本文選題：葉綠素a + 羥醛縮合反應(yīng)�。� 參考：《煙臺大學(xué)》2016年碩士論文

【摘要】：本文首先對葉綠素衍生物的結(jié)構(gòu)修飾及其在光動(dòng)力療法和染料敏化太陽能電池中的應(yīng)用進(jìn)展進(jìn)行了綜述。盡管葉綠素a衍生物合成和應(yīng)用研究已經(jīng)取得了很大進(jìn)展,但無論是其作為光敏劑應(yīng)用于光動(dòng)力療法還是染料敏化太陽能電池,都需要具有更大吸收波長,如何設(shè)計(jì)合成具有近紅外吸收的葉綠素a衍生物仍是目前研究的一大關(guān)鍵課題。葉綠素a衍生物E環(huán)結(jié)構(gòu)變化對其吸收光譜具有重要影響,本文研究內(nèi)容主要針對其E環(huán)結(jié)構(gòu)進(jìn)行結(jié)構(gòu)修飾,以脫鎂葉綠酸a甲酯(MPa)為起始原料,研究了其外接E環(huán)β-酮酯結(jié)構(gòu)在相轉(zhuǎn)移催化條件下的親核取代和親核加成反應(yīng);其衍生物焦脫鎂葉綠酸a甲酯(MPPa)E環(huán)及鄰近結(jié)構(gòu)的羥醛縮合和氧化反應(yīng);由MPPa與甲醛經(jīng)羥醛縮合所得132-氧叉焦脫鎂葉綠酸a甲酯的邁克爾加成反應(yīng)、氧化、還原和1,3-偶極環(huán)加成反應(yīng);及其經(jīng)邁克爾加成所得1,5-二官能團(tuán)化合物的芳環(huán)化反應(yīng)。合成出了80余種未見文獻(xiàn)報(bào)道的新穎結(jié)構(gòu)化合物,尤其是通過多種策略首次合成了一系列苯環(huán)和吡啶環(huán)稠并葉綠素a衍生物,并發(fā)現(xiàn)其吸收光譜迥異于典型葉綠素a衍生物,其Qx和Qy吸收帶均表現(xiàn)出強(qiáng)烈的紅移,以連續(xù)的寬峰形式出現(xiàn)在600-800nm之間,這是首次發(fā)現(xiàn)葉綠素a衍生物出現(xiàn)該種類型的吸收光譜。所有化合物結(jié)構(gòu)均經(jīng)1H NMR、UV-Vis、IR、MS以及元素分析確證。最后還討論了各種反應(yīng)的機(jī)理以及芳環(huán)稠并衍生物的光學(xué)性質(zhì)。
[Abstract]:In this paper, the structure modification of chlorophyll derivatives and their applications in photodynamic therapy and dye sensitized solar cells are reviewed. Although much progress has been made in the synthesis and application of chlorophyll a derivatives, whether they are used as Guang Min agents for photodynamic therapy or dye sensitized solar cells, they need to have greater absorption wavelengths. How to design and synthesize chlorophyll a derivatives with near infrared absorption is still a key research topic. The change of E ring structure of chlorophyll a derivative has an important effect on its absorption spectrum. In this paper, the structure modification of the E ring structure of chlorophyll a derivative is mainly carried out, using methyl dimagnesium chlorophorate (MPA) as the starting material. The nucleophilic substitution and nucleophilic addition reaction of 尾 -ketone ester were studied under the condition of phase transfer catalysis, and the hydroxaldehyde condensation and oxidation reaction of its derivative, methyl pyromagnesiafolate (MPPA) E ring and its adjacent structure, were studied. The Michael addition reaction, oxidation, reduction and 1o 3- dipolar cycloaddition reaction of 132-oxomethylpyrogallofolate a methyl phloromalginate obtained from the condensation of MPPA with formaldehyde by hydroxaldehyde condensation, and the aromatization reaction of 1o 5- difunctional group compounds obtained by Michael addition. More than 80 novel structural compounds have been synthesized, especially a series of benzene ring and pyridine ring dense chlorophyll a derivatives have been synthesized for the first time through various strategies, and their absorption spectra are very different from those of typical chlorophyll a derivatives. The QX and Qy absorption bands both show strong redshift and appear between 600-800nm in the form of continuous broad peaks. This is the first time that chlorophyll a derivatives have this type of absorption spectrum. The structures of all compounds were confirmed by 1H NMR-IR MS and elemental analysis. Finally, the mechanism of various reactions and the optical properties of aromatic ring thickened derivatives are discussed.
【學(xué)位授予單位】：煙臺大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2016
【分類號】：O621.25
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本文編號：2092203