Selective catalytic hydrogenation of polynuclear heteroaromatic compounds using polymer-supported transition-metal compounds as catalyst. [5,6 and 7,8-benzoquinoline and quinoline]
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
- Resource Relation:
- Other Information: Portions of this document are illegible in microfiche products. Original copy available until stock is exhausted
- Country of Publication:
- United States
- Language:
- English
Similar Records
Selective hydrogenation of polynuclear heteroatomic compounds. Final report
Selective catalytic hydrogenation of polynuclear heteroaromatic nitrogen compounds with polymer-supported transition-metal compounds. [Quinoline, 5,6- and 7,8-benzoquinoline, acridine and phenanthridine]
Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ACRIDINES
HYDROGENATION
COAL LIQUIDS
CRESOLS
NMR SPECTRA
CATALYSTS
ORGANIC SOLVENTS
HYDROGEN TRANSFER
QUINOLINES
RHODIUM COMPLEXES
CATALYTIC EFFECTS
THIONAPHTHENES
CATALYST SUPPORTS
EXPERIMENTAL DATA
HYDROGEN 1
NUCLEAR MAGNETIC RESONANCE
POLYCYCLIC AROMATIC HYDROCARBONS
POLYSTYRENE-DVB
SPECIFICITY
TRANSITION ELEMENTS
AROMATICS
AZAARENES
AZINES
CHEMICAL REACTIONS
COMPLEXES
DATA
ELEMENTS
FLUIDS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
INFORMATION
ION EXCHANGE MATERIALS
ISOTOPES
LIGHT NUCLEI
LIQUIDS
MAGNETIC RESONANCE
MATERIALS
METALS
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC ION EXCHANGERS
ORGANIC NITROGEN COMPOUNDS
ORGANIC POLYMERS
ORGANIC SULFUR COMPOUNDS
PHENOLS
POLYMERS
POLYOLEFINS
PYRIDINES
RESONANCE
SOLVENTS
SPECTRA
STABLE ISOTOPES
TRANSITION ELEMENT COMPLEXES
010405* - Coal
Lignite
& Peat- Hydrogenation & Liquefaction
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)