两类含氮稠杂环的合成新方法研究
发布时间：2018-08-12 19:38
【摘要】：含氮稠杂环类化合物不仅在自然界广泛存在,而且往往具有显著的生物活性。因此,开发该类化合物的合成新方法和新策略是有机化学及药物化学的重要研究内容。另一方面,一锅多组分串联反应因其原子经济性、环境友好性和操作简洁性,正日益成为构建含氮稠杂环结构骨架最有效的策略之一。基于以上研究背景,论文研究并建立了吡啶并[2',1':2,3]咪唑并[4,5-c][1,2,3]三氮唑并[1,5-a]喹啉类衍生物和3-酰基喹啉等含氮稠杂环类化合物的一锅高效合成新方法。主要研究内容包括以下两个部分:一、研究了双金属催化下2-(2-溴苯基)咪唑[1,2-a]吡啶、苯乙炔和叠氮化钠的三组分串联反应,并通过该反应“一锅煮”合成了吡啶并[2',1':2,3]咪唑并[4,5-c][1,2,3]三氮唑并[1,5-a]喹啉类含氮稠杂环化合物。机理研究表明,该方法先经由铜催化下的Click反应和C N偶联反应原位生成2-(2-(4-苯基-1H-1,2,3-三氮唑-1-炔基)苯基)咪唑[1,2-a]吡啶中间体,该中间体再经由钯催化下的分子内交叉脱氢偶联反应得到目标产物。与文献方法相比,本方法具有过程简单、效率高、底物适用范围广等优势。二、研究了Cu(OAc)_2/bpy/TEMPO催化下饱和酮与2-氨基芳基羰基化合物的串联反应,并通过该反应高效合成了3-酰基喹啉类化合物。机理研究表明,该方法先经由C(SP~3) H键胺基化原位生成β-氨基酮中间体,随后再经过第二次C(SP~3) H键官能团化,并发生分子内的Michael加成反应,再经芳构化得到目标产物。与文献方法相比,本方法具有原料价廉易得、反应条件温和、官能团耐受性好等优势。
[Abstract]:Nitrogen-containing dense heterocyclic compounds not only exist widely in nature, but also have remarkable biological activity. Therefore, the development of new methods and strategies for the synthesis of these compounds is an important research content in organic chemistry and pharmaceutical chemistry. On the other hand, because of its atomic economy, environmental friendliness and simple operation, a pot of multicomponent series reaction is increasingly becoming one of the most effective strategies for constructing the framework of the nitrogen-containing dense heterocyclic structure. Based on the above research background, a new one pot method for the synthesis of pyridino [1: 2: 2] Imidazolido [4H5-c] [1 + 2 + 3] triazolazo [1] quinoline derivatives and 3-acyl quinoline derivatives containing nitrogen has been studied and established in this paper. The main research contents include the following two parts: first, the three-component series reactions of 2- (2-bromophenyl) imidazole, 2- (2-a) pyridine, phenylacetylene and sodium azide catalyzed by bimetallic catalyst were studied. Pyridino [1: 2: 2] imidazolido [4o 5-c] [1C] triazolido [1a 5-a] quinoline was synthesized by this reaction. The mechanism of the method shows that the intermediate of 2- (2- (4- (4-phenyl-1H-1H-1) 2-triazolyl) phenyl) imidazole [1 (1-a) a] pyridine is first synthesized by the copper-catalyzed Click reaction and the C-N coupling reaction. The target product was obtained by the intramolecular cross-dehydrogenation of the intermediate catalyzed by palladium. Compared with the literature method, this method has the advantages of simple process, high efficiency and wide application range of substrate. Secondly, the series reaction of saturated ketones with 2-amino-aryl carbonyl compounds catalyzed by Cu (OAc) 2 / bpy / tempo was studied, and the 3-acylquinoline compounds were synthesized efficiently by this reaction. The mechanism study shows that the intermediate of 尾 -aminoketone is first synthesized by the amination of C (SP~3) -H bond in situ, then by the second C (SP~3) -H bond functionalization, and then by the intramolecular Michael addition reaction, and then the target product is obtained by aromatization. Compared with the literature method, this method has the advantages of cheap raw material, mild reaction conditions and good tolerance of functional groups.
【学位授予单位】：河南师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626
本文编号：2180142
[Abstract]:Nitrogen-containing dense heterocyclic compounds not only exist widely in nature, but also have remarkable biological activity. Therefore, the development of new methods and strategies for the synthesis of these compounds is an important research content in organic chemistry and pharmaceutical chemistry. On the other hand, because of its atomic economy, environmental friendliness and simple operation, a pot of multicomponent series reaction is increasingly becoming one of the most effective strategies for constructing the framework of the nitrogen-containing dense heterocyclic structure. Based on the above research background, a new one pot method for the synthesis of pyridino [1: 2: 2] Imidazolido [4H5-c] [1 + 2 + 3] triazolazo [1] quinoline derivatives and 3-acyl quinoline derivatives containing nitrogen has been studied and established in this paper. The main research contents include the following two parts: first, the three-component series reactions of 2- (2-bromophenyl) imidazole, 2- (2-a) pyridine, phenylacetylene and sodium azide catalyzed by bimetallic catalyst were studied. Pyridino [1: 2: 2] imidazolido [4o 5-c] [1C] triazolido [1a 5-a] quinoline was synthesized by this reaction. The mechanism of the method shows that the intermediate of 2- (2- (4- (4-phenyl-1H-1H-1) 2-triazolyl) phenyl) imidazole [1 (1-a) a] pyridine is first synthesized by the copper-catalyzed Click reaction and the C-N coupling reaction. The target product was obtained by the intramolecular cross-dehydrogenation of the intermediate catalyzed by palladium. Compared with the literature method, this method has the advantages of simple process, high efficiency and wide application range of substrate. Secondly, the series reaction of saturated ketones with 2-amino-aryl carbonyl compounds catalyzed by Cu (OAc) 2 / bpy / tempo was studied, and the 3-acylquinoline compounds were synthesized efficiently by this reaction. The mechanism study shows that the intermediate of 尾 -aminoketone is first synthesized by the amination of C (SP~3) -H bond in situ, then by the second C (SP~3) -H bond functionalization, and then by the intramolecular Michael addition reaction, and then the target product is obtained by aromatization. Compared with the literature method, this method has the advantages of cheap raw material, mild reaction conditions and good tolerance of functional groups.
【学位授予单位】：河南师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O626
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