Sulfone Explained

In organic chemistry, a sulfone is a organosulfur compound containing a sulfonyl functional group attached to two carbon atoms. The central hexavalent sulfur atom is double-bonded to each of two oxygen atoms and has a single bond to each of two carbon atoms, usually in two separate hydrocarbon substituents.[1]

Synthesis and reactions

By oxidation of thioethers and sulfoxides

Sulfones are typically prepared by organic oxidation of thioethers, often referred to as sulfides. Sulfoxides are intermediates in this route.[2] For example, dimethyl sulfide oxidizes to dimethyl sulfoxide and then to dimethyl sulfone.[1]

From SO2

Sulfur dioxide is a convenient and widely used source of the sulfonyl functional group. Specifically, Sulfur dioxide participates in cycloaddition reactions with dienes.[3] The industrially useful solvent sulfolane is prepared by addition of sulfur dioxide to buta-1,3-diene followed by hydrogenation of the resulting sulfolene.

From sulfonyl and sulfuryl halides

Sulfones are prepared under conditions used for Friedel–Crafts reactions using sources of derived from sulfonyl halides and sulfonic acid anhydrides. Lewis acid catalysts such as and are required.[4] [5] [6]

Sulfones have been prepared by nucleophilic displacement of halides by sulfinates:[7]

ArSO2Na + Ar'Cl -> Ar(Ar')SO2 + NaCl

Reactions

Sulfone is a relatively inert functional group, typically less oxidizing and 4 bel more acidic than sulfoxides. In the Ramberg–Bäcklund reaction and the Julia olefination, sulfones are converted to alkenes by the elimination of sulfur dioxide.[8] However, sulfones are unstable to bases, eliminating to give an alkene.[9]

Sulfones can also undergo desulfonylation.

Applications

Sulfolane is used to extract valuable aromatic compounds from petroleum.

Polymers

Some polymers containing sulfone groups are useful engineering plastics. They exhibit high strength and resistance to oxidation, corrosion, high temperatures, and creep under stress. For example, some are valuable as replacements for copper in domestic hot water plumbing.[10] Precursors to such polymers are the sulfones bisphenol S and 4,4′-dichlorodiphenyl sulfone.

Pharmacology

thumb|222px|Dapsone, an antibiotic used for the treatment of leprosy.[11] Examples of sulfones in pharmacology include dapsone, a drug formerly used as an antibiotic to treat leprosy, dermatitis herpetiformis, tuberculosis, or pneumocystis pneumonia (PCP). Several of its derivatives, such as promin, have similarly been studied or actually been applied in medicine, but in general sulfones are of far less prominence in pharmacology than for example the sulfonamides.[12] [13]

See also

Notes and References

  1. Book: Hornback, Joseph . Organic Chemistry . Thomson Brooks/Cole . Australia . 2006 . 978-0-534-38951-2.
  2. Phenyl Vinyl Sulfone and Sulfoxide. Leo A. Paquette, Richard V. C. Carr. Org. Synth.. 1986. 64. 157. 10.15227/orgsyn.064.0157.
  3. Isoprene Cyclic Sulfone. Robert L. Frank and Raymond P. Seven. Org. Synth.. 1949. 29. 59. 10.15227/orgsyn.029.0059.
  4. Truce, W. E. . Vriesen . C. W. . Friedel—Crafts Reactions of Methanesulfonyl Chloride with Benzene and Certain Substituted Benzenes. 1953 . . 75 . 5032–5036 . 10.1021/ja01116a043 . 20.
  5. Répichet . S. . Le Roux . C. . Hernandez . P. . Dubac . J. . Desmurs . J. R. . Bismuth(III) Trifluoromethanesulfonate: An Efficient Catalyst for the Sulfonylation of Arenes . 10.1021/jo9902603 . The Journal of Organic Chemistry . 64 . 17 . 6479–6482 . 1999 .
  6. Truce, W. E. . Milionis, J. P. . Friedel-Crafts Cyclization of ω-Phenylalkanesulfonyl Chlorides . 1952 . . 74 . 974–977 . 10.1021/ja01124a031 . 4.
  7. 4,4'-Diaminodiphenylsulfone. C. W. Ferry, J. S. Buck, R. Baltzly. Org. Synth.. 1942. 22. 31. 10.15227/orgsyn.022.0031.
  8. Book: Francis A. . Carey . Richard J. . Sundberg . Advanced Organic Chemistry . Springer . Berlin . 2007 . 978-0-387-68354-6.
  9. Smith (2020), March's Organic Chemistry, rxn. 17-10.
  10. Book: Fink, Johannes . High Performance Polymers . William Andrew . Norwich . 2008 . 978-0-8155-1580-7.
  11. Book: Thomas L. Lemke . Foye's Principles of Medicinal Chemistry . 2008 . Lippincott Williams & Wilkins . 9780781768795 . 1142 . live . https://web.archive.org/web/20160304193954/https://books.google.ca/books?id=R0W1ErpsQpkC&pg=PA1142 . 2016-03-04.
  12. Book: Charles R. . Craig . Robert E. . Stitzel . Modern Pharmacology with Clinical Applications . Lippincott Williams & Wilkins . Hagerstwon . 2004 . 978-0-7817-3762-3.
  13. Book: Victor Alexander . Drill . Joseph R. . Di Palma . Drill's Pharmacology in Medicine . McGraw-Hill . New York . 1971 . 978-0-07-017006-3.