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有机化学 ›› 2005, Vol. 25 ›› Issue (03): 319-326. 上一篇    下一篇

研究论文

红紫素-18酰亚胺衍生物的合成

韩光范*,1，王进军2，瞿燕1，沈荣基3   

  1. (1江苏科技大学材料科学与工程学院 镇江 212003)
    (2烟台大学应用化学系 烟台264005)
    (3韩国化学研究所生物有机化学部 大田 韩国)
  • 收稿日期:2004-06-10 修回日期:2004-09-30 发布日期:2005-02-28
  • 通讯作者: 韩光范

Synthesis of Purpurin-18 Imide Derivatives

HAN Guang-Fan*,1,WANG Jin-Jun 2,QU Yan 1,SHIM Young Key 3   

  1. (1 School of Materials Science and Engineering, Jiangsu University of Science and Technol-ogy, Zhenjiang 212003)
    (2 Department of Chemistry, Yantai University, Yantai 262005)
    (3 Division of Bio-Organic Chemistry, Korea Research Institute of Chemical and Technology, Dajen, Korea)
  • Received:2004-06-10 Revised:2004-09-30 Published:2005-02-28
  • Contact: HAN Guang-Fan

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1286

被引次数

17

以脱镁叶绿酸甲酯为原料, 通过对其3-位乙烯基的氧化, 得到3-(2,2-二甲氧基乙基)-3-去乙烯基脱镁叶绿酸甲酯, 经过甲酸处理得到3-(2-氧代乙基)-3-去乙烯基脱镁叶绿酸甲酯, 选择适当的条件, 通过Grignard 反应合成了对应的3-(2-羟基烷基)-3-去乙烯基脱镁叶绿酸甲酯. 实验结果表明: 3-(2-氧代乙基)-3-去乙烯基脱美叶绿酸甲酯和Grignard试剂的反应, 只要反应条件控制得当, 132-位的甲氧甲酰基不会脱去. 结合E环的改造, 将其转变成酸酐环进而转变成N-取代的酰亚胺环. 目标化合物的合成也可以将3-(2,2-二甲氧基乙基)-去乙烯基脱镁叶绿酸甲酯转变成N-取代的酰亚胺后, 再和Grignard试剂反应, 完成目标化合物的合成. 合成的一系列化合物具有长波长的紫外吸收. 化合物的结构变化对紫外吸收的影响作了相应的讨论. 合成的新化合物均由核磁共振、红外光谱、元素分析予以证实.

关键词: 脱镁叶绿酸甲酯, 红紫素-18酰亚胺衍生物, 光敏剂, 光动力疗法

A series of novel purpurin-18 imide derivatives which had long wavelength absorption, were synthesized by modification of methyl pheophorbide-a. The 3-(2,2-dimethoxyethyl)-3-devinyl methyl pheophorbide-a was prepared by oxidation of methyl pheophorbide-a (MPa) with Tl(NO3)3 and transformed to 3-(2-oxo-ethyl)-3-devinyl methyl pheophor-bide-a with formic acid. The Grignard reaction of the formyl group at 3-position was carried out to give efficiently the corresponding 3-(2-hydroxylalkyl)-3-devinyl methyl pheophorbide-a. In basic conditions E-ring was converted into the six-membered cyclic anhydride to form purpurin-18 derivatives by the air-oxidation. The experimental results showed that 132-methyloxy- carbonyl group of methyl pheophorbide-a was not destroyed in the process of Grignard reaction. The spectral data of 1H NMR of the compounds showed that there were two methoxy groups in the molecule after Grignard reaction. It was possible to modify 3-vinyl by Grignard reaction and then transform E-ring as long as controlling reaction conditions. The title compounds were synthesized by transforming E-ring to im-ide-ring and then modifing 3-vinyl by Grignard reaction. They demonstrated a considerable bathochromic shift of the major absorption band in the red region of the optical spectrum. The effect on their visible spec-trum by variation of chemical construction was discussed. The structures of all new compounds were char-acterized by elemental analysis, UV, IR and 1H NMR spectra.

Key words: purpurin-18 imide, methyl pheophorbide-a, photosensitizer, photodynamic ther-apy