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{{short description|Chemical reaction which replaces a hydrogen on an arene with sulfonic acid, –NH–SO3H}}
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'''Aromatic sulfonation''' is an [[organic reaction]] in which a hydrogen atom on an [[aromatic hydrocarbon|arene]] is replaced by a [[sulfonic acid]] [[functional group]] in an [[electrophilic aromatic substitution]].<ref>{{JerryMarch}}.</ref> Aryl sulfonic acids are used as [[detergent]]s, [[dye]], and [[drug]]s.
{{See also|Desulfonation reaction}}

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In [[organic chemistry]], '''aromatic sulfonation''' is an [[organic reaction]] in which a [[hydrogen]] atom on an [[aromatic hydrocarbon|arene]] is replaced by a [[sulfonic acid]] ({{chem2|\sSO2OH}}) [[functional group]] in an [[electrophilic aromatic substitution]].<ref>{{JerryMarch}}.</ref> [[Aryl group|Aryl]] sulfonic acids are used as [[detergent]]s, [[dye]], and [[drug]]s.

[[File:Sulfonation_reaction_equation.svg|left|frameless|349x349px]]

{{Clear|left}}


==Stoichiometry and mechanism==
==Stoichiometry and mechanism==
[[Image:Sulfur-trioxide-2D-dimensions.svg|thumb|120 px|right|[[Sulfur trioxide]] is the active ingredient in many sulfonation reactions.]]
[[File:Sulfur-trioxide-2D-dimensions.svg|thumb|120px|right|[[Sulfur trioxide]] is the active ingredient in many sulfonation reactions.]]
Typical conditions involve heating the aromatic compound with sulfuric acid:<ref>Otto Lindner, Lars Rodefeld "Benzenesulfonic Acids and Their Derivatives" in Ullmann's Encyclopedia of Industrial Chemistry 2005, Wiley-VCH, Weinheim. {{DOI|10.1002/14356007.a03_507}}</ref>
Typical conditions involve heating the aromatic compound with sulfuric acid:<ref>Otto Lindner, Lars Rodefeld "Benzenesulfonic Acids and Their Derivatives" in Ullmann's Encyclopedia of Industrial Chemistry 2005, Wiley-VCH, Weinheim.{{doi|10.1002/14356007.a03_507}}</ref>
:{{chem2|C6H6 + H2SO4 -> C6H5SO3H + H2O}}
:C<sub>6</sub>H<sub>6</sub> + H<sub>2</sub>SO<sub>4</sub> → C<sub>6</sub>H<sub>5</sub>SO<sub>3</sub>H + H<sub>2</sub>O
[[Sulfur trioxide]] or its protonated derivative is the actual [[electrophile]] in this [[electrophilic aromatic substitution]].
[[Sulfur trioxide]] or its protonated derivative is the actual [[electrophile]] in this electrophilic aromatic substitution.


To drive the equilibrium, dehydrating agents such as [[thionyl chloride]] can be added.
To drive the equilibrium, dehydrating agents such as [[thionyl chloride]] can be added.
:{{chem2|C6H6 + H2SO4 + SOCl2 -> C6H5SO3H + SO2 + 2 HCl}}
:C<sub>6</sub>H<sub>6</sub> + H<sub>2</sub>SO<sub>4</sub> + SOCl<sub>2</sub> → C<sub>6</sub>H<sub>5</sub>SO<sub>3</sub>H + SO<sub>2</sub> + 2 HCl

[[Chlorosulfuric acid]] is also an effective agent:
[[Chlorosulfuric acid]] is also an effective agent:
:{{chem2|C6H6 + HSO3Cl -> C6H5SO3H + HCl}}
:C<sub>6</sub>H<sub>6</sub> + HSO<sub>3</sub>Cl → C<sub>6</sub>H<sub>5</sub>SO<sub>3</sub>H + HCl

In contrast to [[aromatic nitration]] and most other electrophilic aromatic substitutions this reaction is [[Reversible reaction|reversible]]. Sulfonation takes place in concentrated acidic conditions and desulfonation is the mode of action in a dilute hot aqueous acid. The reversibility is very useful in [[protection group|protecting]] the aromatic system because of this reversibility.
In contrast to [[aromatic nitration]] and most other electrophilic aromatic substitutions this reaction is [[reversible reaction|reversible]]. Sulfonation takes place in concentrated acidic conditions and desulfonation is the mode of action in a dilute hot aqueous acid. The reaction is very useful in [[protection group|protecting]] the aromatic system because of this reversibility. Due to their [[Electron-withdrawing|electron withdrawing effects]], sulfonate protecting groups can be used to prevent electrophilic aromatic substitution. They can also be installed as [[Electrophilic aromatic directing groups|directing groups]] to affect the position where a substitution may take place.<ref name=Solomons>T.W> Graham Solomons: ''Organic Chemistry'', 11th Edition, Wiley, Hoboken, NJ, 2013, p. 676, {{ISBN|978-1-118-13357-6}}.</ref>


