Chin. J. Org. Chem. ›› 2014, Vol. 34 ›› Issue (10): 2172-2177.DOI: 10.6023/cjoc201403064 Previous Articles     Next Articles



李发旺a,b, 索全伶a, 洪海龙a, 竺宁a, 王亚琦a, 韩利民a   

  1. a. 内蒙古工业大学化工学院 呼和浩特 010051;
    b. 内蒙古化工职业学院化学工程系 呼和浩特 010070
  • 收稿日期:2014-03-29 修回日期:2014-05-16 发布日期:2014-06-03
  • 通讯作者: 索全伶, 韩利民
  • 基金资助:

    国家自然科学基金(Nos. 21266019,21062011,21362019)资助项目.

A Study on C—H Carboxylation Reaction of Terminal Alkynes with CO2 in Supercritical CO2

Li Fawanga,b, Suo Quanlinga, Hong Hailonga, Zhu Ninga, Wang Yaqia, Han Limina   

  1. a. Chemical Engineering College, Inner Mongolia University of Technology, Hohhot 010051;
    b. Department of Chemical Engineering, Inner Mongolia Vocational College of Chemical Engineering, Huhhot 010070
  • Received:2014-03-29 Revised:2014-05-16 Published:2014-06-03
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21266019, 21062011, 21362019).

A organic solvent free, new carboxylation pathway for C—H bond of terminal alkynes with supercritical CO2 (ScCO2) has been developed by using Ag(I)/DBU (1,8-diazabicyclo(5.4.0)undec-7-ene) catalytic system to obtain propiolic acid products with excellent yields in this work. In our reaction system, ScCO2 not only acts as reactive solvent but also as reactant. DBU plays the roles of co-catalyst, nucleophile and base, and obviously enhances the reaction rate in ScCO2. The Ag(I)/DBU catalytic system exhibits higher activity and wide substrate scope. Notably, both liquid and solid terminal alkynes can smoothly react with ScCO2 to produce desired product. The reaction pathway of functionalized propiolic acid formation from the carboxylation of terminal alkynes with CO2 is environment-friendly, simple, and economic.

Key words: AgOAc, DBU, terminal alkyne, ScCO2, carboxylation