脱镁叶绿酸a外接环的化学反应及其衍生物的合成

发布时间：2018-07-03 03:32

  本文选题：叶绿素a + 羟醛缩合反应　； 参考：《烟台大学》2016年硕士论文

【摘要】：本文首先对叶绿素衍生物的结构修饰及其在光动力疗法和染料敏化太阳能电池中的应用进展进行了综述。尽管叶绿素a衍生物合成和应用研究已经取得了很大进展,但无论是其作为光敏剂应用于光动力疗法还是染料敏化太阳能电池,都需要具有更大吸收波长,如何设计合成具有近红外吸收的叶绿素a衍生物仍是目前研究的一大关键课题。叶绿素a衍生物E环结构变化对其吸收光谱具有重要影响,本文研究内容主要针对其E环结构进行结构修饰,以脱镁叶绿酸a甲酯(MPa)为起始原料,研究了其外接E环β-酮酯结构在相转移催化条件下的亲核取代和亲核加成反应;其衍生物焦脱镁叶绿酸a甲酯(MPPa)E环及邻近结构的羟醛缩合和氧化反应;由MPPa与甲醛经羟醛缩合所得132-氧叉焦脱镁叶绿酸a甲酯的迈克尔加成反应、氧化、还原和1,3-偶极环加成反应;及其经迈克尔加成所得1,5-二官能团化合物的芳环化反应。合成出了80余种未见文献报道的新颖结构化合物,尤其是通过多种策略首次合成了一系列苯环和吡啶环稠并叶绿素a衍生物,并发现其吸收光谱迥异于典型叶绿素a衍生物,其Qx和Qy吸收带均表现出强烈的红移,以连续的宽峰形式出现在600-800nm之间,这是首次发现叶绿素a衍生物出现该种类型的吸收光谱。所有化合物结构均经1H NMR、UV-Vis、IR、MS以及元素分析确证。最后还讨论了各种反应的机理以及芳环稠并衍生物的光学性质。
[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.
【学位授予单位】：烟台大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O621.25
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本文编号：2092203