本文選題：8-氨基喹啉 + 芐基化��； 參考：《鄭州大學》2017年碩士論文

【摘要】：本文合成了多種8-氨基喹啉酰胺底物,首次實現(xiàn)了鈷鹽催8-氨基喹啉C5位的芐基化反應,該催化體系具有良好的官能團兼容性,為8-氨基喹啉C5位芐基類取代衍生物的合成提供了一種新的有效方法。主要研究結果如下: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應的酰氯與1.1倍量的8-氨基喹啉合成。其具體反應條件為:以二氯甲烷作為溶劑,三乙胺(Et_3N)為堿,反應12小時得到酰胺產物(圖1),產率為52%-87%。2.鈷催化的8-氨基喹啉C5位的芐基化反應首先,選取8-氨基喹啉酰胺(1a)和2,6-二叔丁基-4-甲基苯酚(2a)作為反應底物,對反應所需要的催化劑、堿、氧化劑、溶劑、溫度等反應條件進行了篩選,得到反應的優(yōu)化條件:以20 mol%四水合醋酸鈷為催化劑,2.0倍量三氟乙酸銀為氧化劑,溴代苯為溶劑,在120℃下反應12小時(圖2)。在此基礎上,對8-氨基喹啉酰胺底物和甲基苯酚類偶聯(lián)試劑分別進行了拓展,共26例,無論苯甲酰胺類底物還是脂肪類酰胺底物,在該反應體系下均能順利進行,以中等到良好的收率得到相應的目標產物,反應產率從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，

本文編號：1988190