芳香羧酸的交叉脱氢偶联反应及菲啶合成新方法研究

发布时间：2018-06-27 19:06

  本文选题：交叉脱氢偶联 + 铑催化　； 参考：《湘潭大学》2016年硕士论文

【摘要】：绿色化学的宗旨是尽量使用廉价易得的化合物作为原料;尽量缩短反应步骤;尽量减少副产物的产生,提高原子经济性;尽量使用温和的反应条件。因此发展新的合成方法和使用温和的反应条件显得越来越重要,这些反应可以提高资源效率,能源效率和化学选择性。本文以此为出发点,开展了以下两部分工作:1、首次利用铑催化剂实现了简单芳香羧酸的交叉脱氢偶联反应。该反应以羧基作为导向基团,直接由两个C-H键活化构建C-C键,反应底物不需要预先官能团化,缩短了反应步骤。该反应区域选择性好,偶联反应发生在羧基的邻位。另外,该反应以水作为反应介质,对空气不敏感,是一类环境友好和高效合成非对称的2,2'-联芳二羧酸化合物的方法。2、发展了一类非过渡金属催化的2-(2-氨基苯基)苯甲醇类化合物为原料制备菲啶的方法。该反应体系简单,通过分子内的氨基和醇缩合成环,以氢氧化钾作为碱,甲苯作为溶剂,在100℃空气氛围下反应24小时得到了较好的产率。
[Abstract]:The aim of green chemistry is to use cheap and easily available compounds as raw materials; to shorten the reaction steps; to minimize the production of by-products and to improve atomic economy; and to use mild reaction conditions as far as possible. Therefore, it is more and more important to develop new synthesis methods and to use mild reaction conditions, which can improve resource efficiency, energy efficiency and chemical selectivity. In this paper, the cross dehydrogenation coupling reaction of simple aromatic carboxylic acids with rhodium catalyst was carried out in the following two parts: 1. The C-C bond was directly activated by two C-H bonds with carboxyl group as the guiding group, and the reaction substrate did not need prefunctional group, which shortened the reaction step. The coupling reaction takes place in the ortho position of carboxyl group. In addition, the reaction takes water as the reaction medium and is not sensitive to air. It is an environmentally friendly and highly efficient method for the synthesis of asymmetric 2'2'2'- biarboxylic acid compounds. A method for the preparation of phenanthroline from a class of non-transition metal catalyzed 2- (2-aminophenyl) benzyl alcohol compounds has been developed. The reaction system is simple. The ring is synthesized by the condensation of amino and alcohol in the molecule, potassium hydroxide as base, toluene as solvent, and the reaction temperature is 100 鈩，

本文编号：2074974