Diels-alder reactivity of polycyclic aromatic hydrocarbons-5: Theoretical correlations

Abstract

Second-order rate constants for the Diels-Alder reaction of 90 aromatic hydrocarbons with maleic anhydride, measured spectrophotometrically at 91.5° in 1,2,4-trichlorobenzene, are correlated with various reactivity indices, namely Herndon's structure count ratios, second-order perturbation energies, Brown's paralocalization energies, Hess-Schaad resonance energy differences and Polansky indices. Apart from the latter theory, all methods yield satisfactory correlations, with the Hess-Schaad theory being marginally better. An explanation is given why the Hess-Schaad theory is superior to para-localization theory although both are based on Hückel π-electron energies. The observed regioselectivity is correctly accounted for by all except Polansky's theory which yields incorrect results for certain phenes and starphenes.