高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (5): 915.

• 研究论文 • 上一篇    下一篇

温控相转移配体及催化(ⅩⅥ)──Rh/PETPP催化的水/有机两相邻氯硝基苯CO还原反应动力学的研究

梅建庭1,2, 蒋景阳1, 王艳华1, 吴小伟1, 金子林1   

  1. 1. 大连理工大学精细化工国家重点实验室, 大连 116012;
    2. 大连舰艇学院三系, 大连 116018
  • 收稿日期:2000-11-27 出版日期:2002-05-24 发布日期:2002-05-24
  • 通讯作者: 蒋景阳(1959年出生),男,博士,副教授,主要从事均相催化研究.E-mail:jingyan@mail.dlptt.ln.cn E-mail:jingyan@mail.dlptt.ln.cn
  • 基金资助:

    国家自然科学基金(批准号:29876004);教育部博士点科研基金(批准号:98014111)资助.

Thermoregulated Phase-transfer Ligands and Catalysis(ⅩⅥ)──Kinetics Investigation of CO Selective Reduction of Aromatic Nitro Compounds Catalyzed by Rh/PETPP in Two-phasic System

MEI Jian-Ting1,2, JIANG Jing-Yang1, WANG Yan-Hua1, WU Xiao-Wei1, JIN Zi-Lin1   

  1. 1. State Key Laboratory of Fine Chemicals- Dalian University of Technology, Dalian 116012, China;
    2. No. Three Department, Dalian Naval Academy, Dalian 116018, China
  • Received:2000-11-27 Online:2002-05-24 Published:2002-05-24

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被引次数

20

摘要： 首次将具有"温控相转移催化"功能的非离子表面活性水溶性膦/铑配合物用于以CO为还原剂的水/有机两相芳香硝基物选择还原反应.以邻氯硝基苯为底物考察了反应温度、CO压力、底物浓度、催化剂浓度和水/有机两相体积比等对反应转化率和选择性的影响.结果表明,当反应条件为150℃和4MPa,反应32h时,邻氯硝基苯的转化率为98%,邻氯苯胺的选择性接近100%.动力学研究表明,底物浓度和催化剂浓度分别对反应速率呈一级,反应的表观活化能Ea=131.13kJ/mol.

关键词: 水溶性膦/铑配合物, 水/有机两相催化, 芳香硝基物, CO选择还原, 温控相转移催化

Abstract: The nonionic water-soluble phosphine ligand P[C6H4-p-(OC2H4)6OH]3(PETP)/Rh complex termed the thermoregulated phase-transfer catalysis (TRPTC) was applied to CO selective reduction of ni-troarenes compounds in the aqueous/organic two-phase.Using o-ClC6H4NO2 as a substrate, the influences of the reaction temperature, COpressure, concentration of substrate, concentration of catalyst and volume ratio of aqueous to organic on the catalyst properties were studied.Under the conditions 423 K, pco=4 MPa and t = 32 h, the conversions of o-ClC6H4NO2 were 98% and the selectivity for the corresponding amine was higher than 99%.The kinetics investigation suggested that first-order dependence was observed for the effect of the concentration of catalyst and o-ClC6H4NO2. The apparent activation energy was 131.13 kJ/mol.

Key words: Water-soluble phosphine rhodium complex, Water-organic biphasic catalysis, Nitroarenes, CO selective reduction, Thermoregulated phase-transfer catalysis

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