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

doi:10.6023/cjoc201612040

Abstract

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

Cite this article

Zhang Wei, Hu Chenxu, Zhou Xiangge. Synthesis of N,N-Dimethyl Benzamide and Benzonitriles through Copper-Catalyzed One-Pot Reaction[J]. Chin. J. Org. Chem., 2017, 37(5): 1246-1251.

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