Efficient amide formation from arylamines and esters promoted by AlCl3/Et3N: an experimental and computational investigation

• Published in: Research on chemical intermediates Vol. 38; no. 8; pp. 1961 - 1968
• Main Authors: Tong, Xinli, Ren, Zhangshun, Qü, Xiaolong, Yang, Qiwu, Zhang, Wenqin
• Format: Journal Article
• Language: English
• Published: Dordrecht Springer Netherlands 01.10.2012
• Subjects: Catalysis; Chemistry; Chemistry and Materials Science; Inorganic Chemistry; Physical Chemistry; N-acylation; Arylamines; Amide; AlCl; N pair; DFT calculations; Et
• ISSN: 0922-6168; 1568-5675
• DOI: 10.1007/s11164-012-0517-x

Efficient and selective preparation of amides from arylamines and esters has been achieved with an AlCl 3 /Et 3 N pair under mild conditions. A large number of arylamines were successfully acylated to the corresponding amides in high yields and short reaction times. For instance, a 94% yield of p -bromoacetanilide was obtained from p -bromoaniline and ethyl acetate in 10 min at room temperature. In addition, a computational study on the N-acylation of amines was performed using density functional theory. It was found that the energy barrier for N-acylation of aniline is 10 kcal/mol higher than that of methylamine. In the presence of AlCl 3 , the activation energy for the N-acylation of aniline was reduced by 27.7 kcal/mol with the endothermic process becoming exothermic. Graphical Abstract In this work, the efficient and selective preparation of amides from arylamines and esters has been performed successfully with an AlCl 3 /Et 3 N pair under mild conditions. A large number of arylamines were acylated to the corresponding amides with high yields and short reaction times. In addition, a computational study on the N-acylation of amines has been carried out using the density functional theory (DFT) method.