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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
引用本文:曾伟鹏,李小红,杜娟,李建梅,张平,胡常伟,孟祥光.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[J].化学学报,2010,68(1):27-32.
作者姓名:曾伟鹏  李小红  杜娟  李建梅  张平  胡常伟  孟祥光
作者单位: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
基金项目:国家自然科学基金(No.20803050);;教育部博士点基金(No.20090181110074);;国家重点基础研究发展计划(973)(No.2007CB210203)资助项目
摘    要: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pH6.5~8.5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
收稿时间:2009-04-02
修稿时间:2009-06-08

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.Kinetic Study on Oxidation of 1-(3,4-Dimethoxyphenyl)ethanol Catalyzed by Copper(Ⅱ) Complexes[J].Acta Chimica Sinica,2010,68(1):27-32.
Authors:Zeng  Weipeng  Li  Xiaohong  Du  Juan  Li  Jianmei  Zhang  Ping  Hu  Changwei  Meng  Xiangguang
Institution:College of Chemistry;Sichuan University;Key Laboratory of Green Chemistry and Technology;Ministry of Education;Chengdu 610064
Abstract:1-(3,4-Dimethoxyphenyl)ethanol (DMPE) was synthesized and used as the model of lignin. Ki-netics 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 k_2 and K_m 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.
Keywords:1-(3  4-dimethoxyphenyl)ethanol  copper(II) complex  hydrogen peroxide  kinetics  lignin
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