EP2858749A2 - Use of thermally-treated supported cobalt catalysts comprising a polycyclic aromatic structure consisting of nitrogen ligands for hyrogenating aromatic nitro compounds - Google Patents
Use of thermally-treated supported cobalt catalysts comprising a polycyclic aromatic structure consisting of nitrogen ligands for hyrogenating aromatic nitro compoundsInfo
- Publication number
- EP2858749A2 EP2858749A2 EP13729648.9A EP13729648A EP2858749A2 EP 2858749 A2 EP2858749 A2 EP 2858749A2 EP 13729648 A EP13729648 A EP 13729648A EP 2858749 A2 EP2858749 A2 EP 2858749A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- phenanthroline
- cobalt
- hydrogenation
- dimethyl
- use according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
- C07C209/365—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst by reduction with preservation of halogen-atoms in compounds containing nitro groups and halogen atoms bound to the same carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D215/38—Nitrogen atoms
- C07D215/40—Nitrogen atoms attached in position 8
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/14—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 6 and unsubstituted in position 7
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Definitions
- the invention relates to the use of thermally treated supported supported cobalt catalysts for the selective hydrogenation of nitroaromatics to the corresponding aromatic amines.
- the invention also relates to novel thermally treated supported cobalt catalysts and their preparation.
- Non-volatile organometallic complexes of iron and cobalt have been described as precursors for heterogeneous catalysts in WO 2010/051619 A1 for the reduction of oxygen in fuel cells.
- nitroaromatics are substituted and unsubstituted nitrobenzenes and substituted and unsubstituted heterocyclic nitroaromatics.
- the nitroaromatics contain one or more functional groups having unsaturated carbon-carbon, carbon-nitrogen and / or carbon-oxygen bonds to substituents of aromatic nuclei and halogens (F, Cl, Br, I) and halogen-carbon compounds.
- the catalyst systems used according to the invention are prepared in situ from cobalt precursor catalysts, immobilized on an inorganic support and then subjected to a thermal treatment (pyrolysis).
- cobalt precursor catalysts are cobalt-amine complexes wherein cobalt is bound to aromatic or heterocyclic nitrogen ligands. They are eg obtained by reaction of cobalt salts with aromatic or heterocyclic nitrogen ligands (L) and thus form the non-volatile organo-cobalt complexes (Co-L). The nitrogen atoms associated with the cobalt remain associated with it and thus form the precursor complex. The interactions between Co and ligand L provide the opportunity to modify the shape, electronic, and chemical properties of cobalt-amine complexes.
- Aromatic nitrogen ligands (L) are known to the person skilled in the art. For the purposes of the invention are suitable as nitrogen ligands all aromatic nitrogen compounds which undergo a poly-aromatic structure with the cobalt atom.
- they are ligands from the group of phenanthrolines having the general formula:
- R to R 8 is identical or different hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkyl, amino, carboxy, halogen, substituted and unsubstituted aryl, substituted and unsubstituted heteroaryl, preferably selected from the group comprising Me, et, OMe, NH 2, COOH, phenyl, F, Cl, Br, .... Etc. or
- Pyridines such as terpyridine, 2,6-ß / 's-benzimidazol-pyridine, 1, 1-bipyridine, pyridine.
- nitrogen ligands which are selected from the group consisting of: L1: 1, 10-phenanthroline (C 12 H 10 N 2) L2: terpyridine (C ⁇ HnNs) L3: 2,6-b / s-benzimidazol-pyridine ( C 19 H 13 N-bipyridine (C 10 H 8 N 2 ) L 5 : pyridine (C 5 H 5 N),
- L4 1, 1'-bipyridine L5 pyridine and the 1, 10-phenantholine derivatives L1b: 2,9-dimethyl-4,7-diphenyl-1, 10-phenanthroline, L1c: 4,7-dimethoxy-1, 10 phenanthroline and L1d: 2,9-dimethyl-1,10-phenanthroline.
- the preparation of the cobalt precursor catalysts is carried out according to methods known per se, e.g. by reacting a cobalt salt such as cobalt (II) acetate tetrahydrate in a solvent with the respective nitrogen ligand.
- a cobalt salt such as cobalt (II) acetate tetrahydrate
- oxides such as TiO 2 or Al 2 O 3 can be used as inorganic supports.
