香豆素基查耳酮衍生物的合成及其荧光性能的研究
发布时间：2018-10-30 16:59
【摘要】：香豆素-查耳酮类化合物因其结构中π轨道的重叠和电荷分布的离域导致了电子云密度的高迁移率。其次,在查耳酮的芳基环上引入吸电子基团或供电子基团,可以提高在基态或激发态的非对称电子分布,大大提高了其荧光性能。因其在农药、光学增白剂、化妆品和食品添加剂中的广泛应用,香豆素-查耳酮衍生物的合成引起了化学家的重视。基于此,本论文合成了三个系列的香豆素-查耳酮衍生物,并且初步探讨了分子结构的变化对其荧光性能的影响。论文主要包括三个部分:第一部分首先介绍了香豆素基查耳酮作为荧光增白剂、激光染料以及在抗肿瘤,抗疟疾,抗真菌和抗病毒等方面的应用。然后总结了香豆素基查耳酮的合成方法,如溶液合成法、微波合成法、绿色合成法等。第二部分研究内容:首先以水杨醛和乙酰乙酸乙酯为原料,通过Knoevenagel反应得到3-乙酰基香豆素,再和不同的取代苯甲醛通过Claisen-Schmidt反应得到香豆素基查耳酮2a-2f和8a-8c。其次,以4-二乙胺基水杨醛为原料,通过Wittig反应和甲酰化反应得到3-醛基香豆素,再和不同的取代苯乙酮通过Claisen-Schmidt反应得到了香豆素基查耳酮衍生物6a-6d。以上所合成的香豆素基查耳酮中,2a-2d和对应的6a-6d互为同分异构体,前者为1-香豆素基-3-苯基丙烯酮类化合物,后者为1-苯基-3-香豆素基丙烯酮类化合物,它们具有相似的分子结构,只是丙烯酮的羰基和双键位置发生了互换。以上化合物的结构通过IR、NMR、MS等方法进行了表征。第三部分研究内容:通过测定上述合成的三个系列香豆素基查耳酮衍生物的紫外-可见吸收光谱、荧光发射光谱和荧光量子产率,对其分子结构与光学性能的关系进行了初步探索。相对于母体3-乙酰基香豆素和3-醛基香豆素,三个系列的化合物都是在其母体结构上引入了带有不同取代基的查耳酮结构,使得化合物的共轭延伸,因此紫外-可见吸收光谱和荧光发射光谱都发生了红移。而同系列的香豆素基查耳酮之间相比,苯环上取代基的不同对化合物的吸收和发射光谱的影响并不明显。但是化合物2a-2d与对应的异构体6a-6d相比,后者的紫外-可见吸收光谱和荧光发射光谱都发生了明显红移,并且荧光量子产率有了明显提高。这说明化合物6a-6d可能比化合物2a-2d的分子平面性更好,也可能具有更好的分子内电荷转移性质。
[Abstract]:The high mobility of electron cloud density is due to the overlap of 蟺 orbitals and the delocalization of charge distribution in the structure of coumarin-chalcone compounds. Secondly, the asymmetric electron distribution in the ground or excited states can be improved by introducing electron-absorbing groups or electron donor groups into the aryl ring of chalcone, and the fluorescence properties are greatly improved. Because of its wide application in pesticides, optical brighteners, cosmetics and food additives, the synthesis of coumarin-chalcone derivatives has attracted the attention of chemists. Based on this, three series of coumarin-chalcone derivatives were synthesized, and the effects of molecular structure on their fluorescence properties were discussed. The thesis mainly includes three parts: the first part introduces coumarin ketone as fluorescent whitening agent, laser dye and its application in anti-tumor, anti-malaria, antifungal and anti-virus. Then the synthetic methods of coumarin ketone were summarized, such as solution synthesis, microwave synthesis, green synthesis and so on. In the second part, 3-acetylcoumarin was synthesized from salicylaldehyde and ethyl acetoacetate by Knoevenagel reaction, then coumarin 2a-2f and 8a-8c were obtained by Claisen-Schmidt reaction with different substituted benzaldehyde. Secondly, 3-Aldocoumarin was obtained by Wittig reaction and formylation reaction from 4-diethylamino salicylic aldehyde. The coumarin derivative 6a-6 d was obtained by Claisen-Schmidt reaction with different substituted acetophenone. In the coumarinyl chalcone synthesized above, 2a-2d and the corresponding 6a-6d are isomers, the former is 1-coumarin-3-phenylpropenone and the latter is 1-phenyl-3-coumarinyl acrylone, the former is 1-coumarin-3-phenyl-acrylonone, and the latter is 1-phenyl-3-coumarin acrylone. They have similar molecular structures, except that the carbonyl and double bond positions of propylene ketone are interchangeable. The structure of the compounds was characterized by IR,NMR,MS and other methods. In the third part, the UV-Vis absorption spectra, fluorescence emission spectra and fluorescence quantum yields of the three series of coumarin derivatives were determined. The relationship between its molecular structure and optical properties was preliminarily explored. Compared with 3-acetylcoumarin and 3-aldocoumarin, the three series of compounds have introduced the chalcone structure with different substituents in their parent structure, which makes the conjugate extension of the compounds. Therefore, both UV-vis absorption spectra and fluorescence emission spectra have a red shift. However, the different substituents on benzene ring have little effect on the absorption and emission spectra of the compounds compared with the series of coumarin ketones. However, compared with the corresponding isomer 6a-6d, the UV-Vis absorption spectra and fluorescence emission spectra of the compound 2a-2d showed a red shift, and the fluorescence quantum yield increased obviously. This suggests that the molecular plane and charge transfer properties of compound 6a-6d may be better than that of compound 2a-2d.
