ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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 O⃛H—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.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560150303
Permalink
