American Chemical Society
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The Azulene-to-Naphthalene Rearrangement Revisited:  a DFT Study of Intramolecular and Radical-Promoted Mechanisms

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journal contribution
posted on 2003-04-12, 00:00 authored by Roger W. Alder, Stephen P. East, Jeremy N. Harvey, Mark T. Oakley
Intramolecular and radical-promoted mechanisms for the rearrangement of azulene to naphthalene are assessed with the aid of density functional calculations. All intramolecular mechanisms have very high activation energies (≥350 kJ mol-1 from azulene) and so can only be competitive at temperatures above 1000 °C. Two radical-promoted mechanisms, the methylene walk and spiran pathways, dominate the reaction below this temperature. The activation energy for an orbital symmetry-allowed mechanism via a bicyclobutane intermediate is 382 kJ mol-1. The norcaradiene−vinylidene mechanism that has been proposed in order to explain the formation of small amounts of 1-phenyl-1-buten-3-ynes from flash thermolysis of azulene has an activation energy of 360 kJ mol-1; subtle features of the B3LYP/6-31G(d) energy surface for this mechanism are discussed. All intermediates and transition states on the spiran and methylene walk radical-promoted pathways have been located at the B3LYP/6-31G(d) level. Interconversion of all n-H-azulyl radicals via hydrogen shifts was also examined, and hydrogen shifts around the five-membered ring are competitive with the mechanisms leading to rearrangement to naphthalene, but those around the seven-membered ring are not. Conversion of a tricyclic radical to the 9-H-naphthyl radical is the rate-limiting transition state on the spiran pathway, and lies 164.0 kJ mol-1 above that of the 1-H-azulyl radical. The transition state for the degenerate hydrogen shift between the 9-H-azulyl and 10-H-azulyl radicals is 7.4 kJ mol-1 lower. Partial equilibration of the intermediates in the spiran pathway via this shift may therefore occur, and this can account for the surprising formation of 1-methylnaphthalene from 2-methylazulene. The rate-limiting transition state for the methylene walk pathway involves the concerted transfer of a methylene group from one ring to the other and lies 182.3 kJ mol-1 above that of the 1-H-azulyl radical. It is shown that rearrangement via a combination of 31% methylene walk and 69% spiran pathways can account semiquantitatively for all the products from 1-13C-azulene, 9-13C-azulene, and 4,7-13C2-azulene, in addition to accounting for the products from methylazulenes, and the formation of naphthalene-d0 and -d2 from azulene-4-d. It is also pointed out that a small extension to the spiran pathway could provide an alternative explanation for the formation of 1-phenyl-1-buten-3-ynes.