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有机化学 ›› 2007, Vol. 27 ›› Issue (03): 391-396. 上一篇    下一篇

研究论文

δ-(甲酰乙烯基)二氢卟吩衍生物的合成

王屹a,b，汪芳明b，瞿燕b，韩光范*,b，王进军c   

  1. (a北华大学化学系 吉林 132021)
    (b江苏科技大学材料科学与工程学院 镇江 212003)
    (c烟台大学应用化学系 烟台 264005)
  • 收稿日期:2006-01-26 修回日期:2006-08-20 发布日期:2007-02-13
  • 通讯作者: 韩光范

Synthesis of Derivatives of δ-(2-Formylvinyl)-Chlorins

WANG Yia,b,WANG Fang-Mingb,QU Yanb,HAN Guang-Fan*,b,WANG Jin-Junc   

  1. (a Department of Chemistry, Beihua University, Jilin 132021)
    (b School of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003)
    (c Department of Chemistry, Yantai University, Yantai 262005)
  • Received:2006-01-26 Revised:2006-08-20 Published:2007-02-13
  • Contact: HAN Guang-Fan

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以脱镁叶绿酸-a甲酯为原料, 利用Vilsmeier反应合成δ-(甲酰乙烯基)二氢卟吩衍生物. 镍(II)脱镁叶绿酸-a甲酯和镍(II)红紫素-18与Vilsmeier试剂作用, 生成了E环被打开的镍(II) δ-(甲酰乙烯基)红紫素-7-三甲酯和镍(II) δ-(甲酰乙烯基)二氢卟吩P6三甲酯. 镍(II) N-乙酰氧基红紫素-18-酰亚胺和Vilsmeier试剂作用, 生成了镍(II) δ-(甲酰乙烯基)-N-乙酰氧基红紫素-18-酰亚胺. 当这些化合物脱去镍离子后, 吸收波长明显红移, δ-(甲酰乙烯基)-N-乙酰氧基红紫素-18-酰亚胺的吸收波长达到742 nm. 同时保留了对δ-位再进行化学修饰的可能性. 合成的新化合物均由核磁共振、红外光谱、元素分析和质谱予以证实.

关键词: 二氢卟吩P6三甲酯, 红紫素-18-酰亚胺, Vilsmeier反应, 红紫素-7-三甲酯

Starting from methyl pheophorbide-a, the derivatives of δ-(2-formylvinyl)-chlorins were synthesized by Vilsmeier reaction. The nickel(II) methyl pheophorbide-a or nickel(II) methyl purpurin-18 reacted with 3-(dimethylamino)-acrolein/phosphoryl chloride to give nickel(II) δ-(2-formylvinyl)-purpurin-7-trimethyl ester or nickel(II) δ-(2-formylvinyl)-chlorin P6 trimethyl ester. When nickel(II) purpurin-18 imide reacted with Vilsmeier agent, the deriva-tives of nickel(II) δ-(2-formylvinyl)-purpurin-18 imide were obtained. By treatment of the deriva-tives of nickel(II) δ-(2-formylvinyl)-chlorin with trifluoroacetic acid, the removal of central nickel(II) ion was accomplished. The derivatives of δ-(2-formylvinyl)-chlorin demonstrated a con-siderable bathochromic shift of the major absorption band in the red region of the optical spectrum. The maximal UV/vis absorption of δ-(2-formylvinyl)-purpurin-18 imide was 742 nm. The structures of all new compounds were characterized by elemental analysis, UV, IR, MS and 1H NMR spec-tra.

Key words: purpurin-18 imide, purpurin-7-trimethyl ester, chlorine P6 trimethyl ester, Vilsmeier reaction