Synlett 2015; 26(01): 76-78
DOI: 10.1055/s-0034-1379501
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© Georg Thieme Verlag Stuttgart · New York

Electrophilic Aromatic Trifluoromethylthiolation with the Second Generation of Trifluoromethanesulfenamide

Sébastien Alazet
Institute of Chemistry and Biochemistry (ICBMS, UMR CNRS 5246), Université de Lyon, Université Lyon 1, CNRS, 43 Bd du 11 novembre 1918, 69622 Lyon, France   Email: Thierry.billard@univ-lyon1.fr
CERMEP, In Vivo Imaging, Groupement Hospitalier Est, 59 Bd Pinel, 69003 Lyon, France
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Thierry Billard*
Institute of Chemistry and Biochemistry (ICBMS, UMR CNRS 5246), Université de Lyon, Université Lyon 1, CNRS, 43 Bd du 11 novembre 1918, 69622 Lyon, France   Email: Thierry.billard@univ-lyon1.fr
CERMEP, In Vivo Imaging, Groupement Hospitalier Est, 59 Bd Pinel, 69003 Lyon, France
› Author Affiliations
Further Information

Publication History

Received: 29 September 2014

Accepted after revision: 03 November 2014

Publication Date:
28 November 2014 (eFirst)

Abstract

Direct trifluoromethylthiolation of various aromatic and heteroaromatic compounds, variously substituted, can be performed with the second generation of trifluoromethanesulfenamide via a ‘Friedel–Crafts-like reaction’. This reaction requires mild conditions with a catalytic amount of protic or Lewis acid. Good results have been obtained, even with aromatic compounds bearing deactivating substituents.

Supporting Information

 
  • References and Notes

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  • 13 Typical Procedure: A 10 mL sealed tube equipped with a magnetic stirrer was charged with the arene (0.50 mmol, 1.0 equiv) and TsNMeSCF3 (1a) or TsNMeSCF2CF3 (1b; 1.2 equiv) in anhyd DCE. The reaction was stirred at r.t. for 1 min and triflic acid was added slowly (0.2 equiv) and the reaction was stirred at 80 °C for 18 h. The progress of the reaction was checked by 19F NMR with PhOCF3 as internal standard. After completion, the reaction was warmed to r.t. and the solvent was removed under vacuum and the residue was purified by flash chromatography to give the desired product.
  • 14 4-[(Trifluoromethyl)sulfanyl]benzene-1,3-diol (3b): brown solid; mp <50 °C. 1H NMR: δ = 7.41 (d, 3 J H,H = 8.6 Hz, 1 H), 6.56 (d, 3 J H,H = 2.7 Hz, 1 H), 6.85 (dd, 3 J H,H = 8.6, 2.7 Hz, 1 H), 4.50–6.10 (br, 2 H). 13C NMR: δ = 161.1, 159.5, 139.6, 128.8 (q, 1 J C,F = 315 Hz), 109.9, 103.0, 99.62 (q, 3 J C,F = 1.7 Hz). 19F NMR: δ = –44.52 (s, 3 F). Anal. Calcd for C7H5F3O2S: C, 40.00; H, 2.40; S, 15.26. Found: C, 40.12; H, 2.29; S, 15.47.
  • 15 Synthesis of 2,4-Dimethoxy-1-[(pentafluoroethyl)sulfanyl]benzene (4a): 1H NMR: δ = 7.51 (d, 3 J H,H = 8.5 Hz, 1 H), 6.50–6.52 (m, 2 H), 3.87 (s, 3 H), 3.83 (s, 3 H). 13C{19F} NMR: δ = 164.3, 162.7, 141.0, 120.0 (CF2), 118.9 (CF3), 105.7, 101.7 (t, 3 J C,F = 2 Hz), 99.3, 56.1, 55.62. 19F NMR: δ = –82.94 (t, 3 J F,F = 3.4 Hz, 3 F), –93.06 (q, 3 J F,F = 3.5 Hz, 2 F). Anal. Calcd for C10H9F5O2S: C, 41.67; H, 3.15; S, 11.12. Found: C, 41.79; H, 2.91; S, 11.4.