Download PDF
Synthesis 2010(6): 947-952  
DOI: 10.1055/s-0029-1218625
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Divinylsulfides

Jan Paradies*
Department of Organic Chemistry, University of Karlsruhe (TH), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany
Fax: +49(721)6088581; e-Mail: jan.paradies@ioc.uka.de;
Further Information

Publication History

Received 19 October 2009
Publication Date:
04 January 2010 (online)

   Permissions and Reprints All articles of this category
Preview

Abstract

Arylacetylenes react with sodium sulfide in the presence of water to yield divinylsulfides. The reaction proceeds in good to excellent yield for both electron-neutral and electron-deficient aromatic systems; for electron-rich aryls, longer reaction times are necessary. The sulfides represent useful substrates for further transformations, for example, oxidation to the corresponding divinylsulfoxides and divinylsulfones. Three selected divinylsulfide derivatives were oxidized selectively to the corresponding sulfoxides or sulfones.

Key words

alkynes - divinylsulfoxide - sulfoxide - sulfone - sodium sulfide

    References

  • 1a Metzner P. Thiuillier A. Sulfur Reagents in Organic Chemistry   Academic Press; San Diego: 1994. 
  • 1b Mikolajczk M. Drabowicz J. Kielbasinski P. Chiral Sulfur Reagents   CRC Press; New York: 1996. 
  • 1c Kagan HB. Diter B. Synthetic and Stereochemical Aspects, In Organosulfur Chemistry   Vol. 2:  Page PCB. Academic Press; London: 1998.  p.1 
    Search in Google Scholar
  • 1d Bolm C. Toru T. Organosulfur Chemistry in Asymmetric Synthesis   Wiley-VCH; Weinheim: 2008. 
  • 2a Pitchen P. Dunach E. Deshmukh MN. Kagan HB. J. Am. Chem. Soc.  1984,  106:  8188 
    Search in Google Scholar
  • 2b Kagan HB. Dunach E. Nemecek C. Pitchen P. Samuel O. Zhao SH. Pure Appl. Chem.  1985,  57:  1911 
    Search in Google Scholar
  • 2c Brunel J.-M. Diter P. Duetsch M. Kagan HB. J. Org. Chem.  1995,  60:  8086 
    Search in Google Scholar
  • 2d Bolm C. Bienewald F. Angew. Chem. Int. Ed. Engl.  1995,  34:  2640 ; Angew. Chem. 1995, 107, 2883
    Search in Google Scholar
  • 2e Delouvrie B. Fensterbank L. Najera F. Malacria M. Eur. J. Org. Chem.  2002,  3507 
  • 2f Aggarwal VK. Steele RM. Ritmaleni . Barrell JK. Grayson I. J. Org. Chem.  2003,  68:  4087 
    Search in Google Scholar
  • 3a For some reviews, see: Zimmerman HE. Thyagarajan BS. J. Am. Chem. Soc.  1960,  82:  2505 
    Search in Google Scholar
  • 3b Block E. Reactions of Organosulfur Compounds   Academic Press; New York: 1978. 
  • 3c Stowell JC. Carbanions in Organic Synthesis   Wiley; New York: 1979. 
  • 3d Solladie G. Zimmermann R. Bartsch R. Tetrahedron Lett.  1983,  24:  755 
    Search in Google Scholar
  • 3e Wolfe S. Sulfur-Containing Carbanions and Related Species, In Studies in Organic Chemistry   Vol. 19:  Bemardi F. Csizmadia IG. Mangini A. ; Amsterdam: 1985.  p.133 
    Search in Google Scholar
  • 4 Paquette LA. Synlett  2001,  1 
  • 5 Gusarova NK. Voronkov MG. Trofimov BA. J. Sulfur Chem.  1989,  9:  95 
    Search in Google Scholar
  • 6a Yamamura H. Kleffel D. Blount JF. Hunkler D. Todaro LJ. Otto HH. Liebigs Ann.  1984,  5:  1013 
    Search in Google Scholar
