Synthesis of methylethers by reaction of alcohols with dimethylcarbonate

A new synthetic procedure to methylethers has been developed by the reaction of alcohols with dimethylcarbonate, a non-toxic and environmentally friendly reagent. The methylation of alcohols is catalysed by alumina or hydrotalcite. The methylcarbonate formed in the first step undergoes decarboxylation in the second step, to give the corresponding methylether. The reactivity follows the order: primary > secondary ≫ tertiary alcohols. The reaction can be efficiently performed under both batch and continuous flow conditions.