Reaction of Polycyclic Aromatic Hydrocarbons with Ozone. Linear Free-Energy Relationships and Tests of Likely Rate-Determining Steps Using Simple Molecular Orbital Correlations

Article abstract of DOI:10.1021/jo00171a008

Nine unsubstituted, polycyclic aromatic hydrocarbons were allowed to react with ozone at 25 deg C, and relative rate constants were obtained by direct competitive techniques.The rate constants show a large variation with substrate structure, with nearly three powers of ten difference between the least reactive (benzene) and most reactive (anthracene, perylene) compounds studied.Linear free-energy relationships between the rate data and calculated molecular orbital parameters have been obtained.The optimum correlations are found for models based on rate-determining ?-complex or ?-complex formation rather than simultaneous addition of ozone to two carbon atoms.Electrophilic attack by ozone to yield a ?-complex also appears to be the rate-determining step based on the results obtained for changes in selectivity with variation of solvents.