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Synlett 2021; 32(10): 1044-1048
DOI: 10.1055/a-1473-7369
DOI: 10.1055/a-1473-7369
letter
Diiiodine/Potassium Persulfate Mediated Synthesis of 1,2,3-Thiadiazoles from N-Tosylhydrazones and a Thiocyanate Salt as a Sulfur Source under Transition-Metal-Free Conditions
We are grateful for financial support from the Xinjiang Natural Science Foundation (2020D01C024), the National Natural Science Foundation of China (21662032, 21562039, and 22061040), and the startup funds of Quzhou University (BSYJ202108).
Abstract
A highly efficient method for the synthesis of 1,2,3-thiadiazoles has been developed by utilizing readily available tosylhydrazones and ammonium thiocyanate with ecofriendly EtOH as the solvent at room temperature. The reaction shows a wide scope of substrates and good functional-group tolerance. This protocol can be scaled up to a gram level and can be applied to coupling reactions with 4-(4-bromophenyl)-1,2,3-thiadiazole as the substrate.
Key words
thiadiazoles - transition-metal-free - tosylhydrazones - ammonium thiocyanate - ecofriendly solventsSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1473-7369.
- Supporting Information
Publication History
Received: 05 February 2021
Accepted after revision: 03 April 2021
Accepted Manuscript online:
03 April 2021
Article published online:
23 April 2021
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4-Phenyl-1,2,3-thiadiazole (3a);4 Typical Procedure
CAUTION: Toxic HCN gas might be formed as a byproduct of this reaction. A mixture of N-tosylhydrazone (1a) (72 mg, 0.25 mmol), NH4SCN (2) (1.0 equiv), I2 (63.5 mg, 0.25 mmol), and K2S4O8 (1.0 equiv) in anhyd EtOH (2.0 mL) was placed in a sealed tube. Test tube (25 mL) equipped with a magnetic stirrer bar, and the mixture was stirred at r.t. for 12 h. The reaction was then quenched with sat. aq Na2S2O3 (5 mL) and, after further stirring, the mixture was extracted with EtOAc (3 × 10 mL). The organic layer was dried (MgSO4), concentrated in vacuo, and purified by flash chromatography [silica gel, PE–EtOAc (8:1)] to give a white solid; yield: 35.5 mg (87%); mp 75–77 °C. 1H NMR (400 MHz, CDCl3): δ = 8.65 (s, 1 H), 8.05 (d, J = 6.8 Hz, 2 H), 7.54–7.43 (m, 3 H). 13C NMR (100 MHz, CDCl3): δ = 162.8, 130.8, 129.9, 129.4, 129.1, 127.4.