Mechanism of the Fischer indole synthesis. Quantum-chemical interpretation of the rearrangement of substituted cyclohexanone arylhydrazones to tetrahydrocarbazoles (in Russian)
Calculations of a number of model structures within the scheme of the Fischer indole synthesis were made on the basis of a bonding variant of perturbation theory in the self-consistent-field (SCF) MO LCAO method. A quantum-chemical interpretation of the effect of substituents on the course of the thermal process is given. The kinetics of the thermal and acid-catalyzed indolization of substituted cyclohexanone arylhydrazones to tetrahydrocarbazoles were studied by spectrophotometry. It was shown that the experimental data are in satisfactory agreement with the calculated values. It was concluded that a concerted mechanism (a (3,3)-sigma-tropic shift) for the step involving the formation of a carbon-carbon bond in the Fischer reaction is preferred.
- OSTI ID:
- 6424839
- Journal Information:
- Chem. Heterocycl. Compd. (Engl. Transl.); (United States), Vol. 22:7; Other Information: Translated from Khim. Geterstsikl. Soedin.; 22: No. 7, 898-907(Jul 1986)
- Country of Publication:
- United States
- Language:
- Russian
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
CARBAZOLES
DEHYDROCYCLIZATION
CYCLOHEXANONE
HYDRAZONES
INDOLES
LCAO METHOD
MOLECULAR ORBITAL METHOD
SYNTHESIS
ACTIVATION ENERGY
ATOMIC MODELS
BINDING ENERGY
CATALYSIS
CHEMICAL BONDS
CHEMICAL REACTION KINETICS
CHROMATOGRAPHY
CONFORMATIONAL CHANGES
ELECTRONIC STRUCTURE
INFRARED SPECTRA
ISOMER SHIFT
MULTIPLETS
NMR SPECTRA
PERTURBATION THEORY
QUANTUM MECHANICS
SELF-CONSISTENT FIELD
SPECTROPHOTOMETRY
SPIN ORIENTATION
ULTRAVIOLET SPECTRA
AROMATICS
AZAARENES
AZOLES
CHEMICAL REACTIONS
ENERGY
HETEROCYCLIC COMPOUNDS
KETONES
KINETICS
MATHEMATICAL MODELS
MECHANICS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORIENTATION
PYRROLES
REACTION KINETICS
SEPARATION PROCESSES
SPECTRA
400201* - Chemical & Physicochemical Properties
640302 - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory