WO2023149559A1 - Catalyst for hydrogenation reactions, method for producing same and method for producing hydrogenated organic compound - Google Patents

Catalyst for hydrogenation reactions, method for producing same and method for producing hydrogenated organic compound Download PDF

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WO2023149559A1
WO2023149559A1 PCT/JP2023/003674 JP2023003674W WO2023149559A1 WO 2023149559 A1 WO2023149559 A1 WO 2023149559A1 JP 2023003674 W JP2023003674 W JP 2023003674W WO 2023149559 A1 WO2023149559 A1 WO 2023149559A1
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copper
hydrogenation reaction
hydrogenated
catalyst
hydrogenation
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French (fr)
Japanese (ja)
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智照 水崎
寿彦 酒井
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エヌ・イーケムキャット株式会社
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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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • 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
    • B01J37/06—Washing
    • 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
    • B01J37/16—Reducing
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    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
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    • 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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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/45—Monoamines
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/78—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
    • C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
    • C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/58—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the carbon skeleton
    • 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
    • C07C41/20—Preparation of ethers by reactions not forming ether-oxygen bonds by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
    • C07C49/784—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic with all keto groups bound to a non-condensed ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
    • C07C49/813—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen polycyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
    • C07C69/616—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety polycyclic
    • 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

Definitions

  • the present disclosure relates to a hydrogenation reaction catalyst, a method for producing the same, and a method for producing a selectively hydrogenated product. More specifically, it relates to a hydrogenation catalyst capable of selectively hydrogenating unsaturated hydrocarbon groups and nitro groups, especially aromatic nitro groups.
  • hydrogenation reactions or hydrocracking reactions are extremely useful reactions.
  • a palladium catalyst has excellent reactivity in the hydrogenation reaction, but there is a problem that sites other than the target functional groups and unsaturated bonds are also hydrogenated during the hydrogenation reaction.
  • aromatic nitro compounds there are also compounds that have one or more functional groups that are hydrogenated or hydrogenolyzed in addition to the nitro group. Such aromatic nitro compounds may require selective hydrogenation or hydrogenolysis of only a portion of the hydrogenated or hydrogenolyzed functional groups.
  • Patent Document 1 a catalyst in which silver is supported on alumina
  • Patent Document 2 a palladium-carbon catalyst in which diphenyl sulfide is co-supported
  • Patent Document 3 a palladium-carbon catalyst in which palladium is selectively supported only on the surface layer of activated carbon
  • the non-platinum group catalysts used in Patent Document 1 generally have lower hydrogenation reactivity than platinum group catalysts, and thus have the problem of being difficult to use in industrial production.
  • the organic sulfur compound poisoned catalyst as proposed in Patent Document 2 has a problem that the catalyst life is short because the reactivity changes with time.
  • the palladium catalyst proposed in Patent Document 3 has a problem that the selectivity is still insufficient.
  • the present disclosure has been made in view of the above problems, and the organic compound to be hydrogenated, which has a plurality of functional groups and/or unsaturated bonds, is treated by a hydrogenation reaction with only some of the functional groups and/or unsaturated bonds. It is an object of the present invention to provide a hydrogenation reaction catalyst capable of selectively hydrogenating and having excellent catalyst durability.
  • the present disclosure has found that in conventional palladium carbon catalysts that have been used in hydrogenation reactions, palladium particles supported on carbon are further supported with copper. Therefore, the inventors have found that the above problems can be solved, and have completed the present disclosure. That is, the gist of the present disclosure is as follows.
  • a hydrogenation reaction catalyst comprising a carrier, palladium supported on the carrier, and copper supported on the palladium.
  • the hydrogenation reaction catalyst of the present disclosure is an organic compound to be hydrogenated having at least two functional groups and/or unsaturated bonds while maintaining at least one of the functional groups and/or unsaturated bonds. /or some of the unsaturated bonds can be selectively hydrogenated.