- a preferred carrier used eg Vulcan XC72R, commercially available from Cabot Corporation US
- Vulcan XC72R is a synthetically produced soot with high surface area (20-300m 2 / g) and electrical conductivity.
- a solution of the previously preformed and unisolated cobalt-ligand complex is absorbed onto the support material and the solvent removed.
- This is followed by the pyrolysis step, preferably under inert gas conditions.
- the thermal treatment can be carried out at 600-1100 ° C, with pyrolyses between 750 and 850 ° C generate catalysts with particularly good catalytic activity and stability. Higher temperatures lead to a loss of catalytic activity, lower temperatures mean lower stabilities.
- cobalt-containing particles are formed on the carbon-nitrogen surface.
- the inventive optimization of the catalyst treatment by pyrolysis has a significant influence on the activity and selectivity of the catalyst, so that the catalytic material according to the invention can be used surprisingly for the hydrogenation of many nitroaromatics.
- the hydrogenation of nitroaromatic compounds is carried out at temperatures of 60 to 200 ° C, preferably at about 90 to 120 ° C.
- the catalysts supported on carbon with the formula Co-L / C are particularly preferably used according to the invention for the hydrogenation of nitroaromatics, where L has the abovementioned meaning for L1 to L5.
- L has the abovementioned meaning for L1 to L5.
- the essential portion of the aromatic amines obtained after the hydrogenation still contains all the multiple bonds to substituents of aromatic nuclei that were present before the hydrogenation.
- the catalyst systems of the invention are tolerant to all functional groups. Furthermore, they are inexpensive and environmentally friendly. They are thus extremely suitable for the industry for the selective hydrogenation of nitroaromatics and lead to corresponding aniline derivatives as well as using heteronitroaromatics to corresponding heteroaromatic amines, which are also valuable building blocks for the production of a variety of agrochemicals and pharmaceuticals.
- the catalysts can be reused several times without loss of activity. They can easily be washed after each reaction and dried overnight.
- the catalyst system Co-Ll / C in the reaction of nitrobenzene to aniline in the 11th cycle after 8 hours still an almost complete conversion> 99% and a yield of 98%.
- the invention also relates to novel supported cobalt-nitrogen ligand complexes, wherein the carrier is a carbon carrier (C) having the formula Co-L / C, which is thermally at 750 - 850 0 C was treated.
- the ligand L is selected from the group comprising:
- L4 1, 1'-bipyridine L5 pyridine and the 1, 10-phenantholine derivatives
- L1 b 2,9-dimethyl-, 7-diphenyl-1, 10-phenanthroline
- L1c 4,7-dimethoxy-1, 10 phenanthroline
- L1d 2,9-dimethyl-1,10-phenanthroline.
- Cobalt (II) acetate tetrahydrate (125 mg, 0.5 mmol) and 1, 10-phenanthroline (180 mg, 1.0 mmol) (Co: phenanthroline 1: 2 molar ratio) are dissolved in ethanol (50 ml) for stirred for about 30 minutes at room temperature.
- carbon black 700 mg
- the reaction mixture is refluxed at 60 ° C for 4 h. Thereafter, the reaction mixture is cooled to room temperature and ethanol is removed under vacuum. The resulting solid is dried at 60 ° C for 12 h and then crushed to a fine powder. Subsequently, the thermal treatment (pyrolysis) of the powder is carried out at 800 ° C for 2 h under argon.
- the measured internal temperature in the autoclave is 104-106 ° C.
- the autoclave is placed in a water bath and cooled to room temperature. Finally, the remaining hydrogen gas is drained and the samples are removed from the autoclave, washed with ethylene chloride and analyzed by GC and GC-MS.
- the reactions are carried out on a larger scale (5 mmol nitroaromatic).
- An autoclave (100 ml) is charged with the cobalt catalyst (100 mg), THF (20 ml), hexadecane as internal standard (1 ml) and nitrobenzene (630 ⁇ l). Hydrogen is introduced twice into the autoclave and hydrogenated at 60 bar. After each reaction, the catalyst is washed thoroughly with ethyl acetate and dried under mild vacuum overnight.
