Model quantum chemical studies of the electronic structure and aspects of reactivity of diol epoxides of aromatic hydrocarbons

✍ Scribed by Richard Lavery; Bernard Pullman

• Publisher: John Wiley and Sons
• Year: 1979
• Tongue: English
• Weight: 498 KB
• Volume: 15
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/qua.560150303

✦ Synopsis

Abstract

This paper offers a unified presentation of the main ring conformers of the diol expoxides, triol carbonium ions, and tetrols related to the “bay‐region” benzo ring of carcinogenic metabolites of PAH and brings forward quantitative information through ab initio SCF computations about their relative energies. It substantiates and evaluates the energy of the syn epoxide‐OH4 hydrogen bond and, on the contrary, refutes the significance of an O ⃛HO or an O^−^ ⃛HO bond in the triol carbonium ions. It provides an explanation for the similar rates of acid‐catalyzed hydrolysis of the syn and anti diol expoxides. It evaluates the stabilization of the triol carbonium ions due to the presence of a neighboring double bond and accounts for the spontaneous opening of protonated epoxides. Finally it accounts for cis hydrolysis of the syn diol epoxide and trans hydrolysis of the anit diol epoxide under acid conditions.