Click Synthesis of 5-Substituted 1H-Tetrazoles from Aldehydes, Hydroxyl­amine, and [bmim]N₃ via One-Pot, Three-Component Reaction

Abstract

An easy and efficient one-pot, three-component method for the synthesis of 5-substituted 1H-tetrazole derivatives, via the reaction of aldehydes, hydroxylamine, and [bmim]N₃, is reported.

Key words

5-substituted 1H-tetrazoles - three-component - click reaction - cyclization - aldehydes - 1-butyl-3-methylimidazolium azide

• References and Notes

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• 24 General Procedure for the Synthesis of 5-Substituted 1H-Tetrazoles 4a–g To a mixture of aldehyde (1 mmol) and hydroxylamine (1.2 mmol) in DMF (5 mL) at 120 °C was added [bmim]N₃ (1.5 mmol) and Cu(OAc)₂ (20 mol%). The mixture was stirred for further 12 h. After completion of the reaction, as indicated by TLC, the reaction mixture was treated with H₂O (10 mL) and extracted with EtOAc (2 × 15 mL). The aqueous layer was treated with 3 M HCl and extracted with EtOAc (2 × 15 mL). The organic layers were dried over anhyd Na₂SO₄ and concentrated to give the 5-substituted 1H-tetrazoles (Table 3). General Procedure for the Synthesis of 1-Butyl-3-methylimidazolium Azide²⁵ Freshly prepared 1-butyl-3-methylimidazolium chloride (20 mmol) and NaN₃ (20 mmol) were added into deionized H₂O (25 mL), and the mixture was stirred for 24 h at r.t. The solvent was removed under reduced pressure at 50 °C to obtain the crude product containing azide ionic liquid and NaCl, which was washed with MeCN (3 × 10 mL). The remaining MeCN was removed under high vacuum to yield yellow transparent liquid that became more viscous upon extensive drying. Isolated yield was 92%. Analytical Data for [bmim]N₃ IR (KBr): ν = 2019, 1636, 1571, 1465, 1337, 1168 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 1.15 (3 H, t, CH₃), 1.48 (2 H, m, CH₂), 1.80 (2 H, m, CH₂), 3.85 (3 H, s, NCH₃), 4.01 (2 H, t, NCH₂), 7.24 (1 H, d, ArH), 7.45 (1 H, d, ArH), 9.21 (1 H, br s, ArH). ¹³C NMR (100 MHz, CDCl₃): δ = 12.30, 19.1, 24.4, 36.4, 38.7, 124.1, 127.0, 142.8. Anal. Calcd (%) for C₈H₁₅N₅: C, 53.02; H, 8.34; N, 38.64. Found (%): C, 53.12; H, 8.36; N, 38.61. Analytical Data for 5-Phenyl-1H-tetrazole (4a) Mp 213–215 °C. ¹H NMR (500 MHz, CDCl₃): δ = 7.50 (m, 3 H), 8.10 (m, 2 H), 10 (br s, 1 H). IR (KBr): ν = 683, 725, 785, 1162, 1561, 1607, 1733, 2606, 2852, 2923, 3424 cm^–1
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