  • the hydrogenation reaction catalysts of the present disclosure hydrogenate nitro groups and/or unsaturated hydrocarbon groups, and hydrogenate aromatic ketones, aromatic chlorines, benzyl protecting groups, nitrile groups, and benzylic hydroxyl groups. It can be preferably used for a selective hydrogenation reaction that does not occur.
  • FIG. 1 is an electron micrograph of the hydrogenation reaction catalyst of Production Example 1 taken with a scanning transmission electron microscope.
  • FIG. 2 is a monochrome photograph in which a portion of FIG. 1 is enlarged and the metal composition is visualized.
  • a hydrogenation catalyst according to the present disclosure comprises a support, palladium supported on the support, and copper supported on the palladium.
  • the hydrogenation reaction catalyst according to the present disclosure supports copper on the palladium active sites in the palladium carbon (Pd/C) catalyst, so that the hydrogenation activity can be appropriately controlled without using a sulfur substance.
  • Pd/C palladium carbon
  • FIG. 1 shows an electron micrograph of the hydrogenation catalyst of Production Example 1 taken with a scanning transmission electron microscope.
  • FIG. 2 shows a photograph in which a local area in FIG. 1 is enlarged and the metal composition is visualized.
  • FIG. 2 is a monochrome photograph of an image obtained by coloring the positions of Pd and Cu. The color photograph shows that Cu particles are supported near the surface of Pd particles.
  • the cyclic voltammetry method it can be determined by the cyclic voltammetry method that copper is supported on the palladium surface without being alloyed. More specifically, when cyclic voltammetry is performed under conditions in which only copper is eluted from a catalyst in which copper is supported on Pd, the copper-derived peak disappears as the number of cycles increases, leaving only the palladium peak. Since such a tendency cannot occur in an alloy, it confirms that copper is supported on the palladium surface.
  • Measurement conditions for cyclic voltammetry under which only copper is eluted are shown below.
  • Electrolyte: 0.1 mM K2SO4 ( pH 5.75)
  • Measurement temperature Room temperature Number of cycles: 50 times
  • Examples of the carrier that constitutes the hydrogenation reaction catalyst of the present disclosure include alumina, silica, silica-alumina, and carbon carriers. Among these, carbon supports are preferred. Although the origin of the carbon carrier is not particularly limited, for example, wood or coconut charcoal pulverized coal, coal, oil furnace method, lamp black method, channel method, gas furnace method, acetylene decomposition method, thermal method, etc. carbon and the like. These carbons may be steam activated or chemically activated.
  • the carbon carrier As for the carbon carrier, a known method such as tumbling granulation or extrusion molding is used to produce a carbon carrier having a large average particle diameter, or after molding, a carbon carrier having a large average particle diameter is selected by sieving or the like. is also possible.
  • the specific surface area (BET value) of the carrier is not limited, it is preferably 50 to 3000 m 2 /g, more preferably 100 to 1500 m 2 /g.
  • a specific surface area value means the value measured based on the method of JISZ8830:2013.
  • the shape of the carbon support is not limited as long as it is shaped, and may be spherical, cylindrical, or pellet. Among them, a spherical shape is preferable.
  • a carbon carrier may be a commercially available product in addition to the one produced as described above. Examples of commercially available products include activated carbon beads (BAC-MP, average particle diameter 500 ⁇ m, specific surface area value 1200 m 2 /g, spherical shape) sold by Kureha Corporation.
  • the method for supporting palladium on a carrier is not limited, but can be carried out, for example, by dissolving a palladium compound in a solvent, introducing the carrier into the solution, and adsorbing or impregnating the palladium compound.
  • a water-soluble palladium compound such as chloropalladium acid
  • water can be used as a solvent.
  • a water-insoluble palladium compound such as bis(2,4-pentanedionato)palladium
  • an organic solvent that dissolves the palladium compound can be used as the solvent.
  • a commercial product may be used as the palladium carrier on which palladium is supported.
  • Examples of such commercial products include "5% by weight Pd/C catalyst K type” (manufactured by N E Chemcat).
  • the method for supporting copper on palladium is not particularly limited.
