喹喔啉类和氧杂吖庚酮类化合物的合成方法研究

发布时间：2018-01-13 00:15

  本文关键词：喹喔啉类和氧杂吖庚酮类化合物的合成方法研究　出处：《山东大学》2017年博士论文　论文类型：学位论文

  更多相关文章： 含氮杂环 喹喔啉 氧杂吖庚酮 吡咯并[1 2-a]喹喔啉 咪唑并[1 5-a]喹喔啉 构建与修饰 方法学 线粒体探针

【摘要】：喹喔啉、氧杂吖庚酮、吡咯并[1,2-a]喹喔啉和咪唑并[1,5-a]喹喔啉衍生物是重要的含氮杂环化合物,因为其广泛的生物活性而受到人们的关注。目前这几类化合物的构建与修饰方法已经得到很多报道,但是我们看到很多方法存在不足之处,比如条件苛刻、需要多步反应、后处理繁琐、较低的分离产率等。我们分别发展了 PTSA催化喹喔啉杂环的构建、钯催化喹喔啉杂环的修饰、碘催化吡咯并[1,2-a]喹喔啉和咪唑并[1,5-a]喹喔啉骨架构建与铜催化氧杂吖庚酮骨架构建的方法学,高效地实现了相关目标化合物的合成。第一部分对甲苯磺酸催化一锅串联构建喹喔啉类化合物此部分发展了一种对甲苯磺酸催化一锅由邻苯二胺和1,2-二芳基-2-羟基乙酮为原料构建2,3-二芳基喹喔啉类化合物的方法。反应用到了无毒易得的DMSO作为氧化剂和溶剂。此方法具有很好的底物适用性和官能团容忍性,都能以较高的产率得到目标化合物。第二部分基于脱氢偶联反应(CDC)高效构建5,8-取代二乙烯基喹喔啉类化合物及其在线粒体荧光探针方面的应用初步探索此部分发展了一种钯催化基于脱氢偶联反应高效构建5,8-取代二乙烯基喹喔啉类化合物的方法。此方法具有很好的底物适用性和官能团容忍性,都能以较高的产率得到目标化合物。我们把反应所得的荧光产物命名为Qu-Fluors。Qu-Fluors具有荧光发射波长可调、较高的荧光量子效率(在二氯甲烷中高达83%)和较大的斯托克斯位移(在二氯甲烷中高达6236 cm-1)。进一步细胞成像实验证明Qu-Fluors在线粒体荧光探针方面具有潜在的应用价值。第三部分基于脱氢偶联反应(CDC)铜催化高效构建氧杂吖庚酮类化合物此部分发展了一种铜催化基于脱氢偶联反应高效构建氧杂吖庚酮类化合物的方法。该反应用到廉价易得的氧化亚铜作为催化剂并涉及到了一种反常的Smiles重排反应。此方法具有很好的底物适用性和官能团容忍性,都能以较高的产率得到目标化合物。第四部分基于脱氢偶联反应碘催化一锅合成吡咯并[1,2-a]喹喔啉和咪唑并[1,5-a]喹喔啉类化合物此部分发展了一种碘单质催化基于脱氢偶联反应高效构建吡咯并[1,2-a]喹喔啉和咪唑并[1,5-a]喹喔啉类化合物的方法。反应用到了无毒易得的碘单质作为催化剂,DMSO作为氧化剂和溶剂。此方法具有很好的底物适用性和官能团容忍性,都能以较高的产率得到目标化合物。
[Abstract]:Quinoxaline, oxa acridine Cycloheptanone, pyrrolo [1,2-a] quinoxaline and imidazo [1,5-a] quinoxaline derivatives are important heterocyclic compounds, and people's attention because of its extensive biological activities. These compounds construction and modification method has been a lot of reports, but we see a lot of methods exist deficiencies, such as conditions harsh, need many steps postprocessing cumbersome, low separation efficiency. We developed to construct PTSA catalytic quinoxaline heterocycles, palladium modified catalytic quinoxaline heterocycles, pyrrole and iodine catalyzed [1,2-a] quinoxaline and imidazo method and copper catalyzed oxa acridine Cycloheptanone skeleton construction construction [1,5-a] quinaxoline skeleton. Efficient synthesis of target compounds. The first part of a series of construction of quinoxaline compounds in this part of the development of a pot of toluene catalyzed by p-toluene sulfonic acid A pot from the adjacent benzene two sulfonic acid catalyzed aryl amine and 1,2- two -2- hydroxy acetophenone as the raw materials to build two 2,3- aryl quinoxaline compounds. Applied to anti non-toxic and readily available DMSO as oxidant and solvent. This method has good applicability and substrate functional tolerance, can get the target compound in high yield. In the second part, based on the dehydrogenation coupling reaction (CDC), construction of two vinyl 5,8- substituted quinoxaline compounds and its application in mitochondrial fluorescence probe preliminary exploration of this part of the development of a palladium catalyzed high efficient method to construct 5,8- two substituted vinyl quinoxaline compounds. This method is based on the dehydrogenation coupling reaction with substrate good applicability and functional tolerance, can obtain the target compounds in high yields. The fluorescent product obtained from the reaction of the named Qu-Fluors.Qu-Fluors with fluorescence Tunable emission wavelength, fluorescence quantum efficiency (higher in dichloromethane as high as 83%) and large Stokes shift (up to 6236 cm-1 in dichloromethane). Further cell imaging experiments show that the Qu-Fluors has potential application value in the mitochondrial fluorescence probe. The third part based on the dehydrogenation coupling reaction catalyzed by copper (CDC), construction of oxygen this part of neptanone compound complex. The development of a copper catalyzed dehydrogenation coupling reaction and efficient construction of oxygen impurity method of neptanone acridine compounds based on the reverse applied to cheap cuprous oxide as the catalyst and relates to an abnormal Smiles rearrangement reaction. This method has good applicability and substrate functional tolerance that can be the target compounds in high yields. The fourth part based on the dehydrogenation coupling reaction catalyzed by iodine ONE-POTSYNTHESIS pyrrolo [1,2-a] quinoxaline and imidazo [1,5-a ] quinoxaline compounds this part developed a method of iodine catalytic dehydrogenation coupling reaction and efficient construction of pyrrolo [1,2-a] quinoxaline and imidazo [1,5-a] quinoxaline compounds. Based on the reverse applied to non-toxic readily available iodine as catalyst, DMSO as oxidant and solvent. This method has good applicability and substrate functional tolerance, can obtain the target compounds in high yields.

【学位授予单位】：山东大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O626
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本文编号：1416620