A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1970, 50, 65
DOI: 10.15227/orgsyn.050.0065
[Thiirene, diphenyl-, 1,1-dioxide]
Submitted by Louis A. Carpino1 and Louis V. McAdams III.
Checked by Timothy P. Higgs and Ronald Breslow.
1. Procedure
Caution! Benzene has been identified as a carcinogen; OSHA has issued emergency standards on its use. All procedures involving benzene should be carried out in a well-ventilated hood, and glove protection is required.
To a magnetically stirred solution of 6.36 g. (0.0157 mole) of crude α,α'-dibromodibenzyl sulfone (m.p. 135–150°; Org. Synth., Coll. Vol. 6, 403 (1988)) in 40 ml. of dichloromethane contained in a 100-ml., round-bottomed flask fitted with a reflux condenser there is added in one portion 5.05 g. (0.0500 mole) of triethylamine. The solution is heated at reflux with stirring for 3 hours (Note 1), filtered, and the precipitate washed with 5 ml. of cold (0°) dichloromethane. The combined dichloromethane solution is washed with two 20-ml. portions of 3 N hydrochloric acid followed by one 10-ml. portion of water. Removal of the solvent by distillation from a water bath at 30° with the aid of a water aspirator gives 3.0 g. (80%) of the vinylene sulfone as a tan solid, m.p. 116–126° (dec.). The crude solid is washed with 5 ml. of cold (0°) ethanol and recrystallized from about 10 ml. of benzene, yielding 2.4–2.5 g. (63–67%) of the pure sulfone as tiny, snow-white needles, m.p. 123–126° (dec.) (Note 2).
2. Notes
1. After about 45 minutes triethylamine hydrobromide began to precipitate.
2. The submitters obtained a similar percent yield on ten times the scale.
3. Discussion
2,3-Diphenylvinylene sulfone has been prepared by dehydrohalogenation of either α,α'-dibromodibenzyl sulfone2 3 or α,α'-dichlorodibenzyl sulfone,4 as well as by oxidation of 2,3-diphenylvinylene sulfoxide.5 The procedure described here illustrates a general technique for the synthesis of diarylvinylene sulfones and has been extended to a number of substituted derivatives.5,6 Aliphatic derivatives have been synthesized in other ways.3,7,8 The vinylene sulfones are a group of compounds of considerable theoretical interest.2,3,9 10 11 12 13

References and Notes
  1. Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003.
  2. L. A. Carpino and L. V. McAdams, III, J. Am. Chem. Soc., 87, 5804 (1965);
  3. L. A. Carpino, L. V. McAdams, III, R. H. Rynbrandt, and J. W. Spiewak, J. Am. Chem. Soc., 93, 476 (1971).
  4. J. C. Philips, J. V. Swisher, D. Haidukewych, and D. Morales, J. Chem. Soc. D, 22 (1971).
  5. L. A. Carpino and H.-W. Chen, J. Am. Chem. Soc., 93, 785 (1971) and 101, 390 (1979).
  6. M. H. Rosen and G. Bonet, J. Org. Chem., 39, 3805 (1974).
  7. L. A. Carpino and R. H. Rynbrandt, J. Am. Chem. Soc., 88, 5682 (1966).
  8. L. A. Carpino and J. R. Williams, J. Org. Chem., 39, 2320 (1974).
  9. C. Müller, A. Schweig, and H. Vermeer, J. Am. Chem. Soc., 100, 8056 (1978) and 97, 982 (1975);
  10. H. L. Hase, C. Müller, and A. Schweig, Tetrahedron, 34, 2983 (1978);
  11. F. de Jong, A. J. Noorduin, T. Bouwman, and M. J. Janssen, Tetrahedron Lett., 1209 (1974);
  12. D. T. Clark, Int. J. Sulfur Chem., (C) 7, 11 (1972);
  13. H. L. Ammon, L. Fallon, and L. A. Plastas, Acta Crystallogr., Sect. B. 32, 2171 (1976).

Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

2,3-Diphenylvinylene sulfone

2,3-diphenylvinylene sulfoxide

ethanol (64-17-5)

hydrochloric acid (7647-01-0)

Benzene (71-43-2)

sulfone (7446-09-5)

sulfur (7704-34-9)

dichloromethane (75-09-2)

triethylamine (121-44-8)

triethylamine hydrobromide (636-70-4)

α,α'-Dibromodibenzyl sulfone (21966-50-7)

Thiirene, diphenyl-, 1,1-dioxide (5162-99-2)

vinylene sulfone

α,α'-dichlorodibenzyl sulfone