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WO2009087994A1 - Procédé pour la déshalogénisation d'un halogénure aromatique - Google Patents

Procédé pour la déshalogénisation d'un halogénure aromatique Download PDF

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Publication number
WO2009087994A1
WO2009087994A1 PCT/JP2009/050037 JP2009050037W WO2009087994A1 WO 2009087994 A1 WO2009087994 A1 WO 2009087994A1 JP 2009050037 W JP2009050037 W JP 2009050037W WO 2009087994 A1 WO2009087994 A1 WO 2009087994A1
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catalyst
aromatic halide
test tube
ether
aromatic
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Japanese (ja)
Inventor
Hisamitsu Nagase
Hironao Sajiki
Yasunari Monguchi
Tomohiro Maegawa
Akiko Ido
Sueo Wada
Shinji Ishihara
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NAGARA BIONICS CO Ltd
Nagoya Industrial Science Research Institute
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NAGARA BIONICS CO Ltd
Nagoya Industrial Science Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B35/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving a change in the type of bonding between two carbon atoms already directly linked
    • C07B35/06—Decomposition, e.g. elimination of halogens, water or hydrogen halides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/37—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
    • C07C1/30—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms by splitting-off the elements of hydrogen halide from a single molecule
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/24—Preparation of ethers by reactions not forming ether-oxygen bonds by elimination of halogens, e.g. elimination of HCl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/04—Monocyclic monocarboxylic acids
    • C07C63/06—Benzoic acid
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/20—Organic substances
    • A62D2101/22—Organic substances containing halogen
    • 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
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium

Definitions

  • the present invention relates to a method for dehalogenation of an aromatic halide, and more particularly to a method that can be used advantageously when decomposing a harmful aromatic halide such as polychlorinated biphenyl (PCB).
  • a harmful aromatic halide such as polychlorinated biphenyl (PCB).
  • PCB polychlorinated biphenyl
  • electrical equipment such as transformers (transformers) and capacitors
  • heat medium for heat exchangers.
  • PCB has the property of being easily soluble in fat, and when it is chronically ingested by humans, it gradually accumulates in the body, and since it has been reported that the accumulated PCB causes various symptoms, in Japan, Currently, the production and use of PCBs is prohibited.
  • PCBs Persistent Organic Pollutants
  • PCB waste waste containing PCB (hereinafter referred to as PCB waste) is incinerated at high temperature, or dechlorination decomposition method.
  • Catalytic hydrogen dechlorination method hydrothermal oxidative decomposition method, reductive thermochemical decomposition method, photolysis method, plasma decomposition method, mechanochemical decomposition method, melt decomposition method and the like are widely known.
  • these conventional processing methods can be used to safely process (decompose) PCBs individually or in combination with two or more methods as required, but generally, high temperature, high pressure, etc. Therefore, there is a problem that the processing equipment becomes large and costs are high.
  • some of the present inventors dilute an aromatic chlorine compound with a soluble solvent of the aromatic chlorine compound, and perform a hydrodechlorination reaction by contact with hydrogen gas in the presence of a metal catalyst.
  • a dechlorination method of the aromatic chlorine compound for removing chlorine from the aromatic chlorine compound the hydrochlorination reaction is performed after adding ammonia or an amine as an additive.
  • a method for dechlorination of a compound has been previously proposed (see Patent Document 1). The method of dechlorination of aromatic chlorine compounds disclosed therein proceeds effectively even under mild conditions, and is simple, less dangerous, and economical. It is a simple method.
  • dehalogenation hydrodehalogenation reaction
  • a method of dehalogenation of aromatic halides which is effective, progresses effectively, is less dangerous and is economical, and has a particularly low impact on the human body and the environment. It is in.
  • the present invention provides an aromatic halide as a substrate together with a heterogeneous platinum group catalyst, metal magnesium and / or metal zinc, water or an organic solvent as a solvent.
  • the gist of the method is to dehalogenate an aromatic halide, which is characterized by bringing hydrogen gas into contact with the liquid mixture obtained by adding to the above.
  • the aromatic halide is 6-chloro-m-cresol, 4-chlorobiphenyl, 4-bromobiphenyl, 4-bromoaniline. , 4-bromoacetanilide, 1-bromonaphthalene, or any of the compounds represented by the following structural formula (I) or (II).
  • the solvent is preferably an alcohol solvent.
  • the heterogeneous platinum group catalyst is supported on a carrier.
