Sulfonyl halide

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In inorganic chemistry, sulfonyl halide groups occur when a sulfonyl (>S(=O)2) functional group is singly bonded to a halogen atom. They have the general formula RSO2X, 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]

Contents

Structure

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

General structure of a sulfonic acid chloride Sulfonyl chloride.png
General structure of a sulfonic acid chloride

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]

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 hydrochloric acid to give the sulfonyl chloride:

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]

Sulfonyl chlorides readily undergo Friedel–Crafts reactions with arenes giving sulfones, for example:

RSO2Cl + C6H6 → RSO2C6H5 + HCl

The desulfonation of arylsulfonyl chlorides provides a route to aryl chlorides:

ArSO2Cl → ArCl + SO2

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:

RCH2SO2Cl → RCH=SO2 + HCl

Sulfonamides can be prepared by reaction of sulfonyl chlorides with amines:

RSO2Cl + R'2NH → RSO2NR'2 + HCl

A readily available sulfonyl chloride source is tosyl chloride. [8]

Reduction with tetrathiotungstate ions (WS2−4) induces dimerization to the disulfide. [9]

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. [7]

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: [10]

SF4 + RSO3H → SOF2 + RSO2F + HF

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-induced homolysis 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]

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.

Related Research Articles

<span class="mw-page-title-main">Haloalkane</span> Group of chemical compounds derived from alkanes containing one or more halogens

The haloalkanes are alkanes containing one or more halogen substituents. They are a subset of the general class of halocarbons, although the distinction is not often made. Haloalkanes are widely used commercially. They are used as flame retardants, fire extinguishants, refrigerants, propellants, solvents, and pharmaceuticals. Subsequent to the widespread use in commerce, many halocarbons have also been shown to be serious pollutants and toxins. For example, the chlorofluorocarbons have been shown to lead to ozone depletion. Methyl bromide is a controversial fumigant. Only haloalkanes that contain chlorine, bromine, and iodine are a threat to the ozone layer, but fluorinated volatile haloalkanes in theory may have activity as greenhouse gases. Methyl iodide, a naturally occurring substance, however, does not have ozone-depleting properties and the United States Environmental Protection Agency has designated the compound a non-ozone layer depleter. For more information, see Halomethane. Haloalkane or alkyl halides are the compounds which have the general formula "RX" where R is an alkyl or substituted alkyl group and X is a halogen.

<span class="mw-page-title-main">Tosyl group</span> Chemical group (–SO₂–C₆H₄–CH₃)

In organic chemistry, a toluenesulfonyl group (tosyl group, abbreviated Ts or Tos) is a univalent functional group with the chemical formula −SO2−C6H4−CH3. It consists of a tolyl group, −C6H4−CH3, joined to a sulfonyl group, −SO2−, with the open valence on sulfur. This group is usually derived from the compound tosyl chloride, CH3C6H4SO2Cl (abbreviated TsCl), which forms esters and amides of toluenesulfonic acid, CH3C6H4SO2OH (abbreviated TsOH). The para orientation illustrated (p-toluenesulfonyl) is most common, and by convention tosyl without a prefix refers to the p-toluenesulfonyl group.

In organic chemistry, an acyl chloride is an organic compound with the functional group −C(=O)Cl. Their formula is usually written R−COCl, where R is a side chain. They are reactive derivatives of carboxylic acids. A specific example of an acyl chloride is acetyl chloride, CH3COCl. Acyl chlorides are the most important subset of acyl halides.

In chemistry, halogenation is a chemical reaction that entails the introduction of one or more halogens into a compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, drugs. This kind of conversion is in fact so common that a comprehensive overview is challenging. This article mainly deals with halogenation using elemental halogens. Halides are also commonly introduced using salts of the halides and halogen acids. Many specialized reagents exist for and introducing halogens into diverse substrates, e.g. thionyl chloride.

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<span class="mw-page-title-main">Acyl halide</span> Oxoacid compound with an –OH group replaced by a halogen

In organic chemistry, an acyl halide is a chemical compound derived from an oxoacid by replacing a hydroxyl group with a halide group.

