Mechanism of flash vacuum pyrolysis of phenyl propargyl ether. Intramolecular deuterium kinetic isotope effect on claisen rearrangement
Journal Article
·
· J. Org. Chem.; (United States)
NMR analyses were performed on the reaction products obtained from the flash vacuum pyrolysis(FVP) of phenyl ..gamma..-deuteropropargyl ether(I) and 2-deuterophenyl propargyl ether(II) to ascertain the reaction mechanism. The FVP was carried out at 460/sup 0/C and 0.02 Torr. The NMR spectrum of undeuterated 2-indanone in carbon tetrachloride displayed peaks at delta 7.15 (singlet, aromatic hydrogen's) and 3.25 (singlet, nonaromatic hydrogen's) and with an integration constant of 1.00 : 1.00, while the NMR spectrum of the deuterated 2-indanone derived from I produced an aromatic protons/nonaromatic protons ratio of 1.30 : 1.00. The NMR analyses of the reaction products from FVP of II indicate that at the rate-determining transition state the oxygen-propargylic (..cap alpha.. carbon) bond is stretched in advance of any significant bond formation between the acetylenic carbon (..gamma.. carbon), the Claisen type rearrangement was classified as a nonsynchronous process and the proposed mechanism agrees with previous studies.
- Research Organization:
- Univ. of Baghdad
- OSTI ID:
- 6509342
- Journal Information:
- J. Org. Chem.; (United States), Journal Name: J. Org. Chem.; (United States) Vol. 43:18; ISSN JOCEA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
DECOMPOSITION
DEUTERIUM
DEUTERIUM COMPOUNDS
ETHERS
HIGH TEMPERATURE
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
ISOTOPE EFFECTS
ISOTOPES
KETONES
KINETICS
LIGHT NUCLEI
MAGNETIC RESONANCE
MEDIUM VACUUM
NUCLEAR MAGNETIC RESONANCE
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PRESSURE DEPENDENCE
PYROLYSIS
REACTION KINETICS
RESONANCE
STABLE ISOTOPES
TEMPERATURE DEPENDENCE
THERMOCHEMICAL PROCESSES
YIELDS
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
DECOMPOSITION
DEUTERIUM
DEUTERIUM COMPOUNDS
ETHERS
HIGH TEMPERATURE
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
ISOTOPE EFFECTS
ISOTOPES
KETONES
KINETICS
LIGHT NUCLEI
MAGNETIC RESONANCE
MEDIUM VACUUM
NUCLEAR MAGNETIC RESONANCE
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PRESSURE DEPENDENCE
PYROLYSIS
REACTION KINETICS
RESONANCE
STABLE ISOTOPES
TEMPERATURE DEPENDENCE
THERMOCHEMICAL PROCESSES
YIELDS