【摘要】：8-氨基喹啉是一種重要的結(jié)構(gòu)片段,其C5位衍生物在醫(yī)藥和化學(xué)分析領(lǐng)域有著廣泛的應(yīng)用。本論文制備了多種8-氨基喹啉酰胺,并以這些酰胺為底物,在廉價金屬鈷的催化下,實(shí)現(xiàn)了8-氨基喹啉C5位的全氟烷基化反應(yīng)。該反應(yīng)對多種底物容忍性良好,能將8-氨基喹啉芳香酰胺和脂肪酰胺順利轉(zhuǎn)化為相應(yīng)的全氟烷基化產(chǎn)物。根據(jù)相關(guān)文獻(xiàn)報道和實(shí)驗(yàn)結(jié)果,對反應(yīng)機(jī)理進(jìn)行了推測。此反應(yīng)簡單高效,為合成8-氨基喹啉全氟烷基衍生物提供了一種新方法。主要研究內(nèi)容如下:1.8-氨基喹啉酰胺的合成將含有多種取代基團(tuán)的苯甲酸和脂肪酸制備為相應(yīng)的酰氯,再與8-氨基喹啉進(jìn)行縮合反應(yīng),進(jìn)而得到一系列8-氨基喹啉苯甲酰胺和脂肪酰胺底物(圖1)。所有8-氨基喹啉酰胺底物均通過此方法制備,產(chǎn)率52-87%。2.鈷催化的8-氨基喹啉C5位的全氟烷基化反應(yīng)以8-氨基喹啉苯甲酰胺為模板底物,2-碘全氟丙烷為全氟烷基來源,對模板反應(yīng)進(jìn)行了條件優(yōu)化。確定的優(yōu)化條件為:5 mol%的乙酰丙酮鈷(Ⅲ),1.0倍量的氧化銀,2.0倍量的醋酸,二氯甲烷為溶劑,120 oC,空氣氛圍下反應(yīng)4小時。在優(yōu)化條件下,對底物范圍進(jìn)行了擴(kuò)展,以中等到良好的產(chǎn)率將全氟烷基引入到了一系列的8-氨基喹啉酰胺底物當(dāng)中(圖2),共計28例,產(chǎn)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，

本文編號：2387365