钯催化N-取代苯胺邻位C-H键选择性活化羰基化合成邻氨基苯甲酰胺

发布时间：2018-06-02 00:26

本文选题：C(sp~2)-H键活化 + 钯催化反应　；参考：《河南师范大学》2017年硕士论文

【摘要】：邻氨基苯甲酰胺类化合物具有重要的生物及药理活性,在医药、农药、有机合成等领域有着广泛的应用。但目前其主要合成方法仍存在许多问题:原子经济性差;环境污染严重;对设备腐蚀性强;成本高;反应步骤冗长等。本文以廉价易得的N-取代苯胺、CO及胺为起始原料,经钯催化的N-取代苯胺邻位C-H键选择性活化羰基化反应来直接合成邻氨基苯甲酰胺类化合物,从而为该类化合物的合成开辟出一条原子经济性高、环境友好、条件温和、成本低、合成路线简短、简单便捷的新途径。本文共分四章,具体内容如下:第一章,文献综述。本章总结了邻氨基苯甲酰胺类化合物在医药、农药、有机合成等领域的重要应用、邻氨基苯甲酰胺类化合物的主要合成方法、以及钯催化C(sp~2)-H键活化羰基化的研究进展。在此基础上,提出了本文的选题构想。第二章,钯催化N-取代苯胺邻位C-H键活化羰基化合成邻氨基苯甲酰胺。本章中,以醋酸钯为催化剂,以N-取代苯胺、CO及胺为起始原料,经钯催化的N-取代苯胺邻位C-H键活化羰基化反应直接合成邻氨基苯甲酰胺,并对反应时间、反应温度、氧化剂种类及用量、添加剂种类及用量、溶剂种类等因素对反应的影响进行了探索和优化。最后,在最优的条件下合成了一系列邻氨基苯甲酰胺类化合物,产率从中等至良好。第三章,钯催化N-取代苯胺邻位C-H键活化羰基化合成邻氨基苯甲酰胺的机理探讨。通过文献调研及相关控制实验,初步探讨了碘化钾、醋酸、醋酸钯、醋酸铜和氧气在改反应体系中的作用,在此基础上提出了该反应的机理。第四章,硒催化5-氨基-1,2,3-噻二唑与胺氧化羰基化合成不对称1,2,3-噻二唑脲。在完成上述研究内容后,本章又进行了硒催化5-氨基-1,2,3-噻二唑与胺羰基化合成不对称1,2,3-噻二唑脲的研究探索。通过条件优化探索,获得了实施该反应的适宜条件。在此基础上合成了一系列不对称1,2,3-噻二唑脲类化合物,目标物产率从中等至良好。
[Abstract]:O-aminobenzoides have important biological and pharmacological activities and are widely used in medicine, pesticide, organic synthesis and so on. However, there are still many problems in the main synthesis methods, such as poor atomic economy, serious environmental pollution, strong corrosion to equipment, high cost, long reaction steps and so on. In this paper, o-aminobenzoamide compounds were directly synthesized by palladium catalyzed selective activation carbonylation of N-substituted aniline with N-substituted aniline CO and amine. Thus, a new way for the synthesis of this kind of compounds with high atomic economy, environmental friendliness, mild conditions, low cost, short synthesis route and simple and convenient synthesis is opened up. This paper is divided into four chapters, the specific contents are as follows: the first chapter, literature review. In this chapter, the important applications of o-aminobenzamide in medicine, pesticide and organic synthesis, the main synthesis methods of o-aminobenzamide, and the research progress of palladium catalyzed carbonylation of C(sp~2)-H bond are summarized. On this basis, this paper puts forward the idea of topic selection. In chapter 2, palladium catalyzed the activation of N-substituted aniline C-H bond to produce o-aminobenzoamide. In this chapter, using palladium acetate as catalyst, N-substituted aniline CO and amine as starting materials, o-aminobenzoamide was directly synthesized by palladium catalyzed carbonylation of N-substituted aniline with C-H bond. The effects of oxidant type and dosage, additive type and amount, solvent type on the reaction were explored and optimized. Finally, a series of o-aminobenzoamide compounds were synthesized under the optimum conditions. The yield of o-aminobenzoamide compounds ranged from medium to good. In chapter 3, the mechanism of synthesis of o-aminobenzoamide by activation carbonylation of N-substituted aniline by C-H bond catalyzed by palladium is discussed. The effects of potassium iodide, palladium acetate, copper acetate and oxygen on the modification of the reaction system were preliminarily discussed by literature investigation and related control experiments, and the mechanism of the reaction was put forward. In chapter 4, 5-amino-1-thiadiazole-3-thiadiazole and amine were synthesized by the oxidation carbonylation of 5-amino-2-thiadiazole-3-thiadiazoluron with selenium. After completing the above research, the synthesis of asymmetric 1H _ 2N _ 3-thiadiazolarbazuron catalyzed by seleno-catalyzed carbonylation of 5-amino-2-thio-3-thiadiazole with amine was studied in this chapter. The optimum conditions for the reaction were obtained by optimizing the conditions. On this basis, a series of asymmetric 1'2'2'3 'thiadiazole ureas were synthesized, and the target yield ranged from medium to good.
【学位授予单位】：河南师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O625.632

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