【学位授予单位】：兰州交通大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.22
本文编号：2300607
[Abstract]:The high mobility of electron cloud density is due to the overlap of 蟺 orbitals and the delocalization of charge distribution in the structure of coumarin-chalcone compounds. Secondly, the asymmetric electron distribution in the ground or excited states can be improved by introducing electron-absorbing groups or electron donor groups into the aryl ring of chalcone, and the fluorescence properties are greatly improved. Because of its wide application in pesticides, optical brighteners, cosmetics and food additives, the synthesis of coumarin-chalcone derivatives has attracted the attention of chemists. Based on this, three series of coumarin-chalcone derivatives were synthesized, and the effects of molecular structure on their fluorescence properties were discussed. The thesis mainly includes three parts: the first part introduces coumarin ketone as fluorescent whitening agent, laser dye and its application in anti-tumor, anti-malaria, antifungal and anti-virus. Then the synthetic methods of coumarin ketone were summarized, such as solution synthesis, microwave synthesis, green synthesis and so on. In the second part, 3-acetylcoumarin was synthesized from salicylaldehyde and ethyl acetoacetate by Knoevenagel reaction, then coumarin 2a-2f and 8a-8c were obtained by Claisen-Schmidt reaction with different substituted benzaldehyde. Secondly, 3-Aldocoumarin was obtained by Wittig reaction and formylation reaction from 4-diethylamino salicylic aldehyde. The coumarin derivative 6a-6 d was obtained by Claisen-Schmidt reaction with different substituted acetophenone. In the coumarinyl chalcone synthesized above, 2a-2d and the corresponding 6a-6d are isomers, the former is 1-coumarin-3-phenylpropenone and the latter is 1-phenyl-3-coumarinyl acrylone, the former is 1-coumarin-3-phenyl-acrylonone, and the latter is 1-phenyl-3-coumarin acrylone. They have similar molecular structures, except that the carbonyl and double bond positions of propylene ketone are interchangeable. The structure of the compounds was characterized by IR,NMR,MS and other methods. In the third part, the UV-Vis absorption spectra, fluorescence emission spectra and fluorescence quantum yields of the three series of coumarin derivatives were determined. The relationship between its molecular structure and optical properties was preliminarily explored. Compared with 3-acetylcoumarin and 3-aldocoumarin, the three series of compounds have introduced the chalcone structure with different substituents in their parent structure, which makes the conjugate extension of the compounds. Therefore, both UV-vis absorption spectra and fluorescence emission spectra have a red shift. However, the different substituents on benzene ring have little effect on the absorption and emission spectra of the compounds compared with the series of coumarin ketones. However, compared with the corresponding isomer 6a-6d, the UV-Vis absorption spectra and fluorescence emission spectra of the compound 2a-2d showed a red shift, and the fluorescence quantum yield increased obviously. This suggests that the molecular plane and charge transfer properties of compound 6a-6d may be better than that of compound 2a-2d.
【学位授予单位】：兰州交通大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.22
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