One-Pot Synthesis of 1-Monosubstituted 1,2,3-Triazoles from Propargyl Alcohol

Abstract

A one-pot synthesis of 1-monosubstituted-1,2,3-triazoles from propargyl alcohol and various aryl azides was achieved. This simple method provides concise and efficient access to various 1-monosubstituted 1,2,3-triazole derivatives through a three-step one-pot ­sequence in good to excellent yields.

Key words

triazoles - propargyl alcohol - aryl azides - copper catalysis

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• 27 1-Substituted 1H-1,2,3-Triazoles; General Procedure Aryl azide 1 (0.3 mmol), propargyl alcohol (2; 0.36 mmol), CuI (0.03 mmol), NaAsc (0.06 mmol), and MeCN (2 mL) were added to a 15 mL pressure tube. The tube was sealed and the mixture was stirred at 80 °C for 5 h until the reaction was complete. KMnO₄ (0.75 mmol) and Na₂CO₃ (0.45 mmol) were added, and the mixture was stirred at 80 °C for 8 h. Ag₂O (0.03 mmol) and K₂S₂O₇ (0.6 mmol) were then added, and the mixture was heated at 100 °C for 24 h until the reaction was complete (TLC). H₂O (25 mL) was added, and the mixture was extracted with EtOAc (3 × 20 mL). The organic layers were combined, washed with brine (3 × 5 mL), dried (Na₂SO₄), and concentrated under reduced pressure to afford a crude product that was purified by column chromatography [silica gel, EtOAc–PE (1:3)]. 1-(4-Tolyl)-1H-1,2,3-triazole (3a) White solid; yield: 42 mg (88%); mp 85.5–86.5 °C. ¹H NMR (500 MHz, CDCl₃): δ = 7.96 (d, J = 0.8 Hz, 1 H), 7.83 (s, 1 H), 7.62 (d, J = 8.4 Hz, 2 H), 7.32 (d, J = 8.2 Hz, 2 H), 2.43 (s, 3 H). 1-(2-Methoxyphenyl)-1H-1,2,3-triazole (3f) White solid; yield: 46 mg (87%); mp 81–82.3 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.13 (d, J = 1.0 Hz, 1 H), 7.82 (d, J = 1.0 Hz, 1 H), 7.79 (dd, J = 7.9, 1.7 Hz, 1 H), 7.46–7.41 (m, 1 H), 7.14–7.08 (m, 2 H), 3.89 (s, 3 H). 4-(1H-1,2,3-Triazol-1-yl)benzenesulfonamide (3g) White solid; yield: 53 mg (79%); mp 187–187.5 °C. ¹H NMR (500 MHz, CDCl₃): δ = 8.93 (s, 1 H), 8.14 (d, J = 8.6 Hz, 2 H), 8.04 (d, J = 6.1 Hz, 3 H), 7.55 (s, 2 H). 1-(3-Chlorophenyl)-1H-1,2,3-triazole (3m) White solid; yield: 40 mg (75%); mp 91.6–92.4 °C. ¹H NMR (400 MHz, CDCl₃): δ = 8.02 (d, J = 1.1 Hz, 1 H), 7.86 (d, J = 1.0 Hz, 1 H), 7.80 (t, J = 2.0 Hz, 1 H), 7.66 (ddd, J = 7.9, 2.0, 1.3 Hz, 1 H), 7.51–7.40 (m, 2 H).