Aromatic sulfonation

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. Aryl sulfonic acids are used as detergents, dye, and drugs.

Typical conditions involve heating the aromatic compound with sulfuric acid:

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 reversibility is very useful in protecting the aromatic system because of this reversibility.

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

A classic named reaction is the Piria reaction (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.

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.

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