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DOI: 10.1055/s-2004-820035
Facile Ionic Liquids-Promoted One-Pot Synthesis of Polyhydroquinoline
Derivatives under Solvent Free Conditions
Publication History
Publication Date:
10 March 2004 (online)
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Abstract
An efficient synthesis of polyhydroquinoline derivatives were reported via four-component coupling reactions of aldehydes, dimedone, ethyl acetoacetate and ammonium acetate in the presence of a catalytic amount of ionic liquid under solvent free conditions. In the meantime, the catalytic effect of different ionic liquids on the reaction has also been investigated.
Key words
ionic liquids - catalyze - one-pot synthesis - polyhydroquinoline derivatives
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References
Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre, CCDC No. 226173 for compounds 2d. Copies of this information may be obtained free of charge from: The Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK [E-mail: linstead@ccdc.cam.ac.uk or deposit@ ccdc.cam.ac.uk; Fax:+44 (1223)336033]. Structural parameters for 2d: data collection: Rigaku Mercury CCD area detector; radiation: MoK. wavelength = 0.71070 Å; crystal size: 0.24 × 0.15 × 0.70 mm3; crystal system: monoclinic; space group: Cc (#9); unit cell: a = 18.607 (6) Å, b = 9.136 (3) Å, c = 12.157 (4) Å, α = 111.623 (5)°.
25Typical Experimental Procedure: 4-Chlorobenzaldehyde (1 mmol), dimedone (1 mmol), ammonium acetate (1.5 mmol), ethyl acetoacetate (1 mmol) and [hmim]BF4 (12 mmol%) were successively charged into a 25 mL round-bottomed flask equipped with a magnetic stirrer. Then the reaction proceeded at 90 °C for 8 min and a solid product gradually formed. After the completion of reaction as indicated by TLC, the resulting solid product was crushed, washed with water, filtered and dried in vacuum to afford the crude product. A pure product was obtained by further recrystallization using absolute alcohol. 2a: IR (KBr): 3290, 1698, 1612 cm-1. 1H NMR (400 MHz, CDCl3): δ = 0.92 (s, 3 H, CH3), 1.06 (s, 3 H, CH3), 1.08 (m, 3 H, CH2CH3), 2.18 (m, 4 H, 2 × CH2), 2.41 (s, 3 H, CH3), 4.08 (q, J 1 = J 2 = 6.0 Hz, 2 H, CH2CH3), 5.06 (s, 1 H, CH), 5.90 (s, 1 H, NH), 7.03-7.4 (m, 5 H, ArH). Anal. Calcd for C21H25NO3: C, 74.31; H, 7.42; N, 4.13. Found: C, 74.57; H, 7.51; N, 4.06. 2f: IR (KBr): 3275, 1702, 1647 cm-1. 1H NMR (400 MHz, CDCl3): δ = 0.92 (s, 3 H, CH3), 1.08 (s, 3 H, CH3), 1.24 (t, J 1 = J 2 = 7.2 Hz, 3 H, CH2CH3), 2.16 (s, 3 H, CH3), 2.26 (m, 4 H, 2 × CH2), 2.40 (s, 3 H, CH3), 4.08 (m, 2 H, CH2CH3), 5.00 (s, 1 H, CH), 5.80 (s, 1 H, NH), 7.00 (d, J = 8.0 Hz, 2 H, ArH) 6.80 (d, J = 8.0 Hz, 2 H, ArH). Anal. Calcd for C22H27NO3: C, 74.76; H, 7.70; N, 3.96. Found: C, 74.92; H, 7.79; N, 3.90. 2i: IR (KBr): 3399, 3293, 1698, 1644 cm-1. 1H NMR (400 MHz, CDCl3): δ = 0.94 (s, 3 H, CH3), 1.06 (s, 3 H, CH3), 1.22 (t, J 1 = J 2 = 7.2 Hz, 3 H, CH2CH3), 2.20 (s, 3 H, CH3), 2.38 (m, 4 H, 2 × CH2), 3.89 (s, 3 H, CH3), 4.12 (q, J 1 = J 2 = 7.2 Hz, 2 H, CH2CH3), 5.00 (s, 1 H, CH), 5.40 (s, 1 H, OH), 5.76 (s, 1 H, NH), 6.74 (m, 2 H, ArH) 7.00 (d, 1 H, ArH). Anal. Calcd for C22H27NO5: C, 68.55; H, 7.06; N, 3.63. Found: C, 68.53; H, 7.11; N, 3.51.