- the catalyst system Co-LI / C according to the invention proves to be particularly reactive and selective. As seen from the above Table 1, in the presence of a homogeneous catalyst complex consisting of cobalt and phenanthroline (Table 1, No. 11), even when 10 times the amount is used, no aniline is formed. Likewise, an iron catalyst analogous to the system of the invention did not lead to aniline formation (Table 1, entry 10).
- Table 2 shows the hydrogenation of substituted nitroaromatics to industrially relevant anilines.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102012209634A DE102012209634A1 (en) | 2012-06-08 | 2012-06-08 | Use of thermally treated supported supported cobalt catalysts for the hydrogenation of nitroaromatics |
PCT/EP2013/061757 WO2013182665A2 (en) | 2012-06-08 | 2013-06-07 | Use of thermally-treated supported cobalt catalysts for hyrogenating aromatic nitro compounds |
Publications (1)
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EP2858749A2 true EP2858749A2 (en) | 2015-04-15 |
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ID=48652012
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EP13729648.9A Withdrawn EP2858749A2 (en) | 2012-06-08 | 2013-06-07 | Use of thermally-treated supported cobalt catalysts comprising a polycyclic aromatic structure consisting of nitrogen ligands for hyrogenating aromatic nitro compounds |
Country Status (4)
Country | Link |
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US (1) | US20150307538A1 (en) |
EP (1) | EP2858749A2 (en) |
DE (1) | DE102012209634A1 (en) |
WO (1) | WO2013182665A2 (en) |
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CN105418439A (en) * | 2015-11-17 | 2016-03-23 | 山东沾化天九化工有限公司 | Method and device for producing 3-chlorine-4-fluoroaniline |
CN110035820A (en) * | 2016-12-19 | 2019-07-19 | 豪夫迈·罗氏有限公司 | Catalyst, preparation method based on nitrogenous biopolymer and its purposes in method for hydrogenation, reductive dehalogenation and oxidation |
CN114345413A (en) * | 2021-04-19 | 2022-04-15 | 杭州师范大学 | Aromatic acid coordinated iron-cobalt nitrogen fixation catalyst and preparation method and application thereof |
CN114618495B (en) * | 2022-03-09 | 2023-10-20 | 中南大学 | Multistage pore carbon-loaded nitrogen-sulfur co-coordinated cobalt monoatomic catalyst and preparation method and application thereof |
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EP0820808B1 (en) * | 1996-07-23 | 2002-09-04 | Degussa AG | Multi-metallic catalyst and method for producing substituted aromatic amines |
AU2002222642A1 (en) * | 2000-12-14 | 2002-06-24 | Nissan Chemical Industries Ltd. | Method for producing indole derivative |
AU2003215241B2 (en) * | 2002-02-14 | 2008-07-31 | Monsanto Technology Llc | Oxidation catalyst and process for its preparation and process for oxidation using it |
DK1828447T3 (en) * | 2004-11-16 | 2011-03-21 | Hyperion Catalysis Int | Process for preparing supported catalysts from metal-applied carbon nanotubes |
US7678728B2 (en) * | 2006-10-16 | 2010-03-16 | Stc.Unm | Self supporting structurally engineered non-platinum electrocatalyst for oxygen reduction in fuel cells |
DE102008028070A1 (en) * | 2008-06-12 | 2009-12-17 | Bayer Technology Services Gmbh | Catalyst and process for the hydrogenation of organic compounds |
US8580704B2 (en) * | 2008-11-10 | 2013-11-12 | Institut National De La Recherche Scientifique | Catalyst precursors, catalysts and methods of producing same |
US8835343B2 (en) * | 2010-09-27 | 2014-09-16 | Uchicago Argonne, Llc | Non-platinum group metal electrocatalysts using metal organic framework materials and method of preparation |
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2012
- 2012-06-08 DE DE102012209634A patent/DE102012209634A1/en not_active Withdrawn
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2013
- 2013-06-07 US US14/405,963 patent/US20150307538A1/en not_active Abandoned
- 2013-06-07 WO PCT/EP2013/061757 patent/WO2013182665A2/en active Application Filing
- 2013-06-07 EP EP13729648.9A patent/EP2858749A2/en not_active Withdrawn
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US20150307538A1 (en) | 2015-10-29 |
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