Indium(III) Chloride Catalyzed Synthesis of 5-Substituted 1H-Tetrazoles from Oximes and Sodium Azide

^◊ Authors contributed equally.

Abstract

A simple and efficient protocol has been developed for the synthesis of 5-substituted 1H-tetrazole derivatives in good to excellent yields from various oximes and sodium azide by using indium(III) chloride as a Lewis acid catalyst. The present method has significant advantages, such as an inexpensive catalyst, low catalyst loading, mild reaction conditions, and simple experimental procedures.

Key words

tetrazoles - Lewis acids - catalysis - indium trichloride - sodium azide

• References and Notes

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• 22 5-Substituted 1H-Tetrazoles 2a–r: General Procedure InCl₃ (3 mol%) was added to a stirred solution of the appropriate aldoxime (1 mmol) and NaN₃ (1.5 mmol) in DMF (5 mL), and the mixture was heated to 120 °C. When the reaction was complete (TLC), the mixture was cooled to r.t., H₂O (5 mL), 2 M aq HCl (10 mL), and EtOAc (10 mL) were successively added, and the mixture was stirred vigorously for 15 min. The organic layer was separated, and the aqueous layer was extracted with EtOAc (3 × 15 mL). The combined organic extracts were washed with H₂O, dried (Na₂SO₄), and filtered. The solvent was evaporated under reduced pressure, and the crude product was purified by column chromatography [silica gel, EtOAc–hexane (9:1)]. 2-[4-(1H-Tetrazol-5-yl)phenoxy]acetohydrazide (2j) White solid; yield: 403 mg (72%); mp 197–199 °C. IR (KBr): 3432, 3318, 2869, 2645, 1614, 1521, 1450, 1280, 1172, 1108, 836 cm^–1. ¹H NMR (500 MHz, DMSO-d ₆): δ = 9.36 (br s, 1 H), 7.92 (d, J = 8.8 Hz, 2 H), 7.00 (d, J = 8.8 Hz, 2 H), 4.49 (s, 2 H). ¹³C NMR (125 MHz, DMSO-d ₆): δ = 166.6, 159.4, 157.4, 127.2, 124.3, 114.6, 66.2. HRMS: m/z [M + H]⁺ calcd for C₉H₁₁N₆O₂: 235.0938; found: 235.0939. 5-(4-Phenyl-2-thienyl)-1H-tetrazole (2p) White solid; yield: 466 mg (83%); mp 240–242 °C. IR (KBr): 3220, 2260, 1574, 1478, 1261, 1153, 1066, 886, 778 cm^–1. ¹H NMR (500 MHz, DMSO-d ₆): δ = 8.21 (s, 1 H), 8.07 (s, 1 H), 7.74 (d, J = 7.2 Hz, 2 H), 7.68 (d, J = 7.2 Hz, 2 H) 7.45–7.33 (m, 1 H). ¹³C NMR (125 MHz, DMSO-d ₆): δ = 162.7, 141.6, 140.8, 134.6, 128.9, 127.4, 127.2, 125.7, 125.6. HRMS: m/z [M + H]⁺ calcd for C₁₁H₉N₄S: 229.0542; found: 229.0543.