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

Yuhan Lu; Yadong Sun; Ablimit Abdukader; Chenjiang Liu

doi:10.1055/a-1473-7369

Synlett, Table of Contents

Synlett 2021; 32(10): 1044-1048
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

Yuhan Lu

^bThe Key Laboratory of Oil and Gas Fine Chemicals, Ministry of Education and Xinjiang Uygur Autonomous Region, Urumqi Key Laboratory of Green Catalysis and Synthesis Technology, School of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, P. R. of China

,

Yadong Sun∗

^aCollege of Chemical and Material Engineering, Quzhou University, Quzhou 324000, P. R. of China

^bThe Key Laboratory of Oil and Gas Fine Chemicals, Ministry of Education and Xinjiang Uygur Autonomous Region, Urumqi Key Laboratory of Green Catalysis and Synthesis Technology, School of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, P. R. of China

,

Ablimit Abdukader∗

^bThe Key Laboratory of Oil and Gas Fine Chemicals, Ministry of Education and Xinjiang Uygur Autonomous Region, Urumqi Key Laboratory of Green Catalysis and Synthesis Technology, School of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, P. R. of China

,

Chenjiang Liu

^bThe Key Laboratory of Oil and Gas Fine Chemicals, Ministry of Education and Xinjiang Uygur Autonomous Region, Urumqi Key Laboratory of Green Catalysis and Synthesis Technology, School of Chemistry and Chemical Engineering, Xinjiang University, Urumqi 830046, P. R. of China

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Abstract

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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 solvents

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References and Notes

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16 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.

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