Dual functions of N,N-dimethylethanolamnium-based ionic liquids for the Knoevenagel reactions at room temperature

• Published in: Catalysis today 2013-02, Vol.200, p.17-23
• Main Authors: Zhu, Anlian, Liu, Ruixia, Li, Lingjun, Li, Liangyun, Wang, Lan, Wang, Jianji
• Format: Article
• Language: English
• Subjects: acetates; anions; Catalysis; Catalytic activity; cations; Chemistry; Exact sciences and technology; General and physical chemistry; Hydrogen bond acceptor; Hydrogen bond donor; hydrogen bonding; Ionic liquid; ionic liquids; Knoevenagel reaction; temperature; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
• ISSN: 0920-5861; 1873-4308
• DOI: 10.1016/j.cattod.2012.06.006

[Display omitted] ► The enhancement of the hydrogen bond formation ability of cations and anions of the ILs can both lead to the increase of the catalytic activity of the ILs. ► The cation of the ILs can activate the electrophiles. ► The anion of the ILs can activate the nucleophiles. ► The optimized catalytic system benefits from wide substrates tolerance, ambient reaction temperature, easy work-up procedure, and easy reuse of the IL. In this work, the hydrogen bond formation ability of cation and anion of the ILs was determined by using the solvatochromic method and was found to be responsible for their catalytic activity in the Knoevenagel reactions. The enhancement in the hydrogen bond donor ability of the cations and the hydrogen bond acceptor ability of the anions can both lead to the increase in the catalytic activity of the ILs. From the proposed reaction mechanism, it was deduced that the cations of the ILs can form hydrogen bond with aldehyde to activate the CO bond as electrophile, and the anions of the ILs can promote active methylene compound to produce carboanion as nucleophile, showing dual function activation effect in the catalytic processes. In addition, the optimized N,N-dimethylethanolamnium acetate as dual function activator for the Koevenagel reactions benefits from wide substrates tolerance, ambient reaction temperature, easy work-up procedure, and easy reuse of the IL.