Sulfone

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.

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. For example, dimethyl sulfide oxidizes to dimethyl sulfoxide and then to dimethyl sulfone.

Sulfur dioxide participates in cycloaddition reactions with dienes.

For example, the industrially useful solvent sulfolane is prepared by addition of sulfur dioxide to buta-1,3-diene followed by hydrogenation of the resulting sulfolene.

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.

Sulfones have been prepared through sulfinate anion alkylation. S_N2 displacement of a wide variety of halides gives exclusively sulfones...ArSO2Na + Ar'Cl -> Ar(Ar')SO2 + NaCl ...but some highly active alkylating agents give a sulfinate ester instead. The ester may or may not rearrange to the sulfone via dissociation-association. Absent a nucleophilic catalyst, sulfinate esters generally do not rearrange thermally to the sulfone, but allyl, propargyl, and benzyl sulfinates can rearrange when heated neat.

Reactions

A relatively inert functional group, sulfones are typically less oxidizing and only 4 bel more acidic than sulfoxides. They eventually eliminate to an alkene in base, but leave about 9 bel more slowly than chloride. In the Ramberg–Bäcklund reaction and the Julia olefination, sulfones eliminate sulfur dioxide to form an alkene.

Sulfones are strongly electron-withdrawing, and

vinyl sulfones are electrophilic Michael acceptors.

The behavior of the α carbon depends on context. Non-nucleophilic bases deprotonate, giving an enolate-like carbanion. Contrariwise, Lewis acids on the sulfone oxygens give a Pummerer-like electrophile that undergoes nucleophilic substitution.

Sulfones can also undergo reductive 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. Precursors to such polymers are the sulfones bisphenol S and 4,4′-dichlorodiphenyl sulfone.

Pharmacology

Dapsone, an antibiotic used for the treatment of leprosy.

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.

References

Hornback, Joseph, Organic Chemistry, Thomson Brooks/Cole, Australia, 2006
Phenyl Vinyl Sulfone and Sulfoxide, Leo A. Paquette, Richard V. C. Carr, Org. Synth., 1986, 64, 10.15227/orgsyn.064.0157
Isoprene Cyclic Sulfone, Robert L. Frank and Raymond P. Seven, Org. Synth., 1949, 29, 59, 10.15227/orgsyn.029.0059
Truce, W. E., Vriesen, C. W., Friedel—Crafts Reactions of Methanesulfonyl Chloride with Benzene and Certain Substituted Benzenes, 1953, J. Am. Chem. Soc., 75, 5032–5036, 10.1021/ja01116a043, 20, 1953JAChS..75.5032T
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
Truce, W. E., Milionis, J. P., Friedel-Crafts Cyclization of ω-Phenylalkanesulfonyl Chlorides, 1952, J. Am. Chem. Soc., 74, 974–977, 10.1021/ja01124a031, 4
4,4'-Diaminodiphenylsulfone, C. W. Ferry, J. S. Buck, R. Baltzly, Organic Syntheses, 1942, 22, 31, 10.15227/orgsyn.022.0031
10.1002/anie.201007100, 21726020, 50, 29, Farewell to the HSAB Treatment of Ambident Reactivity, Angewandte Chemie International Edition, 6497–6499, Mayr, Herbert, 2011, 2011ACIE...50.6470M, none
378–381, PhD dissertation, A Marcus-Theory-Based Approach to Ambident Reactivity, Robert Martin, Breugst, 2010, Ludwig-Maximilians-Universität München
10.1021/ja01157a018, Jan 1950, Thermal rearrangement of allyl-type sulfoxides, sulfones and sulfinates, Arthur C., Cope, Dwight E., Morrison, Lamar, Field, 72, 21 June 1949, Journal of the American Chemical Society, 1, 1950JAChS..72...59C
Braverman, Samuel, Pechenick, Tatiana, Facile preparation and rearrangement of allylic dialkoxy disulfides, Tetrahedron Letters, 43, 3, 2002, 10.1016/S0040-4039(01)02174-8, 499–502, subscription
10.1039/JR9300001676, Joseph, Kenyon, Henry, Phillips, The optical instability of tercovalent carbonium kations, 3 June 1930, Journal of the Chemical Society
Francis A., Carey, Richard J., Sundberg, Advanced Organic Chemistry, Springer, Berlin, 2007
Kharasch, Norman, The Chemistry of Organic Sulfur Compounds, Meyers, Cal Y., 2013-10-22, Elsevier, en
10.1002/047084289X.rd476.pub2, Divinyl Sulfone, Encyclopedia of Reagents for Organic Synthesis, 2021, Lucchi, Ottorino, Fabbri, Davide, Santoyo-Gonzalez, Francisco, Hernandez-Mateo, Fernando, Lopez-Jaramillo, F. Javier, Ortega-Muñoz, Mariano, 1–8
Trost, Barry Martin, 1988-01-01, Chemical Chameleons. Organosulfones as Synthetic Building Blocks, Bulletin of the Chemical Society of Japan, en, 61, 1, 107–124, 10.1246/bcsj.61.107, 0009-2673
Fink, Johannes, High Performance Polymers, William Andrew, Norwich, 2008
Charles R., Craig, Robert E., Stitzel, Modern Pharmacology with Clinical Applications, Lippincott Williams & Wilkins, Hagerstwon, 2004
Victor Alexander, Drill, Joseph R., Di Palma, Drill's Pharmacology in Medicine, McGraw-Hill, New York, 1971

Category:Functional groups

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