【摘要】：含氮稠雜環(huán)類化合物不僅在自然界廣泛存在,而且往往具有顯著的生物活性。因此,開(kāi)發(fā)該類化合物的合成新方法和新策略是有機(jī)化學(xué)及藥物化學(xué)的重要研究?jī)?nèi)容。另一方面,一鍋多組分串聯(lián)反應(yīng)因其原子經(jīng)濟(jì)性、環(huán)境友好性和操作簡(jiǎn)潔性,正日益成為構(gòu)建含氮稠雜環(huán)結(jié)構(gòu)骨架最有效的策略之一。基于以上研究背景,論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]喹啉類衍生物和3-�；群黼s環(huán)類化合物的一鍋高效合成新方法。主要研究?jī)?nèi)容包括以下兩個(gè)部分:一、研究了雙金屬催化下2-(2-溴苯基)咪唑[1,2-a]吡啶、苯乙炔和疊氮化鈉的三組分串聯(lián)反應(yīng),并通過(guò)該反應(yīng)“一鍋煮”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]喹啉類含氮稠雜環(huán)化合物。機(jī)理研究表明,該方法先經(jīng)由銅催化下的Click反應(yīng)和C N偶聯(lián)反應(yīng)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]吡啶中間體,該中間體再經(jīng)由鈀催化下的分子內(nèi)交叉脫氫偶聯(lián)反應(yīng)得到目標(biāo)產(chǎn)物。與文獻(xiàn)方法相比,本方法具有過(guò)程簡(jiǎn)單、效率高、底物適用范圍廣等優(yōu)勢(shì)。二、研究了Cu(OAc)_2/bpy/TEMPO催化下飽和酮與2-氨基芳基羰基化合物的串聯(lián)反應(yīng),并通過(guò)該反應(yīng)高效合成了3-酰基喹啉類化合物。機(jī)理研究表明,該方法先經(jīng)由C(SP~3) H鍵胺基化原位生成β-氨基酮中間體,隨后再經(jīng)過(guò)第二次C(SP~3) H鍵官能團(tuán)化,并發(fā)生分子內(nèi)的Michael加成反應(yīng),再經(jīng)芳構(gòu)化得到目標(biāo)產(chǎn)物。與文獻(xiàn)方法相比,本方法具有原料價(jià)廉易得、反應(yīng)條件溫和、官能團(tuán)耐受性好等優(yōu)勢(shì)。
[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.
【學(xué)位授予單位】：河南師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O626

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本文編號(hào)：2180142