Pure and Applied Chemistry

Abstract: Nowadays available by clean industrial processes, dimethyl carbonate (DMC) possesses properties of nontoxicity and biodegradability which make it a true green reagent/solvent to devise syntheses that prevent pollution at the source. In particular, the versatile reactivity of DMC allows both methylation and carboxymethylation protocols that can replace conventional and highly noxious reagents such as methyl halides (and dimethyl sulfate, DMS) and phosgene. In the field of DMC-mediated methylations, representative examples are the reactions of DMC with CH₂-active compounds and primary aromatic amines. In the presence of organic/inorganic bases or zeolites (faujasites) catalysts, these processes proceed with unprecedented selectivity (up to 99 %, at complete conversion) toward the corresponding mono-C- and mono-N-methyl derivatives, a result hitherto not possible with conventional alkylation reagents. In the case of ambident amines (e.g., aminophenols, aminobenzyl alcohols, aminobenzoic acids, and aminobenzamides), the unique combination of DMC and zeolites allows not only a very high mono-N-methyl selectivity, but also a complete chemoselectivity toward the amino group. The other nucleophilic functionalities (OH, CO₂H, CH₂OH, CONH₂) are fully preserved from alkylation and/or transesterification reactions, usually observed over basic catalysts.