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有机化学
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有机化学 ›› 2001, Vol. 21 ›› Issue (10): 746-750. 上一篇    下一篇

研究论文

区域选择性合成2-硝基-5, 10, 15, 20-四芳基金属卟啉

黄齐茂;陈彰评;徐汉生;吴萱阶;赵勇刚;张小伟   

  1. 武汉大学化学与分子科学学院
  • 发布日期:2001-10-25

Regioselective synthesis of 2-nitro-5, 10, 15, 20- tetraarylporphyrinato metal

Huang Qimao;Chen Zhangping;Xu Hansheng;Wu Xuanjie;Zhao Yonggang;Zhang Xiaowei   

  • Published:2001-10-25

PDF

582

被引次数

56

研究了以硝酸盐为硝化剂与中位四芳基金属卟啉反应、选择性合成2-硝基-5,10,15,20-四芳基卟啉的方法，发现配位金属离子、中位苯环上的取代基对反应产率和时间有明显的影响，当金属离子为铜、镍时，可得定量的2-硝基卟啉，为锌时，完成反应的时间延长，反应产率迅速下降。推电子的甲氧基能加快反应的进行，吸电子的氯原子则延缓反应的进行。讨论了金属离子和取代基团对反应影响的原因。

关键词: 区域选择性, 立体选择性, 金属离子, 取代基效应, 硝酸盐, 卟啉, 金属络合物

A regioselective sythesis of 2-nitro-meso- tetraarylporphyrinato metal was achieved by reaction of mesotetraarylporphyrinato metal with relative metal nitrate salt in acetic acid/acetic anhydride. The yield of 2-nitro substituted porphyrin depended on the coordinated metal. When the metal was Cu(Ⅱ) or Ni(Ⅱ), quantitative yields of 2- NO2-5, 10, 15, 20-tetra(4-methoxyphenyl) porphyrinato Cu(Ⅱ) and Ni(Ⅱ) were obtained in 5 min and 50 min, respectively, at 45℃, while the metals are Co(Ⅱ) and Zn(Ⅱ), 64% and 12% of 2-NO2-5, 10, 15, 20- tetra(4-methoxyphenyl) porphyrinato metal were obtained in 100 min and 120 min, respectively. The same metal effects were also found with other meso-substituted porphyrins. Electron-donating substituents accelerated the reaction and electron-withdrawing substituents had the opposite effect. The effects of complexed metal ions and meso- substituents are discussed.

Key words: REGIOSELECTIVITY, STEREOSELECTIVITY, METAL ION, SUBSTITUENT EFFECT, NITRATE, PORPHYRIN, METAL COMPLEX

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