龙胆醇类海洋天然产物的合成及其应用

发布时间：2018-02-02 14:33

本文关键词： 海洋天然产物龙胆醇季铵盐壳聚糖接枝　出处：《哈尔滨工业大学》2017年硕士论文　论文类型：学位论文

【摘要】：龙胆醇是从海绵中分离提取的海洋天然产物,它不仅具有抗菌、抗氧化、自由基消除、防生物附着等生物活性,而且还可以作为鞘磷脂酶抑制剂。本论文以龙胆醇类海洋天然产物的合成为主线,合成了龙胆醇、氯龙胆醇、龙胆醌、氯龙胆醌和甲基氢醌5种海洋天然产物,其中龙胆醌、氯龙胆醌是首次合成;然后将合成的龙胆醇类化合物2,5-二甲氧基苯甲醛接枝到天然高聚物壳聚糖,制备了壳聚糖两性离子高分子功能材料。主要研究工作分为如下几个部分:1)龙胆醇类海洋天然产物合成相关的方法学研究。氯化反应的区域选择性是合成氯龙胆醌、氯龙胆醇的关键步骤。以2,5-二甲氧基苯甲醛为模板,对其卤化反应进行了研究,得出了与经典的甲氧基和醛基双重定位效应相矛盾的实验结果;出现这种结果是由于醛基钝化了其邻位的甲氧基,最终醛基及其间位的甲氧基共同起定位作用使卤化反应发生在醛基的邻位。此外,将醛基对位溴化反应产物进行单晶培养,通过X-ray对其结构进行了确认。2)龙胆醇类海洋天然产物合成研究。氯龙胆醇的合成主要包含以下步骤:以廉价易得的4-甲氧基苯酚为原料,通过氯化反应制备2-氯-4-甲氧基苯酚;2-氯-4-甲氧基苯酚经过羟甲基化反应制备2-氯-6-羟甲基-4-甲氧基苯酚;2-氯-6-羟甲基-4-甲氧基苯酚经过氧化实现了氯龙胆醌的首次合成;氯龙胆醌经过还原反应制备氯龙胆醇。采用与氯龙胆醇的合成相同或相似的思路和同样的原料,合成了龙胆醇、龙胆醌、甲基氢醌等海洋天然产物。3)龙胆醇类海洋天然产物合成应用研究。龙胆醇类化合物2,5-二甲氧基苯甲醛与壳聚糖反应,制备席夫碱壳聚糖;席夫碱壳聚糖经过还原剂还原制备氮烷基化壳聚糖;碱性条件下,氮烷基化壳聚糖与碘甲烷反应制备了壳聚糖两性离子高分子功能材料。所制备的高分子功能材料经过红外、XRD、热失重等表征,表征结果显示2,5-二甲氧基苯甲醛接枝到壳聚糖。本文完成了龙胆醇、氯龙胆醇、龙胆醌、氯龙胆醌、甲基氢醌等一系列龙胆醇类海洋天然产物的合成;并将其接枝壳聚糖,制备了壳聚糖两性离子高分子功能材料。
[Abstract]:Gentian alcohol is a marine natural product extracted from sponge. It not only has antibacterial, antioxidant, free radical elimination, anti-biological attachment and other biological activities. In this paper, gentian alcohol, chlorogentian, gentian quinone, chlorogentian quinone and methyl hydroquinone were synthesized. Among them, gentian quinone and chlorogentian quinone were synthesized for the first time. Then the synthetic gentian alcohol compound 2o 5- dimethoxy benzaldehyde was grafted to the natural polymer chitosan. Chitosan amphoteric polymer functional materials were prepared. The main research work is divided into the following parts: 1). Methodological studies on the synthesis of gentian alcohols from marine natural products. The regioselectivity of chlorination is the synthesis of chlorogentin quinone. In this paper, the halogenation reaction of chlorogentian was studied by using 2o 5-dimethoxybenzaldehyde as template, and the experimental results contradicted with the classical double localization effects of methoxy and aldehyde groups were obtained. This result is due to the aldehyde group passivation of its adjacent methoxyl group, and finally the aldehyde group and the mutual position of the methoxy group together to make the halogenation reaction occurs in the adjacent position of the aldehyde group. The products of aldehyde para-brominated reaction were cultured in single crystal. The structure was confirmed by X-ray. 2) the synthesis of gentian alcohols from marine natural products. The synthesis of chlorogentian includes the following steps: the cheap 4-methoxy phenol is used as the raw material. 2-chloro-4-methoxy phenol was prepared by chlorination. 2-chloro-6-hydroxymethyl-4-methoxy phenol was prepared by hydroxymethylation of 2-chloro-4-methoxy phenol. The first synthesis of chlorgentin quinone was achieved by oxidation of 2-chloro-6-hydroxymethyl-4-methoxy phenol. Chlorogentin quinone was prepared by reductive reaction. Gentianol and gentian quinone were synthesized by using the same or similar ideas and the same raw materials as chlorogentian. Studies on the Synthesis and Application of Marine Natural products of Methyl hydroquinone etc. 3) Gentian alcohols were synthesized by the reaction of 2-dimethoxybenzaldehyde with chitosan to prepare Schiff base chitosan. Schiff base chitosan was reduced by reductant to prepare nitrogen alkylated chitosan. Chitosan amphoteric polymer functional materials were prepared by the reaction of nitrogen-alkylated chitosan with iodomethane under alkaline conditions. The prepared polymer functional materials were characterized by IR XRD and thermogravimetric analysis. The results showed that 2o 5-dimethoxybenzaldehyde was grafted to chitosan. A series of natural gentian alcohols such as gentian, chlorogentian, gentian quinone, chlorogentian quinone and methyl hydroquinone were synthesized. Chitosan amphoteric polymer functional materials were prepared by grafting chitosan with chitosan.
【学位授予单位】：哈尔滨工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O636.1

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