Chin. J. Org. Chem. ›› 2017, Vol. 37 ›› Issue (5): 1246-1251.DOI: 10.6023/cjoc201612040 Previous Articles     Next Articles



张伟, 胡晨旭, 周向葛   

  1. 四川大学化学学院 成都 610064
  • 收稿日期:2016-12-12 修回日期:2017-01-20 发布日期:2017-02-20
  • 通讯作者: 周向葛
  • 基金资助:


Synthesis of N,N-Dimethyl Benzamide and Benzonitriles through Copper-Catalyzed One-Pot Reaction

Zhang Wei, Hu Chenxu, Zhou Xiangge   

  1. College of Chemistry, Sichuan University, Chengdu 610064
  • Received:2016-12-12 Revised:2017-01-20 Published:2017-02-20
  • Contact: 10.6023/cjoc201612040
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21472128, J1310008).

Amide is one of the most important functional groups in nature. Besides the classical synthetic method by using activated acid with amine, several other transition metal-catalyzed protocols have been developed. Aryl nitriles have also attracted substantial attentions as herbicides, natural products, etc. Traditional methods towards aryl nitriles include Sandmeyer and Rosenmund von Braun reaction. In addition of these methods, researchers have explored various kinds of toxic “CN” sources. In continuation of our previous work on copper catalyzed C-CN bond cleavage and C-N formation reactions, herein our recent work of combination of copper-catalyzed amidation of benzyl cyanide and cyanation of aryl iodides by using N,N-dimethyl formamide (DMF) as amide source is reported. A representative procedure for this reaction is as following: benzyl cyanide (1 mmol), iodobenzene (1 mmol), DMF (2 mL), TsOH (1 mmol), Cu2O (0.2 mmol), 1,10-phenanthroline (0.4 mmol) were added into a 10 mL of Schlenk tube. The mixture was stirred at 130 ℃ under O2 atmosphere for 12 h. The reaction mixture was then cooled down to room temperature, quenched with water, and extracted with ethyl acetate. The organic layer was then dried over anhydrous MgSO4, and the solvent was removed in vacuo. The residue was finally purified by column chromatography on silica gel using petroleum ether-ethyl acetate mixture as eluent. A variety of N,N-dimethyl benzamides and benzonitriles were obtained in yields up to 85% and 75%, respectively.

Key words: copper, catalysis, one pot reaction, amidation, cyanation