Ionic Liquids Made with Dimethyl Carbonate: Solvents as well as Boosted Basic Catalysts for the Michael Reaction

• Published in: Chemistry : a European journal 2009-11, Vol.15 (45), p.12273-12282
• Main Authors: Fabris, Massimo, Lucchini, Vittorio, Noè, Marco, Perosa, Alvise, Selva, Maurizio
• Format: Article
• Language: English
• Subjects: dimethyl carbonate; green chemistry; ionic liquids; Michael addition; NMR spectroscopy
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.200901891

This article describes 1) a methodology for the green synthesis of a class of methylammonium and methylphosphonium ionic liquids (ILs), 2) how to tune their acid–base properties by anion exchange, 3) complete neat‐phase NMR spectroscopic characterisation of these materials and 4) their application as active organocatalysts for base‐promoted carbon–carbon bond‐forming reactions. Methylation of tertiary amines or phosphines with dimethyl carbonate leads to the formation of the halogen‐free methyl‐onium methyl carbonate salts, and these can be easily anion‐exchanged to yield a range of derivatives with different melting points, solubility, acid–base properties, stability and viscosity. Treatment with water, in particular, yields bicarbonate‐exchanged liquid onium salts. These proved strongly basic, enough to efficiently catalyse the Michael reaction; experiments suggest that in these systems the bicarbonate basicity is boosted by two orders of magnitude with respect to inorganic bicarbonate salts. These basic ionic liquids used in catalytic amounts are better even than traditional strong organic bases. The present work also introduces neat NMR spectroscopy of the ionic liquids as a probe for solute–solvent interactions as well as a tool for characterisation. Our studies show that high catalytic efficacy of functional ionic liquids can be achieved by integrating their green synthesis, along with a fine‐tuning of their structure. Demonstrating that ionic liquid solvents can be made by a truly green procedure, and that their properties and reactivity can be tailored to the point of bridging the gap between their use as solvents and as catalysts. It's easy being green: A simple green synthetic procedure based on the use of dimethyl carbonate for the synthesis of a series of new methylammonium‐ and methylphosphonium‐based ionic liquids (ILs) is described (see graphic). These ionic materials are also highly active as basic catalysts for carbon–carbon bond‐forming Michael reactions.