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CC BY-ND-NC 4.0 · SynOpen 2017; 01(01): 0138-0142
DOI: 10.1055/s-0036-1590964
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Metal-Free Oxidative Dimerization of Dithiocarbamates: Direct Access to 3,5-Bis-mercapto-1,2,4-thiadiazoles

Azim Ziyaei Halimehjani*
a   Faculty of Chemistry, Kharazmi University, 49 Mofateh St., PO Box 15719-14911, Tehran, Iran   Email: ziyaei@khu.ac.ir
,
Yazdanbakhsh Lotfi Nosood
a   Faculty of Chemistry, Kharazmi University, 49 Mofateh St., PO Box 15719-14911, Tehran, Iran   Email: ziyaei@khu.ac.ir
,
Shaghayegh Didaran
a   Faculty of Chemistry, Kharazmi University, 49 Mofateh St., PO Box 15719-14911, Tehran, Iran   Email: ziyaei@khu.ac.ir
,
Fezzeh Aryanasab
b   Department of Chemistry and Petrochemical Engineering, Standard Research Institute (SRI), 31745-139, Karaj, Iran
› Author Affiliations
Further Information

Publication History

Received: 05 October 2017

Accepted after revision: 26 October 2017

Publication Date:
13 November 2017 (online)

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Abstract

A facile and efficient protocol for the synthesis of 3,5-bis-mercapto-1,2,4-thiadiazoles by the oxidative dimerization of S-alkyl dithiocarbamates using periodic acid as an inexpensive and commercially available oxidant is reported. High to excellent yields and short reaction times are the main advantages of this procedure.

Key words

3,5-bismercaptoorganyl-1,2,4-thiadiazoles - dithiocarbamate - oxidative dimerization - hypervalent iodine - transition-metal-free

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1590964.
  • Supporting Information
 

  • References and Notes

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  • 16 Synthesis of 3,5-(Bismercaptoorganyl)-1,2,4-thiadiazoles; General Procedure: To a solution of dithiocarbamate 1 (0.5 mmol) in CH2Cl2 (2 mL), periodic acid (0.5 mmol) was added. The resulting mixture was stirred at 0 °C for 15 minutes. After completion of the reaction, water (3 mL) was added and the mixture was extracted with CH2Cl2 (3 × 3 mL). The combined organic extracts were dried over Na2SO4, filtered and evaporated under reduced pressure. The desired product 2 was purified by column chromatography (silica gel; ethyl acetate/hexane, 1:10).Characterization Data for Selected Compounds
    3,5-Bis(benzylthio)-1,2,4-thiadiazole (2a):     Yield: 70 mg (85%); yellow oil. IR (KBr): 1424, 1211, 1041, 699 cm–1; 1H NMR (300 MHz, CDCl3): δ = 4.47 (s, 4 H), 7.27–7.45 (m, 10 H); 13C NMR (75 MHz, CDCl3): δ = 36.4, 38.4, 127.4, 128.1, 128.5, 128.8, 129.0, 129.1, 135.0, 136.8, 170.2, 187.2; Anal. Calcd (%) for C16H14N2S3: C, 58.15; H, 4.27; N, 8.48; Found: C, 58.27; H, 4.17; N, 8.35.3,5-Bis(isopentylthio)-1,2,4-thiadiazole (2b): Yield: 65 mg (89%); yellow oil. IR (KBr): 1427, 1209, 1041 cm–1; 1H NMR (300 MHz, CDCl3): δ = 0.93–0.96 (m, 12 H), 1.63–1.76 (m, 6 H), 3.19–3.25 (m, 4 H); 13C NMR (75 MHz, CDCl3): δ = 22.1, 22.2, 27.4, 27.5, 30.2, 32.3, 37.5, 38.1, 171.1, 187.9; Anal. Calcd (%) for C12H22N2S3: C, 49.61; H, 7.63; N, 9.64; Found: C, 49.32; H, 7.55; N, 9.49.Dibutyl 3,3'-[(1,2,4-Thiadiazole-3,5-diyl)bis(sulfanediyl)]di­-propanoate (2k): Yield: 81 mg (80%); yellow oil. IR (KBr): 1735, 1465, 1430, 1350, 1213, 1063 cm–1; 1H NMR (300 MHz, CDCl3): δ = 0.88–0.93 (m, 6 H), 1.31–1.39 (m, 4 H), 1.57–1.62 (m, 4 H), 2.78–2.85 (m 4 H), 3.40–3.50 (m, 4 H), 4.07–4.12 (m, 4 H); 13C NMR (75 MHz, CDCl3): δ = 13.6, 19.0, 26.9, 29.0, 30.5, 33.1, 33.8, 34.0, 34.4, 34.7, 64.6, 64.8, 169.9, 171.1, 171.6, 187.2; Anal. Calcd (%) for C16H26N2O4S3: C, 47.26; H, 6.45; N, 6.89; Found: C, 47.17; H, 6.32; N, 7.05