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Synlett 2023; 34(01): 45-48
DOI: 10.1055/s-0041-1738425
DOI: 10.1055/s-0041-1738425
letter
Additive-Free Synthesis of 3H-1,2,4-Triazol-3-ones via a Formal [3+2] Cycloaddition Reaction of Hydrazonoyl Chlorides with KOCN
We gratefully acknowledge the Research Council of Tarbiat Modares University, and Iran’s National Elites Foundation for support of this work.
Abstract
A direct and speedy approach for the synthesis of 1,5-disubstitued-3H-1,2,4-triazol-3-ones via a formal [3+2] cycloaddition reaction of hydrazonoyl chlorides with KOCN is described. The reaction proceeds in EtOH at room temperature with no need for any base and catalyst. KCl is the sole byproduct of this efficient synthetic procedure which can be isolated after reaction completion using water in which the products precipitated.
Key words
1,2,4-triazol-3-one - formal [3+2] cycloaddition - hydrazonoyl chlorides - potassium cyanate - Huisgen reactionSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0041-1738425.
- Supporting Information
Publication History
Received: 08 May 2022
Accepted after revision: 06 September 2022
Article published online:
16 November 2022
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- 17 General Procedure for the Synthesis of 1,2,4-Triazole-3-one Derivatives 3a–p A mixture of hydrazonoyl chloride substrate 1 (0.5 mmol, 1 equiv.) and KOCN (0.5 mmol, 1 equiv.) in EtOH (96%, 2 mL) was stirred at room temperature for 4 h. Upon reaction completion (monitored by TLC), water (10 mL) was added, the precipitate was collected and washed with water (3 × 10 mL). The solid was dried under reduced pressure and recrystallized from methanol to afford the pure product 3. 2,5-Diphenyl-2,4-dihydro-3H-1,2,4-triazol-3-one (3a) Colorless solid; 113 mg (95% yield); mp 232–233 °C (lit.3 232.5–233.5 °C). 1H NMR (500 MHz, DMSO-d 6): δ = 12.65 (s, 1 H), 7.99 (d, J = 8.5 Hz, 2 H), 7.91 (d, J = 9.3 Hz, 2 H), 7.52 (d, J = 6.4 Hz, 3 H), 7.46 (t, J = 7.4 Hz, 2H), 7.22 (t, J = 7.3 Hz, 1 H). 13C NMR (126 MHz, DMSO-d 6): δ = 153.4, 145.3, 138.3, 131.1, 129.5, 129.5, 126.6, 125.8, 125.4, 118.5. MS: m/z = 236.9 (43), 194 (16), 103 (21), 91 (100), 77 (41), 64 (60), 51 (28). Anal. Calcd for C14H11N3O (237.3): C, 70.87; H, 4.67; N, 17.71. Found: C, 71.18; H, 4.70; N, 17.76.