区域选择性合成2-硝基-5, 10, 15, 20-四芳基金属卟啉

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。

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

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.