应用化学

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磷酸钾中和法邻甲酚羧化反应的绿色合成

伍琳娟,朱大建,肖瑟,雷以柱,郭园园,张盼盼,李光兴*   

  1. 华中科技大学化学与化工学院 武汉 430074
  • 收稿日期:2014-10-09 出版日期:2015-06-10 发布日期:2015-06-10
  • 通讯作者: 李光兴,教授; Tel/Fax:027-87543032; E-mail:ligxabc@163.com; 研究方向:工业催化、碳一化工
  • 基金资助:
    国家科技部863项目(NC2010 MA0137)资助

Green Process for o-Cersol Carboxylation Using Potassium Phosphate Base

WU Linjuan, ZHU Dajian, XIAO Se, LEI Yizhu, GUO Yuanyuan, ZHANG Panpan, LI Guangxing*   

  1. School of Chemistry & Chemical Engineering,Huazhong University of Science & Technology,Wuhan 430074,China
  • Received:2014-10-09 Published:2015-06-10 Online:2015-06-10
  • Contact: LI Guangxing, professor; Tel/Fax:027-87543032; E-mail:ligxabc@163.com; Research interests:industrial catalysis, C1 chemistry engineering
  • Supported by:
    Supported by the 863 Program of Ministry of Science and Technology of China(No.NC2010MA0137)

摘要: 以邻甲酚和二氧化碳为原料,以磷酸钾为中和剂一步羧化合成邻甲基水杨酸及相关产物。探讨了反应条件对产率的影响。实验结果表明,当磷酸钾与邻甲酚物料比为2.5∶1,反应温度150 ℃,反应压力3.0 MPa时,羧化反应产物总收率达到95.4%,同时邻甲基水杨酸收率也达到最大。与传统碳酸钾中和法相比,磷酸钾中和法产物在后处理过程中无二氧化碳放出,后处理过程中的磷酸根可制备为磷酸钾使用,新工艺是一条绿色化工路线。

关键词: 二氧化碳, 磷酸钾, 邻甲基水杨酸, 绿色合成, 邻甲酚

Abstract: A green process of the carboxylation reaction of o-cresol with CO2 using K3PO4 as a base was studied for the synthesis of 2-hydroxy-3-methylbenzoic acid(o-MSA) and related carboxylated products. Various reaction parameters such as temperature, pressure, and the ratio of the base to substrate had been tested. The results show that 95.4% total yield of all carboxylated products in this Koble-Schmitt reaction is obtained using K3PO4 as a base under 3.0 MPa CO2 and 150 ℃. Additionally, no CO2 is released during the neutralization process following the Koble-Schmitt reaction and the K3PO4 can be recovered and recycled by neutralization of KH2PO4 with KOH. Therefore, this process allows a green fixation of CO2.

Key words: carbon dioxide, potassium phosphate, hydroxy-methylbenzoic acid, green synthesis, o-cersol