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2012 , Vol. 32 >Issue 9: 1700 - 1707

DOI: https://doi.org/10.6023/cjoc1202055

研究论文

焦脱镁叶绿酸-a甲酯的空气氧化反应及其二氢卟吩衍生物的合成

  • 王鲁敏 ,
  • 王朋 ,
  • 刘超 ,
  • 金英学 ,
  • 王进军
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  • a 烟台大学化学化工学院 烟台 264005;
    b 哈尔滨师范大学化学化工学院 哈尔滨 150025;
    c 山东省黄金工程技术研究中心(工业应用) 烟台 264005

收稿日期: 2012-02-05

  修回日期: 2012-05-16

  网络出版日期: 2012-03-27

基金资助

国家自然科学基金(No.20972036 )和山东省自然科学基金(No.Y2008B49)资助项目

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Allomerization of Methyl Pheophorbide-a and Synthesis of Chlorin Derivatives

  • Wang Lumin ,
  • Wang Peng ,
  • Liu Chao ,
  • Jin Yingxue ,
  • Wang Jinjun
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  • a College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005;
    b College of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025;
    c Shandong Applied Research Centre of Gold Nanotechnology (Au-SDARC), Yantai 264002

Received date: 2012-02-05

  Revised date: 2012-05-16

  Online published: 2012-03-27

Supported by

Project supported by the National Natural Science Foundations of China (No.20972036) and the Natural Science Foundation of Shandong Province of China(No.Y2008B49)

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摘要

以焦脱镁叶绿酸-a甲酯为起始原料,在碱性条件下对其实施空气氧化反应,分离出一系列在外接E-环和12-位甲基上的氧化和重排产物,氯代焦脱镁叶绿酸-a甲酯的相同反应也经历了类似的反应历程.132-位和12-位氧化产物的进一步空气氧化给出两种不同的反应结果,前者反应迅速且产物复杂,而后者则基本不发生反应.首次报道的二氢卟吩衍生物均经UV,IR,1H NMR及元素分析确定其化学结构,对相应的化学反应也提出了可能的反应机理.

关键词： 叶绿素-a; 焦脱镁叶绿酸; 二氢卟吩; 空气氧化反应; 反应机理

本文引用格式

王鲁敏 , 王朋 , 刘超 , 金英学 , 王进军 . 焦脱镁叶绿酸-a甲酯的空气氧化反应及其二氢卟吩衍生物的合成[J]. 有机化学, 2012 , 32(9) : 1700 -1707 . DOI: 10.6023/cjoc1202055

Abstract

The allomerization of methyl pyropheophorbide-a, used as starting material, was carried out under the alkaline condition to separate a series of oxidized and rearranged products at exocyclic E-ring and C-12-methyl group. The same reaction of chlorinated methyl pyropheophorbide-a also came through similar processes. The further oxidations of C-132-and C-12-oxidized products gave two different results, the former reacted quickly and produced complicated compounds, the latter HH basically HH unchanged under the same condition. The structures of all new chlorin derivatives were characterized by elemental analysis, UV, IR and 1H NMR spectra. The possible mechanisms about corresponding reactions were tentatively proposed.

Key words： chlorophyll-a; pyropheophorbide; chlorin; allomerization; mechanism

参考文献

[1] Kozyrev, A. N.; Chen, Y.-H.; Goswami, L. N.; Tabaczynski, W. A.; Pandey, P. K. J. Org. Chem. 2006, 71, 1949.

[2] Hynninen, P. H.; Hyvärinen, K. H. J. Org. Chem. 2002, 67, 4055.

[3] Kunieda, M.; Tamiaki, H. J. Org. Chem. 2008, 73, 7686.

[4] Wang, J.-J. Chin. J. Org. Chem. 2005, 25, 1353 (in Chinese).(王进军, 有机化学, 2005, 25, 353.)

[5] Ethirajan, M.; Joshi, P.; Willian, W. H.; Ohkubo, K.; Fukuzumi, S.; Pandey, R. K. Org. Lett, 2011, 13, 1956.

[6] Goslinski, T.; Piskorz, J. J. Photochem. Photobiol., C 2011, 12, 304.

[7] Wu, J.; Yin, J.-G.; Zhang, Q.; Sun, C.-M.; Li, F.-G.; Pei, W.; Wang, J.-J. Chin. J. Org. Chem. 2011, 31, 1653 (in Chinese).(武进, 殷军港, 张千, 孙传民, 李付国, 裴文, 王进军, 有机化学, 2011, 31, 1653.)

[8] Yin, J.-G.; Wu, X.-R.; Liu, C.-L.; Zhao, L.-L.; Jin, Y.-X.; Wang, J.-J. Chin. J. Org. Chem. 2011, 31, 1870 (in Chinese).(殷军港, 邬旭然, 刘春林, 赵丽丽, 金英学, 王进军, 有机化学, 2011, 31, 1870.)

[9] Wang, J.-J.; Zhang, P.; Wang, P.; Chen, G.-L.; Li, F.-G. Chin. J. Org. Chem. 2010, 30, 1192 (in Chinese).(王进军, 张朋, 王朋, 陈冠龙, 李付国, 有机化学, 2010, 30, 1192.)

[10] Smith, K. M.; Gogg, D. A.; Simpson, D. J. J. Am. Chem. Soc. 1985, 107, 4946.

[11] Zhang, G.; Potter, R. P.; Camacho, S. H.; Missert, J. R.; Wang, G. H.; Bellnier, D. A.; Henderson, B. W.; Rodgers, M. A. J.; Dougherty, T. J.; Pander, R. K. J. Med. Chem, 2001, 44, 1540.

[12] (a) Wang, J.-J.; Zhao, L.-L.; Li, J.-J. Chin. J. Org. Chem. 2009, 29, 1598 (in Chinese).(王进军, 赵丽丽, 李家柱, 有机化学, 2009, 29, 1598.)

(b) Li, J.-Z. M.S. Thesis, Yantai University, Yantai, 2007 (in Chinese).(李家柱, 硕士论文, 烟台大学, 烟台, 2007.)  

[13] Juho, H.; Maria, S. M.; Ilkka, K.; Paavo, H. H. J. Org. Chem. 2000, 65, 3700.

[14] Hynninen, P. H.; Kavakka, J. S.; Mesilaakso Tetrahedron Lett. 2005, 46, 1145.  

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