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有机化学 ›› 2007, Vol. 27 ›› Issue (04): 494-501. 上一篇    下一篇

研究论文

具有叶绿素-a碳架的(细菌)卟吩衍生物的合成及其共轭区域变化对光谱性能的影响

纪建业a，王鲁敏b，荆济荣b，韩光范c，王进军*,b   

  1. (a通化师范学院化学系 通化 134002)
    (b烟台大学应用化学系 烟台 264005)
    (c江苏科技大学材料科学工程学院 镇江 212003)
  • 收稿日期:2005-10-24 修回日期:1900-01-01 发布日期:2007-03-29
  • 通讯作者: 王进军

Synthesis of Bacteriochlorin Derivative with Chlorophyll-a Skeleton and Effect on the Spectra by Change in the Conjugate Region

JI Jian-Yea, WANG Lu-Minb, JIN Ji-Rongb, HAN Guang-Fanc, WANG Jin-Jun*,b   

  1. (a Department of Chemistry, College of Teachers, Tonghua 134002)
    (b Department of Applied Chemistry, Yantai University, Yantai 264005)
    (c School of Materials Science and Engineering, Jiangsu University of Technol-ogy, Zhenjiang 212003)
  • Received:2005-10-24 Revised:1900-01-01 Published:2007-03-29
  • Contact: WANG Jin-Jun

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1083

被引次数

12 | 2

以脱镁叶绿酸-a甲酯(MP-a) (1)为起始原料, 通过四氧化锇和高碘酸钠的氧化给出3-位乙烯基和132-位α-氢的氧化产物2和3, 再用四氧化锇继续氧化卟吩醛2则得到细菌卟吩醛4. 经脱甲酸甲酯和硝酸铊氧化, MP-a (1)转化为焦脱镁叶绿酸衍生物5, 将其进一步用四氧化锇氧化则形成细菌卟吩缩醛6. 卟吩醛2在碱性条件下转化为卟吩e6三甲酯7, 2与烷基溴化镁的格氏反应给出脱镁叶绿酸醇9, 选择高钌酸四丙基铵(TPAP)和N-甲基吗啉N-氧化物将3-位羟基氧化成羰基, 所生成的卟吩二酮10在酸性条件下脱去甲酸甲酯生成焦脱镁叶绿酸衍生物11, 用四氧化锇对7和11实施氧化, 则分别转化为细菌卟吩衍生物8和12. 同时, 讨论了叶绿素衍生物的共轭区域变化对其光谱性能的影响. 所合成的新卟吩和细菌卟吩衍生物均经UV, IR, 1H NMR及元素分析证明其结构.

关键词: 叶绿素-a衍生物, 光动力疗法(PDT), 卟吩, 氧化反应, 细菌卟吩

Methyl pheophorbide-a (MP-a) (1) was used as starting material and was oxidized with osmium(VIII) oxide followed by ethylene glycol cleavage with sodium periodate to give 2 and 3 for oxidizing vinyl group at 3-position and for α-hydrogen at 132-poaition respectively. The chlorin aldehyde 2 was oxidized continually with os-mium(VIII) oxide to give bacteriochlorin aldehyde 4. After eliminating for methyl formate and oxi-dizing with thallium(III) nitrate MP-a (1) was converted into pyropheophorbide derivative 5 which was oxidized again with osmium(VIII) oxide to generate becteriochlorin acetal 6. In the basic condition chlorin aldehyde 2 was converted into chlorin e6 derivatives 7. The Grignard reaction of 2 with alkyl magnesium bromide afforded pheophorbide alco-hol 9 followed by oxidation with tetrapropylammonium perruthenate (TPAP) and N-methylmorpholine N-oxide to afford chlorin diketoester 10. The conversion of 10 from pheophorbide to pyropheophorbide was completed in acid condition by refluxing to form methyl 3-alkylcarbonyl-3-devinylpyropheophorbide-a 11. The chlorin e6 7 and chlorin 11 were oxidized further with osmium(VIII) oxide in the same oxidization condition to yield bateriochlorin 8 and 12, respectively. The effect on the spectra by change in the conjugate region was discussed. The structures of the compounds were characterized by elemental analysis, UV, IR and 1H NMR spectra.

Key words: bateriochlorin, oxidation, photodynamic therapy, chlorine, chlorophyll-a