钴催化8-氨基喹啉C5位的苄基化反应研究

发布时间：2018-06-06 21:36

  本文选题：8-氨基喹啉 + 苄基化　； 参考：《郑州大学》2017年硕士论文

【摘要】：本文合成了多种8-氨基喹啉酰胺底物,首次实现了钴盐催8-氨基喹啉C5位的苄基化反应,该催化体系具有良好的官能团兼容性,为8-氨基喹啉C5位苄基类取代衍生物的合成提供了一种新的有效方法。主要研究结果如下:1.8-氨基喹啉酰胺的合成所有的氨基喹啉酰胺底物均由相应的酰氯与1.1倍量的8-氨基喹啉合成。其具体反应条件为:以二氯甲烷作为溶剂,三乙胺(Et_3N)为碱,反应12小时得到酰胺产物(图1),产率为52%-87%。2.钴催化的8-氨基喹啉C5位的苄基化反应首先,选取8-氨基喹啉酰胺(1a)和2,6-二叔丁基-4-甲基苯酚(2a)作为反应底物,对反应所需要的催化剂、碱、氧化剂、溶剂、温度等反应条件进行了筛选,得到反应的优化条件:以20 mol%四水合醋酸钴为催化剂,2.0倍量三氟乙酸银为氧化剂,溴代苯为溶剂,在120℃下反应12小时(图2)。在此基础上,对8-氨基喹啉酰胺底物和甲基苯酚类偶联试剂分别进行了拓展,共26例,无论苯甲酰胺类底物还是脂肪类酰胺底物,在该反应体系下均能顺利进行,以中等到良好的收率得到相应的目标产物,反应产率从50%到98%不等。
[Abstract]:In this paper, a variety of 8-aminoquinolinamide substrates were synthesized and cobalt salt catalyzed benzylation of 8-aminoquinoline C5 was first realized. The catalytic system has good functional compatibility. It provides a new and effective method for the synthesis of 8-aminoquinoline C 5-benzyl derivatives. The main results are as follows: 1. The synthesis of 1. 8-aminoquinolinamide. All the aminoquinolinamide substrates are synthesized from the corresponding acyl chloride and 1. 1 times of 8-aminoquinoline. The specific reaction conditions are as follows: using dichloromethane as solvent, triethylamine et _ 3N as base, the product of amide is obtained after 12 hours of reaction (fig. 1, yield: 52-87). Co-catalyzed benzylation of 8-aminoquinoline C5. First, 8-aminoquinolinamide (1 a) and 2o 6-di-tert-tert Ding Ji -4-methylphenol (2a) were used as substrates for the reaction. The catalyst, alkali, oxidant, solvent were used for the reaction. The optimum reaction conditions were obtained as follows: using 20 mol% cobalt acetate tetrahydrate as catalyst, silver trifluoroacetate 2.0 times as oxidant, bromobenzene as solvent, reaction at 120 鈩，

本文编号：1988190