Sulfonyl halides have tetrahedral sulfur centres attached to two oxygen atoms, an organic radical, and a halide. In a representative example,methanesulfonyl chloride, the S=O, S−C, and S−Cl bond distances are respectively 142.4, 176.3, and 204.6 pm.[3]
Sulfonyl chlorides react with water to give the correspondingsulfonic acid:
RSO2Cl + H2O → RSO3H + HCl
These compounds react readily with many other nucleophiles as well, most notablyalcohols andamines (seeHinsberg reaction). If the nucleophile is an alcohol, the product is a sulfonate ester; if it is an amine, the product is asulfonamide:[citation needed]
RSO2Cl + R'2NH → RSO2NR'2 + HCl
However, sulfonyl chlorides also react frequently as a source of RSO− 2 and Cl+.[6] For examplebenzenesulfonyl chloride chlorinatesketene acetals[7] andmesyl chlorideFriedel-Crafts–chlorinatespara-xylene.[8] Using sodium sulfite as the nucleophilic reagent, p-toluenesulfonyl chloride is converted to itssulfinate salt,CH3C6H4SO2Na.[9] Chlorosulfonated alkanes are susceptible to crosslinking via reactions with various nucleophiles.[10]
Chlorosulfonated polyethylene (CSPE) is produced industrially by chlorosulfonation of polyethylene. CSPE is noted for its toughness, hence its use for roofing shingles.[10]
Perfluorooctanesulfonyl derivatives, such asPFOS, are produced from their sulfonyl fluoride, which are produced byelectrofluorination[14]
In the molecular biology, sulfonyl fluorides are used to label proteins. They specifically react withserine,threonine,tyrosine,lysine,cysteine, andhistidine residues. The fluorides are more resistant than the corresponding chlorides and are therefore better suited to this task.[15]
Some sulfonyl fluorides can also be used asdeoxyfluorinating reagents, such as 2-pyridinesulfonyl fluoride (PyFluor) andN-tosyl-4-chlorobenzenesulfonimidoyl fluoride (SulfoxFluor).[16][17]
Sulfonyl bromides have the general formula RSO2Br. In contrast to sulfonyl chlorides, sulfonyl bromides readily undergolight-inducedhomolysis affording sulfonyl radicals, which can add toalkenes, as illustrated by the use of bromomethanesulfonyl bromide, BrCH2SO2Br inRamberg–Bäcklund reaction syntheses.[18][19]
Sulfonyl iodides, having the general formula RSO2I, are quite light-sensitive. Methanesulfonyl iodide evolves iodine in vacuum and branched-alkyl sulfonyl iodides are worse.[20] Perfluoroalkanesulfonyl iodides, prepared by reaction between silver perfluoroalkanesulfinates andiodine in dichloromethane at −30 °C, react with alkenes to form the normal adducts, RFSO2CH2CHIR and the adducts resulting from loss of SO2, RFCH2CHIR.[21]
Arenesulfonyl iodides, prepared from reaction of arenesulfinates or arenehydrazides with iodine, are much more stable[20] and can initiate the synthesis of poly(methyl methacrylate) containing C–I, C–Br and C–Cl chain ends.[22] Their reduction withsilver gives the disulfone:[20]
^Drabowicz, J.; Kiełbasiński, P.; Łyżwa, P.; Zając, A.; Mikołajczyk, M. (2008). N. Kambe (ed.).Alkanesulfonyl Halides. Science of Synthesis. Vol. 39. pp. 19–38.ISBN9781588905307.
^Hargittai, Magdolna; Hargittai, István (1973). "On the molecular structure of methane sulfonyl chloride as studied by electron diffraction".J. Chem. Phys.59 (5): 2513.Bibcode:1973JChPh..59.2513H.doi:10.1063/1.1680366.
^Hirsch, Elisabeth; Hünig, Siegfried; Reißig, Hans-Ulrich (1982) [21 April 1981]. "Darstellung von (2,2-Dimethyl-1-methylenpropyl)-methansulfonat und trifluoracetat".Chemische Berichte (in German).115 (1):399–401.doi:10.1002/cber.19821150138.{{cite journal}}: CS1 maint: multiple names: authors list (link)
^Hyatt, John A.; White, Alan W. (1984). "Synthesis of aryl alkyl and aryl vinyl sulfones via Friedel-Crafts reactions of sulfonyl fluorides".Synthesis (3). Thieme:214–217.doi:10.1055/s-1984-30774.
^Dhar, Preeti; Ranjan, Rajeev; Chandrasekaran, Srinivasan (1990) [8 Sep 1989]. "Chemistry of Tetrathiotungstates: A Novel Synthesis of Disulfides from Sulfonyl Derivative".Journal of Organic Chemistry.55 (12). American Chemical Society:3728–3729.doi:10.1021/jo00299a010.
^Block, E.; Aslam, M.; Eswarakrishnan, V.; Gebreyes, K.; Hutchinson, J.; Iyer, R.; Laffitte, J.-A.; Wall, A. (1986). "α-Haloalkanesulfonyl Bromides in Organic Synthesis. 5. Versatile Reagents for the Synthesis of Conjugated Polyenes, Enones and 1,3-Oxathiole 1,1-Dioxides".J. Am. Chem. Soc.108 (15):4568–4580.Bibcode:1986JAChS.108.4568B.doi:10.1021/ja00275a051.
^abcDanehy, James P. (1971). "The Sulfur–Iodine Bond". In Senning, Alexander (ed.).Sulfur in Organic and Inorganic Chemistry. Vol. 1. New York: Marcel Dekker. pp. 336–337.ISBN0-8247-1615-9.LCCN70-154612.
^Percec, V.; Grigoras, C. (2005). "Arenesulfonyl iodides: The third universal class of functional initiators for the metal-catalyzed living radical polymerization of methacrylates and styrenes".Journal of Polymer Science Part A: Polymer Chemistry.43 (17):3920–3931.Bibcode:2005JPoSA..43.3920P.doi:10.1002/pola.20860.
