One-Pot Three-Component Synthesis of 2,4,5-Triaryl-1H-imidazoles in the Presence of a Molecular Sieve Supported Titanium Catalyst under Mild Basic Conditions

Abstract

A series of 2,4,5-trisubstituted-imidazoles has been synthesized with good to excellent yields by the one-pot condensation reaction of 1,2-dicarbonyl compounds, benzaldehydes, and ammonium acetate in the presence of 4 Å molecular sieves modified with titanium(IV) as an efficient heterogeneous catalyst. The catalyst could be recovered easily and reused without significant loss of activity.

Keywords

2,4,5-triaryl-1H-imidazoles - multicomponent reactions - titanium - 4 Å molecular sieves - heterogeneous catalysis

• References and Notes

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• 28 ¹H NMR and ¹³C NMR spectra were made on a BRUKER Avance-300 instrument using TMS as an internal standard in DMSO-d₆ . Melting points were determined on SETARAM DSC 92 apparatus, where the initial temperature was 25 °C, followed by programming at 10 °C/min up to 300 °C under nitrogen atmosphere. All compounds and solvents were purchased from Merck Hungary Ltd.
• 29 The catalyst was prepared according to the method described in ref. 26. Samples were heated at 120 °C for 1 h before the reaction. Figure 1 shows the SEM image of the catalyst. The characteristic cuboctahedron shape of the molecular sieve support can be seen, the particles are well defined both in shape and size, and the titanium is evenly distributed on the surface of the support.
• 30 General Procedure for the One-Pot Synthesis of 2,4,5-Triaryl-1H-imidazoles A mixture of benzil (1 mmol, 0.21 g), aldehyde (1 mmol), ammonium acetate (2.2 mmol, 0.17 g), and Ti⁴⁺/4A (0.1 g) was stirred in a 10 mL flask at 100 °C. After 1 h toluene (1 mL) was added because the precipitated product impeded stirring of the melt. The stirring was continued, and progress of the reaction was monitored by TLC. After completion (10 h), the mixture was cooled to room temperature, diluted with acetone (10 mL), any solid was filtered off, and the filtrate was evaporated. The product was purified by recrystallization from ethanol.
• 31 2,4,5-Triphenyl-1H-imidazole (4a) White solid, mp 278 °C (lit.: 274–276 °C²⁰). ¹H NMR (300 MHz): δ = 7.22–7.57 (m, 13 H), 8.09 (d, 2 H), 12.70 (br s, 1 H) ppm. ¹³C NMR (75 MHz): δ = 125.20, 126.53, 127.09, 127.79, 128.20, 128.26, 128.47, 128.69, 130.36, 131.10, 135.19, 137.12, 145.52 ppm. 2-(2-Chlorophenyl)-4,5-diphenyl-1H-imidazole (4b) White solid, mp 197 °C (lit.: 196–198 °C³²). ¹H NMR (300 MHz): δ = 7.28–7.51 (m, 10 H), 7.55 (d, 2 H), 7.61 (t, 1 H), 7.81 (t, 1 H), 12.65 (b rs, 1 H) ppm. ¹³C NMR (75 MHz): δ = 126.51, 127.13, 127.68, 127.99, 128.15, 128.62, 130.01, 130.15, 130.87, 131.48, 131.55, 135.08, 136.86, 143.35 ppm. 2-(4-Chlorophenyl)-4,5-diphenyl-1H-imidazole (4c) White solid, mp 264 °C (lit.: 261–262 °C¹⁹). ¹H NMR (300 MHz): δ = 7.23–7.56 (m, 12 H), 8.11 (d, 2 H), 12.79 (br s, 1 H) ppm. ¹³C NMR (75 MHz): δ = 126.56, 126.80, 127.03, 127.83, 128.16, 128.39, 128.63, 128.73, 129.17, 130.89, 132.71, 134.97, 137.27, 144.38 ppm. 2-(3-Bromophenyl)-4,5-diphenyl-1H-imidazole (4d) White solid, mp 306 °C (lit.: 301–303 °C¹⁸). ¹H NMR (300 MHz): δ = 7.24–7.57 (m, 13 H), 8.10 (d, 1 H), 8.32 (s, 1 H), 12.84 (br s, 1 H) ppm. ¹³C NMR (75 MHz): δ = 121.93, 123.81, 126,49, 126,89, 127.29, 127.71, 128.01, 128.17, 128.45, 130.57, 130.72, 132.27, 134.68, 137.19, 143.64 ppm. 2-(4-Bromophenyl)-4,5-diphenyl-1H-imidazole (4e) White solid, mp 260 °C (lit.: 252–254 °C¹⁶) ppm. ¹H NMR (300 MHz): δ = 7.21–7.53 (m, 10 H), 7.68 (d, 2 H), 8.05 (d, 2 H), 12.83 (br s, 1 H) ppm. ¹³C NMR (75 MHz): δ = 121.90, 126.63, 126.98, 127.62, 127.97, 128.19, 128.69, 129.10, 129.52, 129.71, 130.06, 132.18, 144.99 ppm. 2-(2-Fluorophenyl)-4,5-diphenyl-1H-imidazole (4f) White solid, mp 208 °C (lit.: 205.5–206 °C³³). ¹H NMR (300 MHz): δ = 7.23–7.55 (m, 13 H), 8.00 (t, 1 H), 12.56 (br s, 1 H) ppm. ¹³C NMR (75 MHz): δ = 116.66, 116.82, 119.21, 125.18, 125.21, 127.08, 127.69, 128.33, 128.69, 129.04, 130.14, 130.91, 131.37, 135.49, 137.71, 141.34, 158.35, 160.33 ppm. 4,5-Diphenyl-2-(2-methylphenyl)-1H-imidazole (4g) White solid, mp 253 °C (lit.: 252 °C³³). ¹H NMR (300 MHz): δ = 2.65 (s, 3 H), 7.21 (t, 1 H), 7.29–7.37 (m, 6 H), 7.43 (t, 2 H), 7.52 (d, 2 H), 7.56 (d, 2 H), 7.72 (t, 1 H), 12.49 (br s, 1 H) ppm. ¹³C NMR (75 MHz): δ = 21.63, 126.21, 126.88, 127.52, 127.96, 128.12, 128.67, 128.72, 128.84, 129.13, 129.21, 130.49, 131.59, 135.89, 136.77, 137.11, 146.61 ppm. 4,5-Diphenyl-2-(3-methylphenyl)-1H-imidazole (4h) White solid, mp 299 °C (lit.: 296–298 °C²⁰). ¹H NMR (300 MHz): δ = 2.39 (s, 3 H), 7.20–7.55 (m, 12 H), 7.88 (d, 1 H), 7.94 (s, 1 H), 12.64 (br s, 1 H) ppm. ¹³C NMR (75 MHz): δ = 21.62, 122.88, 126.25, 127.00, 127.58, 128.24, 128.68, 128.92, 129.14, 129.43, 130.03, 130.11, 130.78, 131.61, 135.72, 137.54, 138.31, 146.11 ppm. 4,5-Diphenyl-2-(4-methylphenyl)-1H-imidazole (4i) White solid, mp 239 °C (lit.: 230–233 °C¹⁸). ¹H NMR (300 MHz): δ = 2.35 (s, 3 H), 7.22 (t, 1 H), 7.29 (t, 4 H), 7.37 (t, 1 H), 7.44 (t, 2 H), 7.50 (d, 2 H), 7.56 (d, 2 H), 7.98 (d, 2 H), 12.60 (br s, 1 H) ppm. ¹³C NMR (75 MHz): δ = 21.40, 125.67, 126.95, 127.56, 128.20, 128.43, 128.66, 128.91, 129.13, 129.74, 131.66, 135.76, 137.42, 138.16, 146.16 ppm. 4,5-Diphenyl-2-(3-methoxyphenyl)-1H-imidazole (4k) White solid, mp 266 °C (lit.: 259–262 °C¹⁸). ¹H NMR (300 MHz): δ = 3.84 (s, 3 H), 6.95 (d, 1 H), 7.26–7.57 (m, 11 H), 7.68–7.71 (m, 2 H), 12.70 (br s, 1 H) ppm. ¹³C NMR (300 MHz): δ = 55.72, 110.7, 114.72, 118.13, 127.02, 127.57, 128.31, 128.69, 128.99, 129.16, 130.0, 130.11, 130.31, 131.59, 132.15, 135.64, 136.04, 137.58, 145.86, 160.06 ppm. 4,5-Diphenyl.2-(4-methoxyphenyl)-1H-imidazole (4l) White solid, mp 228.5 °C (lit.: 228–231 °C¹⁸). ¹H NMR (300 MHz): δ = 3.82 (s, 3 H), 7.05 (d, 2 H), 7.21 (t, 1 H), 7.29 (t, 2 H), 7.36 (t, 1 H), 7.44 (t, 2 H), 7.50 (d, 2 H), 7.55 (d, 2 H), 7.79 (s, 2 H), 8.03 (d, 2 H), 12.51 (br s, 1 H) ppm. ¹³C NMR (75 MHz): δ = 55.21, 114.09, 123.14, 126.39, 126.69, 127.04, 127.60, 128.14, 128.35, 128.62, 131.24, 135.33, 136.76, 145.62, 159.41 ppm. 4-(4,5-Diphenyl-1H-imidazol-2-yl)-phenol (4m) Light-yellow solid, mp 214 °C (lit.: 215 °C³⁴). ¹H NMR (300 MHz): δ = 6.94–7.01 (m, 2 H), 7.28 (t, 2 H), 7.30–7.49 (m, 5 H), 7.54 (d, 4 H), 8.06 (d, 1 H), 13.02 (br s, 1 H). ¹³C NMR (75 MHz): δ = 112.88, 116.82, 118.84, 124.94, 128.62, 130.06, 145.87, 156.70 ppm.
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