香豆素基查耳酮衍生物的合成及其熒光性能的研究
發(fā)布時間：2018-10-30 16:59
【摘要】：香豆素-查耳酮類化合物因其結(jié)構(gòu)中π軌道的重疊和電荷分布的離域?qū)е铝穗娮釉泼芏鹊母哌w移率。其次,在查耳酮的芳基環(huán)上引入吸電子基團或供電子基團,可以提高在基態(tài)或激發(fā)態(tài)的非對稱電子分布,大大提高了其熒光性能。因其在農(nóng)藥、光學(xué)增白劑、化妝品和食品添加劑中的廣泛應(yīng)用,香豆素-查耳酮衍生物的合成引起了化學(xué)家的重視�；诖�,本論文合成了三個系列的香豆素-查耳酮衍生物,并且初步探討了分子結(jié)構(gòu)的變化對其熒光性能的影響。論文主要包括三個部分:第一部分首先介紹了香豆素基查耳酮作為熒光增白劑、激光染料以及在抗腫瘤,抗瘧疾,抗真菌和抗病毒等方面的應(yīng)用。然后總結(jié)了香豆素基查耳酮的合成方法,如溶液合成法、微波合成法、綠色合成法等。第二部分研究內(nèi)容:首先以水楊醛和乙酰乙酸乙酯為原料,通過Knoevenagel反應(yīng)得到3-乙酰基香豆素,再和不同的取代苯甲醛通過Claisen-Schmidt反應(yīng)得到香豆素基查耳酮2a-2f和8a-8c。其次,以4-二乙胺基水楊醛為原料,通過Wittig反應(yīng)和甲酰化反應(yīng)得到3-醛基香豆素,再和不同的取代苯乙酮通過Claisen-Schmidt反應(yīng)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和對應(yīng)的6a-6d互為同分異構(gòu)體,前者為1-香豆素基-3-苯基丙烯酮類化合物,后者為1-苯基-3-香豆素基丙烯酮類化合物,它們具有相似的分子結(jié)構(gòu),只是丙烯酮的羰基和雙鍵位置發(fā)生了互換。以上化合物的結(jié)構(gòu)通過IR、NMR、MS等方法進行了表征。第三部分研究內(nèi)容:通過測定上述合成的三個系列香豆素基查耳酮衍生物的紫外-可見吸收光譜、熒光發(fā)射光譜和熒光量子產(chǎn)率,對其分子結(jié)構(gòu)與光學(xué)性能的關(guān)系進行了初步探索。相對于母體3-乙�；愣顾睾�3-醛基香豆素,三個系列的化合物都是在其母體結(jié)構(gòu)上引入了帶有不同取代基的查耳酮結(jié)構(gòu),使得化合物的共軛延伸,因此紫外-可見吸收光譜和熒光發(fā)射光譜都發(fā)生了紅移。而同系列的香豆素基查耳酮之間相比,苯環(huán)上取代基的不同對化合物的吸收和發(fā)射光譜的影響并不明顯。但是化合物2a-2d與對應(yīng)的異構(gòu)體6a-6d相比,后者的紫外-可見吸收光譜和熒光發(fā)射光譜都發(fā)生了明顯紅移,并且熒光量子產(chǎn)率有了明顯提高。這說明化合物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內(nèi)電荷轉(zhuǎn)移性質(zhì)。
[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.
【學(xué)位授予單位】：蘭州交通大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O621.22
本文編號：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.
【學(xué)位授予單位】：蘭州交通大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O621.22
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