Structure and tautomerism of cyclopentadiene derivatives. I. Reversible migrations of a nitro group in the cyclopentadiene ring

Journal Article · Tue Oct 20 04:00:00 EDT 1987 · J. Org. Chem. USSR (Engl. Transl.); (United States)

OSTI ID:7076437

Mikhailov, I E; Kompan, O E; Struchkov, Yu T; Minkin, V I; Dushenko, G A; Klenkin, A A; Olekhnovich, L P

Intramolecular migrations of the nitro group around the perimeter of the five-membered ring, which take place during the mutual transformations of 5-nitro-5-alkyl-1,2,3,4- and 5-nitro-2-alkyl-1,3,4,5-tetramethoxycarbonylcyclopentadienes with a free energy of activation (..delta..G/sup= //sub 298/) of 100.2-111.2 kJ/mole, were detected and investigated by PMR spectroscopy. The effect of steric and electronic factors on the activation parameters of the rearrangements of the nitro group and also on the position of equilibrium between the isomers formed during the rearrangements was studied. The structure of such isomers was proved by x-ray crystallographic analysis for the case of 5-nitro-5-methyl-1,2,3,4- and 5-nitro-2-methyl-1,3,4,5-tetramethoxycarbonylcyclopentadienes and also 5-nitro-1,2,3,4,5-pentamethoxycarbonylcyclopentadiene. The /sup 1/H NMR spectra were obtained on a Tesla BS-487C spectrometer at 80 MHz with adiabatic signal transmission in chlorobenzene solutions.

• Research Organization: M. A. Suslov Rostov State Univ. (USSR)
• OSTI ID: 7076437
• Journal Information: J. Org. Chem. USSR (Engl. Transl.); (United States), Journal Name: J. Org. Chem. USSR (Engl. Transl.); (United States) Vol. 23:5; ISSN JOCYA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
640302 -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ACTIVATION ENERGY
ALKENES
ANGULAR MOMENTUM
CHEMICAL REACTIONS
CHEMICAL SHIFT
COHERENT SCATTERING
CONFORMATIONAL CHANGES
COUPLING
COUPLING CONSTANTS
CRYSTAL LATTICES
CRYSTAL STRUCTURE
CYCLOALKENES
CYCLOPENTADIENE
DIENES
DIFFRACTION
ENERGY
HYBRIDIZATION
HYDROCARBONS
HYDROGEN 1
HYDROGEN ISOTOPES
INFRARED SPECTRA
INTERMEDIATE COUPLING
ISOMERIZATION
ISOMERS
ISOTOPES
J-J COUPLING
LATTICE PARAMETERS
LIGHT NUCLEI
MOLECULAR STRUCTURE
MONOCLINIC LATTICES
NITRATION
NITRO COMPOUNDS
NMR SPECTRA
NUCLEI
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PARTICLE PROPERTIES
POLYENES
SCATTERING
SPECTRA
SPIN
STABLE ISOTOPES
TRICLINIC LATTICES
X-RAY DIFFRACTION