  • 6b Yamamura H. Kleffel D. Grossmann S. Otto HH. Arch. Pharm.  1985,  318:  280 
    Search in Google Scholar
  • 6c Potapov VA. Amosova SV. Doron’kina IV. Korsun OV. J. Organomet. Chem.  2003,  674:  104 
    Search in Google Scholar
  • 6d Gusarova NK. Yas’ko SV. Chernysheva NA. Korchevin NA. Trofimov BA. Russ. J. Gen. Chem.  2008,  78:  678 
    Search in Google Scholar
  • 7 Gusarova NK. Bogdanova MV. Ivanova NI. Chernysheva NA. Tatarinova AA. Trofimov BA. Russ. J. Gen. Chem.  2006,  76:  1201 
    CrossrefSearch in Google Scholar
  • 8a Otto HH. Yamamura H. Arch. Pharm.  1975,  308:  768 
    Search in Google Scholar
  • 8b Otto HH. Yamamura H. Liebigs Ann.  1977,  9:  1500 
    Search in Google Scholar
  • 8c Reddy DB. Muralidhar M. Padmavathi V. Vijayalakshmi S. Indian J. Heterocycl. Chem.  1995,  4:  259 
    Search in Google Scholar
  • 9a Naidu MSR. Rani RM. Phosphorus Sulfur  1984,  19:  259 
    Search in Google Scholar
  • 9b Reddy DB. Reddy PVR. Padmavathi V. Phosphorus Sulfur  1994,  90:  1 
    Search in Google Scholar
  • 10a Reddy DB. Padmavathi V. Reddy S. Reddy MVR. Sulfur Lett.  1991,  13:  123 
    Search in Google Scholar
  • 10b Padmavathi V. Reddy KV. Balaiah A. Reddy TVR. Reddy DB. Heteroat. Chem.  2002,  13:  677 
    Search in Google Scholar
  • 11 Dimroth K. Follmann H. Pohl G. Chem. Ber.  1966,  99:  642 
    CrossrefSearch in Google Scholar
  • 12 Carson JF. Boggs LE. J. Org. Chem.  1967,  32:  673 
    CrossrefSearch in Google Scholar
  • 13a Diederich F. Stang PJ. Tykwinski RR. Acetylene Chemistry: Chemistry, Biology, and Material Science   Wiley-VCH; Weinheim: 2005. 
  • 13b Trofimov BA. Gusarova NK. Russ. Chem. Rev.  2007,  76:  507 
    Search in Google Scholar
  • 14a Trofimov BA. Amosova SV. Alpert ML. Skatova NN. Russ. J. Org. Chem.  1977,  13:  2229 
    Search in Google Scholar
  • 14b Vasiltsov AM. Trofimov BA. Amosova SV. Voronov VK. Russ. Chem. Bull.  1982,  31:  2155 
    Search in Google Scholar
  • 14c Trofimov BA. Amosova SV. Sulfur Rep.  1984,  3:  323 
    Search in Google Scholar
  • 14d Vasiltsov AM. Amosova SV. Trofimov BA. Russ. Chem. Bull.  1985,  34:  1350 
    Search in Google Scholar
  • 18 Kissane M. Lynch D. Chopra J. Lawrence SE. Maguire AR. Tetrahedron: Asymmetry  2008,  19:  1256 
    CrossrefSearch in Google Scholar
  • 19 Yamamura H. Otto HH. Arch. Pharm.  1978,  311:  762 
    CrossrefPubMedSearch in Google Scholar
  • 20 Uhlig E. Borek B. Ngu LM. Z. Anorg. Allg. Chem.  1977,  432:  33 
    CrossrefSearch in Google Scholar
  • 21 Tsuchiya T. Shimizu T. Kamigata N. J. Am. Chem. Soc.  2001,  123:  11534 
    CrossrefPubMedSearch in Google Scholar
15

The addition of 3 and 4 equivalents of water did not furnish better yields but resulted in the formation of more side products.

16

When the reaction was performed with a more activated alkyne, such as 2-pyridyl-acetylene in DMF, the major product was the addition product of dimethylamine to the double bond.

17

When the reaction was performed with more activated alkynes, such as 4-acetyl- or 4-cyanophenylacetylene at -20 ˚C, 0 ˚C and room temperature, the only reaction products obtained were oligomeric and polymeric material.