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
Sulfonic acid chlorides, or sulfonyl chlorides, are a sulfonyl halide with the general formula RSO2Cl.
Production
Arylsulfonyl chlorides are made industrially in a two-step, one-pot reaction from an
arene (in this case,
benzene) and
chlorosulfuric acid:[4]
For alkylsulfonyl chlorides, one synthetic procedure is the
Reed reaction:
Reactions
Sulfonyl chlorides react with water to give the corresponding
sulfonic acid:
RSO2Cl + H2O → RSO3H + HCl
These compounds react readily with many other nucleophiles as well, most notably
alcohols and
amines (see
Hinsberg reaction). If the nucleophile is an alcohol, the product is a sulfonate ester; if it is an amine, the product is a
sulfonamide. Using sodium sulfite as the nucleophilic reagent, p-toluenesulfonyl chloride is converted to its
sulfinate salt, CH3C6H4SO2Na.[6] Chlorosulfonated alkanes are susceptible to crosslinking via reactions with various nucleophiles.[7]
Chlorosulfonated polyethylene (CSPE) is produced industrially by chlorosulfonation of polyethylene. CSPE is noted for its toughness, hence its use for roofing shingles.[7]
Perfluorooctanesulfonyl derivatives, such as
PFOS, are produced from their sulfonyl fluoride, which are produced by
electrofluorination[11]
In the molecular biology, sulfonyl fluorides are used to label proteins. They specifically react with
serine,
threonine,
tyrosine,
lysine,
cysteine, and
histidine residues. The fluorides are more resistant than the corresponding chlorides and are therefore better suited to this task.[12]
Some sulfonyl fluorides can also be used as
deoxyfluorinating reagents, such as 2-pyridinesulfonyl fluoride (PyFluor) and N-tosyl-4-chlorobenzenesulfonimidoyl fluoride (SulfoxFluor).[13][14]
Sulfonyl bromides
Sulfonyl bromides have the general formula RSO2Br. In contrast to sulfonyl chlorides, sulfonyl bromides readily undergo
light-inducedhomolysis affording sulfonyl radicals, which can add to
alkenes, as illustrated by the use of bromomethanesulfonyl bromide, BrCH2SO2Br in
Ramberg–Bäcklund reaction syntheses.[15][16]
Sulfonyl iodides
Sulfonyl iodides, having the general formula RSO2I, are quite light-sensitive. Perfluoroalkanesulfonyl iodides, prepared by reaction between silver perfluoroalkanesulfinates and
iodine in dichloromethane at −30 °C, react with alkenes to form the normal adducts, RFSO2CH2CHIR and the adducts resulting from loss of SO2, RFCH2CHIR.[17] Arenesulfonyl iodides, prepared from reaction of arenesulfinates or arenehydrazides with iodine, can be used as initiators to facilitate the synthesis of poly(methyl methacrylate) containing C–I, C–Br and C–Cl chain ends.[18]
^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.
^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.
doi:
10.1021/ja00275a051.
^Huang, W.-Y.; L.-Q., Hu (1989). "The chemistry of perfluoroalkanesulfonyl iodides". Journal of Fluorine Chemistry. 44 (1): 25–44.
doi:
10.1016/S0022-1139(00)84369-9.
^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.