区域选择性合成2—硝基—5，10，15，20—四芳基金属卟啉  

Regioselective Synthesis of 2-Nitro-5,10,15,20-tetraarylporphyrinato Metal

作　　者：黄齐茂[1] 陈彰评[1] 徐汉生[1] 吴萱阶[1] 赵勇刚[1] 张小伟[1] 

机构地区：[1]武汉大学化学与分子科学学院,

出　　处：《有机化学》2001年第10期746-750,共5页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金

摘　　要：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.A regioselective synthesis of 2-nitro-meso-tetzaarylporphyrinato metal was achieved by reaction of mesotetraarylporphyrinato metal with relative metal nib-ate 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 degreesC, 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.

关 键 词：硝酸盐 区域选择性合成 2-硝基取代金属卟啉 金属离子 取代基效应 2-硝基-5 10 15 20-四芳基金属卟啉 

分 类 号：O626.13[理学—有机化学]