==Specialized sulfonation methods==
==Specialized sulfonation methods==
Many method have been developed for introducing sulfonate groups aside from direction sulfonation.
Many method have been developed for introducing sulfonate groups aside from direction sulfonation.
===Piria reaction===
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A classic named reaction is the '''Piria reaction''' ([[Raffaele Piria|R. Piria]], 1851) in which [[nitrobenzene]] is reacted with a metal [[bisulfite]] forming an aminosulfonic acid as a result of combined [[nitro group reduction]] and sulfonation.<ref>{{cite journal |last1= Piria|first1=Raffaele |authorlink=Raffaele Piria |year= 1851|title=Über einige Produkte der Einwirkung des schwefligsäuren Ammoniaks auf Nitronaphtalin|journal=Annalen der Chemie und Pharmacie |volume=78 |issue= |pages= 31–68|publisher= |doi= 10.1002/jlac.18510780103|url= |issn=0075-4617}}
</ref><ref>''THE PIRIA REACTION. I. THE OVER-ALL REACTION'' W. H. Hunter, Murray M. Sprung [[J. Am. Chem. Soc.]], 1931, 53 (4), pp 1432–1443 {{DOI|10.1021/ja01355a037}}.</ref>


⚫
A classic named reaction is the '''Piria reaction''' ([[Raffaele Piria]], 1851) in which [[nitrobenzene]] is reacted with a metal [[bisulfite]] forming an aminosulfonic acid as a result of combined [[nitro group reduction]] and sulfonation.<ref>{{cite journal |last1= Piria|first1=Raffaele |author-link=Raffaele Piria |year= 1851|title=Über einige Produkte der Einwirkung des schwefligsäuren Ammoniaks auf Nitronaphtalin|journal=Annalen der Chemie und Pharmacie |volume=78 |pages= 31–68|doi= 10.1002/jlac.18510780103|url= https://zenodo.org/record/1427038|issn=0075-4617}}</ref><ref>''THE PIRIA REACTION. I. THE OVER-ALL REACTION'' W. H. Hunter, Murray M. Sprung [[Journal of the American Chemical Society|J. Am. Chem. Soc.]], 1931, 53 (4), pp 1432–1443 {{doi|10.1021/ja01355a037}}.</ref>
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[[File:Piria reaction.png|400px|center||The Piria Reaction]]


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[[File:Piria reaction.png|400px|center|The Piria reaction]]
===Tyre sulfonation process===
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In the '''Tyrer sulfonation process''' (1917),<ref>{{US patent|1,210,725}}</ref> at some time of technological importance, benzene vapor is led through a vessel containing 90% sulfuric acid the temperature of which is increased from 100 to 180°C. Water and benzene are continuously removed in a condenser and the benzene layer fed back to the vessel. In this way an 80% yield is obtained.


⚫
In the '''Tyrer sulfonation process''' (1917),<ref>{{US patent|1,210,725}}</ref> at some time of technological importance, benzene vapor is led through a vessel containing 90% sulfuric acid the temperature of which is increased from 100 to 180°C. Water and benzene are continuously removed and the benzene fed back to the vessel. In this way an 80% yield is obtained.
⚫
[[File:Amino Sulfonic Acid Synthesis V.1.svg|thumb|360px|right|Synthesis of sulfanilic acid from aniline and sulfuric acid.<ref name=Hauptmann>Siegfried Hauptmann: ''Organische Chemie'', 2nd Edition, VEB Deutscher Verlag für Grundstoffindustrie, Leipzig, 1985, p. 511, ISBN 3-342-00280-8.</ref>]]

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[[File:Amino Sulfonic Acid Synthesis V.1.svg|thumb|360px|right|Synthesis of [[sulfanilic acid]] from aniline and sulfuric acid.<ref name=Hauptmann>Siegfried Hauptmann: ''Organische Chemie'', 2nd Edition, VEB Deutscher Verlag für Grundstoffindustrie, Leipzig, 1985, p. 511, {{ISBN|3-342-00280-8}}.</ref>]]
{{clear}}


==Applications==
==Applications==
Aromatic sulfonic acids are intermediates in the preparation of [[dye]]s and many pharmaceuticals. Sulfonation of [[aniline]] produces p-aminobenzenesulfonic acid or [[sulfanilic acid]] which is a [[zwitterion]] with an unusual high [[melting point]]. The amide of this compound and related compounds form a large group of [[Sulfonamide (medicine)|sulfa drug]]s.
Aromatic sulfonic acids are intermediates in the preparation of [[dye]]s and many pharmaceuticals. Sulfonation of [[aniline]]s lead to a large group of [[Sulfonamide (medicine)|sulfa drug]]s.

