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2012 >Issue 03: 632 - 638

DOI: https://doi.org/10.6023/cjoc1108192

研究简报

132-氧代焦脱镁叶绿酸的E-环修饰及其二氢卟吩类衍生物的合成

  • 邬旭然 ,
  • 刘超 ,
  • 杨泽 ,
  • 姚楠楠 ,
  • 王进军
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  • 烟台大学化学化工学院 烟台 264005

收稿日期: 2011-08-19

  修回日期: 2011-10-18

  网络出版日期: 2012-03-24

基金资助

国家自然科学基金(No. 20972036)、山东省自然科学基(No. Y2008B49)和中匈政府间科技合作(No. 2008-333-4-32)资助项目.

收起

Modification for the E-Ring of 132-Oxo-pyropheophorbide-a and Synthesis of Chlorin Derivatives

  • Wu Xuran ,
  • Liu Chao ,
  • Yang Ze ,
  • Yao Nannan ,
  • Wang Jinjun
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  • College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005

Received date: 2011-08-19

  Revised date: 2011-10-18

  Online published: 2012-03-24

Supported by

Project supported by the National Natural Science Foundation of China (No. 20972036), the Natural Science Foundation of Shangdong Province of China (No. Y2008B49), and the International Science and Technology Project between Governments of China and Hungary (No. 2008-333-4-32).

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摘要

以132-氧代焦脱镁叶绿酸-a 甲酯为起始原料, 碱性条件下的空气氧化和重排反应定量地将其转化成红紫素-18 甲酯; 在三氟化硼催化下, 与苯乙酮的羟醛缩合反应分别给出131-苯甲酰亚甲基取代的二氢卟吩酮和绿卟啉酮; E-环二酮与丙二腈的Knoevenagel 反应、与氨基硫脲的缩合反应和与重氮甲烷的重排反应以及与苄基氯化镁的Grignard 反应生成一系列具有长波吸收的叶绿素类二氢卟吩衍生物. 首次报道的具有叶绿素基本碳架的二氢卟吩衍生物的化学结构均经UV, IR, 1H NMR 及元素分析得以证实.

关键词： 叶绿素; 132-氧代焦脱镁叶绿酸-a 甲酯; 二氢卟吩; 化学修饰; 合成

本文引用格式

邬旭然 , 刘超 , 杨泽 , 姚楠楠 , 王进军 . 132-氧代焦脱镁叶绿酸的E-环修饰及其二氢卟吩类衍生物的合成[J]. 有机化学, 2012 , (03) : 632 -638 . DOI: 10.6023/cjoc1108192

Abstract

The methyl 132-oxo-pyropheophorbide-a was used as a starting material and converted quantitatively into purpourin- 18 by allomerization and rearrangement in the basic condition. Under the catalysis of BF3, the aldol reaction of acetophenone gave 131-phenylacylmethylene-substituted chlorin and keto-rhodin, respectively. The Knoevenagel reaction with malononitrile, condensation with aminothiocarbamide, rearrangement with diazomethane and Grignard reaction with benzyl megnesium bromide afforded a series of chlorins possessing long wavelength absorption. The structures of all the new chlorins with basic skeleton of chlorophyll were characterized by UV, IR, 1H NMR spectra and elemental analysis.

Key words： chlorophyll; methyl 132-oxo-pyropheophorbide-a; chlorin; chemical modification; synthesis

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