Synthesis of Substituted Aryl Ketones by Addition of Alcohols to Alkynes Using Amberlyst-15/Ionic Liquid as a Recyclable Catalytic System

Abstract

A highly efficient protocol for the synthesis of substituted aryl ketones by using Amberlyst-15 immobilized in [Bmim][PF₆] ionic liquid has been firstly developed. The present protocol works under metal-free, solvent-free, mild reaction conditions with 100% atom efficiency. The various aryl ketones were obtained in good to excellent yields. The developed catalytic system was recycled efficiently up to five cycles without significant loss in catalytic activity.

Key words

heterogeneous catalysis - ionic liquid - addition reaction - aryl ketone - atom economy

• References and Notes

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• 15 General Experimental Procedure for the Addition of Alcohols with Alkynes To a well-stirred mixture of Amberlyst-15 [H⁺ exchange capacity (4.2 meq/g) and high surface area (42 m²/g)] (5 equiv) in [Bmim][PF₆] (2 mL), 1a (1.2 mmol) and 2a (1 mmol) were added. The reaction mixture was stirred at 80 °C, and the progress of the reaction was monitored by GC/TLC. After completion of reaction, the mixture was cooled to r.t., and diisopropyl ether (5 mL) was added with vigorous shaking. The ether phase was separated, and the extraction procedure was repeated (3 × 5 mL). The organic extracts were combined, dried over anhydrous Na₂SO₄, filtered, and evaporated under reduced pressure. The residue was purified by column chromatography [silica gel, 60–120 mesh; PE–EtOAc (9:1)] to give 1,3,3-triphenylpropan-1-one (3a) in 75% yield. After extraction, the reaction vessel containing the recovered Amberlyst-15/[Bmim][PF₆] was dried in vacuo for an hour and then charged with 1a and 2a directly for the next run. The various ionic liquids used were prepared as previously reported.¹⁴ 1,3,3-Triphenylpropan-1-one (3a) White solid; yield: 213 mg (75%). ¹H NMR (400 MHz, CDCl₃): δ = 7.98–7.96 (m, 2 H), 7.58–7.56 (m, 1 H), 7.49–7.45 (m, 2 H), 7.31–7.28 (m, 8 H), 7.23–7.18 (m, 2 H), 4.87 (t, J = 8 Hz, 1 H), 3.78 (d, J = 8 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 198.01, 144.17, 137.11, 128.61, 128.57, 128.07, 127.86, 126.39, 45.97, 44.76. GC–MS (EI): m/z = 286 (10.5) [M⁺], 167 (31.3), 165 (15.5), 155 (28.0), 105 (100.0), 77 (28.3), 71 (10.5), 43 (11.4). 3,3-Diphenyl-1-p-tolylpropan-1-one (3b) White solid; yield: 228 mg (76%). ¹H NMR (400 MHz, CDCl₃): δ = 7.90–7.88 (m, 2 H), 7.31–7.26 (m, 7 H), 7.23–7.20 (m, 5 H), 4.87 (t, J = 8 Hz, 1 H), 3.76 (d, J = 8 Hz, 2 H), 2.44 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 197.63, 144.27, 143.88, 134.65, 129.29, 128.56, 128.22, 127.88, 126.36, 46.01, 44.62, 21.65. GC–MS (EI): m/z = 300 (10.7) [M⁺], 167 (25.8), 165 (12.8), 120 (9.9), 119 (100.0), 91 (24.8), 77 (4.9).