  • the heterogeneous platinum group catalyst is selected from the group consisting of a Pt / C catalyst, a Rh / C catalyst, a Ru / C catalyst, a Pd / C catalyst, and an Ir / C catalyst. It is at least one kind.
  • the hydrodehalogenation reaction (dehalogenation) of the aromatic halide proceeds advantageously even under mild conditions by the action of the metal magnesium and / or metal zinc. It is a simple and less dangerous dehalogenation method.
  • the dehalogenation according to the present invention since the inorganic salt (magnesium chloride and / or zinc chloride) generated during the dehalogenation can be easily extracted and the influence on the human body and the environment can be reduced, the dehalogenation according to the present invention.
  • the construction of an aromatic halide decomposition plant using a chlorination method is also highly expected.
  • any aromatic halide can be used as long as it is conventionally known that a hydrodehalogenation reaction proceeds by contact with hydrogen gas. It can be used even if it exists. Further, according to what the present inventors have learned, even in the case of polychlorinated biphenyl, which has been difficult to efficiently dehalogenate in the conventional dehalogenation method by contact with hydrogen gas, It is possible to effectively dehalogenate.
  • a heterogeneous platinum group catalyst is used.
  • a conventionally known heterogeneous platinum group catalyst is used. Any of the catalysts can be used.
  • the platinum group metal can be exemplified by a carbon material such as activated carbon supported by a carrier made of carbon material such as activated carbon, alumina, silica, diatomaceous earth, molecular sieve, silk, or various polymers.
  • a heterogeneous platinum group catalyst supported on can be advantageously used.
  • heterogeneous platinum group catalysts supported by such a carbon material in particular, selected from the group consisting of a Pd / C catalyst, a Pt / C catalyst, a Rh / C catalyst, a Ru / C catalyst, and an Ir / C catalyst. At least one or more are advantageously used, more preferably a Pd / C catalyst.
  • Pd / C catalyst Pd / C catalyst, Rh / C catalyst, Ru / C catalyst, Ir / C catalyst
  • the supported amount (content) of Pd Pt, Rh, Ru, Ir
  • those comprising 1 to 30% by weight, preferably 3 to 20% by weight, of the total weight of the catalyst are advantageously used.
  • a catalyst having a higher platinum group metal content such as Pd shows a use effect (catalytic effect)
  • a heterogeneous platinum group catalyst supported by carbon as described above is generally expensive. From the viewpoint of cost effectiveness, a platinum group metal having a content of 30% by weight or less is generally used.
  • the amount of the heterogeneous platinum group catalyst as described above is appropriately determined according to the type and amount of the substrate used. In general, if the amount used is too small, a sufficient use effect (catalytic effect) will not be exhibited. On the other hand, if the amount used is too large, an improvement in the effect according to the amount used is not recognized, In the liquid mixture, mixing with the substrate and stirring do not proceed sufficiently, and as a result, contact with hydrogen gas may be insufficient.
  • the heterogeneous platinum group catalyst is, for example, in the case of a platinum group metal / C catalyst having a platinum group metal content of 10% by weight, based on 100 parts by weight of the substrate. It is used in such an amount that the ratio is about 3 to 20 parts by weight.
  • an aromatic halide or a heterogeneous platinum group catalyst as described above is added, and water or an organic solvent is used as a solvent used when preparing a liquid mixture.
  • organic solvent hydrogen gas is used. Any conventionally known organic solvent can be used as long as it does not inhibit the hydrodehalogenation reaction of the aromatic halide due to contact with.
  • an alcohol solvent such as methanol and ethanol and water are particularly advantageously used as a solvent for preparing the liquid mixture, and methanol is most advantageously used.
  • Such a solvent is used so that the aromatic halide, the heterogeneous platinum group catalyst, and metal magnesium and / or metal zinc described later are uniformly dispersed in the liquid mixture, and sufficient stirring can be performed. Used in various amounts.
  • the inventors have not yet fully clarified that the hydrodehalogenation reaction of aromatic halides proceeds effectively, but the present inventors In the liquid mixture, the oxidation-reduction potential of the benzene ring in the aromatic halide and the oxidation-reduction potential of metal magnesium and / or metal zinc substantially coincide with each other, so that the aromatic halide and metal magnesium, etc. It is believed that one-electron transfer proceeds reasonably between them, and thus the hydrodehalogenation reaction of the aromatic halide proceeds more effectively.
