Aromatic sulfonation explained

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 functional group in an electrophilic aromatic substitution.^[1] Aryl sulfonic acids are used as detergents, dye, and drugs.

Stoichiometry and mechanism

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

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.

Chlorosulfuric acid is also an effective agent:

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

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

Piria reaction

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]}

Tyrer sulfonation process

In the Tyrer sulfonation process (1917), 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.

Applications

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

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

Reactions of aryl sulfonic acids

As a functional group, aryl sulfonic acids undergo desulfonation when heated in water:

When treated with strong base, benzenesulfonic acid derivatives convert to phenols.^[6]

See also

• Electrophilic halogenation
• Nitration
• Perchlorylbenzene

Notes and References

1. .
2. Otto Lindner, Lars Rodefeld "Benzenesulfonic Acids and Their Derivatives" in Ullmann's Encyclopedia of Industrial Chemistry 2005, Wiley-VCH, Weinheim.
3. T.W> Graham Solomons: Organic Chemistry, 11th Edition, Wiley, Hoboken, NJ, 2013, p. 676, .
4. Piria. Raffaele . Raffaele Piria . 1851. Über einige Produkte der Einwirkung des schwefligsäuren Ammoniaks auf Nitronaphtalin. Annalen der Chemie und Pharmacie . 78 . 31–68. 10.1002/jlac.18510780103. 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 .
6. 10.15227/orgsyn.003.0037. p-Cresol. Organic Syntheses. 3. 37. 1923. W. W. Hartman.