  • a copper compound is added to a solution containing carbon on which palladium is supported, and the copper compound is supported on palladium. can.
  • reduction treatment may be performed as necessary.
  • gaseous hydrogen can be used in addition to reducing agents such as methanol, formaldehyde and formic acid.
  • gaseous hydrogen is used, but it is also possible to dilute hydrogen gas with an inert gas such as nitrogen and use it.
  • Copper compounds include, for example, copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper caprate, copper undecylate, lauric acid Copper, copper tridecylate, copper myristate, copper pentadecylate, copper palmitate, copper margarate, copper stearate, copper nonadesylate, copper arachidate, copper heneicosylate, copper behenate, copper tricosylate, copper lignocerate, Copper cerrotate, copper montanate, copper melisinate, copper benzoate, copper oxalate, copper malonate, copper succinate, copper terephthalate, copper isophthalate, copper phthalate, copper salicylate, copper citrate, copper tartrate, etc.
  • Inorganic copper salts such as copper sulfate, copper carbonate, and copper nitrate; Copper halides such as copper iodide, copper bromide, and copper chloride; Copper hydroxides such as copper hydroxide; Copper such as copper oxide oxides.
  • the valence of copper in these copper compounds may be either monovalent or divalent, and two or more copper salts may be used in combination. These copper salts may be hydrates.
  • the copper compound is not particularly limited as long as it contains a copper atom, but from the viewpoint of high solubility in water and polar solvents, for example, copper formate, copper acetate, copper nitrate, copper chloride, copper sulfate, etc. Salts or hydrated salts of divalent organic or inorganic copper ions of are preferred.
  • the solution may be water, a polar solvent, or a non-polar solvent, but water or a polar solvent is preferable, and water is more preferable.
  • the amount of copper supported is not limited, but it preferably contains 10 to 200% by mass, more preferably 15 to 150% by mass, and 20 to 100% by mass with respect to 100% by mass of palladium. is more preferred.
  • the supported amount of copper is set within the above range, it is possible to improve the reaction rate of the hydrogenation reaction while maintaining the functional group selectivity. That is, if the supported amount of copper is too small, the functional group selectivity will decrease. On the other hand, if the supported amount of copper is excessive, copper may cover all the active sites of palladium, preventing the hydrogenation reaction from occurring.
  • the supported amounts of copper and palladium can be calculated as follows. First, the object is immersed in aqua regia to dissolve the metal. Next, carbon, which is an insoluble component, is removed from the aqua regia. Thereafter, by analyzing the aqua regia from which the carbon has been removed by ICP emission spectrometry, the supported amounts of copper and palladium can be calculated.
  • the amount of copper and palladium supported on the hydrogenation reaction catalyst can be adjusted by adjusting the amount of the copper compound added.
  • hydrogenation is selective hydrogenation of nitro groups and/or unsaturated hydrocarbon groups in a plurality of functional groups hydrogenated by the hydrogenation reaction. is preferred.
  • Multiple functional groups hydrogenated by hydrogenation reaction include, for example, a nitro group, an unsaturated hydrocarbon group, an aromatic ketone, an aromatic chlorine atom, a benzyl protective group, a nitrile group, and a benzylic hydroxyl group.
  • Niro group refers to a nitro group bonded to an aliphatic hydrocarbon group, a nitro group bonded to an aromatic ring, or a nitro group bonded to a heterocyclic ring.
  • Unsaturated hydrocarbon group refers to a carbon-carbon double bond or a carbon-carbon triple bond.
  • Aromatic chlorine atom refers to a chlorine atom connected to an aromatic or heterocyclic ring.
  • Benzyl protecting group refers to a benzyl group used as a protecting group for a hydroxyl group or a carboxylic acid group.
  • Benzyl-position hydroxyl group refers to a hydroxyl group that binds to a carbon atom that connects to an aromatic or heterocyclic ring.
  • the hydrogenation reaction catalyst of the present disclosure has only a part of the functional groups and/or unsaturated bonds of the organic compound to be hydrogenated, which has two or more functional groups and/or unsaturated bonds.
