铑催化芳香羧酸邻位苯基化及GO催化芳烃碘代反应研究

发布时间：2018-04-26 19:00

本文选题：羧基导向 + 苯基化　；参考：《湘潭大学》2017年硕士论文

【摘要】：联苯结构是有机化合物的碳骨架之一,广泛存在于农药、医药以及多功能材料中。与传统合成联苯结构的方法相比,经C-H键活化直接构建Ar-Ar键的方法,具有反应步骤少、成本低、原子利用率高等优点。近年来,多种导向基团存在下芳烃的芳基化反应相继被报道,反应通常需要使用昂贵的芳基化试剂、存在苛刻的反应条件。碘代芳烃是一类重要的有机合成中间体,可与多种化合物发生反应,广泛存在于生物活性分子中。传统碘代芳烃的合成方法一般需多ki反应,强酸或金属催化,反应条件苛刻。因此发展一种高效、简便的合成方法具有重要的研究意义。具体研究工作分为以下两部分:1.发展了一种铑催化的羧基导向的芳烃邻位苯基化反应。该方法以芳香羧酸为底物,四苯基硼酸钠为廉价的苯基化试剂,氟化钾为添加剂,在催化量铜盐存在下,以空气为终端氧化剂。该反应无银盐参与,一步反应,原料廉价易得,反应规模可扩大到克级,含多种官能团的芳香羧酸均能以较高产率转化为目标化合物。2.发展了一种氧化石墨烯催化的芳烃直接碘代的方法。该方法以氧化石墨烯为催化剂,单质碘为碘源,一步反应合成碘代烃。该反应具有以下优点:非金属催化,对空气和水不敏感,中性介质反应,操作简单,催化效率高,反应可扩大到克级规模。另外,该反应底物适用范围较广,含多种官能团的芳烃、苯并噻吩均具有很高的反应活性。羰基的α-氢也可以顺利地发生碘化反应。通过调控反应时间和碘的用量,可选择性的得到单碘代或双碘代产物。
[Abstract]:Biphenyl structure is one of the carbon skeletons of organic compounds. It is widely used in pesticide, medicine and multifunctional materials. Compared with the traditional method of synthesis of biphenyl structure, the C-H bond activation method has the advantages of less reaction steps, lower cost and higher atom utilization rate. In recent years, arylation reactions of aromatics in the presence of a variety of guided groups have been reported one after another. The reactions usually require expensive aromatization reagents, and there are harsh reaction conditions. Iodinated aromatics are an important intermediate in organic synthesis, which can react with many compounds and widely exist in bioactive molecules. The traditional method of synthesis of iodide aromatics usually requires multi-Ki reaction, strong acid or metal catalysis, and the reaction conditions are harsh. Therefore, it is of great significance to develop an efficient and simple synthetic method. The specific research work is divided into the following two parts: 1. A rhodium-catalyzed carboxyl-oriented o-phenylation of aromatics was developed. In this method, aromatic carboxylic acid as substrate, sodium tetraphenylborate as cheap phenylation reagent, potassium fluoride as additive, air as terminal oxidant in the presence of catalytic amount of copper salt. This reaction is without silver salt, one step reaction, the raw material is cheap and easy to get, the scale of the reaction can be expanded to gram level, the aromatic carboxylic acid containing many functional groups can be converted into target compound. 2. A method of direct iodization of aromatics catalyzed by graphene oxide was developed. Using graphene oxide as catalyst and iodine as iodine source, iodinated hydrocarbons were synthesized by one step reaction. The reaction has the following advantages: nonmetallic catalysis, insensitive to air and water, neutral medium reaction, simple operation, high catalytic efficiency, and the reaction can be extended to g scale. In addition, the reaction substrate is suitable for a wide range of aromatics containing a variety of functional groups, benzothiophene has a high reaction activity. The 伪-hydrogen of carbonyl group can also be iodized smoothly. By adjusting the reaction time and the amount of iodine, the monoiodide or diiodide can be obtained selectively.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251

【相似文献】