Sulfonyl halide

Short description: Chemical group made of an –S(=O)2 group bound to a halogen

In chemistry, a sulfonyl halide consists of a sulfonyl (>S(=O)
2) group singly bonded to a halogen atom. They have the general formula RSO
2X, where X is a halogen. The stability of sulfonyl halides decreases in the order fluorides > chlorides > bromides > iodides, all four types being well known. The sulfonyl chlorides and fluorides are of dominant importance in this series.[1][2]

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]

## Contents

* 1 Sulfonyl chlorides
* 1.1 Production
* 1.2 Reactions
* 1.3 Common sulfonyl chlorides
* 2 Sulfonyl fluorides
* 3 Sulfonyl bromides
* 4 Sulfonyl iodides
* 5 In popular culture
* 6 References

## Sulfonyl chlorides

General structure of a sulfonic acid chloride

Sulfonic acid chlorides, or sulfonyl chlorides, are a sulfonyl halide with the general formula RSO
2Cl.

### Production

Arylsulfonyl chlorides are made industrially in a two-step, one-pot reaction from an arene (in this case, benzene) and chlorosulfuric acid:[4]

6 \+ HOSO
2Cl → C

5SO
3H + HCl

5SO
3H + HOSO
2Cl → C

5SO
2Cl + H
2SO

The intermediate benzenesulfonic acid can be chlorinated with thionyl chloride as well. Benzenesulfonyl chloride, the most important sulfonyl halide, can also be produced by treating sodium benzenesulfonate with phosphorus pentachlorides.[5]

Benzenediazonium chloride reacts with sulfur dioxide and copper(I) chloride to give the sulfonyl chloride:

2]Cl + SO
2 → C

5SO
2Cl + N

For alkylsulfonyl chlorides, one synthetic procedure is the Reed reaction:

RH + SO
2 \+ Cl
2 → RSO
2Cl + HCl

### Reactions

Sulfonyl chlorides react with water to give the corresponding sulfonic acid:

RSO
2Cl + H
2O → RSO
3H + 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: :RSO
2Cl + R'
2NH → RSO
2NR'
2 \+ HCl

However, sulfonyl chlorides also react frequently as a source of RSO−2 and Cl+.[6] For example benzenesulfonyl chloride chlorinates ketene acetals[7] and mesyl chloride chlorinates para-xylene under Friedel-Crafts conditions.[8] Using sodium sulfite as the nucleophilic reagent, p-toluenesulfonyl chloride is converted to its sulfinate salt, CH

4SO
2Na.[9] Chlorosulfonated alkanes are susceptible to crosslinking via reactions with various nucleophiles.[10]

RSO
2Cl + C

6 → RSO

5 \+ HCl

A readily available arylsulfonyl chloride source is tosyl chloride.[11] The desulfonation of arylsulfonyl chlorides provides a route to aryl chlorides:

ArSO
2Cl → ArCl + SO

1,2,4-Trichlorobenzene is made industrially in this way.

Treatment of alkanesulfonyl chlorides having α-hydrogens with amine bases can give sulfenes, highly unstable species that can be trapped:

RCH
2SO
2Cl → RCH=SO
2 \+ HCl

Reduction with tetrathiotungstate ions (WS2−
4) induces dimerization to the disulfide.[12]

### Common sulfonyl chlorides

Chlorosulfonated polyethylene (CSPE) is produced industrially by chlorosulfonation of polyethylene. CSPE is noted for its toughness, hence its use for roofing shingles.[10]

An industrially important derivative is benzenesulfonyl chloride. In the laboratory, useful reagents include tosyl chloride, brosyl chloride, nosyl chloride and mesyl chloride.

## Sulfonyl fluorides

Sulfonyl fluorides have the general formula RSO2F. They can be produced by treating sulfonic acids with sulfur tetrafluoride:[13]

4 \+ RSO
3H → SOF
2 \+ RSO
2F + HF

Perfluorooctanesulfonyl derivatives, such as PFOS, are produced from their sulfonyl fluoride, which are produced by electrofluorination[14]

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.[15]

Some sulfonyl fluorides can also be used as deoxyfluorinating reagents, such as 2-pyridinesulfonyl fluoride (PyFluor) and N-tosyl-4-chlorobenzenesulfonimidoyl fluoride (SulfoxFluor).[16][17]

## Sulfonyl bromides

Sulfonyl bromides have the general formula RSO2Br. In contrast to sulfonyl chlorides, sulfonyl bromides readily undergo light-induced homolysis affording sulfonyl radicals, which can add to alkenes, as illustrated by the use of bromomethanesulfonyl bromide, BrCH2SO2Br in Ramberg–Bäcklund reaction syntheses.[18][19]

## Sulfonyl iodides

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 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.[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 with silver gives the disulfone:[20]

2 ArSO2I \+ 2Ag → (ArSO2)2 \+ 2 AgI

## In popular culture

In the episode "Encyclopedia Galactica" of his TV series Cosmos: A Personal Voyage, Carl Sagan speculates that some intelligent extraterrestrial beings might have a genetic code based on polyaromatic sulfonyl halides instead of DNA.

## References

1. ↑ Kosswig, Kurt (2000). "Ullmann's Encyclopedia of Industrial Chemistry". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a25_503.
2. ↑ Drabowicz, J.; Kiełbasiński, P.; Łyżwa, P.; Zając, A.; Mikołajczyk, M. (2008). N. Kambe. ed. Alkanesulfonyl Halides. Science of Synthesis. 39. pp. 19–38. ISBN 9781588905307.
3. ↑ Hargittai, Magdolna; Hargittai, István (1973). "On the molecular structure of methane sulfonyl chloride as studied by electron diffraction". J. Chem. Phys. 59 (5): 2513. doi:10.1063/1.1680366. Bibcode: 1973JChPh..59.2513H.
4. ↑ Lindner, Otto; Rodefeld, Lars. "Ullmann's Encyclopedia of Industrial Chemistry". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a03_507.
5. ↑ Adams, Roger; Marvel, C. S.; Clarke, H. T.; Babcock, G. S.; Murray, T. F. (1921). "Benzenesulfonyl chloride". Organic Syntheses 1: 21. http://www.orgsyn.org/demo.aspx?prep=CV1P0084. ;  Collective Volume, 1, pp. 84
6. ↑ Dong Jiajia; Krasnova, Larissa; Finn, M. G.; Sharpless, K. Barry (2014). "Sulfur(VI) fluoride exchange (SuFEx)". Angewandte Chemie International Edition in English (Wiley-VCH) 53 (36): 9433. doi:10.1002/anie.201309399. PMID 25112519. https://www.researchgate.net/publication/264675433.
7. ↑ Hirsch, Elisabeth; Hünig, Siegfried; Reißig, Hans-Ulrich (1982). "Darstellung von (2,2-Dimethyl-1-methylenpropyl)-methansulfonat und trifluoracetat" (in de). Chemische Berichte 115 (1): 399–401. doi:10.1002/cber.19821150138.
8. ↑ Hyatt, John A.; White, Alan W. (1984). "Synthesis of aryl alkyl and aryl vinyl sulfones via Friedel-Crafts reactions of sulfonyl fluorides". Synthesis (Thieme) (3): 214–217. doi:10.1055/s-1984-30774.
9. ↑ Field, L; Clark, R.D. (1958). "Methyl p-Tolyl Sulfone". Organic Syntheses 38: 62. doi:10.15227/orgsyn.038.0062. http://orgsyn.org/demo.aspx?prep=CV4P0674. Retrieved 9 July 2023.
10. ↑ 10.0 10.1 Happ, Michael; Duffy, John; Wilson, G. J.; Pask, Stephen D.; Buding, Hartmuth; Ostrowicki, Andreas (2011). "Ullmann's Encyclopedia of Industrial Chemistry". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.o23_o05.
11. ↑ Organic Syntheses, Coll. Vol. 5, p.39 (1973); Vol. 48, p.8 (1968) Online Article
12. ↑ Dhar, Preeti; Ranjan, Rajeev; Chandrasekaran, Srinivasan (1990). "Chemistry of Tetrathiotungstates: A Novel Synthesis of Disulfides from Sulfonyl Derivative". Journal of Organic Chemistry (American Chemical Society) 55 (12): 3728–3729. doi:10.1021/jo00299a010.
13. ↑ Boswell, G. A.; Ripka, W. C.; Scribner, R. M.; Tullock, C. W. (2011). "Fluorination by Sulfur Tetrafluoride". Organic Reactions. pp. 1–124. doi:10.1002/0471264180.or021.01. ISBN 978-0-471-26418-7.
14. ↑ Lehmler, H. J. (2005). "Synthesis of Environmentally Relevant Fluorinated Surfactants—a review". Chemosphere 58 (11): 1471–1496. doi:10.1016/j.chemosphere.2004.11.078. PMID 15694468. Bibcode: 2005Chmsp..58.1471L.
15. ↑ Narayanan, Arjun; Jones, Lyn H. (2015). "Sulfonyl fluorides as privileged warheads in chemical biology". Chemical Science 6 (5): 2650–2659. doi:10.1039/C5SC00408J. PMID 28706662.
16. ↑ Nielsen, Matthew K.; Ugaz, Christian R.; Li, Wenping; Doyle, Abigail G. (5 August 2015). "PyFluor: A Low-Cost, Stable, and Selective Deoxyfluorination Reagent". Journal of the American Chemical Society 137 (30): 9571–9574. doi:10.1021/jacs.5b06307. PMID 26177230. Bibcode: 2015JAChS.137.9571N.
17. ↑ Guo, Junkai; Kuang, Cuiwen; Rong, Jian; Li, Lingchun; Ni, Chuanfa; Hu, Jinbo (28 May 2019). "Rapid Deoxyfluorination of Alcohols with N-Tosyl-4-chlorobenzenesulfonimidoyl Fluoride (SulfoxFluor) at Room Temperature". Chemistry – A European Journal 25 (30): 7259–7264. doi:10.1002/chem.201901176. PMID 30869818.
18. ↑ Block, E.; Aslam, M. (1993). "A General Synthetic Method for the Preparation of Conjugated Dienes from Olefins using Bromomethanesulfonyl Bromide: 1,2-Dimethylenecyclohexane". Organic Syntheses. http://www.orgsyn.org/demo.aspx?prep=cv8p0212. ;  Collective Volume, Coll. Vol. 8, pp. 212
19. ↑ 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. Bibcode: 1986JAChS.108.4568B.
20. ↑ 20.0 20.1 20.2 Danehy, James P. (1971). "The Sulfur-Iodine Bond". in Senning, Alexander. Sulfur in Organic and Inorganic Chemistry. 1. New York: Marcel Dekker. pp. 336–337. ISBN 0-8247-1615-9.
21. ↑ 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. Bibcode: 1989JFluC..44...25H.
22. ↑ 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. doi:10.1002/pola.20860. Bibcode: 2005JPoSA..43.3920P.

