Theoretical study of the mechanisms of 1,5-sigmatropic rearrangements and valence isomerizations of 5-nitroso-1,3-cyclopentadiene
The reaction pathways for the 1,5-sigmatropic displacement of the nitroso group along the ring perimeter of 5-nitroso-1,3-cyclopentadiene and its valence isomerization were studied using the semiempirical MINDO/3 method. The mechanism for the 1,3-shift of the nitroso group in the 1,5-sigmatropic carousel reaction is as probable as the ordinary 1,2-shift mechanism. In contrast to nitroso derivatives of other (n)-annulenes (n = 3, 4, 6), the calculations for 5-nitroso-1,3-cyclopentadiene did not reveal other isomeric ..pi..-complex structures with perpendicular or parallel orientation of the nitroso group relative to the ring plane. The transition state were localized for the thermally forbidden concerted isomerizations of 5-nitroso-1,3-cyclopentadiene to pyridine N-oxide and 1,2-oxazepin as well as of the isomerization of pyridine N-oxide to the unknown, kinetically stable isomer, bicyclo(4.1.0)-1-aza-7-oxa-2,4-heptadiene.
- Research Organization:
- M. A. Suslov Rostov State Univ. (USSR)
- OSTI ID:
- 7076472
- Journal Information:
- J. Org. Chem. USSR (Engl. Transl.); (United States), Journal Name: J. Org. Chem. USSR (Engl. Transl.); (United States) Vol. 23:6; ISSN JOCYA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
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Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ALKENES
ATOMIC MODELS
CHARGE DISTRIBUTION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPUTERIZED SIMULATION
CONFIGURATION INTERACTION
CONFORMATIONAL CHANGES
CYCLOALKENES
CYCLOPENTADIENE
DIENES
DIPOLE MOMENTS
ELECTRON DENSITY
ELECTRON TRANSFER
ELECTRONIC STRUCTURE
ENERGY LEVELS
ENTHALPY
EXCITED STATES
FORMATION HEAT
HARTREE-FOCK METHOD
HYDROCARBONS
ISOMERIZATION
KINETICS
MATHEMATICAL MODELS
MECHANICS
MOLECULAR MODELS
MOLECULAR STRUCTURE
NITROSO COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHYSICAL PROPERTIES
POLYENES
QUANTUM MECHANICS
REACTION HEAT
REACTION KINETICS
SIMULATION
THERMODYNAMIC PROPERTIES