Asymmetrical reaction pathways for thermal and photocyclization of 1,3,5-hexatriene to 1,3-cyclohexadiene

Journal Article · Sat Aug 01 04:00:00 EDT 1987 · Dokl. Phys. Chem. (Engl. Transl.); (United States)

OSTI ID:5796562

Pichko, V A; Simkin, B Ya; Minkin, V I

The theory of conservation of orbital symmetry in concerted reactions, outlined by Woodward and Hoffman, plays the dominant role in the prediction of the stereospecificity of these reactions both in the ground state and in excited states. Despite the importance of this theory with regard to preference for the conrotatory or dysrotatory pathway of cyclization, quantum chemical calculations of the critical portions of the potential energy surface of the ground and excited states become necessary in understanding the detailed mechanism of both thermal and photochemical transformations. The authors use these calculations to find, in the absence of symmetry, the potential energy surfaces of these states for 1,3,5-hexatriene and analyze the allowed and forbidden reaction pathways in its cyclization.

• Research Organization: M. A. Suslov Rostov State Univ., USSR
• OSTI ID: 5796562
• Journal Information: Dokl. Phys. Chem. (Engl. Transl.); (United States), Journal Name: Dokl. Phys. Chem. (Engl. Transl.); (United States) Vol. 292:4-6; ISSN DKPCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400500 -- Photochemistry
640302 -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ACTIVATION ENERGY
ALKENES
ASYMMETRY
ATOMIC MODELS
BUTADIENE
BUTENES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CONSERVATION LAWS
CONVERSION
CYCLOALKENES
DECAY
DEHYDROCYCLIZATION
DIENES
ELECTRONIC STRUCTURE
ENERGY
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EXCITATION
EXCITED STATES
GROUND STATES
HARTREE-FOCK METHOD
HYDROCARBONS
INTERNAL CONVERSION
KINETICS
MATHEMATICAL MODELS
MECHANICS
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
POLYENES
POTENTIAL ENERGY
QUANTUM MECHANICS
REACTION KINETICS
SYNTHESIS