  • functional groups and/or some of the unsaturated bonds That is, the hydrogenation site can be selectively hydrogenated.
  • “Functional groups and/or unsaturated bonds that are hydrogenated by a hydrogenation reaction” include, for example, the aforementioned “multiple functional groups that are hydrogenated by a hydrogenation reaction”.
  • non-hydrogenated sites sites not hydrogenated by the hydrogenation reaction
  • examples of non-hydrogenated sites (sites not hydrogenated by the hydrogenation reaction) of the organic compound to be hydrogenated include aromatic ketones, aromatic chlorine atoms, benzyl protective groups, nitrile groups, and benzylic hydroxyl groups.
  • examples of the hydrogenation site of the organic compound to be hydrogenated include a nitro group and an unsaturated hydrocarbon group.
  • the hydrogenation reaction catalyst described above can be produced by bringing Pd/C into contact with a copper salt solution, raising the temperature and stirring, and then washing.
  • the method of bringing Pd/C into contact with the copper salt solution is as described above.
  • the elevated temperature is not limited as long as the copper compound can be dissolved, but is preferably 25 to 100°C, more preferably 35 to 90°C, and even more preferably 50 to 80°C.
  • the stirring time is not limited as long as copper can be supported on palladium, but is preferably 5 to 60 minutes, more preferably 10 to 50 minutes, and even more preferably 20 to 40 minutes.
  • gaseous hydrogen can be used in addition to reducing agents such as methanol, formaldehyde and formic acid.
  • gaseous hydrogen is used, but it is also possible to dilute hydrogen gas with an inert gas such as nitrogen and use it.
  • Washing is not limited, but can be performed, for example, by filtering the stirred solution and applying a solvent to the filtrate.
  • the solvent used for washing is preferably about 0° C. to 25° C., and washing is preferably performed 1 to 3 times.
  • the method for producing a hydrogenation reaction catalyst of the present disclosure preferably does not substantially include sintering under reduction after washing.
  • sintering refers to subjecting the washed material to a temperature at which copper and palladium are alloyed, for example, 700 to 1000° C. at 1 atm. Thus, as long as the copper and palladium do not alloy, for example, they may be heated for drying.
  • Functional groups and/or unsaturated bonds that are selectively hydrogenated include nitro groups and unsaturated hydrocarbon groups, as described above.
  • the method for producing a hydrogenated organic compound of the present disclosure for example, in the field of organic synthesis, in addition to raw materials for gene introduction agents, intermediates for pharmaceuticals and agricultural chemicals, image quality improvers for inkjet inks It is useful as a method for synthesizing various derivatives obtained by hydrogenation of aromatic nitro compounds, which are being studied for use as raw materials for functional polymers such as raw materials for photosensitive polymer compounds.
  • the hydrogenation reaction catalyst of the present disclosure is a catalyst in which palladium/copper is supported on carbon, it can be easily recovered by, for example, filtration after the completion of the hydrogenation reaction. After that, it can be reused.
  • Example 1 Using the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, a hydrogenation reaction represented by the following formula was carried out. Specifically, p-nitroacetophenone was dissolved in 1 ml of ethyl acetate, 10 mg of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1 was added, and hydrogen was dissolved at 0.2 MPa. A hydrogenation reaction was carried out at 60° C. for 2 hours in an atmosphere. The obtained reaction product was analyzed by GC-MS, and its conversion and selectivity were calculated. Table 2 shows the results.
  • the other compound (3) in the reaction formula below is a mixture of compounds other than the starting material (1) and the target compound (2).
  • Examples 2-3> Instead of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, the hydrogenation reaction catalyst produced in Production Examples 2 and 3 (5% Pd-1.5% Cu/ C) A hydrogenation reaction was carried out in the same manner as in Example 1, except that a hydrogenation reaction catalyst (5% Pd-4.5% Cu/C) was used. The obtained reaction product was analyzed by GC-MS, and its conversion and selectivity were calculated. Table 2 shows the results.
  • Examples 1, 4 to 13> Using the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, a hydrogenation reaction represented by the following formula was carried out. Specifically, the raw materials shown in Table 3 are dissolved in 1 ml of the solvent shown in Table 3, 10 mg of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1 is added, and hydrogen A hydrogenation reaction was carried out at the reaction temperature and reaction time shown in Table 3 under an atmosphere of 0.2 MPa. The obtained reaction product was analyzed by GC-MS, and its conversion and selectivity were calculated. Table 3 shows the results.
  • Example 6 Using the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, the hydrogenation reaction represented by the following reaction formula was carried out. Specifically, o-chloronitrobenzene is dissolved in 1 ml of ethyl acetate, 10 mg of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1 is added, and hydrogen is heated to 0.2 MPa. A hydrogenation reaction was carried out at 60° C. for 2 hours in an atmosphere. The obtained reaction product was analyzed by GC-MS, and its conversion and selectivity were calculated. The results are shown in Tables 4 and 5.
  • the other compound (3) in the reaction formula below is a mixture of compounds other than the starting material (1) and the target compound (2).
  • Example 6 After the hydrogenation reaction in Example 6, the catalyst was recovered by filtering and separating the catalyst from the reaction system. The recovered catalyst was put into the reaction system again and used repeatedly in the hydrogenation reaction. Specifically, instead of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, the recovered catalyst was used, and the reaction time was shortened to 1 hour. , the hydrogenation reaction was repeated 1 to 4 times in the same manner as in Example 6. The reactants obtained in the first, second, third and fourth hydrogenation reactions were each analyzed by GC-MS, and their conversion and selectivity were calculated. In addition, the catalyst recovered from each hydrogenation reaction was analyzed by ICP-MS (manufactured by Agilent) to measure the amounts of palladium and copper that flowed out into the solvent. Table 4 shows the results.
  • ICP-MS manufactured by Agilent

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Abstract

[Problem] The present invention provides a catalyst for hydrogenation reactions, the catalyst having excellent catalyst durability and being capable of selectively hydrogenating only some functional groups and/or unsaturated bonds of an organic compound to be hydrogenated, the organic compound having a plurality of functional groups and/or unsaturated bonds and having been conventionally hydrogenated by a hydrogenation reaction that uses a palladium carbon catalyst. [Solution] A catalyst for hydrogenation reactions according to the present disclosure comprises a carrier, palladium that is loaded on the carrier, and copper that is loaded on the palladium.

Description

水素化反応用触媒およびその製造方法、ならびに水素化有機化合物の製造方法Catalyst for hydrogenation reaction, method for producing the same, and method for producing hydrogenated organic compound
　本開示は、水素化反応用触媒およびその製造方法、ならびに選択的に水素化した生成物の製造方法に関する。より詳しくは、不飽和炭化水素基やニトロ基、とりわけ芳香族ニトロ基を選択的に水素化できる水素化触媒に関する。 The present disclosure relates to a hydrogenation reaction catalyst, a method for producing the same, and a method for producing a selectively hydrogenated product. More specifically, it relates to a hydrogenation catalyst capable of selectively hydrogenating unsaturated hydrocarbon groups and nitro groups, especially aromatic nitro groups.
　有機合成や石油化学分野において、水素化反応または水素化分解反応（以下、水素化反応と称することがある）は極めて有用な反応である。パラジウム触媒は、水素化反応において優れた反応性を有するが、目的とする官能基や不飽和結合以外の部位も水素化反応中に水素化してしまうという問題がある。 In the fields of organic synthesis and petrochemistry, hydrogenation reactions or hydrocracking reactions (hereinafter sometimes referred to as hydrogenation reactions) are extremely useful reactions. A palladium catalyst has excellent reactivity in the hydrogenation reaction, but there is a problem that sites other than the target functional groups and unsaturated bonds are also hydrogenated during the hydrogenation reaction.
