Chinese Journal of Organic Chemistry ›› 2019, Vol. 39 ›› Issue (10): 2898-2905.DOI: 10.6023/cjoc201904021 Previous Articles     Next Articles



王亚琦, 尹强, 郭墩, 韩利民, 孙琪, 洪海龙, 索全伶*()   

  1. 内蒙古工业大学化工学院 呼和浩特 010051
  • 收稿日期:2019-04-09 修回日期:2019-05-14 出版日期:2019-10-25 发布日期:2019-05-28
  • 通讯作者: 索全伶
  • 基金资助:
    国家自然科学基金(21266019);内蒙古自然科学基金(No. 2015MS0204)

Carbonyl Cobalt-Catalyzed Cyclotrimerization of Terminal Alkynes in Supercritical Carbon Dioxide

Wang, Yaqi, Yin, Qiang, Guo, Dun, Han, Limin, Sun, Qi, Hong, Hailong, Suo, Quanling, Suo. Quanling*()   

  1. Chemical Engineering College, Inner Mongolia University of Technology, Hohhot 010051
  • Received:2019-04-09 Revised:2019-05-14 Online:2019-10-25 Published:2019-05-28
  • Contact: Suo. Quanling
  • Supported by:
    Project supported by the National Natural Science Foundation of China(21266019);the Natural Science Foundation of Inner Mongolia Autonomous Region of China(No. 2015MS0204)

Atom-efficient [2+2+2] cycloaddition reaction of alkynes in green solvent supercritical carbon dioxide (ScCO2) is an environmentally friendly reaction process that conforms to the principles of green chemistry. Cyclotrimerization of terminal alkynes catalyzed by Co2(CO)8 in pure ScCO2 has been studied to obtain 1,2,4-trisubstituted benzene derivatives with excellent selectivity. The reaction conditions for the cyclotrimerization were optimized, such as concentration of catalyst, CO2 pressure, reaction temperature and time. The solubility and phase behavior of the reaction materials and catalysts in ScCO2 medium were discussed, and the mechanism of Co2(CO)8 catalyzed cyclotrimerization of terminal alkynes was assumed. The reaction substrate was extended from C≡C (alkyne) to C≡N (nitrile), and the alkyne-nitrile cycloaddition reaction in ScCO2 was preliminary explored. Our optimized catalytic system for the cyclotrimerization of terminal alkynes exhibited wide substrate scope and high product selectivity, in which no organic co-solvent or additives were added. It provided a green synthetic method for 1,2,4-trisubstituted benzenes.

Key words: supercritical carbon dioxide, terminal alkyne, cyclotrimerization reaction, carbonyl cobalt catalyst, alkyne-nitrile cycloaddition reaction