The isomerization of unsubstituted azulene to naphthalene was the first reported thermal transformation of an aromatic hydrocarbon, and has consequently been the most widely studied rearrangement. However, the following mechanisms are generalized to all thermal isomerizations of aromatic hydrocarbons. Many mechanisms have been suggested for this isomerization, yet none have been unequivocally determined as the only correct mechanism. Five mechanisms were originally considered: a reversible ring-closure mechanism, which is shown above, a norcaradiene-vinylidene mechanism, a diradical mechanism, a methylene walk mechanism, and a spiran mechanism. It was quickly determined that the reversible ring-closure mechanism was inaccurate, and it was later decided that there must be multiple reaction pathways occurring simultaneously. This was widely accepted, as at such high temperatures, one mechanism would have to be substantially energetically favored over the others to be occurring alone. Energetic studies displayed similar activation energies for all possible mechanisms.
Four mechanisms for thermal isomerizations have been proposed: a dyotropic mechanism, a diradical mechanism, and two benzene ring contraction mechanisms; a 1,2-carbon shift to a carbene preceding a 1,2-hydrogen shift, and a 1-2-hydrogen shift to a carbene followed by a 1,2-carbon shift. The dyotropic mechanism involves concerted 1,2-shifts as displayed below. Electronic studies show this mechanism to be unlikely, but it must still be considered a viable mechanism as it has not yet been disproven.
The diradical mechanism has been supported by kinetic studies performed on the reaction, which have revealed that the reaction is not truly unimolecular, as it is most likely initiated by hydrogen addition from another gas-phase species. However, the reaction still obeys first-order kinetics, which is a classical characteristic of radical chain reactions. A mechanistic rational for the thermal rearrangement of azulene to naphthalene is included below. Homolysis of the weakest bond in azulene occurs, followed by a hydrogen shift and ring closure so as to retain the aromaticity of the molecule.
Benzene ring contractions are the last two mechanisms that have been suggested, and they are currently the preferred mechanisms. These reaction mechanisms proceed through the lowest free energy transition states compared to the diradical and dyotropic mechanisms. The difference between the two ring contractions is minute however, so it has not been determined which is favored over the other. Both mechanisms are shown as follows for the ring contraction of biphenylene:
The first involves a 1,2-hydrogen shift to a carbene followed by a 1,2-carbon shift on the same C-C bond but in opposite directions. The second differs from the first only by the order of the 1,2-shifts, with the 1,2-carbon shift preceding the 1,2-hydrogen shift.
The four described mechanisms would all result in the isomerization from azulene to naphthalene. Kinetic data and C-labeling have been used to elucidate the correct mechanism, and have led organic chemists to believe that one of the benzene ring contractions is the most likely mechanism through which these isomerizations of aromatic hydrocarbons occur.