Regioselective reduction of polynuclear heteroaromatics catalyzed by transition metal complexes and hydrodenitrogenation chemistry. [Chlorotris(triphenylphosphine)rhodium(I), dichlorotris(triphenylphosphine)ruthenium(II), and dicarbonyldichlorobis(triphenylphosphine)ruthenium(II)]
The use of transition metal complexes as catalysts for the reduction of the heteroatom containing ring in polynuclear heteroaromatic compounds has been investigated. Additionally, a study has been made of the heterogeneously catalyzed cleavage of carbon-nitrogen bonds in the regioselectively reduced compound, 1,2,3,4-tetrahydroquinoline. Chlorotris(triphenylphosphine)rhodium(I) (both homogeneous and polymer-supported), dichlorotris-(triphenylphosphine)ruthenium(II) and dicarbonyldichloro-bis(triphenylphosphine)ruthenium(II) have been used as catalysts for the selective reductions of a variety of compounds, including: quinoline, 5,6-benzoquinoline, 7,8-benzoquinoline, acridine, phenanthridine, indole and benzothiophene. Both molecular hydrogen and easily dehydrogenated saturated nitrogen aromatics have been used as hydrogen sources. The rates of reduction of single compounds and various mixtures of compounds have been determined. The ability of a substrate to bind to the catalyst has been found to be a primary factor in determining reduction rates. Deuterium gas has been substituted for hydrogen gas in the reduction of quinoline and phenanthridine. The deuterium incorporation into the products was examined by /sup 1/H NMR and mass spectroscopy. These results indicate that the reduction of quinoline is a two step process, a reversible hydrogenation of the 1-2 carbon-nitrogen bond followed by an irreversible reduction of the 3-4 carbon-carbon bond. Mixtures of quinoline and chlorotris(triphenylphosphine)rhodium(I), in the presence and absence of hydrogen, have been examined by /sup 31/P NMR. Several quinoline rhodium complexes have been identified in these mixtures. Various heterogeneous catalysts have been investigated for the cleavage of the carbon-nitrogen bonds in 1,2,3,4-tetrahydroquinoline. Two highly loaded nickel on silica catalysts have proven to be active for this reaction. 93 refs., 43 figs., 38 tabs.
- Research Organization:
- Lawrence Berkeley Lab., CA (USA); California Univ., Berkeley (USA). Dept. of Chemical Engineering
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 5108785
- Report Number(s):
- LBL-22209; ON: DE87001719
- Resource Relation:
- Other Information: Thesis. Microfiche only, copy does not permit paper copy reproduction. Thesis submitted by A.D. Thormodsen
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
01 COAL, LIGNITE, AND PEAT
ACRIDINES
DENITRIFICATION
HYDROGENATION
REDUCTION
CATALYSTS
INDOLES
NICKEL
CATALYTIC EFFECTS
QUINOLINES
RHODIUM COMPLEXES
RUTHENIUM COMPLEXES
SILICA
THIONAPHTHENES
DEUTERIUM
EXPERIMENTAL DATA
HIGH TEMPERATURE
HYDROGEN 1
MASS SPECTROSCOPY
MEDIUM PRESSURE
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
ORGANIC CHLORINE COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
PHOSPHORUS 31
TRACER TECHNIQUES
AROMATICS
AZAARENES
AZINES
AZOLES
CHALCOGENIDES
CHEMICAL REACTIONS
COMPLEXES
DATA
ELEMENTS
HETEROCYCLIC COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE APPLICATIONS
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
METALS
MINERALS
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDE MINERALS
OXIDES
OXYGEN COMPOUNDS
PHOSPHORUS ISOTOPES
PYRIDINES
PYRROLES
RESONANCE
SILICON COMPOUNDS
SILICON OXIDES
SPECTRA
SPECTROSCOPY
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENTS
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)
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010402 - Coal
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