化学学报 ›› 2006, Vol. 64 ›› Issue (12): 1269-1272. 上一篇    下一篇

研究论文

茂钛类络合物催化碳酸二甲酯和苯酚酯交换反应合成碳酸二苯酯的研究

牛红英1,3,郭海明1,2,3,姚洁1,王越1,王公应*,1   

  1. (1中国科学院成都有机化学研究所 成都 610041)
    (2河南师范大学化学与环境科学学院 新乡 453002)
    (3中国科学院研究生院 北京 100039)
  • 投稿日期:2005-09-28 修回日期:2006-02-20 发布日期:2006-06-28
  • 通讯作者: 王公应

Transesterification of Dimethyl Carbonate and Phenol to Diphenyl Carbonate Catalyzed by Titanocene Complexes

NIU Hong-Ying1,3, GUO Hai-Ming1,2,3, YAO Jie1, WANG Yue1, WANG Gong-Ying*,1   

  1. (1 Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041)
    (2 Henan Normal University, College of Chemistry and Environmental Science, Xinxiang 453002)
    (3 Graduate School of Chinese Academy of Sciences, Beijing 100039)
  • Received:2005-09-28 Revised:2006-02-20 Published:2006-06-28
  • Contact: WANG Gong-Ying

首次将二氯二茂钛用于碳酸二甲酯和苯酚酯交换合成碳酸二苯酯的反应, 发现二氯二茂钛对该反应来讲是一种性能优良的催化剂; 和钛酸酯类催化剂相比, 茂钛类催化剂在空气中更稳定, 从而更适合于工业化应用. 同时探讨了不同种类茂钛类化合物的催化性能, 发现位阻效应、环戊二烯环的电子分散效应以及取代基的吸电子效应等, 都会影响中心钛原子的Lewis酸性以及相应的催化活性. 总体来讲, 位阻效应越小、环戊二烯环的电子分散效应越大、与中心钛原子连接的取代基的吸电子能力越强, 越有利于反应的进行.

关键词: 碳酸二甲酯, 碳酸二苯酯, 二氯二茂钛, 茂钛类化合物, 酯交换反应

Titanocene dichloride Cp2TiCl2 was found to be a novel and efficient catalyst for the transesterification between dimethyl carbonate and phenol to produce diphenyl carbonate. Cp2TiCl2 is more stable in air and more convenient for industrial application than titanium esters. Various titanocene complexes were used as catalysts for the transesterification on the basis of Cp2TiCl2. It was found that titanocene catalysts modified by various substituents would strongly influence the steric and electronic properties of the catalytic centers, the stability of the transition states, and their catalytic behaviors. When the substituent was smaller and more electron withdrawing, or the substituent could make the transition state more stable, the reaction would take place with better results.

Key words: dimethyl carbonate, diphenyl carbonate, titanocene dichloride, titanocene complex, transesterification