C(3)-乙烯基的化学修饰与含氧基团取代的叶绿素-a衍生物的合成  

Modification of C(3)-Vinyl Group and Synthesis of Oxygenic Group-Substituted Chorophyll-a Derivatives

作　　者：王进军[1,2] 李付国[2] 李韵伟[2] 

机构地区：[1]烟台大学化学生物理工学院,烟台264005 [2]烟台大学药学院,烟台264005

出　　处：《有机化学》2011年第1期68-74,共7页Chinese Journal of Organic Chemistry

基　　金：国家科技部中匈政府间合作(No.2008333);山东省自然科学基(No.Y2008B49)资助项目

摘　　要：以焦脱镁叶绿酸-a甲酯为起始原料,通过加成和氧化反应将其3-位上的乙烯基转化为羟乙基、溴乙基、二羟乙基、二溴乙基和溴羟乙基,再经过二甲亚砜/乙酸酐或者高钌酸四丙基铵(TPAP)/N-甲基吗啉-N-氧化物所组成的混合氧化剂的氧化反应,得到多种C(3)-多酮基取代的二氢卟吩衍生物.其单羟基作为离去基团与不同的活泼亚甲基化合物经过重排过程,得到相应的酮基取代的二氢卟吩衍生物.所得新叶绿素衍生物的化学结构均经UV,IR,1H NMR及元素分析得以证实,并对相应的反应提出可能的反应机理。The vinyl group at 3-position of methyl pyropheophorbide-a, used as starting material, was convetted into hydroxyethyl, bromoethyl, dihydroxyethyl, dibromoethyl and bromo-hydroxyethyl groups by addition and oxidation reactions. The multi-keto groups-substituted chlorin derivatives were obtained by oxidations with dimethyl sulfoxide/acetic anhydride or tetrappropylammonium perruthenate/N-methylmorpholine N-oxide as a mixing oxidant. The nucleophilic substitution of the mono-hydroxyl group as a leaving group with active methlene derivatives produced many unexpected processes to give corresponding keto-substituted chlorin derivatives. The structures of new chlorophyll derivatives were characterized by UV, IR, ^1H NMR spectra and elemental analysis. The possible mechanisms about corresponding oxidation, substitution and rearrangement reactions were tentatively proposed.

关 键 词：叶绿素-A 焦脱镁叶绿酸-a甲酯 二氢卟吩衍生物 化学修饰 反应机理 光动力疗法(PDT) 

分 类 号：O629[理学—有机化学]