有机化学 ›› 2013, Vol. 33 ›› Issue (11): 2357-2366.DOI: 10.6023/cjoc201305006 上一篇    下一篇

研究论文

红紫素-18的周环结构修饰及其叶绿素类二氢卟吩衍生物的合成

梁波颖a, 刘洋b, 徐希森b, 金英学a, 祁彩霞c, 王进军b,c   

  1. a 哈尔滨师范大学化学化工学院 哈尔滨 150025;
    b 烟台大学化学化工学院 烟台 264005;
    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:2013-05-03 修回日期:2013-07-14 发布日期:2013-07-19
  • 通讯作者: 金英学,王进军 E-mail:wjj1955@163.com
  • 基金资助:

    国家自然科学基金(No. 21272048)和山东省黄金工程技术研究中心(2011年度)资助项目.

Modifications for Peripheral Structures of Purpurin-18 and Synthesis of Chlorophyllous Chlorin Derivatives

Liang Boyinga, Liu Yangb, Xu Xisenb, Jin Yingxuea, Qi Caixiac, Wang Jinjunb,c   

  1. a College of Chemistry & Chemical Engineering, Harbin Normal University, Harbin 150025;
    b College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005;
    c Shandong Applied Research Centre of Gold Nanotechnology Au-SDARC, Yantai 264005
  • Received:2013-05-03 Revised:2013-07-14 Published:2013-07-19
  • Supported by:

    Project supported by the National Natural Science Foundations of China (No. 21272048) and the Project of Shandong Applied Reaearch Centre of Gold Nano-technology (2011).

以红紫素-18甲酯为起始原料,利用其3-位乙烯基的多电子性,通过氧化、还原、亲电加成和1,3-偶极环加成等反应,对其N21-N23轴的端向结构进行化学修饰,在周环的3-位上引进了能与大环色基以不同方式形成共轭效应的取代基团,完成了11个未见报道具有红紫素-18碳架的叶绿素类二氢卟吩衍生物的合成,其化学结构均经UV,1H NMR,IR及元素分析予以证实; 讨论了红紫素-18的周环结构对其电子光谱所产生的影响,并对相应的化学反应提出了可能的反应机理.

关键词: 叶绿素-a, 二氢卟吩, 红紫素-18, 化学修饰, 合成

Purpurin-18 methyl ester was used as a starting material, and the modifications for the structure on the terminal of its N21-N23-axis were completed making use of electron-richous properties of C (3)-vinyl group by various reactions including oxidation, reduction, electrophilic addition and 1, 3-polar cycloaddition. The substituted groups, which could conjugated with macrocyclic chromophore in different form, were introduce to 3-position on the periphery, respectively. The synthesis of 11 unreported chlorophyllous chlorins with basic skeloton of purpurin-18 was accomplished and their chemical structures were characterized by elemental analysis, UV, IR and 1H NMR spectra. The influence of peripheric structure of purpurin-18 on their electronic spectrum was discussed and the possible mechanisms about corresponding reactions were tentatively proposed.

Key words: chlorophyll-a, chlorin, purpurin-18, chemical modification, synthesis