Synthesis of α-Ketothioamides via Willgerodt–Kindler Reaction of Arylglyoxals with Amines and Sulfur under Solvent-Free Conditions

Bagher Eftekhari-Sis; Saleh Vahdati Khajeh; Orhan Büyükgüngör

doi:10.1055/s-0032-1316897

Synlett, Table of Contents

Synlett 2013; 24(8): 977-980
DOI: 10.1055/s-0032-1316897

letter

Synthesis of α-Ketothioamides via Willgerodt–Kindler Reaction of Arylglyoxals with Amines and Sulfur under Solvent-Free Conditions

Bagher Eftekhari-Sis*

^aDepartment of Chemistry, University of Maragheh, Golshar, P. O. Box. 55181-83111, Maragheh, Iran Fax: +98(421)2276066 Email: eftekharisis@maragheh.ac.ir Email: eftekhari.sis@gmail.com

,

Saleh Vahdati Khajeh

^aDepartment of Chemistry, University of Maragheh, Golshar, P. O. Box. 55181-83111, Maragheh, Iran Fax: +98(421)2276066 Email: eftekharisis@maragheh.ac.ir Email: eftekhari.sis@gmail.com

,

Orhan Büyükgüngör

^bOndokuz Mayis University, Department of Physics, 55139, Samsun, Turkey

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Abstract

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Abstract

Willgerodt–Kindler reaction of arylglyoxal hydrates with secondary amines and elemental sulfur under solvent-free conditions at 80 °C is developed, in which α-ketothioamides are obtained in 70–90% yield in 0.6–1 hour. The X-ray crystal-structure analysis for one compound was obtained.

Key words

α-ketothioamides - Willgerodt–Kindler reaction - arylglyoxals - green chemistry - solvent-free

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References

References and Notes

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29 Spectroscopic and Analytical Data for Selected Novel Compounds 1-(3,4-Dimethoxyphenyl)-2-(pyrrolidin-1-yl)-2-thioxo-ethanone (3g) Dark yellow solid; mp 113–115 °C. FTIR (KBr): 2967 (CH), 1648 (C=O), 1589 (C=C), 1508 (C=S), 1451 (CH₂ bending), 1270 (CO), 1229 (CN), 1019 (C=S) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.59–7.63 (dd, J = 2.0, 8.4 Hz, 1 H, CH_Ar), 7.57 (d, J = 2.0 Hz, 1 H, CH_Ar), 6.90 (d, J = 8.4 Hz, 1 H, CH_Ar), 3.96–3.99 (m, 2 H, CH₂N), 3.98 (s, 3 H, OCH₃), 3.96 (s, 3 H, OCH₃), 3.56–3.59 (m, 2 H, CH₂N), 2.06–2.17 (m, 4 H, CH₂). ¹³C NMR (100 MHz, CDCl₃): δ = 193.1 (C=S), 188.3 (C=O), 154.3, 149.4, 126.0, 125.8, 111.1, 110.2, 56.2, 51.3, 26.1, 23.9. Calcd for C₁₄H₁₇NO₃S: C, 60.19; H, 6.13; N, 5.28. Found: C, 60.20; H, 6.13; N, 4.99. 1-(3-Methoxyphenyl)-2-morpholino-2-thioxoethanone (3r) Dark yellow oil. FTIR (KBr): 2920 (CH), 1642 (C=O), 1600 (C=C), 1489 (C=S), 1435 (CH₂ bending), 1268 (CO), 1246 (CN), 1110 (C=S) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.51–7.56 (m, 2 H, CH_Ar), 7.40 (t, J = 8.0 Hz, 1 H, CH_Ar), 7.16–7.19 (m, 1 H, CH_Ar), 4.32–4.35 (m, 2 H, CH₂O), 3.90–3.93 (m, 2 H, CH₂O), 3.87 (s, 3 H, OCH₃), 3.70–3.72 (m, 2 H, CH₂N), 3.60–3.62 (m, 2 H, CH₂N). ¹³C NMR (400 MHz, CDCl₃): δ = 195.6 (C=S), 187.7 (C=O), 160.1, 134.5, 130.2, 122.8, 121.8, 113.4, 66.7, 55.6, 51.9, 47.1. Anal. Calcd for C₁₃H₁₅NO₃S: C, 58.85; H, 5.70; N, 5.28. Found: C, 58.44; H, 5.39; N, 5.00. 1-(4-Methoxyphenyl)-2-morpholino-2-thioxoethanone (3s) Yellow solid; mp 117–118.5 °C. FTIR (KBr): 3110, 2969 (CH), 1654 (C=O), 1595 (C=C), 1500 (C=S), 1437 (CH₂ bending), 1263 (CO), 1234 (CN), 1110 (C=S) cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 7.97–8.01 (m, 2 H, CH_Ar), 6.97–7.01 (m, 2 H, CH_Ar), 4.34–4.37 (m, 2 H, CH₂O), 3.92–3.94 (m, 2 H, CH₂O), 3.91 (s, 3 H, OCH₃), 3.70–3.73 (m, 2 H, CH₂N), 3.62–3.63 (m, 2 H, CH₂N). ¹³C NMR (400 MHz, CDCl₃): δ = 196.2 (C=S), 187.3 (C=O), 164.6, 132.3, 126.1, 114.3, 66.5, 55.7, 51.9, 47.1. Anal. Calcd for C₁₄H₁₇NO₄S: C, 56.93; H, 5.80; N, 4.74. Found: C, 56.61; H, 5.80; N, 4.42.

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