[[Image:Allura Red AC Structural Formula V1.png|thumb|180 px|left|[[Allura Red AC]], a food coloring agent, is made by a multistep process that includes two sulfonations.]]
[[File:Allura Red AC Structural Formula V1.svg|thumb|180 px|left|[[Allura Red AC]], a food coloring agent, is made by a multistep process that includes two sulfonations.]]
Sulfonation of [[polystyrene]] is used to make [[sodium polystyrene sulfonate]], a common [[ion exchange resin]] for [[water softening]].
Sulfonation of [[polystyrene]] is used to make [[sodium polystyrene sulfonate]], a common [[ion exchange resin]] for [[water softening]].
{{clear}}


==See also==
==See also==
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*[[Nitration]]
*[[Nitration]]
*[[Perchlorylbenzene]]
*[[Perchlorylbenzene]]
{{clear}}


==References==
==References==

Latest revision as of 20:20, 30 August 2024

See also: Desulfonation reaction

In organic chemistry, aromatic sulfonation is an organic reaction in which a hydrogen atom on an arene is replaced by a sulfonic acid (−SO2OH) functional group in an electrophilic aromatic substitution.[1] Aryl sulfonic acids are used as detergents, dye, and drugs.

Stoichiometry and mechanism

[edit]
Sulfur trioxide is the active ingredient in many sulfonation reactions.

Typical conditions involve heating the aromatic compound with sulfuric acid:[2]

C6H6 + H2SO4 → C6H5SO3H + H2O

Sulfur trioxide or its protonated derivative is the actual electrophile in this electrophilic aromatic substitution.

To drive the equilibrium, dehydrating agents such as thionyl chloride can be added.

C6H6 + H2SO4 + SOCl2 → C6H5SO3H + SO2 + 2 HCl

Chlorosulfuric acid is also an effective agent:

C6H6 + HSO3Cl → C6H5SO3H + HCl

In contrast to aromatic nitration and most other electrophilic aromatic substitutions this reaction is reversible. Sulfonation takes place in concentrated acidic conditions and desulfonation is the mode of action in a dilute hot aqueous acid. The reaction is very useful in protecting the aromatic system because of this reversibility. Due to their electron withdrawing effects, sulfonate protecting groups can be used to prevent electrophilic aromatic substitution. They can also be installed as directing groups to affect the position where a substitution may take place.[3]

Specialized sulfonation methods

[edit]

Many method have been developed for introducing sulfonate groups aside from direction sulfonation.

A classic named reaction is the Piria reaction (Raffaele Piria, 1851) in which nitrobenzene is reacted with a metal bisulfite forming an aminosulfonic acid as a result of combined nitro group reduction and sulfonation.[4][5]

The Piria reaction
The Piria reaction

In the Tyrer sulfonation process (1917),[6] at some time of technological importance, benzene vapor is led through a vessel containing 90% sulfuric acid the temperature of which is increased from 100 to 180°C. Water and benzene are continuously removed and the benzene fed back to the vessel. In this way an 80% yield is obtained.

Synthesis of sulfanilic acid from aniline and sulfuric acid.[7]

Applications

[edit]

Aromatic sulfonic acids are intermediates in the preparation of dyes and many pharmaceuticals. Sulfonation of anilines lead to a large group of sulfa drugs.

Allura Red AC, a food coloring agent, is made by a multistep process that includes two sulfonations.

Sulfonation of polystyrene is used to make sodium polystyrene sulfonate, a common ion exchange resin for water softening.

See also

[edit]

References

[edit]
  1. ^ March, Jerry (1985), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 3rd edition, New York: Wiley, ISBN 9780471854722, OCLC 642506595.
  2. ^ Otto Lindner, Lars Rodefeld "Benzenesulfonic Acids and Their Derivatives" in Ullmann's Encyclopedia of Industrial Chemistry 2005, Wiley-VCH, Weinheim.doi:10.1002/14356007.a03_507
  3. ^ T.W> Graham Solomons: Organic Chemistry, 11th Edition, Wiley, Hoboken, NJ, 2013, p. 676, ISBN 978-1-118-13357-6.
  4. ^ Piria, Raffaele (1851). "Über einige Produkte der Einwirkung des schwefligsäuren Ammoniaks auf Nitronaphtalin". Annalen der Chemie und Pharmacie. 78: 31–68. doi:10.1002/jlac.18510780103. ISSN 0075-4617.
  5. ^ THE PIRIA REACTION. I. THE OVER-ALL REACTION W. H. Hunter, Murray M. Sprung J. Am. Chem. Soc., 1931, 53 (4), pp 1432–1443 doi:10.1021/ja01355a037.
  6. ^ U.S. patent 1,210,725
  7. ^ Siegfried Hauptmann: Organische Chemie, 2nd Edition, VEB Deutscher Verlag für Grundstoffindustrie, Leipzig, 1985, p. 511, ISBN 3-342-00280-8.
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