Synthesis of 1,8-dioxo-octahydro-xanthene and tetrahydrobenzo[b]pyran derivatives promoted by two bis-imidazolium-based ionic liquids

Abstract

In this work, we have prepared two bis-dicationic ionic liquids with the same cationic core (Bis-imidazole) and different counter-anions using sulfuric acid and perchloric acids. After that, the efficiency and ability of these compounds as catalysts were investigated and compared in the promotion of Knoevenagel condensation and synthesis of benzo[b]pyran derivatives to see the effect of the anionic counter-part in the reaction. In a 25 mL round-bottomed flask, a mixture of aldehyde (1.0 mmol), 1,3-cyclodicarbonyl (2.0 mmol) and the desired amount of the mentioned acidic ionic liquids was heated at 90°C in the absence of solvent (Reaction A) or In a 25 mL round-bottomed flask, a mixture of aldehyde (1.0 mmol), 1,3-cyclodicarbonyl (1.0 mmol), malononitrile, (1.1 mmol) and optimized amounts of the ionic liquid in water (3.0 mL) was heated at 80°C (Reaction B) for the appropriated time. After the completion of the reactions which were monitored by TLC (n-hexane: EtOAc; 3:1), 10 mL of water was added and the mixture was stirred for 2 minutes. Then, the products were separated by filtration and were washed several times with water. After drying, the pure products were obtained while there was no need to further. Comparison of the obtained results from both of the ionic liquids revealed that [H2-Bisim][HSO4]2 because of its more acidic structure had a more catalytic activity for the preparation of 1,8-dioxo-octahydro-xanthene derivatives but [H2-Bisim][ClO4]2 was relatively more efficient for the synthesis of tetrahydrobenzo[b]pyran derivatives since the stronger acidic nature of [H2-Bisim][HSO4]2 may prevent the simple activation of malononitrile in the reaction media. In this study, we have introduced efficient methods for the synthesis of 1,8-dioxo-octahydro-xanthene and tetrahydrobenzo[b]pyran derivatives in the presence of catalytic amounts of [H2-Bisim][ClO4]2 and [H2-Bisim][HSO4]2 These methods have several advantages such as ease of preparation and handling of the catalysts, high reaction rates, excellent yields, eco-friendly procedures and simple work-up.