含氮五元杂环化合物5-氨基吡唑与吡咯类衍生物的合成方法研究

发布时间：2018-04-22 11:03

  本文选题：杂环化合物 + 5-氨基吡唑　； 参考：《兰州大学》2016年博士论文

【摘要】：杂环化学是近现代有机化学的重要组成部分,也是有机化学领域近年来研究最为活跃的领域之一。杂环化合物存在于大量的天然产物和具有生物活性的化合物中,其总数已超过已知有机化合物的三分之一,而含氮杂环化合物是杂环化合物中数量最多的一类。吡唑和吡咯衍生物是两类重要的含氮杂环化合物,他们存在于许多有生物活性的化合物和人工合成的功能材料中。因此,很多化学合成工作者们的兴趣也一直聚焦在对含氮杂环结构的化合物的构建和功能改造上。当今社会需要的化学合成方法不仅仅是传统地对化学、区域和立体选择性做出要求,而且对新方法也有一些要求,总结如下:1.使用简单且容易制备的原料;2.实验操作简单可行;3.有利的经济因素:包括原材料、人力资源和能源的成本;4.对环境的影响小:包括减少溶剂的使用,催化剂的可重复利用以及原子经济等。利用简单易得的原料制备有机化合物是当今有机合成工作者们面临的巨大挑战之一,以及在一个单一的操作中创建多个新化学键的形成,也已经成为一个更具吸引力的目标。另外,探索更为环境友好的合成方法也是化学工作者们的重要任务。本论文主要致力于用简单易得的原料合成含氮杂环化合物的方法研究。我们用高效、绿色的方法合成了5-氨基吡唑衍生物和吡咯衍生物,具体包含如下两个章节:第一章:我们对5-氨基吡唑类化合物在医药、农业和合成中的应用以及对近年来报道的合成5-氨基吡唑衍生物的方法进行了文献综述。在此基础上,我们以乙腈和腙的衍生物为底物,发展了一种用醋酸钯和乙酰丙酮铜联合催化通过C-C键和C-N键的形成高效合成5-氨基吡唑衍生物的新方法,该方法具有反应物简单易得,操作简便和反应条件温和等优点。利用该反应体系,各种取代的乙腈和腙都能顺利参与反应并且给出良好的产品收率。相比于脂肪族和芳香杂环取代的底物,芳香基取代的底物表现出了更好的反应活性。产物5-氨基吡唑的氨基还可以作为反应官能团与其他分子进行衍生化反应,比如氨基磺酰化,氨基羰基化和重氮化反应。第二章:我们对吡咯衍生物在医药、农药、高分子材料等领域的应用及吡咯类化合物的合成方法研究做了介绍,同时对微波和蒙脱土K10在有机合成中的应用也进行了文献综述。在此基础上,我们研究了一种用α-氨基酮衍生物和苯乙醛衍生物通过C-C键和C-N键的形成高效合成多取代吡咯化合物的新方法,此方法通过微波辐射、蒙脱土K10催化来实现。该方法对带有各种取代基的底物适用性良好,并且可以得到中等至良好的收率,最高产率可达98%。与常规加热反应方式相比,该方法具有无污染、反应速率快、产品产率高且产物易于分离的特点,是一种环境友好并可能有广泛应用前景的合成方法。
[Abstract]:Heterocyclic chemistry is an important part of modern organic chemistry and one of the most active fields in the field of organic chemistry in recent years. Heterocyclic compounds are found in a large number of natural products and biologically active compounds. The total number of heterocyclic compounds is more than 1/3 of known organic compounds, while the heterocyclic compounds containing nitrogen are the most numerous heterocyclic compounds. Pyrazole and pyrrole derivatives are two important nitrogen-containing heterocyclic compounds. They exist in many bioactive compounds and synthetic functional materials. Therefore, the interest of many chemical synthesizers has been focused on the construction and functional transformation of nitrogen-containing heterocyclic compounds. The chemical synthesis methods that are needed in today's society are not only traditionally required for chemical, regional and stereoselectivity, but also for new methods, as summarized below: 1: 1. Use simple and easily prepared raw materials. The experiment is simple and feasible. Favorable economic factors: including raw materials, human resources and energy costs. Small environmental impact: reducing the use of solvents, catalyst reuse and atomic economy. The preparation of organic compounds from simple and easily available raw materials is one of the great challenges faced by organic synthesis workers today, and the formation of multiple new chemical bonds in a single operation has become a more attractive goal. In addition, exploring more environmentally friendly synthetic methods is also an important task for chemists. This paper is devoted to the synthesis of heterocyclic compounds containing nitrogen from simple and easily available raw materials. We have synthesized 5-aminopyrazole derivatives and pyrrole derivatives in a highly efficient and green way, including the following two chapters: chapter 1: we have a response to 5-aminopyrazole derivatives in medicine, The applications of agriculture and synthesis and the methods of synthesis of 5-aminopyrazole derivatives reported in recent years were reviewed. On this basis, we developed a novel method for the efficient synthesis of 5-aminopyrazole derivatives by the formation of C-C bond and C-N bond using palladium acetate and copper acetylacetone as the substrates of acetonitrile and Hydrazone derivatives. The method has the advantages of simple and easy to obtain reactants, simple operation and mild reaction conditions. With this reaction system, all substituted acetonitrile and Hydrazone can participate in the reaction smoothly and give a good yield. Compared with aliphatic and aromatic heterocyclic substrates, aromatic substrates exhibit better reactivity. The amino of 5-aminopyrazole can also be used as a functional group for the derivation of other molecules, such as amino sulfonylation, amino carbonylation and diazotization. Chapter 2: we introduce the applications of pyrrole derivatives in medicine, pesticides, polymer materials and the synthesis of pyrrole compounds. At the same time, we review the application of microwave and montmorillonite K10 in organic synthesis. On this basis, we have studied a new method of synthesis of polysubstituted pyrrole compounds by the formation of C-C bond and C-N bond by 伪 -aminoketone derivative and phenylacetaldehyde derivative. This method is realized by microwave irradiation and montmorillonite K10 catalysis. The method is suitable for substrates with various substituents and can obtain moderate to good yield with the highest yield of 98%. Compared with the conventional heating reaction method, this method has the advantages of no pollution, fast reaction rate, high product yield and easy separation. It is an environmentally friendly synthesis method with potential application prospects.
【学位授予单位】：兰州大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：O626
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本文编号：1786906