【摘要】 Friedl?nder喹啉合成法是以邻胺基芳基醛或酮与有α-亚甲基的酮环化制备喹啉的反应,报道了一种喹啉钌络合物催化Friedl?nder法合成喹啉的方法.首先,以8-羟基喹啉钌络合物为催化剂,对模板反应邻氨基苯甲醇和苯乙酮合成2-苯基喹啉进行了反应条件优化实验.重点对比研究了8-羟基喹啉钌络合物配体上不同取代基对反应收率的影响,其中5-甲基-8-羟基喹啉（1e）钌络合物催化邻氨基苯甲醇和苯乙酮合成2-苯基喹啉获得了73%的最高收率.结合IR, UV以及密度泛函理论（DFT）计算讨论了配体结构与催化性能之间的关系.提出了β-H消除形成醛过渡态,交叉aldol反应再亚胺环化,最后脱水生成目标产物的可行机理.以（1e）₃Ru为催化剂,在优化的反应条件下进行了底物扩展研究,以69%～94%的收率合成了32个不同取代的喹啉衍生物,验证了方法的普适性.更多还原

【Abstract】 The Friedl?nder quinoline synthesis method is a reaction of o-aminoaryl aldehyde or ketone with methyl ketone to obtain quinoline. In this paper, a method for synthesizing quinoline catalyzed by ruthenium complexes of quinoline was reported. Using 8-hydroxyquinoline ruthenium complex as catalyst, the reaction conditions were optimized. The effects of different substituents of 8-hydroxyquinoline ruthenium complexes on the reaction yield were comparatively studied. Among them, 5-methyl-8-hydroxyquinoline（1e） ruthenium complex catalyzed the synthesis of 2-phenylquinoline from o-aminobenzyl alcohol and acetophenone with the highest yield of 73%. The relationship between ligand structure and catalytic performance was discussed by combining IR, UV and density functional theory（DFT） calculations. A possible mechanism was proposed,which included the formation of aldehyde transition state through β-H elimination, cross aldol reaction, imination cyclization and finally dehydration to produce the target product. Using（1e）₃Ru as catalyst, 32 quinoline derivatives with different substitutions were synthesized with 69%～94% yields under the optimized reaction conditions, which confirmed the generality of this method.更多还原