Pure and Applied Chemistry

Abstract: Dimethyl carbonate (DMC) is considered as an environmentally benign chemical due to negligible ecotoxicity, low bioaccumulation, and low persistence. However, the traditional process of DMC synthesis via phosgene and methanol is limited in industry owing to the toxic raw material involved. Thus, environmentally friendly phosgene-free processes for DMC production have been proposed and developed in the past decades. Until now, the alternatives appear to be the oxidative carbonylation of methanol, the transesterification of propylene or ethylene carbonate (PC or EC), the methanolysis of urea, and the direct synthesis of DMC from CO₂ with methanol. In this review, we present some recent developments of these phosgene-free approaches and their prospects for industrialization.