Base-catalyzed deuterium exchange of 6,6-dimethylfulvene
- Ohio State Univ., Columbus
The kinetics of the deuterium exchange of 6,6-dimethylfulvene have been studied in the presence of sodium methoxide-methanol-d and potassium tert-butoxide-tert-butyl alcohol-d. The rate of disappearance of undeuterated starting material was followed by mass spectral measurements. The rate of introduction of deuterium into the methyl groups and into the ring was followed by H NMR. The rates of methyl exchange and ring exchange were of the same order of magnitude. The reaction of tert-butyl alcohol-d was speeded by addition of cryptate (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo(8.8.8)hexacosane). The occurrence of methyl exchange establishes a deprotonation mechanism (Scheme I) in both solvents. The greater rate in tert-butyl alcohol-d than in methanol-d is evidence that an addition-elimination mechanism for ring exchange is not important in tert-butyl alcohol-d solution, but its importance in methanol-d cannot be proven or disproven. 3 figures, 3 tables.
- OSTI ID:
- 5439866
- Journal Information:
- J. Org. Chem.; (United States), Vol. 45:6
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DEUTERIUM
ION EXCHANGE
BASES
BUTANOLS
BUTOXY RADICALS
CATALYSIS
KINETICS
MASS SPECTRA
METHANOL
NUCLEAR MAGNETIC RESONANCE
ORGANIC COMPOUNDS
SODIUM COMPOUNDS
ALCOHOLS
ALKALI METAL COMPOUNDS
ALKOXY RADICALS
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEI
ODD-ODD NUCLEI
RADICALS
RESONANCE
SPECTRA
STABLE ISOTOPES
400303* - Organic Chemistry- Isotope Exchange & Isotope Separation- (-1987)