Indications of thermal rearrangements of aromatic hydrocarbons were first noted in the early 20th century by natural products chemists who were working with sesquiterpenes. At the time, they noticed the automerization of a substituted azulene shown below, but no  further structural or mechanistic investigations were made.
The oldest characterized thermal rearrangement of an aromatic compound was that of the isomerization of azulene to naphthalene by Heilbronner et al. in 1947. Since then, many other isomerizations have been recorded, however the rearrangement of azulene to naphthalene has received the most attention. Likewise, since the characterization of the automerization of naphthalene by Scott in 1977, similar atom scramblings of other aromatic hydrocarbons such as pyrene, azulene, [[Benz(a)anthracene|benz[a]anthracene]] and even benzene have been described. While the existence of these reactions has been confirmed, the isomerization and automerization mechanisms remain unknown.