  • a liquid mixture obtained by using a predetermined aromatic chlorinated product, a Pd / C catalyst as a heterogeneous platinum group catalyst, and metallic magnesium and adding them to a predetermined solvent is considered.
  • the hydrodechlorination reaction of the aromatic chlorinated compound proceeds according to the reaction mechanism shown in FIG. That is, as shown in FIG. 1, first, as a first-stage reaction, a Pd / C catalyst is coordinated with an aromatic chlorinated product.
  • the present inventors consider that an aromatic compound which is a dechlorinated product of an aromatic chlorinated product is obtained, thereby completing a hydrodechlorination reaction of the aromatic chlorinated product.
  • magnesium metal becomes magnesium ions as the reaction proceeds, and chlorine desorbed from the aromatic chlorinated product is generated in the liquid mixture as chlorine ions.
  • metal magnesium and / or metal zinc is used in an amount necessary for effectively proceeding the hydrodehalogenation reaction of the aromatic halide. It has been found by the present inventors that when carrying out the dehalogenation of an aromatic halide according to the present invention, it is advantageous to use an aromatic halide containing one halogen atom in one molecule. 0.5 mol or more of metallic magnesium or the like is used with respect to 1 mol.
  • metal magnesium and metal zinc used in the present invention any shape that is generally available on the market, specifically, any shape such as a powder shape, a ribbon shape, and a turning shape is used. It is possible.
  • a predetermined amount of a solvent prepared in advance in a reaction vessel equipped with a stirrer a predetermined amount of each of an aromatic halide, a heterogeneous platinum group catalyst, and metallic magnesium and / or metallic zinc as a substrate.
  • the reaction vessel is sealed, and the inside is filled with hydrogen gas, and the liquid mixture is stirred for a predetermined time in such a state to bring the liquid mixture and hydrogen gas into contact with each other.
  • the chemical dehalogenation reaction proceeds.
  • the inside of the reaction tank is heated or the pressure of hydrogen gas in the reaction tank is set to a normal pressure or higher.
  • the dehalogenation method of the present invention it is not always necessary to heat the reaction tank or to increase the hydrogen gas pressure because metal magnesium and / or metal zinc is used.
  • the hydrogen gas pressure is set to 1 atm at normal temperature, it is possible to effectively dehalogenate the aromatic halide. For this reason, the processing facility using the dehalogenation method of the present invention can be made smaller than that using the conventional dehalogenation method.
  • the heterogeneous platinum group catalyst used is expressed as “10% Pd / C catalyst” or the like. In this case, the proportion of the amount of Pd supported (weight) in the total weight of the catalyst is 10% (wt%). Further, when filtering the catalyst, unless otherwise indicated, a membrane filter manufactured by Millipore (Millere-LH, filter pore size: 0.45 ⁇ m), and when stirring the solution in the test tube, A magnetic stirrer was used for each.
  • the dehalogenation rate (dechlorination rate or debromination rate) is obtained by dissolving the product obtained after the final distillation under reduced pressure in methanol: 2 mL, except as specifically indicated below.
  • methanol solution as a sample, gas chromatograph mass spectrometry (GC-Mass) is performed, and the residual amount (mol) of the aromatic halide as a substrate obtained from the measurement result, and dehalogenation of the aromatic halide. This is calculated from the amount (mol) of the aromatic compound that is a compound and the amount (mol) of the aromatic halide used.
  • a dehalogenation rate (dechlorination rate or debromination rate) of 100% means that all of the aromatic halide used in the reaction has been dehalogenated.
  • Each compound was identified by comparison with a commercially available standard in 1 H-NMR measurement and GC-Mass retention time.
  • Example 1- Methanol in a test tube: 2 mL, 6-chloro-m-cresol: 0.2 mmol (28.4 mg), 10% Pd / C catalyst: 2.8 mg, magnesium metal (in powder form, hereinafter referred to as Mg). ): 0.2 mmol (4.9 mg) was added and suspended, and then a balloon filled with hydrogen gas was attached to the test tube port. With the balloon attached, the inside of the test tube was stirred at room temperature for 24 hours. Thereafter, the reaction solution in the test tube was filtered, and the residue obtained by distilling off the filtrate under reduced pressure was extracted with ether: 10 mL and 1 mol / L hydrochloric acid: 5 mL.
  • Example 2- 4-Chloroanisole: 0.2 mmol (28.4 mg), 10% Pd / C catalyst: 2.8 mg, and Mg: 0.2 mmol (4.9 mg) were added to 2 mL of methanol in a test tube, After suspending, a balloon filled with hydrogen gas was attached to the test tube port. With the balloon attached, the inside of the test tube was stirred at room temperature for 24 hours. Then, ether: 10mL and water: 10mL were added to the reaction liquid in a test tube, the mixed solution was prepared, and this mixed solution was filtered. The obtained filtrate was separated into an ether layer and an aqueous layer, and then the aqueous layer was extracted with 10 mL of ether.
  • the total amount of the ether layer thus obtained was washed with 10 mL of saturated saline and then dehydrated with anhydrous magnesium sulfate, and GC-Mass was performed. As a result, dechlorination in Example 3 was performed. The conversion rate was found to be 100%.
  • Example 4- 4-Chlorobenzamide: 0.2 mmol (31.1 mg), 10% Pd / C catalyst: 3.1 mg, and Mg: 0.2 mmol (4.9 mg) were added to 2 mL of methanol in a test tube, After suspending, a balloon filled with hydrogen gas was attached to the test tube port. With the balloon attached, the inside of the test tube was stirred at room temperature for 24 hours. Thereafter, the reaction solution in the test tube was filtered, and the residue obtained by distilling off the filtrate under reduced pressure was extracted with ether: 10 mL and saturated aqueous ammonium chloride solution: 10 mL to obtain an ether layer and an aqueous layer. It was.
  • the pH of the obtained aqueous layer was 6-7, and when this aqueous layer was analyzed by thin layer chromatography, 4-chlorobenzamide and its dechlorinated product (benzamide) were not detected.
  • the extracted ether layer was washed with 10 mL of saturated brine, dehydrated with anhydrous magnesium sulfate, and then the ether was distilled off under reduced pressure to obtain a product.
  • GC-Mass gas chromatograph mass spectrometry
  • Example 7- Methanol in a test tube 2 mL, polychlorinated biphenyl represented by the following structural formula taken out from a transformer (transformer): 0.2 mmol (53.2 mg), 10% Pd / C catalyst: 5.3 mg, Mg : 0.62 mmol (15.1 mg) was added and suspended, and then a balloon filled with hydrogen gas was attached to the test tube port. With the balloon attached, the inside of the test tube was stirred at room temperature for 3 hours. Thereafter, the reaction solution in the test tube was filtered, and the residue obtained by distilling off the filtrate under reduced pressure was extracted with ether: 10 mL and water: 10 mL to obtain an ether layer and an aqueous layer.
  • polychlorinated biphenyl represented by the following structural formula taken out from a transformer (transformer): 0.2 mmol (53.2 mg), 10% Pd / C catalyst: 5.3 mg, Mg : 0.62 mmol (15.1 mg) was added and suspended, and then a balloon filled with hydrogen
  • Example 8- 4-Bromobiphenyl: 0.2 mmol (46.6 mg), 10% Pd / C catalyst: 4.7 mg, and Mg: 0.2 mmol (4.9 mg) were added to 2 mL of methanol in a test tube, After suspending, a balloon filled with hydrogen gas was attached to the test tube port. With the balloon attached, the inside of the test tube was stirred at room temperature for 12 hours. Thereafter, the reaction solution in the test tube was filtered, and the residue obtained by distilling off the filtrate under reduced pressure was extracted with ether: 10 mL and water: 10 mL to obtain an ether layer and an aqueous layer.
  • Example 8 The obtained ether layer was washed with 10 mL of saturated brine, dehydrated using anhydrous magnesium sulfate, and then the ether was distilled off under reduced pressure to obtain a product. When this product was subjected to GC-Mass, the debromination rate in Example 8 was found to be 100%.
  • Example 9 The obtained ether layer was washed with 10 mL of saturated brine, dehydrated using anhydrous magnesium sulfate, and then the ether was distilled off under reduced pressure to obtain a product. When this product was subjected to GC-Mass, the dechlorination rate in Example 9 was found to be 100%.
  • Example 9 the same as Example 9 except that Mg was not used and the stirring time (reaction time) in the test tube was changed to 1 hour, 2 hours, 4 hours, 8 hours, 12 hours, 24 hours, or 72 hours.
  • 4-Chlorobiphenyl was dechlorinated according to the above procedure (Comparative Examples 1a to 1g).
  • a graph showing the relationship between the reaction time and the dechlorination rate in Example 9 and Comparative Examples 1a to 1g is shown in FIG.