<span class="mw-page-title-main">Hydrogen bromide</span> Chemical compound

Hydrogen bromide is the inorganic compound with the formula HBr. It is a hydrogen halide consisting of hydrogen and bromine. A colorless gas, it dissolves in water, forming hydrobromic acid, which is saturated at 68.85% HBr by weight at room temperature. Aqueous solutions that are 47.6% HBr by mass form a constant-boiling azeotrope mixture that boils at 124.3 °C (255.7 °F). Boiling less concentrated solutions releases H2O until the constant-boiling mixture composition is reached.

<span class="mw-page-title-main">Acetyl chloride</span> Organic compound (CH₃COCl)

Acetyl chloride is an acyl chloride derived from acetic acid. It belongs to the class of organic compounds called acid halides. It is a colorless, corrosive, volatile liquid. Its formula is commonly abbreviated to AcCl.

<span class="mw-page-title-main">Sulfonic acid</span> Organic compounds with the structure R−S(=O)2−OH

In organic chemistry, sulfonic acid refers to a member of the class of organosulfur compounds with the general formula R−S(=O)2−OH, where R is an organic alkyl or aryl group and the S(=O)2(OH) group a sulfonyl hydroxide. As a substituent, it is known as a sulfo group. A sulfonic acid can be thought of as sulfuric acid with one hydroxyl group replaced by an organic substituent. The parent compound is the parent sulfonic acid, HS(=O)2(OH), a tautomer of sulfurous acid, S(=O)(OH)2. Salts or esters of sulfonic acids are called sulfonates.

<span class="mw-page-title-main">Thionyl chloride</span> Inorganic compound (SOCl2)

Thionyl chloride is an inorganic compound with the chemical formula SOCl2. It is a moderately volatile, colourless liquid with an unpleasant acrid odour. Thionyl chloride is primarily used as a chlorinating reagent, with approximately 45,000 tonnes per year being produced during the early 1990s, but is occasionally also used as a solvent. It is toxic, reacts with water, and is also listed under the Chemical Weapons Convention as it may be used for the production of chemical weapons.

<span class="mw-page-title-main">Triphenylphosphine</span> Chemical compound

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<span class="mw-page-title-main">Trimethylsilyl chloride</span> Organosilicon compound with the formula (CH3)3SiCl

Trimethylsilyl chloride, also known as chlorotrimethylsilane is an organosilicon compound, with the formula (CH3)3SiCl, often abbreviated Me3SiCl or TMSCl. It is a colourless volatile liquid that is stable in the absence of water. It is widely used in organic chemistry.

<span class="mw-page-title-main">Triflic acid</span> Chemical compound

Triflic acid, the short name for trifluoromethanesulfonic acid, TFMS, TFSA, HOTf or TfOH, is a sulfonic acid with the chemical formula CF3SO3H. It is one of the strongest known acids. Triflic acid is mainly used in research as a catalyst for esterification. It is a hygroscopic, colorless, slightly viscous liquid and is soluble in polar solvents.

<span class="mw-page-title-main">Finkelstein reaction</span> Chemistry

The Finkelstein reaction, named after the German chemist Hans Finkelstein, is an SN2 reaction that involves the exchange of one halogen atom for another. It is an equilibrium reaction, but the reaction can be driven to completion by exploiting the differential solubility of halide salts, or by using a large excess of the halide salt.

<span class="mw-page-title-main">Thiophosphoryl chloride</span> Chemical compound

Thiophosphoryl chloride is an inorganic compound with the chemical formula PSCl3. It is a colorless pungent smelling liquid that fumes in air. It is synthesized from phosphorus chloride and used to thiophosphorylate organic compounds, such as to produce insecticides.

<span class="mw-page-title-main">4-Toluenesulfonyl chloride</span> Chemical compound

4-Toluenesulfonyl chloride (p-toluenesulfonyl chloride, toluene-p-sulfonyl chloride) is an organic compound with the formula CH3C6H4SO2Cl. This white, malodorous solid is a reagent widely used in organic synthesis. Abbreviated TsCl or TosCl, it is a derivative of toluene and contains a sulfonyl chloride (−SO2Cl) functional group.

<span class="mw-page-title-main">Sulfenyl chloride</span> Chemical group (R–S–Cl)

In organosulfur chemistry, a sulfenyl chloride is a functional group with the connectivity R−S−Cl, where R is alkyl or aryl. Sulfenyl chlorides are reactive compounds that behave as sources of RS+. They are used in the formation of RS−N and RS−O bonds. According to IUPAC nomenclature they are named as alkyl thiohypochlorites, i.e. esters of thiohypochlorous acid.

<span class="mw-page-title-main">Sulfinyl halide</span> Class of chemical compounds

Sulfinyl halide have the general formula R−S(O)−X, where X is a halogen. They are intermediate in oxidation level between sulfenyl halides, R−S−X, and sulfonyl halides, R−SO2−X. The best known examples are sulfinyl chlorides, thermolabile, moisture-sensitive compounds, which are useful intermediates for preparation of other sufinyl derivatives such as sulfinamides, sulfinates, sulfoxides, and thiosulfinates. Unlike the sulfur atom in sulfonyl halides and sulfenyl halides, the sulfur atom in sulfinyl halides is chiral, as shown for methanesulfinyl chloride.

<span class="mw-page-title-main">Tetraethylammonium chloride</span> Chemical compound

Tetraethylammonium chloride (TEAC) is a quaternary ammonium compound with the chemical formula [N(CH2CH3)4]+Cl−, sometimes written as [NEt4]Cl. In appearance, it is a hygroscopic, colorless, crystalline solid. It has been used as the source of tetraethylammonium ions in pharmacological and physiological studies, but is also used in organic chemical synthesis.

<span class="mw-page-title-main">Sulfonamide</span> Organosulfur compounds containing –S(=O)2–N< functional group

In organic chemistry, the sulfonamide functional group is an organosulfur group with the structure R−S(=O)2−NR2. It consists of a sulfonyl group connected to an amine group. Relatively speaking this group is unreactive. Because of the rigidity of the functional group, sulfonamides are typically crystalline; for this reason, the formation of a sulfonamide is a classic method to convert an amine into a crystalline derivative which can be identified by its melting point. Many important drugs contain the sulfonamide group.

References

  1. ↑ Kosswig, Kurt (2000). "Sulfonic Acids, Aliphatic". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a25_503. ISBN   978-3527306732.
  2. ↑ Drabowicz, J.; Kiełbasiński, P.; Łyżwa, P.; Zając, A.; Mikołajczyk, M. (2008). N. Kambe (ed.). Alkanesulfonyl Halides. Science of Synthesis. Vol. 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. Bibcode:1973JChPh..59.2513H. doi:10.1063/1.1680366.
  4. ↑ Lindner, Otto; Rodefeld, Lars. "Benzenesulfonic Acids and Their Derivatives". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a03_507. ISBN   978-3527306732.
  5. ↑ Adams, Roger; Marvel, C. S.; Clarke, H. T.; Babcock, G. S.; Murray, T. F. (1921). "Benzenesulfonyl chloride". Organic Syntheses . 1: 21; Collected Volumes, vol. 1, p. 84.
  6. ↑ Field, L; Clark, R.D. (1958). "Methyl p-Tolyl Sulfone". Organic Syntheses. 38: 62. doi:10.15227/orgsyn.038.0062 . Retrieved 9 July 2023.
  7. 1 2 Happ, Michael; Duffy, John; Wilson, G. J.; Pask, Stephen D.; Buding, Hartmuth; Ostrowicki, Andreas (2011). "Rubber, 8. Synthesis by Polymer Modification". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.o23_o05. ISBN   978-3527306732.
  8. ↑ Organic Syntheses, Coll. Vol. 5, p.39 (1973); Vol. 48, p.8 (1968) Online Article
  9. ↑ 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: 3728–3729. doi:10.1021/jo00299a010.{{cite journal}}: Unknown parameter |original-date= ignored (help)
  10. ↑ 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.
  11. ↑ Lehmler, H. J. (2005). "Synthesis of Environmentally Relevant Fluorinated Surfactants—a review". Chemosphere. 58 (11): 1471–1496. Bibcode:2005Chmsp..58.1471L. doi:10.1016/j.chemosphere.2004.11.078. PMID   15694468.
  12. ↑ Narayanan, Arjun; Jones, Lyn H. (2015). "Sulfonyl fluorides as privileged warheads in chemical biology". Chemical Science. 6 (5): 2650–2659. doi:10.1039/C5SC00408J. PMC   5489032 . PMID   28706662.
  13. ↑ 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 .
  14. ↑ 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.
  15. ↑ 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 ; Collected Volumes, vol. Coll. Vol. 8, p. 212.
  16. ↑ 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.
  17. ↑ 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.
  18. ↑ 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.
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