绿色导向的咪唑并杂环的官能团化与吡咯环的构建研究
发布时间：2019-01-12 14:56
【摘要】：咪唑并杂环和吡咯是重要的药物优势骨架,广泛存在于天然产物及药物分子之中,大部分具有独特的生物活性,在生物医药、功能材料等领域有着广泛的应用。因此,探索和研究咪唑并杂环和吡咯的合成以及基于其骨架的修饰一直是有机化学研究的热点。面对日益突出的环境问题,发展咪唑并杂环和吡咯的绿色合成方法显得尤为重要。本论文基于绿色化学发展的理念,重点研究了咪唑并杂环碳氢官能团化与构建吡咯环的新方法。本论文分为五部分:(1)归纳总结了近年来吡咯并喹啉的合成方法;对咪唑并杂环碳氢官能化的反应类型进行了归纳,分别对咪唑并杂环的芳基化、烯基化、羰基化、硫化等反应进行了评述。(2)探究了六氟磷酸铵促进的α-氨基酮的碳氢环化,有效合成吡咯并喹啉和吲哚衍生物的反应。该反应无金属参与、唯一的副产物是水、后处理简单、溶剂易于回收循环使用,有利于环境保护。(3)探究了咪唑并杂环与硫醚的选择性碳氢键硫化反应。该反应以碘为催化剂,过氧化氢为氧化剂,乙醇为溶剂,室温下反应。通过这一绿色的策略能够在温和条件下合成多样性的硫代咪唑并杂环。(4)探究了咪唑并杂环与Langlois试剂的选择性碳氢键三氟甲基化反应。该反应是在绿色溶剂离子液体和水的混合溶液中进行的。反应官能团兼容性好,利用这一绿色的策略可以合成多种三氟甲基化的咪唑杂环,也可以合成多种三氟甲基化的苯基取代的咪唑。(5)探究了咪唑并杂环与2-氨基苯并噻唑的选择性碳氢键杂芳基化反应。该反应无需过渡金属参与,在亚硝酸叔丁基酯作用下,首次实现了咪唑并杂环与2-氨基苯并噻唑的氧化脱氨交叉偶联反应,通过这种简单、实用的方法合成了多种高度共轭的杂环化合物,副产物是水和氮气。
[Abstract]:Imidazolium heterocyclic and pyrrole are important drug dominant skeletons, which widely exist in natural products and drug molecules. Most of them have unique biological activities and are widely used in biomedicine, functional materials and other fields. Therefore, exploring and studying the synthesis of imidazolium heterocyclic and pyrrole and modification based on its skeleton has been a hot spot in organic chemistry. In the face of increasingly prominent environmental problems, it is particularly important to develop green synthesis methods of imidazole heterocyclic and pyrrole. Based on the concept of green chemistry, this paper focuses on the study of imidazolium heterocyclic hydrocarbon functionalization and the construction of pyrrole ring. This paper is divided into five parts: (1) summarized the synthesis methods of pyrrolidone quinoline in recent years; The reaction types of imidazolium heterocyclic hydrocarbon functionalization were summarized, and the arylation, alkylation, carbonylation of imidazolium heterocyclic were summarized, respectively. (2) the hydrocarbon cyclization of 伪 -aminophenone promoted by ammonium hexafluorophosphate was investigated, and the reaction of pyrroroquinoline and indole derivatives was effectively synthesized. There is no metal participation in the reaction, the only by-product is water, the reprocessing is simple, the solvent is easy to recycle, which is beneficial to environmental protection. (3) the selective hydrocarbon bond vulcanization reaction between imidazolium heterocyclic and sulfides was studied. The reaction was carried out with iodine as catalyst, hydrogen peroxide as oxidant and ethanol as solvent at room temperature. Through this green strategy, various thioimidazole heterocycles can be synthesized under mild conditions. (4) the selective hydrocarbon bond trifluoromethylation of imidazolidazole heterocycles with Langlois reagent was investigated. The reaction was carried out in a mixture of green solvent ionic liquids and water. This green strategy can be used to synthesize various trifluoromethylated imidazole heterocycles. A variety of trifluoromethylphenyl substituted imidazoles can also be synthesized. (5) the selective hydrocarbon bond arylation of imidazolyl heterocycles with 2-aminobenzothiazole was investigated. In the presence of tert-Ding Ji nitrite, the oxidative deamination of 2-aminobenzothiazole with imidazolium heterocyclic was first realized without transition metal participation. A variety of highly conjugated heterocyclic compounds have been synthesized by the practical method. The by-products are water and nitrogen.
【学位授予单位】：温州大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O626
本文编号：2407906
[Abstract]:Imidazolium heterocyclic and pyrrole are important drug dominant skeletons, which widely exist in natural products and drug molecules. Most of them have unique biological activities and are widely used in biomedicine, functional materials and other fields. Therefore, exploring and studying the synthesis of imidazolium heterocyclic and pyrrole and modification based on its skeleton has been a hot spot in organic chemistry. In the face of increasingly prominent environmental problems, it is particularly important to develop green synthesis methods of imidazole heterocyclic and pyrrole. Based on the concept of green chemistry, this paper focuses on the study of imidazolium heterocyclic hydrocarbon functionalization and the construction of pyrrole ring. This paper is divided into five parts: (1) summarized the synthesis methods of pyrrolidone quinoline in recent years; The reaction types of imidazolium heterocyclic hydrocarbon functionalization were summarized, and the arylation, alkylation, carbonylation of imidazolium heterocyclic were summarized, respectively. (2) the hydrocarbon cyclization of 伪 -aminophenone promoted by ammonium hexafluorophosphate was investigated, and the reaction of pyrroroquinoline and indole derivatives was effectively synthesized. There is no metal participation in the reaction, the only by-product is water, the reprocessing is simple, the solvent is easy to recycle, which is beneficial to environmental protection. (3) the selective hydrocarbon bond vulcanization reaction between imidazolium heterocyclic and sulfides was studied. The reaction was carried out with iodine as catalyst, hydrogen peroxide as oxidant and ethanol as solvent at room temperature. Through this green strategy, various thioimidazole heterocycles can be synthesized under mild conditions. (4) the selective hydrocarbon bond trifluoromethylation of imidazolidazole heterocycles with Langlois reagent was investigated. The reaction was carried out in a mixture of green solvent ionic liquids and water. This green strategy can be used to synthesize various trifluoromethylated imidazole heterocycles. A variety of trifluoromethylphenyl substituted imidazoles can also be synthesized. (5) the selective hydrocarbon bond arylation of imidazolyl heterocycles with 2-aminobenzothiazole was investigated. In the presence of tert-Ding Ji nitrite, the oxidative deamination of 2-aminobenzothiazole with imidazolium heterocyclic was first realized without transition metal participation. A variety of highly conjugated heterocyclic compounds have been synthesized by the practical method. The by-products are water and nitrogen.
【学位授予单位】：温州大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O626
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