钴催化8-氨基喹啉C5位的全氟烷基化反应
发布时间：2018-12-19 19:44
【摘要】：8-氨基喹啉是一种重要的结构片段,其C5位衍生物在医药和化学分析领域有着广泛的应用。本论文制备了多种8-氨基喹啉酰胺,并以这些酰胺为底物,在廉价金属钴的催化下,实现了8-氨基喹啉C5位的全氟烷基化反应。该反应对多种底物容忍性良好,能将8-氨基喹啉芳香酰胺和脂肪酰胺顺利转化为相应的全氟烷基化产物。根据相关文献报道和实验结果,对反应机理进行了推测。此反应简单高效,为合成8-氨基喹啉全氟烷基衍生物提供了一种新方法。主要研究内容如下:1.8-氨基喹啉酰胺的合成将含有多种取代基团的苯甲酸和脂肪酸制备为相应的酰氯,再与8-氨基喹啉进行缩合反应,进而得到一系列8-氨基喹啉苯甲酰胺和脂肪酰胺底物(图1)。所有8-氨基喹啉酰胺底物均通过此方法制备,产率52-87%。2.钴催化的8-氨基喹啉C5位的全氟烷基化反应以8-氨基喹啉苯甲酰胺为模板底物,2-碘全氟丙烷为全氟烷基来源,对模板反应进行了条件优化。确定的优化条件为:5 mol%的乙酰丙酮钴(Ⅲ),1.0倍量的氧化银,2.0倍量的醋酸,二氯甲烷为溶剂,120 oC,空气氛围下反应4小时。在优化条件下,对底物范围进行了扩展,以中等到良好的产率将全氟烷基引入到了一系列的8-氨基喹啉酰胺底物当中(图2),共计28例,产率47-84%。
[Abstract]:8-aminoquinoline is an important structural fragment, and its C _ 5 derivatives have been widely used in medicine and chemical analysis. In this paper, a variety of 8-aminoquinolinamide was prepared, and the perfluoroalkylation of 8-aminoquinoline C5 was realized by using these amides as substrates under the catalysis of cheap cobalt. The reaction has good tolerance to various substrates and can transform 8-aminoquinoline aromatic amide and aliphatic amide into corresponding perfluoroalkylation products. According to the related literature reports and experimental results, the reaction mechanism was speculated. This reaction is simple and efficient and provides a new method for the synthesis of 8-aminoquinoline perfluoroalkyl derivatives. The main research contents are as follows: 1.8-aminoquinolinamide was synthesized from benzoic acid and fatty acid containing many substituted groups into corresponding acyl chloride, and then condensed with 8-aminoquinoline. A series of 8-aminoquinoline benzoamide and aliphatic amide substrates were obtained (Fig. 1). All 8-aminoquinolinamide substrates were prepared by this method in 52-87.2. Co-catalyzed perfluoroalkylation of 8-aminoquinoline C5 was carried out using 8-aminoquinoline benzamide as template substrate and 2-iodoperfluoropropane as the source of perfluoroalkyl. The conditions of template reaction were optimized. The optimum conditions were determined as follows: cobalt acetylacetone (鈪，
本文编号：2387365
[Abstract]:8-aminoquinoline is an important structural fragment, and its C _ 5 derivatives have been widely used in medicine and chemical analysis. In this paper, a variety of 8-aminoquinolinamide was prepared, and the perfluoroalkylation of 8-aminoquinoline C5 was realized by using these amides as substrates under the catalysis of cheap cobalt. The reaction has good tolerance to various substrates and can transform 8-aminoquinoline aromatic amide and aliphatic amide into corresponding perfluoroalkylation products. According to the related literature reports and experimental results, the reaction mechanism was speculated. This reaction is simple and efficient and provides a new method for the synthesis of 8-aminoquinoline perfluoroalkyl derivatives. The main research contents are as follows: 1.8-aminoquinolinamide was synthesized from benzoic acid and fatty acid containing many substituted groups into corresponding acyl chloride, and then condensed with 8-aminoquinoline. A series of 8-aminoquinoline benzoamide and aliphatic amide substrates were obtained (Fig. 1). All 8-aminoquinolinamide substrates were prepared by this method in 52-87.2. Co-catalyzed perfluoroalkylation of 8-aminoquinoline C5 was carried out using 8-aminoquinoline benzamide as template substrate and 2-iodoperfluoropropane as the source of perfluoroalkyl. The conditions of template reaction were optimized. The optimum conditions were determined as follows: cobalt acetylacetone (鈪，
本文编号：2387365
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