发出了多种合成路线和方法。本论文基于课题组之前在高价碘化物介导下碳碳键偶联制备吲哚类衍生物相关的研究成果，提出在二三氟乙酸碘苯（PIFA）作用下，，通过非金属条件下碳碳键氧化偶联的方式构建碳碳键，从而实现对该类化合物的分子内环合构建。本论文以环己酮、环庚酮、以及含有各种取代基的苯胺为最初始原料，通过已有文献方法，制备了一系列的2-取代氨基环己基-2-烯酮类化合物和2-取代氨基环庚基-2-烯酮类化合物作为底物。这两类底物，在二三氟乙酸碘苯（PIFA）的氧化作用下，分别以乙酸酐（Ac2O）和三氟乙醇（TFE）作为溶剂，顺利生成了相应的环合产物，反应效率高，操作简单易行，方便快捷。在此条件下，我们构建了一系列的四氢咔唑酮类产物及其衍生物，并在研究此方法学应用范围与限度之后，进一步研究了此反应的反应机制，提出了我们的设想，并做了相关验证。本文用上述方法得一系列四氢咔唑酮类化合物及其衍生物，产物的结构均得到高分辨质谱、核磁共振氢谱、核磁共振碳谱等表征数据的佐证。
[Abstract]:Tetrahydrocarbazolones, as an important class of nitrogen-containing heterocyclic compounds, have been found in recent years in the field of medicine and chemical industry with outstanding biological activities, including antibacterial, anti-HIV, anti-human papillomavirus. Anti-prion, anticancer, etc. As a result, more and more researchers have devoted their efforts to the synthesis of these compounds, and many synthetic routes and methods have been developed. Based on the previous studies on the preparation of indole derivatives by carbon-carbon bond coupling under the guidance of high valence iodides, this paper proposes a novel method for the preparation of indole derivatives under the action of PIFA (difluoroacetic acid). Carbon bonds were constructed by oxidative coupling of carbon and carbon bonds under nonmetallic conditions, thus the intramolecular cyclization of these compounds was realized. In this paper, cyclohexanone, cycloheptanone and aniline containing various substituents were used as the initial raw materials. A series of 2-substituted amino cyclohexyl-2-enones and 2-substituted amino cycloheptyl-2-enones were prepared as substrates. These two kinds of substrates were oxidized by difluoroacetic acid iodibenzylidene (PIFA) with acetic anhydride (Ac2OO) and trifluoroethanol (TFEE) as solvents respectively. The corresponding cyclization products were produced successfully. The reaction efficiency was high, the operation was simple and convenient. Under these conditions, we have constructed a series of tetrahydrocarbazolones and their derivatives. After studying the scope and limits of the methodology, we have further studied the reaction mechanism and put forward our ideas. And the relevant verification is done. In this paper, a series of tetrahydrocarbazolones and their derivatives were obtained by using the above method. The structures of the products were confirmed by the characterization data of high resolution mass spectrometry, nuclear magnetic resonance (NMR) and nuclear magnetic resonance (NMR) carbon spectroscopy.
【学位授予单位】：天津大学
【学位级别】：硕士
【学位授予年份】：2014
【分类号】：R914.5

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