Chapter 12 : Reactions of Arenes.

Electrophilic Aromatic Substitution

Reactions and Reagents

The following table contains a summary of the key reactions to introduce a substituent onto an aromatic system. More detailed information on each reaction can be accessed by following the link from the reaction column. Reactions that can be used to convert existing aromatic substituents are listed separately.

Study Tips: The reagent combinations and reaction conditions for reactions of benzenes are usually more severe than reactions of alkenes.... this tends to make them more readily recognisable. Recognise the electrophile present in the reagent combination.

Reaction Nitration

Reagents HNO3 / H2SO4

Electrophile NO2+

Product

Comments E+ formed by loss of water from nitric acid

Sulfonation H2SO4 or SO3 / H2SO4

SO3

Reversible (heat with aq. acid)

Cl2 / Fe or FeCl3 Halogenation Br2 / Fe or FeBr3

Cl+

E+ formed by Lewis acid removing Cl-

Br+

E+ formed by Lewis acid removing Br-

R-Cl / AlCl3

R+

E+ formed by Lewis acid removing Cl-

Alkylation

R-OH / H+

R+

E+ formed by loss of water from alcohol

C=C / H+

R+

E+ formed by protonation of alkene

RCOCl / AlCl3 Acylation

RCO+

E+ formed by Lewis acid removing Cl-

RCO2COR / AlCl3

RCO+

E+ formed by Lewis acid removing RCO2-

Dr. Ian Hunt, Department of Chemistry, University of Calgary