  • Example 9 using magnesium according to the present invention, the dechlorination rate was low even though the stirring time (reaction time) in the test tube was only 2 hours.
  • Comparative Examples 1a to 1g using no magnesium the dechlorination rate reached 100% even when the reaction time was 72 hours (Comparative Example 1g). It was admitted not to. From these results, it was confirmed that by using magnesium as in the present invention, in other words, by allowing magnesium to exist in the reaction system, the dechlorination of 4-chlorobiphenyl proceeds effectively. is there.
  • Example 10a to 10j Comparative Examples 2a to 2j- 4-Chlorobenzoic acid: 0.2 mmol (31.2 mg), 10% Pd / C catalyst: 3.1 mg, and Mg: 0.2 mmol (4.9 mg) were added to 2 mL of methanol in a test tube. After suspending, a balloon filled with hydrogen gas was attached to the test tube port. With the balloon attached, the inside of the test tube was stirred at room temperature for 10 minutes (Example 10a).
  • Example 10b the same method as in Example 10a, except that the stirring time (reaction time) in the test tube was 20 minutes, 30 minutes, 45 minutes, 1 hour, 2 hours, 3 hours, 6 hours, 10 hours, or 12 hours.
  • 4-Chlorobenzoic acid was dechlorinated according to (Examples 10b to 10j). In all of Examples 10b to 10j, the dechlorination rate was 100%.
  • Example 14- 4-Bromobiphenyl was dechlorinated under the same conditions as in Example 8 except that the stirring time was 2 hours. After completion of the stirring, the reaction liquid in the test tube was filtered, and the residue obtained by distilling off the filtrate under reduced pressure was extracted with ether: 10 mL and water: 10 mL to obtain an ether layer and an aqueous layer. . The obtained ether layer was washed with 10 mL of saturated brine, dehydrated using anhydrous magnesium sulfate, and then the ether was distilled off under reduced pressure to obtain a product. When this product was subjected to GC-Mass, it was found that the dechlorination rate in Example 14 was 100%.
  • Example 15- Aroclor 1254 (Aroclor 1254): 0.2 mmol (65.0 mg), 10% Pd / C catalyst: 6.5 mg, and Mg: 1.98 mmol (48.1 mg) were added to 2 mL of methanol in a test tube. After suspending, a balloon filled with hydrogen gas was attached to the test tube port. The test tube equipped with such a balloon was fixed in a water bath (water temperature: 25 to 30 °), and the inside of the test tube was stirred at room temperature for 12 hours. Thereafter, the reaction solution in the test tube was filtered, and the residue obtained by distilling off the filtrate under reduced pressure was extracted with ether: 10 mL and water: 10 mL to obtain an ether layer and an aqueous layer.
  • Example 15 The obtained ether layer was washed with 10 mL of saturated brine, dehydrated using anhydrous magnesium sulfate, and then the ether was distilled off under reduced pressure to obtain a product. When this product was subjected to GC-Mass, the dechlorination rate in Example 15 was found to be 100%.
  • Example 16- 4-bromoaniline: 0.2 mmol (34.4 mg), 10% Pd / C catalyst: 3.4 mg, and Mg: 0.2 mmol (4.9 mg) were added to 2 mL of methanol in a test tube, After suspending, a balloon filled with hydrogen gas was attached to the test tube port. With the balloon attached, the inside of the test tube was stirred at room temperature for 24 hours. Then, ether: 10mL and water: 10mL were added to the reaction liquid in a test tube, the mixed solution was prepared, and this mixed solution was filtered. The obtained filtrate was separated into an ether layer and an aqueous layer, and then the aqueous layer was extracted with 10 mL of ether.
  • Example 17- 4-bromoacetanilide: 0.2 mmol (42.8 mg), 10% Pd / C catalyst: 4.3 mg, and Mg: 0.2 mmol (4.9 mg) were added to 2 mL of methanol in a test tube.
  • a balloon filled with hydrogen gas was attached to the test tube port. With the balloon attached, the inside of the test tube was stirred at room temperature for 24 hours.
  • ether: 10mL and water: 10mL were added to the reaction liquid in a test tube, the mixed solution was prepared, and this mixed solution was filtered. The obtained filtrate was separated into an ether layer and an aqueous layer, and then the aqueous layer was extracted with 10 mL of ether.
  • Example 18 To 1 mL of methanol in a test tube, 1-bromonaphthalene: 0.2 mmol (41.4 mg), 10% Pd / C catalyst: 4.1 mg, and Mg: 0.2 mmol (4.9 mg) were added. After suspending, a balloon filled with hydrogen gas was attached to the test tube port. With the balloon attached, the inside of the test tube was stirred at room temperature for 24 hours. Then, ether: 10mL and water: 10mL were added to the reaction liquid in a test tube, the mixed solution was prepared, and this mixed solution was filtered. The obtained filtrate was separated into an ether layer and an aqueous layer, and then the aqueous layer was extracted with 10 mL of ether.
  • the 10% Pd / C catalyst recovered by filtration of the reaction solution was washed 5 times with 5 mL of methanol per time on the filter paper and then twice with 5 mL of water per time. Further, after washing 3 times with 5 mL of methanol per time, it was dried at room temperature. The weight of the 10% Pd / C catalyst after drying was measured, and the recovery rate (%) was calculated from the weight and the amount used (50.0 mg in Example 19a).
  • Example 19a to 19f The above-described “dechlorination of 4-chlorobenzoic acid ⁇ recovery of 10% Pd / C catalyst” was made into one cycle, and this was carried out 6 times in total (Examples 19a to 19f). The same conditions as in Example 19a described above were followed except that the amount of 4-chlorobenzoic acid used as a substrate was changed according to the amount of 10% Pd / C catalyst used. Table 4 below shows the dechlorination rate and the recovery rate of 10% Pd / C catalyst in Examples 19a to 19f.
  • the extracted aqueous layer was neutralized with NaOH (pH: 7.26), and then transferred to a 50 mL volumetric flask, and water was added to make a total volume of 50 mL.
  • the measurement of the amount of magnesium contained in this solution was outsourced to an external inspection organization (NE Chemcat. Co., Ltd. Daiichi Factory Chemical Catalyst Technology Center), and the amount of magnesium contained in this solution was 4780 ppm. Was found to correspond to 99.6% of the amount of magnesium used (240 mg) in this example. From this result, it was recognized that the dehalogenation method according to the present invention is a method capable of efficiently recovering magnesium metal.

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Abstract

L'invention porte sur un procédé pour déshalogéniser un halogénure aromatique, dans lequel un gaz hydrogène est amené en contact avec un mélange liquide qui est obtenu par addition d'un halogénure aromatique concerné dans de l'eau jouant le rôle de solvant ou un solvant organique conjointement avec un catalyseur du groupe platine hétérogène et un métal magnésium et/ou un métal zinc. Dans ce procédé, une réaction d'hydrogénation-déshalogénisation est effectuée de façon efficace même sous des conditions douces. Le procédé pour la déshalogénisation d'un halogénure aromatique est simple et peu dangereux, tout en étant économique. De plus, le procédé n'a que peu d'effets défavorables sur l'environnement ou sur le corps humain.
PCT/JP2009/050037 2008-01-07 2009-01-06 Procédé pour la déshalogénisation d'un halogénure aromatique Ceased WO2009087994A1 (fr)

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JP2015010036A (ja) * 2013-06-26 2015-01-19 Ｊｆｅケミカル株式会社 芳香族ハロゲン化物の分解方法
JP2015013832A (ja) * 2013-07-05 2015-01-22 日立化成株式会社 芳香族化合物の製造方法及び有機エレクトロニクス材料
TWI507355B (zh) * 2010-08-18 2015-11-11 Shiono Chemical Co Ltd Hydrogenation or rehydration of organic compounds, and dehalogenation of halogenated organic compounds
WO2016146556A1 (fr) * 2015-03-17 2016-09-22 Akzo Nobel Chemicals International B.V. Procédé de purification d'acide monochloroacétique
JP2018012725A (ja) * 2017-10-04 2018-01-25 日立化成株式会社 芳香族化合物の製造方法及び有機エレクトロニクス材料
EP4321238A1 (fr) * 2022-08-08 2024-02-14 Grillo-Werke Aktiengesellschaft Déhalogénation des hydrocarbures halogénés

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JP2015010036A (ja) * 2013-06-26 2015-01-19 Ｊｆｅケミカル株式会社 芳香族ハロゲン化物の分解方法
JP2015013832A (ja) * 2013-07-05 2015-01-22 日立化成株式会社 芳香族化合物の製造方法及び有機エレクトロニクス材料
WO2016146556A1 (fr) * 2015-03-17 2016-09-22 Akzo Nobel Chemicals International B.V. Procédé de purification d'acide monochloroacétique
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