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Synlett 2014; 25(08): 1121-1123
DOI: 10.1055/s-0033-1340985
letter
© Georg Thieme Verlag Stuttgart · New York

A Copper-Catalyzed Synthesis of Symmetrical Diarylsulfanes

Issa Yavari*
Department of Chemistry, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran   Fax: +98(21)82883455   Email: yavarisa@modares.ac.ir
,
Majid Ghazanfarpour-Darjani
Department of Chemistry, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran   Fax: +98(21)82883455   Email: yavarisa@modares.ac.ir
,
Yazdan Solgi
Department of Chemistry, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran   Fax: +98(21)82883455   Email: yavarisa@modares.ac.ir
› Author Affiliations
Further Information

Publication History

Received: 25 January 2014

Accepted after revision: 19 February 2014

Publication Date:
10 April 2014 (online)

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Abstract

A room-temperature, copper-catalyzed synthesis of symmetrical diarylsulfanes has been developed. The reaction proceeds from aryl iodides and elemental sulfur (S8) by the action of copper(I) salts in the presence of N-ethyl-N-isopropylpropan-2-amine to afford the corresponding diarylsulfanes in good yields.

Key words

S-arylation - copper(I) iodide - diarylsulfanes - sulfur
 

  • References and Notes

  • 1 Evano G, Blanchard N, Toumi M. Chem. Rev. 2008; 108: 3054
    CrossrefPubMed
  • 2 Monnier F, Taillefer M. Angew. Chem. Int. Ed. 2009; 48: 2
    Crossref
  • 3 Liu G, Huth JR, Olejniczak ET, Mendoza F, DeVries P, Leitza S, Reilly EB, Okasinski GF, Fesik SW, Von Geldern TW. J. Med. Chem. 2001; 44: 1202
    CrossrefPubMed
  • 4 Nielsen SF, Nielsen EØ, Olsen GM, Liljefors T, Peters D. J. Med. Chem. 2000; 43: 2217
    Crossref
  • 5 Murata M, Buchwald SL. Tetrahedron 2004; 60: 7397
    Crossref
  • 6 Fernandez MA, Shen Q, Hartwig JF. J. Am. Chem. Soc. 2006; 128: 2180
    Crossref
  • 7 Zhang Y, Ngeow KN, Ying JY. Org. Lett. 2007; 9: 3495
  • 8 Correa A, Carril M, Bolm C. Angew. Chem. Int. Ed. 2008; 47: 2880
    CrossrefPubMed
  • 9 Buchwald SL, Bolm C. Angew. Chem. Int. Ed. 2009; 48: 5586
    Crossref
  • 10 Sperotto E, van Klink GP. M, de Vries JG, van Koten G. J. Org. Chem. 2008; 73: 5625
    Crossref
  • 11 Xu H, Zhao X, Fu Y, Feng Y. Synlett 2008; 3063
    Article in Thieme Connect
  • 12 Xu R, Wan J, Mao H, Pan Y. J. Am. Chem. Soc. 2010; 132: 15531
    Crossref
  • 13 Prasad D, Sekar G. Synlett 2010; 79
  • 14 Firouzabadi H, Iranpoor N, Gholinejad M. Adv. Synth. Catal. 2010; 352: 119
    Crossref
  • 15 Wang H, Jiang L, Chen T, Li Y. Eur. J. Org. Chem. 2010; 2324
  • 16 Ramana T, Saha P, Das M, Punniyamurthy T. Org. Lett. 2010; 12: 84
    Crossref
  • 17 Ke F, Qu Y, Jiang Z, Li Z, Wu D, Zhou X. Org. Lett. 2011; 13: 454
    Crossref
  • 18 Yavari I, Ghazanfarpour-Darjani M, Ahmadian S, Solgi Y. Synlett 2011; 1745
    Article in Thieme Connect
  • 19 General Procedure for the Synthesis of Products 2 A mixture of aryl iodide (2 mmol), CuI (0.10 mmol), ligand (1.1 mmol), and S8 (1.1 mmol) were added to an oven-dried reaction tube equipped with a septum. The reaction tube was evacuated and back-filled with argon. Under a counterflow of argon, EIPA (0.258 g, 2 mmol) and DMSO (2 mL) were added, and the mixture stirred at r.t. for 8 h. After complete disappearance of aryl iodide (monitored by TLC), H2O (5 mL) was added, and the mixture was extracted with CH2Cl2 (3 × 5 mL). The combined organic phases were dried (on MgSO4) and filtered before evaporation of the solvent. The residue was purified on silica gel, eluting with PE–EtOAc (20:1), to give product 2. Analytical and spectroscopic data for all derivatives, except 2g–i have been reported previously.19 Bis(2-trifluoromethylphenyl)sulfane (2g) Colorless oil; yield: 0.23 g (71%). IR (KBr): νmax = 2915, 1591, 1443, 1313, 1264, 1170, 1128, 1034, 756 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.24 (2 H, d, 3 J = 8.0 Hz, 2 CH), 7.36–7.44 (4 H, m, 4 CH), 7.74 (2 H, d, 3 J = 7.5 Hz, 2 CH). 13C NMR (125.7 MHz, CDCl3): δ = 123.6 (2 CF3, q, 1 J CF = 272.0 Hz), 126.9 (2 CH, q, 3 J CF = 5.5 Hz), 127.5 (2 CH), 131.0 (2 C, q, 2 J CF = 30.2 Hz), 132.4 (2 CH), 134.7 (2 CH), 134.8 (2 C, q, 3 J CF = 5.0 Hz). MS (EI, 70 eV): m/z (%) = 322 [M + 1], 301 (55), 252 (33), 233 (99), 184 (59), 157 (50), 133 (17), 108 (36). Bis(3-trifluoromethylphenyl)sulfane (2h) Colorless oil; yield: 0.26 g (81%). IR (KBr): νmax = 2928, 1589, 1422, 1316, 1145, 755 cm–1. 1H NMR (500 MHz, CDCl3) δ = 7.46 (2 H, d, 3 J = 7.2 Hz, 2 CH), 7.49–7.55 (4 H, m, 4 CH), 7.62 (2 H, s, 2 CH). 13C NMR (125.7 MHz, CDCl3): δ = 123.6 (2 CF3, q, 1 J CF = 271 Hz), 124.4 (2 CH, q, 3 J CF = 3.5 Hz), 127.7 (2 CH, q, 3 J CF = 3.7 Hz), 129.9 (2 CH), 131.9 (2 C, q, 2 J CF = 32.4 Hz), 134.2 (2 CH), 136.2 (2 C). MS (EI, 70 eV): m/z (%) = 322 [M + 1], 301 (26), 233 (69), 184 (35), 157 (40), 133 (11), 108 (25). Bis(4-cyanophenyl)sulfane (2i) Colorless solid; mp 174–176 °C; yield: 0.19 g (80%). IR (KBr): νmax = 3424, 2370, 2218, 1582, 1482, 818 cm–1. 1H NMR (500 MHz, CDCl3): δ = 7.55 (4 H, d, 3 J = 8.4 Hz, 4 CH), 7.61 (4 H, d, 3 J = 8.4 Hz, 4 CH).13C NMR (125.7 MHz, CDCl3): δ = 110.9 (2 C), 118.1 (2 CN), 126.5 (4 CH), 132.8 (4 CH), 142.1 (2 C). MS (EI, 70 eV): m/z (%) = 236 [M + 1], 204 (14), 166 (11), 134 (100), 107 (30), 90 (51), 82 (15), 75 (24), 69 (45), 63 (46), 57 (16), 51 (16).