焦脱镁叶绿酸N^(21)-N^(23)轴向的氰化反应及其二氢卟吩衍生物的合成  

Cyanation Reactions of Pyropheophorbide-a along N^(21)-N^(23) Axis and Synthesis of Chlorophyllous Chlorin Derivatives

作　　者：李彦龙[1] 张善国[1] 王进军[1] 

机构地区：[1]烟台大学化学化工学院,山东烟台264005

出　　处：《烟台大学学报（自然科学与工程版）》2016年第2期96-102,共7页Journal of Yantai University(Natural Science and Engineering Edition)

基　　金：国家自然科学基金资助项目(21272048)

摘　　要：以脱镁叶绿酸-a甲酯为起始原料,在三乙胺催化下与丙二腈进行瑙文格尔反应,在外接环上构建了β,β-二氰亚甲基结构.选择四氧化锇和高碘酸钠为混合氧化剂,将其3-位乙烯基转化为甲酰基;碱性条件下的空气氧化反应在焦脱镁叶绿酸-a甲酯的132-位上形成碳氧双键.所得二氢卟吩氧化产物再与2-氰乙酰基噻唑进行缩合,分别合成出具有差向异构特征和立体选择性的叶绿素类二氢卟吩衍生物,其化学结构均经UV、IR、1H NMR及元素分析予以证实.同时,对相应的反应机理和立体结构进行了讨论.Methyl pyropheophorbide-a is used as starting material and its Knoevenagel reaction with malononitrile is carried out by catalysis of triethylamine to structure β,β-dicyanomethylene moity on the exocyclic ring. Osmium tetroxide and sodium periodate are chosen as mixed oxidizing agent,the vinyl group linked in 3-position is converted into formyl group. In alkaline condition the carbon oxygen double bond is formed at the 132-position of methyl pyropheophorbide-a by allomerization. The chlorophyllous chlorin derivatives possessing epimerism-isomeric and stereoselective characters are synthesized by condensation of obtained chlorin oxidative products with 2-cyanoacetylthiazole and their chemical structures are characterized by elemental analysis,UV,IR and1 H NMR spectra. The relevant reaction mechanisms and stereostructure are also discussed.

关 键 词：叶绿素-A 焦脱镁叶绿酸 氰化二氢卟吩 瑙文格尔反应 立体选择性 

分 类 号：O644.1[理学—物理化学]