Green approaches to highly selective processes: Reactions of dimethyl carbonate over both zeolites and base catalysts*
Maurizio Selva
Environmental Sciences Department, Ca' Foscari University and Interuniversity Consortium "Chemistry for the Environment", Calle Larga S. Marta 2137, 30123 Venice, Italy
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.
Keywords: dimethyl carbonate; methylation reaction; base catalysts; faujasite catalysts; organic synthesis.
*Pure Appl. Chem. 79, 1831-2100. An issue of reviews and research papers based on lectures presented at the 1st International IUPAC Conference on Green-Sustainable Chemistry, held in Dresden, Germany, 10-15 September 2006.