本文關(guān)鍵詞：喹喔啉類和氧雜吖庚酮類化合物的合成方法研究　出處：《山東大學(xué)》2017年博士論文　論文類型：學(xué)位論文

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【摘要】：喹喔啉、氧雜吖庚酮、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雜環(huán)化合物,因為其廣泛的生物活性而受到人們的關(guān)注。目前這幾類化合物的構(gòu)建與修飾方法已經(jīng)得到很多報道,但是我們看到很多方法存在不足之處,比如條件苛刻、需要多步反應(yīng)、后處理繁瑣、較低的分離產(chǎn)率等。我們分別發(fā)展了 PTSA催化喹喔啉雜環(huán)的構(gòu)建、鈀催化喹喔啉雜環(huán)的修飾、碘催化吡咯并[1,2-a]喹喔啉和咪唑并[1,5-a]喹喔啉骨架構(gòu)建與銅催化氧雜吖庚酮骨架構(gòu)建的方法學(xué),高效地實(shí)現(xiàn)了相關(guān)目標(biāo)化合物的合成。第一部分對甲苯磺酸催化一鍋串聯(lián)構(gòu)建喹喔啉類化合物此部分發(fā)展了一種對甲苯磺酸催化一鍋由鄰苯二胺和1,2-二芳基-2-羥基乙酮為原料構(gòu)建2,3-二芳基喹喔啉類化合物的方法。反應(yīng)用到了無毒易得的DMSO作為氧化劑和溶劑。此方法具有很好的底物適用性和官能團(tuán)容忍性,都能以較高的產(chǎn)率得到目標(biāo)化合物。第二部分基于脫氫偶聯(lián)反應(yīng)(CDC)高效構(gòu)建5,8-取代二乙烯基喹喔啉類化合物及其在線粒體熒光探針方面的應(yīng)用初步探索此部分發(fā)展了一種鈀催化基于脫氫偶聯(lián)反應(yīng)高效構(gòu)建5,8-取代二乙烯基喹喔啉類化合物的方法。此方法具有很好的底物適用性和官能團(tuán)容忍性,都能以較高的產(chǎn)率得到目標(biāo)化合物。我們把反應(yīng)所得的熒光產(chǎn)物命名為Qu-Fluors。Qu-Fluors具有熒光發(fā)射波長可調(diào)、較高的熒光量子效率(在二氯甲烷中高達(dá)83%)和較大的斯托克斯位移(在二氯甲烷中高達(dá)6236 cm-1)。進(jìn)一步細(xì)胞成像實(shí)驗證明Qu-Fluors在線粒體熒光探針方面具有潛在的應(yīng)用價值。第三部分基于脫氫偶聯(lián)反應(yīng)(CDC)銅催化高效構(gòu)建氧雜吖庚酮類化合物此部分發(fā)展了一種銅催化基于脫氫偶聯(lián)反應(yīng)高效構(gòu)建氧雜吖庚酮類化合物的方法。該反應(yīng)用到廉價易得的氧化亞銅作為催化劑并涉及到了一種反常的Smiles重排反應(yīng)。此方法具有很好的底物適用性和官能團(tuán)容忍性,都能以較高的產(chǎn)率得到目標(biāo)化合物。第四部分基于脫氫偶聯(lián)反應(yīng)碘催化一鍋合成吡咯并[1,2-a]喹喔啉和咪唑并[1,5-a]喹喔啉類化合物此部分發(fā)展了一種碘單質(zhì)催化基于脫氫偶聯(lián)反應(yīng)高效構(gòu)建吡咯并[1,2-a]喹喔啉和咪唑并[1,5-a]喹喔啉類化合物的方法。反應(yīng)用到了無毒易得的碘單質(zhì)作為催化劑,DMSO作為氧化劑和溶劑。此方法具有很好的底物適用性和官能團(tuán)容忍性,都能以較高的產(chǎn)率得到目標(biāo)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.

【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O626
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本文編號：1416620