A Novel and Green Method for the Synthesis of Indeno[2,1-c]pyridine Derivatives in Ionic Liquid Catalyzed by Malononitrile

Abstract

1-Aryl-9H-indeno[2,1-c]pyridine-4-carbonitrile derivatives were unexpectedly obtained from the reaction of 2-(2,3-dihydroinden-3-ylidene) malononitrile, benzaldehyde and malononitrile in ionic liquid at 90 °C. Modification of the novel reaction protocol resulted in a two-component reaction between 2-(2,3-dihydroinden-3-ylidene) malononitrile, and benzaldehyde catalyzed by 10 mol% malononitrile. A 1,5-hydrogen transfer was proposed to occur in the formation of the product.

indeno[2,1-c]pyridine - ionic liquids - malononitrile - 1,5-hydrogen transfer - synthesis

References and Notes

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General Procedure for the Syntheses of 1-Aryl-9 H -indeno[2,1- c ]pyridine-4-carbonitrile Derivatives
A dry 50 mL flask was charged with benzaldehyde (2.0 mmol), malononitrile (0.2 mmol), 2-(2,3-dihydroinden-3-ylidene)malononitrile (2.0 mmol), and ionic liquid of [bmim⁺][BF₄ ^-] (1 mL). The reaction mixture was stirred at 90 °C for 3-8 h. Then, H₂O (5 mL) was added to the mixture, the solid was isolated by filtration. The water in the filtrate was removed by evaporation at reduced pressure, and the ionic liquid could be recovered easily 80 °C in vacuo for 4 h. The crude yellow products were washed with H₂O and purified by recrystallization from DMF to give 4.
1-(4-Methylphenyl)-9H-indeno[2,1-c]pyridine-4-carbonitrile (4a): mp 201-203 °C. ¹H NMR (400 MHz, CDCl₃): d = 2.43 (s, 3H, CH₃), 4.02 (s, 2H, CH₂), 7.29 (d, J = 8.0 Hz, 2H, ArH), 7.44-7.52 (m, 4H, ArH), 7.58-7.60 (m, 1H, ArH), 8.31 (s, 1H, ArH), 8.59 (d, J = 8.0 Hz, 1H, ArH) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 167.2, 147.3, 141.1, 137.5, 136.6, 135.7, 134.3, 132.4, 130.9, 129.8, 128.2, 126.0, 125.3, 115.4, 115.1, 112.4, 37.4, 21.6 ppm. HRMS (EI): m/z calcd for C₂₀H₁₄N₂ [M⁺]: 282.1157; found: 282.1151. IR (KBr): ν = 3052, 2215, 1619, 1603, 1523, 1414, 1331, 1314, 1218, 1188, 1164, 1122, 1105, 1019, 942, 896, 848, 806, 770, 720 cm^-1.