Cyclohexadienyl cations. VI. Methyl group isotope effects in the dienone--phenol rearrangement
Journal Article
·
· J. Am. Chem. Soc.; (United States)
Rates of rearrangement of 4,4-di(trideuteriomethyl)cyclohexadienone (1-DD) and 4-methyl-4-trideuteriomethylcyclohexadienone (1-HD) are compared with the unlabeled material (1-HH). The observed isotope effects are k/sub HH//k/sub DD/ = 1.149 +- 0.017 and k/sub HH//k/sub HD/ = 1.060 +- 0.012. The product isotope effect obtained from 1-HD by converting the rearrangement product to 3,4-dimethyl-4-dichloromethylcyclohexadienone and NMR integration of the two methyl resonances is 1.36 +- 0.05. Suitable combination of these results give k/sub H//sup ..cap alpha../ (methyl migrational isotope effect) = 1.25 and k/sub H//sup ..beta../ (remnant methyl group isotope effect) = 0.92. The magnitude and direction of these isotope effects are compared with others in the literature.
- Research Organization:
- Univ. of Maryland, Baltimore
- OSTI ID:
- 7347437
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 98:19; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Kinetic isotope effects in the gas-phase reaction of hydroxyl radicals with ethylene in the temperature range 343-1173 K and at 1-atm pressure
Rate-controlling two-proton transfer coupled with heavy-atom motion in the 2-pyridinone-catalyzed mutarotation of tetramethylglucose. Experimental and calculated deuterium isotope effects
Mechanism of the Meyer--Schuster rearrangement
Journal Article
·
Thu Jun 30 00:00:00 EDT 1988
· J. Phys. Chem.; (United States)
·
OSTI ID:6478915
Rate-controlling two-proton transfer coupled with heavy-atom motion in the 2-pyridinone-catalyzed mutarotation of tetramethylglucose. Experimental and calculated deuterium isotope effects
Journal Article
·
Wed Jul 13 00:00:00 EDT 1983
· J. Am. Chem. Soc.; (United States)
·
OSTI ID:5414494
Mechanism of the Meyer--Schuster rearrangement
Journal Article
·
Fri Oct 14 00:00:00 EDT 1977
· J. Org. Chem.; (United States)
·
OSTI ID:5241328
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
ALKENES
CATIONS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CYCLOALKENES
DEUTERIUM
HYDROCARBONS
HYDROGEN ISOTOPES
INTERMEDIATE STRUCTURE
IONS
ISOTOPE EFFECTS
ISOTOPES
KETONES
KINETICS
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUCLEI
ODD-ODD NUCLEI
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
REACTION KINETICS
RESONANCE
STABLE ISOTOPES
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
ALKENES
CATIONS
CHARGED PARTICLES
CHEMICAL REACTION KINETICS
CYCLOALKENES
DEUTERIUM
HYDROCARBONS
HYDROGEN ISOTOPES
INTERMEDIATE STRUCTURE
IONS
ISOTOPE EFFECTS
ISOTOPES
KETONES
KINETICS
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUCLEI
ODD-ODD NUCLEI
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
REACTION KINETICS
RESONANCE
STABLE ISOTOPES