Efficient Synthesis of 2,3,4-Trisubstituted Quinolines via Friedländer Annulation with Nanoporous Cage-Type Aluminosilicate AlKIT-5 Catalyst

Abstract

2-Aminoaryl ketones undergo smooth Friedländer condensation/annulation with α-methyleneketones on the surface of nanoporous aluminosilicate catalyst to afford the corresponding quinoline derivatives in good yields with high selectivity due to its high surface area, large pore volume, and high acidity. The use of highly acidic and reusable AlKIT-5 catalyst makes the Friedländer annulation simple, convenient, and practical.

o-aminoaryl ketones - nanoporous catalysts - domino ­reactions - quinolines

References and Notes

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General Procedure A mixture of 2-aminoaryl ketone (1.0 mmol), α-methylene ketone (1.0 mmol), and AlKIT-5 (50 mg) in EtOH (5 mL) was stirred at 80 ˚C for the specified time (see Table  [¹] ). After completion of the reaction, as monitored by TLC, the catalyst was separated by filtration, and the residue was washed with EtOH (10 mL). The combined organic layers were concentrated under reduced pressure, and the crude product was purified by silica gel column chromatography using EtOAc-n-hexane (1:9) as eluent to afford the pure quinoline derivative.
Spectral Data for Selected Products
Ethyl 2-Methyl-4-phenylquinoline-3-carboxylate (3a) Solid, mp 98 ˚C. IR (KBr): ν = 3030, 2960, 1700, 1605, 1568, 1482, 905 cm^-¹. ^¹H NMR (200 MHz, CDCl₃): δ = 0.95 (t, J = 7.0 Hz, 3 H), 2.80 (s, 3 H), 4.05 (q, J = 7.0 Hz, 2 H), 7.35-7.50 (m, 6 H), 7.55 (d, J = 8.1 Hz, 1 H), 7.70 (t, J = 7.9 Hz, 1 H), 8.05 (d, J = 8.1 Hz, 1 H). MS (EI): m/z = 291 [M]⁺, 85, 263, 246, 218, 176, 150.
3-Acetyl-2-methyl-4-phenylquinoline (3d) Solid, mp 115 ˚C. IR (KBr): ν = 3027, 2960, 1705, 1610, 1569, 1485, 705 cm^-¹. ^¹H NMR (200 MHz, CDCl₃): δ = 1.95 (s, 3 H), 2.60 (s, 3 H), 7.25-7.30 (m, 2 H), 7.35 (t, J = 8.0 Hz, 1 H), 7.40-7.50 (m, 3 H), 7.55 (d, J = 8.2 Hz, 1 H), 7.65 (t, J = 8.0 Hz, 1 H), 8.00 (d, J = 8.2 Hz, 1 H). MS (EI): m/z = 261 [M]⁺, 246, 218, 176, 150, 43. 9-Phenyl-1,2,3,4-tetrahydroacridine (3e) Solid, mp 137 ˚C. IR (KBr): ν = 3057, 2945, 1609, 1575, 1480, 1210, 708 cm^-¹. ^¹H NMR (200 MHz, CDCl₃): δ = 1.75-1.85 (m, 2 H), 1.95-2.05 (m, 2 H), 2.60 (t, J = 6.7 Hz, 2 H), 3.20 (t, J = 6.9 Hz, 2 H), 7.20-7.32 (m, 3 H), 7.40-7.60 (m, 5 H), 8.00 (d, J = 8.2 Hz, 1 H). MS (EI): m/z = 259 [M]⁺, 230, 182, 176, 57.

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Syntheses of AlKIT-5 Catalyst with Different n _Si /n _Al Ratio
The AlKIT-5 materials with different n_Si/n_Al ratios were synthesized using Pluronic F127 as the template in an acidic medium. In a typical synthesis, 5.0 g of F127 was dissolved in 3 g of HCl (35 wt%) and 240 g of distilled H₂O. To this mixture, 24.0 g of TEOS and the required amount of the aluminium isopropoxide were added, and the resulting mixture was stirred for 24 h at 45 ˚C. Subsequently, the reaction mixture was heated for 24 h at 100 ˚C under static conditions for hydrothermal treatment. After hydrothermal treatment, the final solid product was filtered off and then dried at 100 ˚C without washing. The product was calcined at 540 ˚C for 10 h. The samples are denoted as AlKIT-5 (x)where x denotes the n_Si/n_Al ratio in the final product.
The molar gel composition of the reaction mixture was
SiO₂/Al₂O₃/F127/HCl/H₂O = 1.0:0.041-0.071:0.0035:0.25:116.6.