Selective catalytic hydrogenation of polynuclear heteroaromatic compounds using polymer-supported transition-metal compounds as catalyst. [5,6 and 7,8-benzoquinoline and quinoline]

Technical Report · Sat Jun 01 04:00:00 EDT 1985

OSTI ID:5555088

Fish, R H; Heinemann, H

This research program focused on the utilization of polymer-supported (polystyrene-divinylbenzene, PS-DVB) transition-metal catalysts in the selective catalytic hydrogenation of polynuclear heteroaromatic compounds that are known to be present in coal and coal liquids. We found that the polymer-supported chlorotris(triphenyl-phosphine)rhodium(1) was the most efficient catalyst for the regiospecific reduction of the nitrogen-containing ring in model-coal compounds such as quinoline, 5,6- and 7,8-benzoquinoline and acridine, and in one case, a heteroaromatic sulfur compound, benzothiophene. Interestingly, the polymer-supported rhodium catalyst was more active than the corresponding homogeneous analogue by relative rate factors of 10 to 20 depending on the substrate studied in the reduction. More importantly, a model coal liquid was found to have a relative rate of reduction of quinoline to 1,2,3,4-tetrahydroquinoline (THQ) that was 2.2 times faster than a similar experiment without the coal liquid constituents consisting of pyrene, tetralin, methylnaphthalene, p-cresol, quinoline, and 2-methylpyridine. Further experimentation clearly showed that the model coal liquid constituent, p-cresol, was responsible for the relative rate enhancement in the highly regiospecific reduction of quinoline to THQ. Nuclear magnetic resonance spectroscopy (NMR) experiments have given some insight into this rate-enhancement phenomena. We also found that 9,10-dihydrophenanthridine was an excellent catalytic transfer hydrogenation reagent in the presence of several homogeneous and polymer-supported transition-metal catalysts. Hydrogen was transferred to such acceptors as quinoline and acridine. We also evaluated dihydroquinoline as a donor solvent since THQ has been used as a donor solvent in coal liquefaction experiments. 48 refs., 4 figs., 2 tabs.

• Research Organization: Lawrence Berkeley Lab., CA (USA)
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 5555088
• Report Number(s): LBL-19772; ON: DE85016529
• Country of Publication: United States
• Language: English

Related Subjects

01 COAL, LIGNITE, AND PEAT
010405* -- Coal
Lignite
& Peat-- Hydrogenation & Liquefaction
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ACRIDINES
AROMATICS
AZAARENES
AZINES
CATALYST SUPPORTS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTIONS
COAL LIQUIDS
COMPLEXES
CRESOLS
DATA
ELEMENTS
EXPERIMENTAL DATA
FLUIDS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
HYDROGEN 1
HYDROGEN ISOTOPES
HYDROGEN TRANSFER
HYDROGENATION
HYDROXY COMPOUNDS
INFORMATION
ION EXCHANGE MATERIALS
ISOTOPES
LIGHT NUCLEI
LIQUIDS
MAGNETIC RESONANCE
MATERIALS
METALS
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC ION EXCHANGERS
ORGANIC NITROGEN COMPOUNDS
ORGANIC POLYMERS
ORGANIC SOLVENTS
ORGANIC SULFUR COMPOUNDS
PHENOLS
POLYCYCLIC AROMATIC HYDROCARBONS
POLYMERS
POLYOLEFINS
POLYSTYRENE-DVB
PYRIDINES
QUINOLINES
RESONANCE
RHODIUM COMPLEXES
SOLVENTS
SPECIFICITY
SPECTRA
STABLE ISOTOPES
THIONAPHTHENES
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENTS