铜催化的氧化条件下肟酯和甘氨酸酯合成多取代吡啶类化合物

发布时间：2018-04-04 10:56

本文选题：2　切入点：4　出处：《兰州大学》2017年硕士论文

【摘要】：吡啶和喹喔啉是两类非常重要的含氮杂环化合物。本文详细介绍了近几十年来吡啶类化合物的应用及其合成方法的研究进展,铜催化合成多取代吡啶的新方法以及合成喹喔啉类化合物的新方法。主要由以下三部分组成:第一部分,主要是对吡啶类化合物的应用及其合成进展的综合概述。首先,吡啶类化合物因吡啶环结构的存在而具有的生物和医药活性,使其在生物化学、药物化学、农药化学、有机合成化学、功能材料、染料等诸多领域有着广泛的应用。其次,根据合成吡啶类化合物有无金属催化以及金属催化下的合成类型进行分类,并对其合成方法进行综述。我们发现,非金属催化合成吡啶的方法具有经济、环保、低毒等优点,因而有着很好的发展前景。然而,大部分吡啶合成方法需要金属催化剂的加入,我们主要对金属催化下环异构法、[4+2]环加成、[3+3]环加成、[3+2+1]环加成、[2+2+2]环加成、[2+2+1+1]环加成法等六大类的吡啶合成方法进行了综述。第二部分,2,4,6-三取代吡啶类化合物的合成。多取代吡啶是一种广泛存在于天然产物、医药、功能材料和农业化学等领域的结构骨架。该部分介绍了一种合成多取代吡啶类化合物的新方法,即铜催化氧化条件下,肟酯类化合物与N-苯甘氨酸酯类化合物发生[3+2+1]环加成反应,快速有效的合成2,4,6-三取代吡啶类化合物。该方法有着良好的官能团兼容性,同时产物上酯基的保留为进一步合成吡啶衍生物提供了可能。特别的,该方法为合成2,6-对称取代异烟酸酯这类多取代吡啶提供了一条新颖的合成路线。第三部分,喹喔啉类化合物的合成。该部分介绍了一种合成喹喔啉类化合物的新方法,即以碘化亚铜为催化剂,L-脯氨酸为配体,在碱性条件下,邻碘苯胺、叠氮钠和1-苯基-2-(苯基氨基)乙酮通过三组分一锅法成功合成了喹喔啉类化合物。在该方法中,叠氮钠作为氮源成功地为目标产物提供了一个氮原子,从而解决了传统方法中以邻苯二胺为底物时容易生成同分异构体这一难题。
[Abstract]:Pyridine and quinoxaline are two kinds of important nitrogenous heterocyclic compounds. This paper describes the research progress in recent years application of pyridine compounds and synthetic methods, a new method of copper catalyzed synthesis of substituted pyridine and a new method of synthesis of quinoxaline compounds. The main consists of three parts: the first part mainly. Is a comprehensive overview of application of pyridine compounds and their synthesis. Firstly, pyridine compounds due to the presence of pyridine ring structure with biological and medicinal activities, the biochemistry, pharmaceutical chemistry, pesticide chemistry, organic synthesis, functional materials, dyes and other fields are widely used. Secondly, according to the synthesis of pyridine compounds with metal catalysis and synthesis of type metal catalyzed to classify and summarize the synthesis method. We found that non metal catalyzed synthesis Pyridine method has the advantages of economy, environmental protection, low toxicity, and has a very good development prospects. However, adding most pyridine synthesis methods need metal catalyst, we focused on the metal catalyzed heterogeneous ring method, [4+2] cycloaddition, [3+3] cycloaddition, [3+2+1] cycloaddition, [2+2+2] cycloaddition, pyridine methods for the synthesis of six kinds of [2+2+1+1] ring plus method were reviewed. The second part, the synthesis of 2,4,6- three substituted pyridine compounds. Multi substituted pyridine is widely present in natural products, pharmaceuticals, agricultural chemical and functional materials such as the structure of the skeleton. This part introduces a new method of substituted pyridine many compounds, namely copper catalyzed oxidation conditions, oxime esters and N- phenylglycine ester compounds [3+2+1] cycloaddition reaction, synthesis of fast and effective 2,4,6- three substituted pyridine compounds. This method has a good Functional compatibility, while retaining the ester product provides the possibility for further synthesis of pyridine derivatives. In particular, the method for the synthesis of 2,6- substituted isonicotinic acid ester of this kind of symmetrical polysubstituted pyridine provides a novel synthetic route. The third part, the synthesis of quinoxaline compounds. This part introduces a new method the synthesis of quinoxaline compounds, namely cuprous iodide as catalyst, L- as ligand of proline, under alkaline conditions, o-iodine aniline, sodium azide and 1- phenyl -2- (phenylamino) ethanone synthesis of quinoxaline compounds through the three component one pot method. In this method, sodium azide as nitrogen the source of success for the target product provides a nitrogen atom, so as to solve the traditional method in the adjacent benzene two amine is easy to generate the problem of isomeric substrate.

【学位授予单位】：兰州大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626

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