A Mild and Efficient Method for N-Arylation of Nitrogen Heterocycles with Aryl Halides Catalyzed by Cu(II)-NaY Zeolite

Abstract

A mild and efficient method for N-arylation of nitrogen-containing heterocycles with aryl halides to afford N-arylheterocycles in excellent yields using a Cu(II)-NaY catalyst in the presence of K₂CO₃ base is reported.

Key words

N-arylation - nitrogen heterocycles - aryl halides - Cu(II)-NaY zeolite

References and Notes

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10

Catalyst preparation: Cu(II)-NaY zeolite was prepared by ion-exchange of zeolite NaY (10 g) with a solution of copper(II) acetate (2.86 g, 15.75 mmol in deionized water (150 mL) at r.t. for 24 h. The material was recovered by filtration, dried (110 °C) and calcined (550 °C) in a flow of air. AAS analysis showed that the zeolite contained 6.84 wt% of Cu.

11

Typical Experimental Procedure: A mixture of 4-bromo-toluene (1 mmol), imidazole (1.2 mmol), K₂CO₃ (2 mmol) and Cu(II)-NaY (100 mg) in DMF (3 mL) was heated to 120 °C for the specified time (Table [2] ). The progress of the reaction was monitored by GC or TLC. The reaction mixture was filtered to separate the catalyst and the filtrate was quenched with aq NaHCO₃ and the product extracted with EtOAc. The combined organic layers were washed with brine, dried over Na₂SO₄ and concentrated. The residue was purified by column chromatography to afford pure 1-(4-methylphenyl)-1H-imidazole.
1-(4-Methylphenyl)-1 H -imidazole (Table [2] , entry 7). ¹H NMR (CDCl₃): δ = 7.76 (br s, 1 H), 7.24 (br s, 4 H), 7.19 (br s, 1 H), 7.13 (br s, 1 H), 2.39 (s, 3 H); MS (EI): m/z (%) = 158, 131, 104, 91 (100) 50; Anal. Calcd for C₁₀N₂H₁₀: C, 75.95; N, 17.72; H, 6.33. Found: C, 76.09; N, 17.75; H, 6.16.
1-(4-Nitrophenyl)-1 H -imidazole (Table [2] , entry 1): mp 203 °C; ¹H NMR (CDCl₃): δ = 8.37 (d, J = 9.0 Hz, 2 H), 7.93 (br s, 1 H), 7.58 (d, J = 9.0 Hz, 2 H), 7.32 (br s, 1 H), 7.24 (br s, 1 H); MS (EI): m/z (%) = 189 (100), 159, 141, 116, 89, 50; Anal. Calcd for C₉N₃O₂H₇: C, 57.14; N, 22.2; H, 3.7; Found C, 57.42; N, 22.59; H, 3.19.
All products are reported compounds and have been identified by ¹H NMR and mass spectrometric data. [5]