Thermal rearrangements of aromatic hydrocarbons are considered to be unimolecular reactions that directly involve the atoms of an aromatic ring structure and require no other reagent than heat. These reactions can be categorized in two major types: one that involves a complete and permanent skeletal reorganization (isomerization), and one in which the atoms are scrambled but no net change in the aromatic ring occurs (automerization). The general reaction schemes of the two types are illustrated in Figure 1.
This class of reactions was uncovered through studies on the automerization of naphthalene as well as the isomerization of unsubstituted azulene, to naphthalene. Research on thermal rearrangements of aromatic hydrocarbons has since been expanded to isomerizations and automerizations of benzene and polycyclic aromatic hydrocarbons.