Selective formation of trans-2-butene-1,4-d/sub 2/ and (E)-2-methyl-2-butene-1,4-d/sub 2/ in deuteration of 1,3-butadiene derivatives over thorium oxide catalyst
Stereoselective hydrogenations of 1,3-butadiene and 2-methyl-1,3-butadiene over thorium oxide catalyst were investigated to elucidate the intermediates of the reactions. Hydrogenation of 1,3-butadiene produced predominantly trans-2-butene. Deuterium tracer studies provided direct evidence that 1,4-addition was a dominant mechanism. Deuteration of 1,3-butadiene yielded exclusively monoenes-d/sub 2/, while no deuterium was exchanged with hydrogen in 1,3-butadiene. Deuteration of 2-methyl-2-butene gave mainly (E)-2-methyl-2-butene-1,4-d/sub 2/. For both reactants, most stable conformations of starting diens (s-trans form) were reflected on the structure of the products. The geometrical structures as well as molecular identity of a hydrogen molecule were maintained during hydrogenation. Reaction of a mixture containing 1-butene and 1,3-butadiene-d/sub 6/ in the presence of hydrogen revealed that 1-butene and 1,3-butadiene independently underwent isomerization and hydrogenation, respectively. The nature of their active sites is discussed. Key intermediate of the hydrogenation of conjugated diene is postulated to be the syn form of methyl- or dimethyl-..pi..-allyl carbanion which is hydrogenated before interconverting to their isomeric anti form of the ..pi..-allyl carbanion. 5 figures, 6 tables.
- Research Organization:
- Hokkaido Univ., Sapporo, Japan
- OSTI ID:
- 6337644
- Journal Information:
- J. Catal.; (United States), Journal Name: J. Catal.; (United States) Vol. 56:3; ISSN JCTLA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400303* -- Organic Chemistry-- Isotope Exchange & Isotope Separation-- (-1987)
ACTINIDE COMPOUNDS
ALKENES
AMMONIA
BUTENES
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON MONOXIDE
CARBON OXIDES
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMPARATIVE EVALUATIONS
CRYOGENIC FLUIDS
DATA
DATA FORMS
DEUTERIUM
DEUTERIUM COMPOUNDS
DIENES
DISPERSIONS
ELEMENTS
EXPERIMENTAL DATA
FLUIDS
HYDRIDES
HYDROCARBONS
HYDROGEN
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
ISOLATED VALUES
ISOMERIZATION
ISOTOPE APPLICATIONS
ISOTOPES
ISOTOPIC EXCHANGE
KINETICS
LABELLING
LIGHT NUCLEI
LOW PRESSURE
MAGNETIC RESONANCE
MASS SPECTRA
MEDIUM TEMPERATURE
MIXTURES
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NONMETALS
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
OXIDES
OXYGEN
OXYGEN COMPOUNDS
POISONING
POLYENES
PRESSURE DEPENDENCE
REACTION INTERMEDIATES
REACTION KINETICS
RESONANCE
SPECTRA
SPECTRAL SHIFT
STABLE ISOTOPES
TEMPERATURE DEPENDENCE
THORIUM COMPOUNDS
THORIUM OXIDES
TIME DEPENDENCE
TRACER TECHNIQUES
WATER
YIELDS