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)

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.

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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.