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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (24): 2211-2215. 上一篇    下一篇

研究论文

由氢醌与2-硝基卟啉直接合成2-氢醌卟啉的反应研究

陈世清1，黄齐茂*,1，陈彰评2，徐汉生2   

  1. (1武汉化工学院化工与制药系 湖北省新型反应器与绿色化学工艺重点实验室 武汉 430073)
    (2武汉大学化学与分子科学学院 武汉 430072)
  • 投稿日期:2005-02-01 修回日期:2005-09-14 发布日期:2005-12-28
  • 通讯作者: 黄齐茂

Study on the Direct Synthesis of 2-Hydroquinon-2'-yl Porphyrin from 2-Nitroporphyrin and Hydroquinone

CHEN Shi-Qing1, HUANG Qi-Mao*,1, CHEN Zhang-Ping2, XU Han-Sheng2   

  1. (1 Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430073)
    (2 College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072)
  • Received:2005-02-01 Revised:2005-09-14 Published:2005-12-28
  • Contact: HUANG Qi-Mao

PDF

946

被引次数

11

由氢醌与2-硝基-5,10,15,20-四苯基卟啉或其金属配合物(2-NO2MTPP)直接反应合成2-氢醌卟啉I, 同时得到了另一产物II. 通过MS, IR, 1H NMR及 2D NMR测定, 确定I与II中的2-取代基分别为氢醌与半醌, 两者为互变异构体, 且II是生成I的前体. 高温下, 水与空气介入反应体系能明显提高反应速率及产率, 此时氧气的介入是提高反应速率的关键, 而水介入反应体系将导致较强的酸性环境, 更有利于II异构为产物I. 整个反应可能为单电子转移(SET)的自由基反应.

关键词: 2-氢醌卟啉, 合成, 单电子转移, 自由基机理

2-(Hydroquinon-2-yl)-5,10,15,20-tetraphenyl porphyrin and its metal complexes I were synthesized by the direct reaction of 2-nitro-5,10,15,20-tetraphenyl porphyrin with neutral hydroquinone in 60%～80% yields. 2-Substituted porphyrin tautomers II were also obtained as byproduct and characterized by MS, IR, 1H NMR and 2D NMR as precursor and dynamic isomer of I. In applications of water and O2 intrusion at high temperature, both the rate and the yield of the system were increased obviously. The O2 intrusion would be the key for the increase of the rate and the water intrusion would lead to the more acidic environment resulting in the isomerization of II to I. From these experiments it was concluded that single-electron transfer free radical reaction mechanism was involved in the reaction.

Key words: 2-hydroquinon-2'-yl porphyrin, synthesis, single-electron transfer, free radical mechanism