Synthesis of Substituted 1-Benzyl-2H-1,2,3-Triazoles by a Click Reaction Using Calcium Carbide as an Acetylene Source

Rugang Fu; Yuming Lei; Yuyu Wang; Baoqian Huang; Dong Qiu; Junke Wang

doi:10.1055/a-2414-2708

Synlett, Inhaltsverzeichnis

Synlett 2025; 36(07): 874-878
DOI: 10.1055/a-2414-2708

letter

Synthesis of Substituted 1-Benzyl-2H-1,2,3-Triazoles by a Click Reaction Using Calcium Carbide as an Acetylene Source

Rugang Fu

^aCollege of Chemistry and Chemical Engineering, Key Laboratory of Hexi Corridor Resources Utilization of Gansu, Hexi University, Zhangye, Gansu 734000, P. R. of China

,

Yuming Lei

^bCollege of Agriculture and Ecological Engineering, Key Laboratory of Hexi Corridor Resources Utilization of Gansu, Hexi University, Zhangye, Gansu 734000, P. R. of China

,

Yuyu Wang

^aCollege of Chemistry and Chemical Engineering, Key Laboratory of Hexi Corridor Resources Utilization of Gansu, Hexi University, Zhangye, Gansu 734000, P. R. of China

,

Baoqian Huang

^aCollege of Chemistry and Chemical Engineering, Key Laboratory of Hexi Corridor Resources Utilization of Gansu, Hexi University, Zhangye, Gansu 734000, P. R. of China

,

Dong Qiu

^aCollege of Chemistry and Chemical Engineering, Key Laboratory of Hexi Corridor Resources Utilization of Gansu, Hexi University, Zhangye, Gansu 734000, P. R. of China

,

Junke Wang

^aCollege of Chemistry and Chemical Engineering, Key Laboratory of Hexi Corridor Resources Utilization of Gansu, Hexi University, Zhangye, Gansu 734000, P. R. of China

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Abstract

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Abstract

An effective strategy for constructing substituted 1-benzyl-1H-1,2,3-triazoles was developed through click reactions of benzylic halides with sodium azide and calcium carbide as sources of nitrogen and acetylene, respectively. The advantages of this method are an easily handled inexpensive source of acetylene, a wide range of substrates, satisfactory yields, and simple workup procedures, which could promote the use of calcium carbide as a sustainable acetylene source in modern industrial chemistry.

Key words

sodium azide - calcium carbide - click chemistry - benzyl halides - triazoles

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References and Notes

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19 1-(2-Phenoxybenzyl)-1H-1,2,3-triazole (2t); Typical Procedure A mixture of 1-(chloromethyl)-2-phenoxybenzene (0.5 mmol, 0.109 g), 72–82% pure calcium carbide (2.4 mmol, 0.153 g), NaN₃ (0.6 mmol, 0.040 g, 1.2 equiv), CuI (0.05 mmol, 0.0095 g, 10 mol%), Et₃N (0.5 mmol, 0.5ml), H₂O (3 mmol, 54 μL, 6.0 equiv) in DMF (3 mL) was heated with stirring in an oil bath at 80 °C for 10 h until the reaction complete (TLC). The resulting mixture was filtered to remove the solids and the liquor was extracted with EtOAc (3 × 10 mL). The extracts were washed with sat. brine (3 × 10 mL), dried (Na₂SO₄), and concentrated under reduced pressure. The crude product was crystallized from PE–EtOAc to give a white solid; yield: 80.8 mg (65%); mp 82–85 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.67 (d, J = 1.0 Hz, 1 H), 7.57 (d, J = 1.0 Hz, 1 H), 7.41–7.26 (m, 4 H), 7.18–7.07 (m, 2 H), 7.00–6.92 (m, 2 H), 6.87 (dd, J = 8.2, 1.1 Hz, 1 H), 5.65 (s, 2 H). ¹³C NMR (101 MHz, CDCl₃): δ = 156.5, 154.9, 133.9, 130.6, 130.3, 130.0, 125.8, 123.9, 123.9, 123.7, 118.7, 118.4, 48.8. HRMS (ESI): m/z [M + Na]⁺ calcd for C₁₅H₁₃N₃NaO: 274.0951; found: 274.0953. 1-(2-Bromo-5-methoxybenzyl)-1H-1,2,3-triazole (2ad) White solid: 94.5 mg (71%); mp 74–76 °C (PE–EtOAc). ¹H NMR (400 MHz, CDCl₃): δ = 7.71 (d, J = 1.1 Hz, 1 H), 7.61 (d, J = 1.0 Hz, 1 H), 7.47 (d, J = 8.8 Hz, 1 H), 6.76 (dd, J = 8.8, 3.0 Hz, 1 H), 6.64 (d, J = 3.0 Hz, 1 H), 5.63 (s, 2 H), 3.71 (s, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 159.4, 135.1, 134.2, 133.8, 123.8, 116.2, 115.7, 113.5, 55.5, 53.7. HRMS (ESI): m/z [2M + Na]⁺ calcd for C₂₀H₂₀Br₂N₆NaO₂: 558.9887; found: 558.9886.

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