叶绿素-a及其降解产物的化学修饰与二氢卟吩醇类衍生物的合成有机化学.pdfVIP

2010 年第 30 卷 有 机 化 学 Vol. 30, 2010 第 8 期, 1192～1200 Chinese Journal of Organic Chemistry No. 8, 1192～1200 ·研究论文· 叶绿素-a 及其降解产物的化学修饰与二氢卟吩醇类衍生物的合成 王进军* 张 朋 王 朋 陈冠龙 李付国 a ( 烟台大学化学生物理工学院 烟台 264005) 摘要 以叶绿素-a 为基本原料, 在酸性条件下一锅法完成脱金属、酯交换、空气氧化和重排反应, 以不同的产率生成 多种叶绿素-a 的降解和氧化产物. 通过加成、氧化和还原反应, 对其主要降解产物脱镁叶绿酸-a 甲酯和焦脱镁叶绿酸-a 甲酯的 3-位乙烯基和 E-环羰基实施化学修饰, 在叶绿素-a 基本碳架的不同位置上引进羟基, 完成 9 种未见报道的二氢 卟吩醇类衍生物的合成. 所合成的新化合物均经 UV, IR, 1H NMR 及元素分析证明其结构. 关键词 叶绿素-a; 氧化降解; 化学修饰; 二氢卟吩醇; 光动力治疗(PDT) Synthesis of Chorin Alcohol Derivatives by Chemical Modifications for Chlorophyll-a and Its Degradation Products Wang, Jinjun* Zhang, Peng Wang, Peng Chen, Guanlong Li, Fuguo (Science and Engineering College of Chemistry and Biology, Yantai University, Yantai 264005) Abstract The demetal, ester exchange, allomerization and rearrangement reactions were accomplished by one pot method using chlorophyll-a as a basic material to yield various degraded and oxidized chlorin de- rivatives in different yields. The chemical modification for the vinyl group on 3-position and carbonyl group on the E-ring of methyl pheophorbide-a and methyl pyropheophorbide-a, as primary degraded products were carried out by addition, oxidation and reduction. The hydroxyl groups were introduced into the different po- sitions on the basic skeleton of chlorophyll-a derivatives to complete the synthesis of 9 different new chlorin 1 alcohols. The structures of al