Abstract
Publisher Summary This chapter discusses stable carbocations and onium ions from polycondensed aromatic and heteroaromatic compounds as models for biological electrophiles and DNA-transalkylating agents. Polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants commonly known as mutagenic/carcinogenic agents. They exert their biological activity principally through metabolic formation of their diolepoxides (DEs) and generation of carbocations by DE ring opening. PAH arenium ions are typically generated in low concentrations at low temperatures in FSO 3 H/SO 2 CIF. A series of regioisomeric tertiary and secondary methylcarbenium ions bearing 1-pyrenyl, 4-pyrenyl, and 2-pyrenyl substitutents were generated from their carbinol precursors and the charge delocalization into the pyrene moiety was evaluated. It was found that for both tertiary and secondary 1-pyrenylmethylcarbenium ions, the positive charge was effectively delocalized. Charge delocalization mode in the BA carbocation framework was deduced from natural population analysis-derived changes in charges, and substitution by methyl or fluorine was studied at different positions selected on the basis of carbocation charge density. It was observed that the stability of the carbocations generated from oxidized metabolites of DBahAcr and dibenzo[ a , h ]anthracene (DBahA) correlated with the data on the biological activities of their DE.
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