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化学学报
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化学学报 ›› 2010, Vol. 68 ›› Issue (01): 27-32. 上一篇    下一篇

研究论文

金属铜配合物催化氧化1-(3,4-二甲氧基苯)乙醇的动力学研究

曾伟鹏，李小红，杜娟，李建梅，张平，胡常伟，孟祥光   

  1. (四川大学化学学院 绿色化学与技术教育部重点实验室 成都 610064)
  • 投稿日期:2009-04-02 修回日期:2009-06-08 发布日期:2009-09-01
  • 通讯作者: 孟祥光 E-mail:mengxgchem@163.com
  • 基金资助:

    国家自然科学基金项目(No.: 20107004;20803050 )和国家重点基础研究发展计划（973）（No.:2007CB210203）

Kinetic Study on Oxidation of 1-(3,4-dimethoxyphenyl)ethanol Catalyzed by Copper(II) Complexes

Zeng Weipeng, Li Xiaohong, Du Juan, Li Jianmei, Zhang Ping, Hu Changwei, Meng Xiangguang   

  1. (College of Chemistry, Sichuan University, Key Laboratory of Green Chemistry and Technology, Ministry of Education, Chengdu 610064)
  • Received:2009-04-02 Revised:2009-06-08 Published:2009-09-01
  • Contact: Xiang-Guang Meng E-mail:mengxgchem@163.com

PDF

1586

被引次数

25

合成了1-(3,4-二甲氧基苯)乙醇(DMPE)作为木质素模型物, 并用初始速率法研究了40 ℃时在pH 6.5～8.5磷酸缓冲溶液中N,N-双(2-乙基-5-甲基-咪唑-4-亚甲基)乙醇胺合铜、N,N-双(2-(2-羟乙基胺基)乙基)草酰胺合铜和5,7,12,14-四甲基-1,4,8,11-四氮杂环十四-4,7,11,14-四烯合铜催化氧化1-(3,4-二甲氧基苯)乙醇的动力学, 提出了1-(3,4-二甲氧基苯)乙醇氧化反应动力学模型, 并由此计算出不同pH值条件下催化反应动力学参数k2和Km. 铜配合物的催化活性随着pH的增大而增大. 具有大共轭体系的配体催化剂表现出更好的催化活性. 提出并讨论了H2O2氧化DMPE的催化氧化反应机理.

关键词: 1-(3,4-二甲氧基苯)乙醇, 铜配合物, 过氧化氢, 动力学, 木质素

1-(3,4-Dimethoxyphenyl)ethanol (DMPE) was synthesized and used as the model of lignin. Kinetics of the reaction of DMPE with hydrogen peroxide catalyzed by three copper(II) complexes was studied in phosphoric acid buffer solution at 40 ℃. A kinetic model of catalytic oxidation of DMPE was suggested, and the kinetic parameters k2 and Km under different conditions were obtained. The catalytic efficiency of the copper(II) complexes increased with increasing pH. The complex with the electron conjugated ligand showed the best catalytic activity on the oxidation reaction. A possible catalytic mechanism of the oxidation of DMPE was proposed and discussed in detail.

Key words: 1-(3,4-dimethoxyphenyl)ethanol, copper(II) complex, hydrogen peroxide, kinetics, lignin