Summary

Aromatic rings are a common part of many biological structures and are particularly important in nucleic acid chemistry and in the chemistry of several amino acids. In this chapter, we’ve seen how and why aromatic compounds are different from such apparently related compounds as cycloalkenes.

The word aromatic is used for historical reasons to refer to the class of compounds related structurally to benzene. Aromatic compounds are systematically named according to IUPAC rules, but many common names are also used. Disubstituted benzenes are referred to as ortho (1,2 disubstituted), meta (1,3 disubstituted), or para (1,4 disubstituted) derivatives. The ${\text{C}}_{\text{6}}{\text{H}}_{\text{5}}–$ unit itself is referred to as a phenyl group, and the ${\text{C}}_6{\text{H}}_5{\text{CH}}_2–$ unit is a benzyl group.

Benzene is described by valence-bond theory as a resonance hybrid of two equivalent structures and is described by molecular orbital theory as a planar, cyclic, conjugated molecule with six π electrons. According to the Hückel rule, a molecule must have 4n + 2 π electrons, where n = 0, 1, 2, 3, and so on, to be aromatic. Planar, cyclic, conjugated molecules with other numbers of π electrons are antiaromatic.

Other substances besides benzene-like compounds are also aromatic. The cyclopentadienyl anion and the cycloheptatrienyl cation, for instance, are aromatic ions. Pyridine and pyrimidine are six-membered, nitrogen-containing, aromatic heterocycles. Pyrrole and imidazole are five-membered, nitrogen-containing heterocycles. Naphthalene, quinoline, indole, and many others are polycyclic aromatic compounds.

Aromatic compounds have the following characteristics:

• Aromatic compounds are cyclic, planar, and conjugated.
• Aromatic compounds are unusually stable. Benzene, for instance, has a heat of hydrogenation 150 kJ/mol less than we might expect for a cyclic triene.
• Aromatic compounds react with electrophiles to give substitution products, in which cyclic conjugation is retained, rather than addition products, in which conjugation is destroyed.
• Aromatic compounds have 4n + 2 π electrons, which are delocalized over the ring.