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High-Temperature Isomerization of Benzenoid Polycyclic Aromatic Hydrocarbons. Analysis through the Bent Bond and
Jean-François Parent1, Pierre Deslongchamps1
1Département de Chimie, Faculté des Sciences et de Génie , 1045 avenue de la médecine , Université Laval , Québec , QC G1 V 0A6 , Canada.
Abstract:
L. T. Scott has discovered the 1,2-swapping of carbon and hydrogen atoms which is known to take place on benzenoid aromatics (up to ∼1000 °C range). For example, 13C-1-naphthalene is specifically converted to 13C-2-naphthalene, and there is evidence that this occurs through the formation of benzofulvene and a naphthalene-carbene intermediate. Application of the bent bond/antiperiplanar hypothesis leads to the postulate that higher in energy pyramidal singlet diradical intermediates can be used to propose a mechanism that rationalizes various atom rearrangements on benzenoid aromatics and related isomeric compounds.
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