Selective N-Alkylation of Amines with DMC over Biogenic Cu-Zr Bimetallic Nanoparticles

Abstract

Herein, we report the green synthesis of copper-zirconium bimetallic nanoparticles (Cu-Zr BNPs) from aqueous solutions using Azadirachta indica leaf extract as a reducing and stabilizing agent. The CuO, ZrO2 NP, and Cu-Zr BNP samples were characterized by X-ray diffraction and Fourier transform infrared (FTIR) spectroscopy, and the morphologies of the samples were analyzed by high-resolution transmission electron microscopy (HR-TEM) with selected area electron diffraction analysis (SAED). The synthesized Cu-Zr BNPs have been employed as efficient catalysts for the selective N-methylation of aromatic and aliphatic amines with dimethyl carbonate. The effect of process conditions on the percentage conversion of benzylamine with dimethyl carbonate as a model reaction has been investigated. The Cu-Zr bimetallic nanoparticle catalytic system in a 1:2 molar ratio was able to convert amines into the corresponding N-methylated amines with a selectivity up to 91% at 180 °C in 4 h. The analysis of catalytic reusability confirmed that the reported heterogeneous catalyst can be used for five consecutive cycles without much loss in activity. Thus, the current protocol can be considered as a simpler, reproducible, and environmentally benign approach for N-methylation of amines.