* v
* t
* e

Functional groups

| Only carbon,
hydrogen,
and oxygen|

| Hydrocarbons|

* Allene
* Alkene (Allyl group

|

Other|

* Acetoxy
* Acetyl
* Acryloyl
* Acyl
* Aldehyde
* Alkoxy (Methoxy)
* Benzoyl
* Carbonyl
* Carboxyl
* Carboxylic anhydride
* Dioxirane
* Epoxide
* Ester
* Ether
* Ethylenedioxy
* Hydroxy
* Ketone
* Methylenedioxy
* Peroxide (Organic)
* Ynone

Only one
element
apart from
C, H, O|

| Nitrogen|

* Amine
* Azo compound
* Cyanate
* Hydrazone
* Imide
* Imine
* Isocyanate
* Isonitrile
* Nitrene
* Nitrile
* Nitro compound
* Nitroso compound
* Organic amide
* Oxime

|

Phosphorus|

* Phosphonate
* Phosphonous

Sulfur|

* Disulfide
* Sulfone
* Sulfonic acid
* Sulfoxide
* Thial
* Thioester
* Thioether
* Thioketone
* Thiol

Selenium|

* Selenol
* Selenonic acid
* Seleninic acid
* Selenenic acid
* Selone

Tellurium|

* Tellurol
* Telluroketone

Other|

* Isothiocyanate
* Phosphoramide
* Sulfenyl chloride
* Sulfonamide
* Thiocyanate

See also chemical classification, chemical nomenclature ([[Chemistry:IUPAC nomenclature of inorganic, IUPAC nomenclature of organic chemistry|organic]])

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