用有机锌试剂制备芳基硼酸及其联反应的研究

发布时间：2018-02-11 18:28

本文关键词： 有机锌试剂芳基硼酸 Suzuki偶联反应芳基硼酸酯　出处：《兰州交通大学》2016年硕士论文　论文类型：学位论文

【摘要】：芳基硼酸在空气中比较稳定,对湿气不太敏感,可以长期保存而且反应活性很高,使得各种取代的芳环硼酸成为重要的有机合成中间体以及医药、化工、农药中间体[1-2],是Suzuki交叉偶联反应的重要原料[3],可以形成C-O键、C-N键、C-S键也可以与含α,β不饱和键的羧基化合物进行共轭加成反应[4],以及合成染料,合成液晶显示材料中间体,生物传感器以及除草剂,在有机化学方面应用非常广泛。由于它具有毒性低和最终降解成为对环境友好的硼酸,所以取代芳基硼酸被认为是绿色化合物。由于有机锌试剂具备良好的官能团兼容性,很高的化学区域和立体选择性等,本课题以有机锌试剂作为亲核试剂,硼酸三甲酯作为亲电试剂,在室温无氧的条件下反应合成了各种官能团化的芳基硼酸,并且进行了表征。考察了反应温度,反应时间,物料配比等主要因素对合成反应产率的影响,并且对其最重要的应用Suzuki偶联反应进行了研究。本论文分为三部分:第一部分:总结了取代芳基硼酸的应用,芳基硼酸的三种合成方法:有机锂试剂法;格氏试剂法;钯催化氧硼基化法;以及有机锌试剂的应用和制备方法。第二部分:用有机锌试剂制备芳基硼酸。本文对有机锌试剂制备芳基硼酸的合成过程,合成路线进行了说明,以及反应条件进行了优化,并进行底物拓展,得到了一系列芳基硼酸,并通过1HNMR、13CNMR等对产物进行了表征,使得该方法的可行性得到了验证,而且此方法产率高,选择性好,条件温和,是一种合成芳基硼酸的新途径。第三部分:Suzuki偶联反应利用芳基硼酸酯不经水解直接“一锅法”和卤代烃发生Suzuki偶联反应,利用芳基硼酸酯避免了部分苯硼酸发生脱硼作用,还有部分脱水形成酸酐,来减少反应过程中硼酸的损失。而“一锅法”芳基硼酸酯不经提纯直接用于Suzuki反应,该反应操作简便,反应速度快,丰富了Suzuki反应的合成方法。
[Abstract]:Aryl boric acid is stable in air, is not very sensitive to moisture, can be preserved for a long time and has high reaction activity, making various substituted aromatic boric acids become important organic synthetic intermediates, as well as medicine and chemical industry. Pesticide intermediate [1-2], an important raw material for Suzuki cross-coupling reaction, can form C-O bond, C-N bond, C-S bond and conjugate addition reaction with carboxyl compounds containing 伪, 尾 unsaturated bonds [4], as well as synthetic dyes to synthesize intermediate of liquid crystal display materials. Biosensors and herbicides are widely used in organic chemistry because of their low toxicity and eventual degradation into environmentally friendly boric acid. Therefore, substituted aryl boric acid is considered as a green compound. Due to the good functional compatibility, high chemical region and stereoselectivity of organic zinc reagents, organic zinc reagents are used as nucleophilic reagents. Trimethyl borate was used as an electrophilic reagent to synthesize aryl boric acid with various functional groups at room temperature and without oxygen. The reaction temperature, reaction time and reaction time were investigated. The effect of material ratio on the yield of the synthetic reaction was studied, and the most important application of Suzuki coupling reaction was studied. This paper is divided into three parts: the first part: the application of substituted aryl boric acid is summarized. Keywords three synthetic methods of aryl boric acid: organic lithium reagent method; Grignard reagent method; palladium catalyzed boronylation method; And the application and preparation methods of organic zinc reagent. Part two: preparation of aryl boric acid from organic zinc reagent. In this paper, the synthesis process, synthesis route and reaction conditions of aryl boric acid prepared from organic zinc reagent are described, and the reaction conditions are optimized. A series of aryl boric acid was obtained by substrate expansion, and the product was characterized by 1HNMR-13CNMR. The feasibility of the method was verified, and the yield of the method was high, the selectivity was good, and the conditions were mild. It is a new way to synthesize aryl boric acid. Part 3: Suzuki coupling reaction takes place Suzuki coupling reaction between aryl borate ester and halogenated hydrocarbon without hydrolysis, and aryl borate ester avoids partial boric acid deboration. Some of them were dehydrated to form anhydride to reduce the loss of boric acid in the reaction process, while "one-pot" aryl borate was directly used in Suzuki reaction without purification. The reaction was simple, rapid and enriched the synthetic method of Suzuki reaction.
【学位授予单位】：兰州交通大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.25

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