Quantum mechanical studies of the structure and reactivities of the diol epoxides of benzo[c]phenanthrene. 1995

L Lewis-Bevan, and S B Little, and J R Rabinowitz
Carcinogenesis and Metabolism Branch, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina 27711, USA.

Benzo[c]phenanthrene has a crowded bay region that has been called a fjord region. As a result of the interaction between the atoms across the fjord region, it is a nonplanar molecule with a significant barrier between two helical structures. The crowding in the fjord region also affects the three-dimensional structure of the fjord region diol epoxide. Quantum mechanical studies have been performed to determine the structure and reactivities of the fjord region diol epoxides. Eight local minimum energy three-dimensional structures have been found for the trans diol of 1,2,3,4-tetrahydro-3,4-dihydroxybenzo[c]phenanthrene 1,2-epoxide. They can be characterized by three dichotomies: one between syn and anti, one between quasidiaxial and quasidiequatorial, and the third that depends on nonplanarity of the parent polycyclic aromatic hydrocarbon due to interactions in the crowded bay region, that we have named "in" and "out" based on the position of the epoxide oxygen relative to the distal ring. The structures with the epoxide oxygen on the same side of the saturated ring as the distal ring (in-) are more stable than the structures where the epoxide is on the opposite side (out-). The calculated lowest energy syn and anti structures for the diol epoxide of benzo[c]-phenanthrene are both in-quasidiequatorial, in agreement with experiment. Analysis of the results indicates that the electrostatic interaction across the fjord region could be responsible for the increased stability of the syn-in-quasidiequatorial structure compared to the syn-in-quasidiaxial structure and the stability of the in- structures in general when compared to the out- structures.(ABSTRACT TRUNCATED AT 250 WORDS)

UI MeSH Term Description Entries
D008968 Molecular Conformation The characteristic three-dimensional shape of a molecule. Molecular Configuration,3D Molecular Structure,Configuration, Molecular,Molecular Structure, Three Dimensional,Three Dimensional Molecular Structure,3D Molecular Structures,Configurations, Molecular,Conformation, Molecular,Conformations, Molecular,Molecular Configurations,Molecular Conformations,Molecular Structure, 3D,Molecular Structures, 3D,Structure, 3D Molecular,Structures, 3D Molecular
D009153 Mutagens Chemical agents that increase the rate of genetic mutation by interfering with the function of nucleic acids. A clastogen is a specific mutagen that causes breaks in chromosomes. Clastogen,Clastogens,Genotoxin,Genotoxins,Mutagen
D010616 Phenanthrenes POLYCYCLIC AROMATIC HYDROCARBONS composed of three fused BENZENE rings.
D011789 Quantum Theory The theory that the radiation and absorption of energy take place in definite quantities called quanta (E) which vary in size and are defined by the equation E Quantum Theories,Theories, Quantum,Theory, Quantum
D002627 Chemistry, Physical The study of CHEMICAL PHENOMENA and processes in terms of the underlying PHYSICAL PHENOMENA and processes. Physical Chemistry,Chemistries, Physical,Physical Chemistries
D004852 Epoxy Compounds Organic compounds that include a cyclic ether with three ring atoms in their structure. They are commonly used as precursors for POLYMERS such as EPOXY RESINS. Epoxide,Epoxides,Epoxy Compound,Oxiranes,Compound, Epoxy,Compounds, Epoxy
D013329 Structure-Activity Relationship The relationship between the chemical structure of a compound and its biological or pharmacological activity. Compounds are often classed together because they have structural characteristics in common including shape, size, stereochemical arrangement, and distribution of functional groups. Relationship, Structure-Activity,Relationships, Structure-Activity,Structure Activity Relationship,Structure-Activity Relationships
D055598 Chemical Phenomena The composition, structure, conformation, and properties of atoms and molecules, and their reaction and interaction processes. Chemical Concepts,Chemical Processes,Physical Chemistry Concepts,Physical Chemistry Processes,Physicochemical Concepts,Physicochemical Phenomena,Physicochemical Processes,Chemical Phenomenon,Chemical Process,Physical Chemistry Phenomena,Physical Chemistry Process,Physicochemical Phenomenon,Physicochemical Process,Chemical Concept,Chemistry Process, Physical,Chemistry Processes, Physical,Concept, Chemical,Concept, Physical Chemistry,Concept, Physicochemical,Concepts, Chemical,Concepts, Physical Chemistry,Concepts, Physicochemical,Phenomena, Chemical,Phenomena, Physical Chemistry,Phenomena, Physicochemical,Phenomenon, Chemical,Phenomenon, Physicochemical,Physical Chemistry Concept,Physicochemical Concept,Process, Chemical,Process, Physical Chemistry,Process, Physicochemical,Processes, Chemical,Processes, Physical Chemistry,Processes, Physicochemical

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