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2013 , Vol. 33 >Issue 04: 820 - 826

DOI: https://doi.org/10.6023/cjoc201301077

研究论文

蒙脱土负载Pd/Cu双金属纳米微粒催化Sonogashira偶联反应

  • 徐伟 ,
  • 孙原龙 ,
  • 郭萌涵 ,
  • 张伟强 ,
  • 高子伟
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  • 陕西师范大学化学化工学院 西安 710062

收稿日期: 2013-01-29

  修回日期: 2013-03-18

  网络出版日期: 2013-03-22

基金资助

国家自然科学基金(Nos. 21271124, 21041004, 20771071)、教育部新世纪优秀人才项目支持计划(No. NCET-07-0528)、中央高校基本业务费(Nos. GK201004010, GK201002031)及“春笋计划”(No. 2010-2011西安中学)资助项目.

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Montmorillonite Supported Pd/Cu Bimetallic Nanoparticle Catalyzed Sonogashira Coupling

  • Xu Wei ,
  • Sun Yuanlong ,
  • Guo Menghan ,
  • Zhang Weiqiang ,
  • Gao Ziwei
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  • School of Chemisty & Chemical Engineering, Shaanxi Normal University, Xi'an 710062

Received date: 2013-01-29

  Revised date: 2013-03-18

  Online published: 2013-03-22

Supported by

Project supported by the National Natural Science Foundation of China (Nos. 21271124, 21041004, 20771071), the Program for New Century Excellent Talents in University (No. NCET-07-0528), the Fundamental Research Funds for the Central Universities (Nos. GK201002031, GK201004010) and the Doctoral Fund of Ministry of Education of China (No. 20120202120005).

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摘要

为了证实过渡金属催化碳碳键交叉偶联反应的双金属效应, 首次研究蒙脱土负载纳米钯铜双金属微粒催化Sonogahira交叉偶联反应. 结合蒙脱土重金属吸附特性与DMF溶剂热羰化还原, 发展了一种新的双金属纳米微粒合成方法, 制备了钯铜比例为1∶1的双金属纳米微粒. 催化条件优化实验发现, 乙二醇二甲醚/水(V∶V＝1∶4)混合体系为最佳溶剂. 碳酸钾与三苯基膦存在下, MMT@Pd/Cu高效催化芳基碘与系列端炔的交叉偶联反应, 以较好产率分离得到15个炔烃衍生物. 动力学研究表明, 水对蒙脱土片层的溶胀作用与Pd/Cu双金属协同效应是该催化剂高活性的关键.

关键词： 过渡金属催化; 蒙脱土; 碳—碳键交叉偶联; 双金属效应

本文引用格式

徐伟 , 孙原龙 , 郭萌涵 , 张伟强 , 高子伟 . 蒙脱土负载Pd/Cu双金属纳米微粒催化Sonogashira偶联反应[J]. 有机化学, 2013 , 33(04) : 820 -826 . DOI: 10.6023/cjoc201301077

Abstract

To demonstrate the bimetallic effect of transition metal catalyzed C—C cross coupling, the montmorillonite (MMT) supported mixed palladium and copper nanoparticles were prepared and applied to catalytic Sonogashira couplings. A new method of preparing mixed metal nanoparticles was invented based on unique metal ion adsorption capacity of montmorillonite and sequential reductive carbonylation via thermolysis of N,N-dimethylformide, and Pd/Cu bimetallic nanoparticals was prepared in the ratio of 1∶1. A mixed solvent system, dimethoxyethane/water (V∶V＝1∶4) was identified as the best solvent of the catalytic coupling. MMT@Pd/Cu catalyzed efficiently the cross-coupling of aryl iodides and terminal aryl- and alkyl-ynes in presence of potassium carbonate and triphenyl phosphine. 15 cross-coupling yne derivatives were isolated in excellent to moderate yields. Experimental kinetic study reveals that both swelling of montmorillonite promoted by water and Pd/Cu bimetallic synergistic effect play critical roles in high activity of the catalyst.

Key words： transition metal catalysis; montmorillonite; C—C cross-coupling; bimetallic effect

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