硝基甲苯类化合物的氧化偶联反应研究
发布时间：2019-01-04 11:04
【摘要】：喹唑啉类化合物是一类重要的含氮杂环化合物,具有广泛的生物和药理活性,其骨架存在于多种生物活性分子和天然产物之中,是合成各种功能材料的重要中间体,受到人们越来越多的关注。本论文在前人研究基础上提供了一种硝基甲苯类化合物参与的C-N氧化偶联合成喹唑啉的方法,并在其研究过程中意外发现硝基甲苯类化合物的自身C-C氧化偶联反应。而氧化偶联反应作为构建碳碳及各类碳杂键强有力的化学工具,研究成果广泛应用于生物、医药、农药、仿生、材料、天然产物全合成等各个领域当中,极大地促进了有机化学的发展。因此,本论文的另一研究目的在于发展一种新型的氧化偶联策略以实现1,2-二芳基乙酮/醇和2-[2-(喹啉-2-基)乙烯基]-喹啉类化合物的合成。主要研究内容包括以下三个部分:1.硝基甲苯类参与的C-N氧化偶联反应合成喹唑啉类化合物。以2-硝基甲苯和苄胺为原料,经氧化缩合实现喹唑啉的合成,并对其反应条件进行优化,以及底物拓展研究,得到了一系列含有不同取代基的喹唑啉类化合物。该方法具有原料廉价易得、反应条件温和、操作简单等优点。2.硝基甲苯类化合物参与的C-C氧化偶联反应。在喹唑啉的合成研究中,发现硝基甲苯类化合物在碱和DMSO体系中可以发生自身氧化偶联反应,其化学选择性可以通过控制碱的种类调控。30°C下,在KOtBu/DMSO体系中获得唯一产物1,2-二芳基乙酮类化合物;在K2CO3/DMSO体系中进行反应时,仅产生1,2-二芳基乙醇类化合物。该方法避免了过渡金属催化剂的使用,为1,2-二芳基乙酮/醇类化合物的合成提供了一种新的途径。3.硝基甲苯类化合物C-C氧化偶联反应的衍生。受2-硝基甲苯在碱性条件下自身可以发生氧化偶联反应的启示,本论文尝试以与2-硝基甲苯电子效应及结构类似的2-甲基喹啉为底物来实现其自身氧化偶联反应。实验证明该理论是成立的,成功得到了2-甲基喹啉类化合物的自身氧化偶联产物2-[2-(喹啉-2-基)乙烯基]-喹啉类化合物。
[Abstract]:Quinazoline compounds are a kind of important nitrogen-containing heterocyclic compounds, which have a wide range of biological and pharmacological activities. Their skeletons exist in a variety of bioactive molecules and natural products, and they are important intermediates for the synthesis of various functional materials. Get more and more attention. In this paper, based on previous studies, a method of C-N oxidative coupling of nitrotoluene compounds to quinazoline was proposed, and the self-C-C oxidative coupling reaction of nitrotoluene compounds was discovered by accident. However, oxidative coupling reaction is a powerful chemical tool for the construction of carbon and all kinds of carbon heterogeneity bonds. The research results have been widely used in biology, medicine, pesticides, bionics, materials, natural products, etc. It greatly promoted the development of organic chemistry. Therefore, another aim of this thesis is to develop a novel oxidative coupling strategy for the synthesis of 1- [(quinoline-2-vinyl) vinyl] -quinoline compounds. The main research contents include the following three parts: 1. Quinazoline compounds were synthesized by C-N oxidative coupling reaction involving nitrotoluene. Quinazoline was synthesized by oxidative condensation of 2-nitrotoluene and benzylamine. The reaction conditions were optimized and the substrate was developed. A series of quinazoline compounds containing different substituents were obtained. The method has the advantages of cheap raw material, mild reaction conditions, simple operation and so on. 2. C-C oxidative coupling reaction of nitrotoluene compounds. In the study of the synthesis of quinazoline, it was found that nitrotoluene compounds can undergo autooxidative coupling reaction in alkali and DMSO system, and their chemical selectivity can be controlled by controlling the type of base at 30 掳C. In the KOtBu/DMSO system, the unique product, 1h2- diarylethanone, was obtained. When the reaction is carried out in the K2CO3/DMSO system, only 1o 2-diaryl alcohol compounds are produced. This method avoids the use of transition metal catalysts and provides a new way for the synthesis of 1 ~ (2) -diarylacetone / alcohols. Derivation of C-C oxidative Coupling reaction of Nitrotoluene compounds. Inspired by the oxidative coupling reaction of 2-nitrotoluene in alkaline condition, this paper attempts to realize the self-oxidative coupling reaction by using 2-nitrotoluene as substrate with electronic effect and similar structure of 2-methylquinoline. It is proved that this theory is true and the self-oxidative coupling product of 2-methylquinoline compounds 2- [2- (quinoline-2-yl) vinyl] -quinoline compounds has been successfully obtained.
【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25
，
本文编号：2400200
[Abstract]:Quinazoline compounds are a kind of important nitrogen-containing heterocyclic compounds, which have a wide range of biological and pharmacological activities. Their skeletons exist in a variety of bioactive molecules and natural products, and they are important intermediates for the synthesis of various functional materials. Get more and more attention. In this paper, based on previous studies, a method of C-N oxidative coupling of nitrotoluene compounds to quinazoline was proposed, and the self-C-C oxidative coupling reaction of nitrotoluene compounds was discovered by accident. However, oxidative coupling reaction is a powerful chemical tool for the construction of carbon and all kinds of carbon heterogeneity bonds. The research results have been widely used in biology, medicine, pesticides, bionics, materials, natural products, etc. It greatly promoted the development of organic chemistry. Therefore, another aim of this thesis is to develop a novel oxidative coupling strategy for the synthesis of 1- [(quinoline-2-vinyl) vinyl] -quinoline compounds. The main research contents include the following three parts: 1. Quinazoline compounds were synthesized by C-N oxidative coupling reaction involving nitrotoluene. Quinazoline was synthesized by oxidative condensation of 2-nitrotoluene and benzylamine. The reaction conditions were optimized and the substrate was developed. A series of quinazoline compounds containing different substituents were obtained. The method has the advantages of cheap raw material, mild reaction conditions, simple operation and so on. 2. C-C oxidative coupling reaction of nitrotoluene compounds. In the study of the synthesis of quinazoline, it was found that nitrotoluene compounds can undergo autooxidative coupling reaction in alkali and DMSO system, and their chemical selectivity can be controlled by controlling the type of base at 30 掳C. In the KOtBu/DMSO system, the unique product, 1h2- diarylethanone, was obtained. When the reaction is carried out in the K2CO3/DMSO system, only 1o 2-diaryl alcohol compounds are produced. This method avoids the use of transition metal catalysts and provides a new way for the synthesis of 1 ~ (2) -diarylacetone / alcohols. Derivation of C-C oxidative Coupling reaction of Nitrotoluene compounds. Inspired by the oxidative coupling reaction of 2-nitrotoluene in alkaline condition, this paper attempts to realize the self-oxidative coupling reaction by using 2-nitrotoluene as substrate with electronic effect and similar structure of 2-methylquinoline. It is proved that this theory is true and the self-oxidative coupling product of 2-methylquinoline compounds 2- [2- (quinoline-2-yl) vinyl] -quinoline compounds has been successfully obtained.
【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.25
，
本文编号：2400200
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