Vinyl sulfone

A vinyl sulfone is an organic compound with the formula O₂S(CH=CH₂)₂. The molecule consisting of two vinyl groups bonded to a sulfone. It is the parent of several vinyl sulfones of the type O₂S(CH=CH₂)R.^[1] Many vinyl sulfones are known.

Vinyl sulfone

Identifiers
CAS Number	77-77-0
PubChem CID	6496
Properties
Chemical formula	C4H6O2S
Molar mass	118.15 g·mol−1
Appearance	colorless oil
Density	1.177 g cm−3
Melting point	-26 °C
Boiling point	90–92 °C (194–198 °F; 363–365 K) 8 mmHg
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). Infobox references

Vinyl sulfones

Examples include phenyl vinyl sulfone,^[2] methyl vinyl sulfone,^[3] and ethyl vinyl sulfone.^[4]

Preparation

Divinyl sulfone is prepared from the diacetate bis(2-hydroxyethyl)sulfide. Oxidation of this diester with hydrogen peroxide gives the sulfone. The sulfone is then pyrolyzed to induce elimination of two equivalents of acetic acid:^[5]

(AcOCH₂CH₂)₂SO₂ → (CH₂=CH)₂SO₂ + 2 HOAc (Ac = acetyl)

Other vinyl sulfones are prepared analogously to the vinyl sulfone, i.e. by H₂O₂-oxidation of the sulfide.^[6]

Reactions and uses

Vinyl sulfones are dienophiles. Subsequent to the cycloaddition to a vinyl sulfone, the phenylsulfonyl group can be removed by reduction with zinc.^[7]

Vinyl sulfones are a Michael acceptors.^[8] Vinyl sulfones add thiols, such as cysteine residues.^[9] This same reactive nature is responsible for their major industrial use in vinyl sulfone dyes.^[10]

Phenyl vinyl sulfone has been applied to ruthenium chemistry as part of olefin metathesis reactions.^[11]

Vinyl sulfone has applications to protein purification, especially when linked with mercaptoethanol.^[12]

Commercial applications

Vinyl sulfone has uses as a molluscicide pesticide.^[13]

Safety

Like similar compounds, vinyl sulfone is a lacrymator and skin irritant. These properties are somewhat mitigated because of its low volatility.^[8]

References

1. Leonard, Edward C. (1970). Vinyl and Diene Monomers, Part 3. Wiley-Interscience. p. 1466.
2. Gustavson, Clarence (1952). Reactions of Phenyl Vinyl Sulfone with Organometallic Reagents. Syracuse University.
3. Keith, Lawrence H.; Walters, Douglas B. (1991). The National Toxicology Program's Chemical Data Compendium (Volume 8 ed.). CRC Press. ISBN 9780873717229.
4. Leonard, Edward C. (1970). Vinyl and Diene Monomers, Part 3. Wiley-Interscience. p. 1475.
5. Overberger, C. G.; Schoene, D. L.; Kamath, P. M.; Tashlick, Irving (1954). "A Convenient Synthesis of Vinyl Sulfone". The Journal of Organic Chemistry. 19 (9): 1486–1489. doi:10.1021/jo01374a012.
6. Leo A. Paquette and Richard V. C. Carr (1986). "Phenyl Vinyl Sulfone and Sulfoxide". Organic Syntheses. 64: 157. doi:10.15227/orgsyn.064.0157.
7. Ho-shen Lin and Leo A. Paquette (1989). "Reductive Annulation of Vinyl Sulfones: Bicyclo[4.3.0.]Non-1-En-4-One". Organic Syntheses. 67: 163. doi:10.15227/orgsyn.067.0163.
8. Lucchi, Ottorino; Fabbri, Davide; Santoyo-Gonzalez, Francisco; Hernandez-Mateo, Fernando; Lopez-Jaramillo, F. Javier; Ortega-Muñoz, Mariano (2021). "Divinyl Sulfone". Encyclopedia of Reagents for Organic Synthesis. pp. 1–8. doi:10.1002/047084289X.rd476.pub2. ISBN 978-0-471-93623-7.
9. Patterson, Cam; Cyr, Douglas M., eds. (2005). Ubiquitin-Proteasome Protocols. Springer Science & Business Media. p. PA7. ISBN 9781592598953.
10. Research In Technology Of Synthetic Dyes, Pigments And Intermediates. Engineers India. 2005. ISBN 9788186732519.
11. Bruneau, Christian; Dixneuf, Pierre H. (2004). Ruthenium Catalysts and Fine Chemistry. Springer Science & Business Media. ISBN 9783540205432.
12. Scopes, Robert K. (1993). Protein Purification: Principles and Practice. Springer Science & Business Media. p. 184. ISBN 9780387940724.
13. Pesticides Abstracts. U.S. Environmental Protection Agency, Office of Pesticide Programs, Program Support Division. 1975.