SIOC English
有机化学
高级检索

有机化学 >

2012 >Issue 03: 544 - 551

DOI: https://doi.org/10.6023/cjoc1105231

研究论文

红紫素-18 的卤化反应及其二氢卟吩类衍生物的合成

  • 刘冉冉 ,
  • 殷军港 ,
  • 李家柱 ,
  • 武进 ,
  • 陈冠龙 ,
  • 金英学 ,
  • 王进军
展开
  • 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

收稿日期: 2011-05-23

  修回日期: 2011-07-16

  网络出版日期: 2012-03-24

基金资助

山东省自然科学基金(No. Y2008B49)、科技部中匈政府间科技合作(No. 2009-2010 年度)资助项目.

收起

Halogenation Reaction of Purpurin-18 and Synthesis of Chlorin Derivatives

  • Liu Ranran ,
  • Yin Jungang ,
  • Li Jiazhu ,
  • Wu Jin ,
  • Chen Guanlong ,
  • Jin Yingxue ,
  • Wang Jinjun
Expand
  • a Colledge of Chemistry and Chemical Engineering, Yantai University, Yantai 264005;
    b College of Chemistry and Chemical Engineering, Harbin Normal University, Harbin 150025

Received date: 2011-05-23

  Revised date: 2011-07-16

  Online published: 2012-03-24

Supported by

Project supported by the Natural Science Foundation of Shandong Province of China (No. Y2008B49) and the International Science and Technology Project between the Government of China and Hungary (No. 2008-444-4-32)

Fold

摘要

从红紫素-18 甲酯开始, 通过对其3-位乙烯基和20-meso-位的亲电加成和亲电取代反应, 区域选择性地给出相应的氯代或者溴代产物. 红紫素-18 甲酯与重氮甲烷的1,3 偶极环加成反应生成C(3)-吡唑啉基取代的红紫素-18, 继续与N-溴代丁二酰亚胺(NBS)和N-氯代丁二酰亚胺(NCS)进行亲电取代反应, 生成相应的卤代吡唑啉基取代二氢卟吩. 3-吡唑啉基红紫素-18 热裂解后的卤代反应则给出3-环丙基-20-卤代二氢卟吩. 选择脱镁叶绿酸-a 甲酯为另一起始反应物,通过C(3)-乙烯基和E-环结构的一系列化学转换和20-meso-位的溴代反应, 区域选择性地得到20-溴代红紫素-18 衍生物. 新报道的标题化合物均经UV, IR, 1H NMR 及元素分析证明其结构.

关键词： 叶绿素-a; 红紫素-18; 焦脱镁叶绿酸-a 甲酯; 化学修饰; 二氢卟吩; 光动力疗法(PDT)

本文引用格式

刘冉冉 , 殷军港 , 李家柱 , 武进 , 陈冠龙 , 金英学 , 王进军 . 红紫素-18 的卤化反应及其二氢卟吩类衍生物的合成[J]. 有机化学, 2012 , (03) : 544 -551 . DOI: 10.6023/cjoc1105231

Abstract

From purpurin-18 methyl ester the electrophilic addition of C(3)-vinyl group and electrophilic substitution at 20-meso-position produced regioselectively corresponding chloro-substituted or bromo-substituted products. The 3-pyrazolinylpurpurin- 18 ester, obtained by 1,3-dipolar cycloaddition of purpurin-18 with diazomethane, reacted with N-bromosuccinimide (NCS) or N-chlorosuccinimide (NBS) to generate halogenated pyrazolinyl-substituted chlorins. After pyrolysis the halogenations of 3-pyrazolinylpurpurin-18 ester gave 20-halogenated 3-cyclopropylchlorins. Methyl pheophorbide-a was used another starting material and converted into 20-bromopurpurin-18 derivatives by a series of chemical conversion for C(3)- vinyl group and bromination at 20-position. The structures of newly-reported title compounds were characterized by elemental analysis, UV, IR and 1H NMR spectra.

Key words： chlorophyll-a; purpurin-18; methyl pyropheophorbide-a; chemical modification; chlorin; photodynamic therapy (PDT)

参考文献

[1] (a) Bellnier, D. A.; Greco, W. R.; Loewen, G. M.; Nava, H.;Oseroff, A. R.; Pandey, R. K.; Tsuchida, T.; Dougherty, T. J. CancerRes. 2003, 63, 1806.(b) Li, J.-J.; Wang, J.-J.; Yoon, I.; Cui, B.-C.; Shim, Y.-K. Bioorg.Med. Chem. Lett, 2012, 22, 1866.

[2] (a) Steruberg, E. D.; Dolphin, D. Tetrahedron 1998, 54, 4151.(b) 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, 王进军, 有机化学,2011, 31, 1653).(c) Wang, P.; Yang, Z.; Li, J.-Z.; Yao, N.-N.; Wang, J.-J. Chin. J.Org. Chem. 2012, 32, 368 (in Chinese).(王朋, 杨泽, 李家柱, 姚楠楠, 王进军, 有机化学, 2012, 32,368.)

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

[4] Rungta, A.; Zheng, G.; Missert, J. R.; Potter, W. R.; Dougherty, T.;Pandey, R. K. Bioorg. Med. Chem. Lett. 2000, 10, 1463.  

[5] Zheng, G.; Potter, W. R.; Camacho, S. H.; Missert, J. R.; Wang,G.-C.; Bellnier, D. A.; Henderson, B. W.; Michael, H.; Rodgers, M.A. J.; Dougherty, T. J.; Pandey, R. K. J. Med. Chem. 2001, 44,1540.  

[6] Rungta, A.; Zheng, G.; Missert, J. R.; Potter, W. R.; Dougherty, T.;Pandey, R. K. Bioorg. Med. Chem. Lett. 2000, 10, 1463.  

[7] Wang, J.-J.; Han, G.-F.; Wu, X.-Y.; Shim, Y.-K. Chin. J. Org.Chem. 2005, 25, 101 (in Chinese).(王进军, 韩光范, 邬旭然, 沈荣基, 有机化学, 2005, 25, 101.)

[8] Wang, J.-J.; Li, J.-Z.; Wu, X.-R.; Shim, Y.-K. Chin. J. Chem. 2006,24, 933.

[9] Wang, J.-J.; Ji, J.-Y.; Jing, J.-R.; Li, J.-Z.; Han, G. F.; Shim, Y.-K.Chin. J. Org. Chem. 2006, 26, 470 (in Chinese).(王进军, 纪建业, 荆济荣, 李家柱, 韩光范, 沈荣基, 有机化学,2006, 26, 470.)

[10] (a) Wang, J.-J.; Wu, X.-R.; Shim, Y.-K. Chin. J. Chem. 2005, 23,76.(b) Liu, R.-R.; Wang, L.-M.; Yin, J.-G.; Wu, J.; Liu, C.; Zhang, P.;Wang, J.-J. Chin. J. Org. Chem. 2012, 32, 318 (in Chinese).(刘冉冉, 王鲁敏, 殷军港, 武进, 刘超, 张朋, 王进军, 有机化学, 2012, 32, 318.)(c) 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, 1879.)

[11] Wang, J.-J.; Han, G.-F.; Wu, X.-R.; Wang, L.-M.; Shim, R.-J. Chin.J. Org. Chem. 2004, 24, 537 (in Chinese).(王进军, 韩光范, 邬旭然, 王鲁敏, 沈荣基, 有机化学, 2004,24, 537.)

[12] Tatar, J.; Stojanovic, M. B.; Stojanovic, M.; Markovic, R. TetrahedronLett. 2009, 50, 700.  
Options
文章导航

/

〈 〉