Acid-catalysed reactions of amines with dimethyl carbonate

O demonstrated highly selective monomethylation of aromatic amines. In addition, both silica sulfuric acid and silica perchlorate at 90 °C exhibited no conversion for secondary amines but enhanced carboxymethylation with high conversions of 80.7-87.5% and selectivity of >99.00% at 150 °C in a pressure reactor. At 1.0 equivalent, both promoted excellent conversion and selectivity of primary aliphatic amines at 90 °C. In addition, they were easily recovered and reused for at least four additional reactions without significant loss of efficiency with consistent conversions and selectivity. Green metrics evaluation for the silica sulfuric acid-catalysed reaction highlighted the sustainability features of the process. Silica-supported catalysts are highly stable, making them ideal alternative catalysts for the methylation and carbonylation of various amines with DMC. Acid-catalysed DMC reactions of amines may expand the substrate scope and offer new opportunities for developing sustainable organic synthetic methodologies.