环己酮参与的C-N键生成反应研究

发布时间：2018-06-04 06:28

本文选题：含氮化合物 + C-N键　；参考：《湘潭大学》2017年博士论文

【摘要】：含氮化合物广泛存在于天然产物、医药、农药以及功能材料等领域,因此,C-N键的选择性构建一直是有机合成化学研究的重点和热点。环己酮作为一种廉价易得的大宗化工原料,在合成化学中也被广泛应用。近年来的研究结果表明,环己酮可以“脱氢”作为潜在的芳基来源用于进一步转化反应。随着环境友好绿色化学的概念逐步推广,发展简单、高效、绿色以及条件温和的有机合成方法已经成为当今有机合成化学的研究重点。本论文围绕“环己酮参与的选择性C-N键生成反应”这一核心主题,以环己酮为主要原料,开展了一系列构建C-N键的研究工作,主要内容如下:1、发展了一种钯催化芳香硝基化合物和环己酮“一锅”合成二芳胺的新方法。该反应首次利用芳香硝基化合物和环己酮衍生物为原料在钯催化下采用“借氢战略”合成二芳基胺。利用该方法我们高选择性、高产率地合成了一系列的二芳胺。硝基被环己酮脱下来的氢直接还原并用于进一步转化反应,在无需添加额外还原剂和氧化剂的条件下实现了硝基的还原、环己酮脱氢、亚胺的形成及还原,为二芳胺的合成提供了一条高效的新途径。2、发展了一种无过渡金属条件下脒和酮“一锅”高效合成4,5-二氢-1H-咪唑-5-酮衍生物的新方法。各种带取代基的脒与酮都能发生反应并以较好的产率得到相应的产物。当使用环状酮作为反应底物时,能高选择性、高产率的得到的含螺环的4,5-二氢-1H-咪唑-5-酮衍生物,反应中发生了基团的迁移重排。该方法条件简单,不需要使用过渡金属催化剂,为合成咪唑啉酮类化合物特别是含有螺环的4,5-二氢-1H-咪唑-5-酮衍生物提供了一条有效途径。3、发展了一种无金属条件下2-氨基吡啶类化合物和环己酮衍生物高效合成苯并[4,5]咪唑并[1,2-a]吡啶衍生物的新方法。非芳香性的环己酮类化合物在绿色的氧化剂氧气的作用下实现脱氢芳构化作为芳基来源。该方法为具有生物活性的含氮杂环化合物苯并[4,5]咪唑并[1,2-a]吡啶类化合物的合成提供了一条高效的途径。4、发展了一种无金属条件下以环状酮和2-氨基苯并噻唑为原料“一锅”合成咪唑并[2,1-b]苯并噻唑衍生物的新方法。单质硫在无金属参与的条件下能有效的促进反应的进行。环己酮衍生物以及一些大环环状酮在该反应体系下能顺利的与2-氨基苯并噻唑发生反应构建两个新的C-N键得到相应的产物。
[Abstract]:Nitrogen-containing compounds are widely used in natural products, medicine, pesticides and functional materials, so the selective construction of C-N bonds has been the focus and hotspot of organic synthesis chemistry. Cyclohexanone, as a cheap and easily available chemical raw material, is also widely used in synthetic chemistry. Recent studies have shown that cyclohexanone can be used as a potential aryl source for further conversion. With the gradual promotion of the concept of environmentally friendly green chemistry, the development of simple, efficient, green and mild organic synthesis methods has become the focus of organic synthesis chemistry. In this paper, a series of studies on the construction of C-N bond were carried out with cyclohexanone as the main raw material, focusing on the core theme of "selective C-N bond formation reaction involving cyclohexanone". The main contents are as follows: 1. A new palladium catalyzed "one pot" synthesis method of aromatic nitro compounds and cyclohexanone was developed. In this reaction, aromatic nitro compounds and cyclohexanone derivatives were used as raw materials to synthesize diaryl amines under the catalysis of palladium for the first time. A series of diarylamines were synthesized with high selectivity and high yield by this method. Nitro was directly reduced by hydrogen removed from cyclohexanone and used for further conversion reaction. The reduction of nitro, the dehydrogenation of cyclohexanone, the formation and reduction of imine were realized without adding additional reductant and oxidant. This paper provides a new efficient way for the synthesis of diarylamine, and develops a new method for the synthesis of 4o 5-dihydro-1H-imidazole-5-one derivatives under the condition of transition metal free from amidine and ketone "one pot". All kinds of substituted amidines can react with ketones and obtain the corresponding products in a better yield. When cycloketone was used as the substrate of the reaction, the group migration rearrangement occurred in the reaction, which was characterized by high selectivity and high yield of 4H _ 5H _ 1H _ (imidazole-5-one) derivatives containing snails. The method is simple and does not require the use of transition metal catalysts. This paper provides an effective way for the synthesis of Imidazolinone compounds, especially 4H- dihydro-1H-imidazole-5-one derivatives containing snails, and develops a highly efficient combination of 2-aminopyridine compounds and cyclohexanone derivatives under metal-free conditions. A New method for the formation of Benzo [4H _ 5] imidazo [1o _ 2-a] pyridine Derivatives. Non-aromatic cyclohexanone compounds were dehydroaromorphic to aryl source under the action of green oxidant oxygen. This method provides a high efficient way for the synthesis of benzo [4o 5] imidazo [1o 2-a] pyridine compounds with biological activity, and develops a metal-free method based on cyclic ketone and 2-aminobenzothiazole. A new method for the synthesis of imidazo [2o 1 b] benzothiazole derivatives from one pot. Elemental sulfur can effectively facilitate the reaction without metal participation. Cyclohexanone derivatives and some macrocyclic ketones can successfully react with 2-aminobenzothiazole to form two new C-N bonds.
【学位授予单位】：湘潭大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O621.25

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