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.
出处
《有机化学》
SCIE
CAS
CSCD
北大核心
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
