碘催化氮杂芳烃C-H键反应研究

发布时间：2018-05-31 13:26

本文选题：碘催化 + 氮杂芳烃　；参考：《湘潭大学》2016年硕士论文

【摘要】：氮杂环化合物作为各种具有生物活性的化合物关键结构单元,其合成与应用一直倍受化学家们的关注。近些年来随着C-H活化的快速发展,为化合物的合成提供了更加的简便、经济和绿色的方法。因此将C-H活化应用于吡啶及喹啉衍生物的合成,也成为了这些年来研究的热点。碘催化因其具有原子经济性高、反应条件温和、容易分离除去等优点,解决了金属催化中存在金属残余的问题,使其更具有优势、更加的绿色、经济,而受到化学家们的关注。结合我们课题组的研究兴趣,我们以单质碘作催化剂对氮杂芳烃的反应进行研究,设计了本论文。论文主要分为以下两部分内容:第一部分主要研究碘催化氮杂芳烃苄位C-H键的氧化氨化反应。以2-甲基喹啉和邻氨基苯甲酰胺为反应模板,合成取代的喹唑啉酮,经过一系列的条件优化和筛选发现:以单质碘作为催化剂,DMSO作为溶剂,氧气氛围下反应得到了较高的产率。该反应使用非预活化的烷基氮杂芳烃作为底物,在无金属存在条件下,氧气作为最终的氧化剂,高效地合成了多种杂环取代的喹唑啉酮。第二部分主要是碘催化氮杂芳烃的苄基化反应研究。综述相关文献和我们课题组的工作,在以异喹啉和对二甲苯作为反应模板,得到芳香环上苄基化的异喹啉产物;经过一系列的条件优化,确定了以单质碘作为催化剂,TBP作为氧化剂得到较好的收率,该反应底物普适性较好,为氮杂芳烃的苄基化提供了新方法。
[Abstract]:As the key structural units of various bioactive compounds, the synthesis and application of nitrogen heterocyclic compounds have attracted much attention from chemists. With the rapid development of C-H activation in recent years, it provides a more simple, economical and green method for the synthesis of compounds. Therefore, the application of C-H activation to the synthesis of pyridine and quinoline derivatives has become a hot topic in recent years. Iodine catalysis is concerned by chemists because of its advantages of high atomic economy, mild reaction conditions and easy separation and removal, which solves the problem of metal residue in metal catalysis and makes it more advantageous, green and economical. Combined with the research interest of our research group, we studied the reaction of azarene with simple iodine as catalyst, and designed this thesis. The thesis is divided into the following two parts: the first part mainly studies the oxidative ammoniation of benzyl C-H bond of azarene catalyzed by iodine. Substituted quinazolinone was synthesized by using 2-methylquinoline and o-aminobenzamide as reaction templates. After a series of optimization and screening, it was found that the yield of quinazolinone was higher under oxygen atmosphere with the catalyst DMSO as the solvent. In this reaction, various heterocyclic substituted quinazolinones were synthesized efficiently by using non-preactivated alkyl azarene as substrate and oxygen as the final oxidant in the absence of metal. The second part is mainly about the benzylation of azarene catalyzed by iodine. The benzylation of isoquinoline on aromatic ring was obtained by using isoquinoline and p-xylene as templates, which were optimized by a series of conditions. A better yield was obtained by using TBP as catalyst, and the substrate was more general, which provided a new method for benzylation of azarene.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.251

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