　有機合成分野において、例えば、芳香族ニトロ化合物の水素化により得られる種々の誘導体は、遺伝子導入剤の原料、医薬、農薬の中間体の他、インクジェットインキの画質の向上剤の原料、感光性高分子化合物原料などの機能性重合体の原料としての利用が検討されている。このような芳香族ニトロ化合物の誘導体の例としては、アミノスチレン等が知られている。 In the field of organic synthesis, for example, various derivatives obtained by hydrogenation of aromatic nitro compounds are used as raw materials for gene transfer agents, intermediates for pharmaceuticals and agricultural chemicals, raw materials for improving the image quality of inkjet inks, and highly photosensitive compounds. Its use as a raw material for functional polymers such as raw materials for molecular compounds is being studied. Aminostyrene and the like are known as examples of derivatives of such aromatic nitro compounds.
　しかしながら、芳香族ニトロ化合物のなかには、ニトロ基の他、水素化または水素化分解される官能基を１または複数有する化合物も存在する。このような芳香族ニトロ化合物では、水素化または水素化分解される官能基の一部のみを選択的に水素化または水素化分解することが求められる場合がある。 However, among aromatic nitro compounds, there are also compounds that have one or more functional groups that are hydrogenated or hydrogenolyzed in addition to the nitro group. Such aromatic nitro compounds may require selective hydrogenation or hydrogenolysis of only a portion of the hydrogenated or hydrogenolyzed functional groups.
　石油化学分野においても、ポリエチレン製造時に、原料中の不純物であるアセチレン（アルキン）をエチレン（アルケン）に転化することが行われている。この場合も、アセチレンのみを選択的に水素化し、エチレンを水素化しない触媒が求められている。 In the petrochemical field, acetylene (alkyne), which is an impurity in raw materials, is converted to ethylene (alkene) during polyethylene production. Again, there is a need for a catalyst that selectively hydrogenates only acetylene and not ethylene.
　一部の官能基や不飽和結合部位のみを選択的に水素化するために、パラジウム（Ｐｄ）を鉛（Ｐｂ）で被毒したリンドラー触媒や、硫酸バリウムに担持したパラジウム触媒を、キノリン－Ｓ共存下で反応させるローゼンムント還元を利用することが知られている。 In order to selectively hydrogenate only some functional groups and unsaturated bond sites, a Lindlar catalyst in which palladium (Pd) is poisoned with lead (Pb), a palladium catalyst supported on barium sulfate, and a quinoline-S It is known to use the Rosenmund reduction to react in coexistence.
　また、近年では、アルミナに銀を担持させた触媒（特許文献１）、ジフェニルスルフィドを共存担持したパラジウムカーボン触媒（特許文献２）、活性炭の表層のみにパラジウムを選択担持したパラジウムカーボン触媒（特許文献３）等も検討されている。 In recent years, a catalyst in which silver is supported on alumina (Patent Document 1), a palladium-carbon catalyst in which diphenyl sulfide is co-supported (Patent Document 2), and a palladium-carbon catalyst in which palladium is selectively supported only on the surface layer of activated carbon (Patent Document 3), etc. are also being considered.
特開２０１１－３６７４８号公報Japanese Unexamined Patent Application Publication No. 2011-36748 特開２００７－１５２１９９号公報JP 2007-152199 A 特開２００８－１８３５５７号公報JP 2008-183557 A
　しかしながら、特許文献１に用いられる非白金族系触媒は、一般に、白金族系触媒と比べて水素化反応性が低いため、工業生産に用いることは難しいという課題がある。
　また、特許文献２に提案されているような有機硫黄化合物被毒触媒は、経時的に反応性が変化するため、触媒寿命が短いという課題がある。
　さらに、特許文献３に提案されているパラジウム触媒は、選択性が未だ不十分であるという課題がある。 However, the non-platinum group catalysts used in Patent Document 1 generally have lower hydrogenation reactivity than platinum group catalysts, and thus have the problem of being difficult to use in industrial production.
Further, the organic sulfur compound poisoned catalyst as proposed in Patent Document 2 has a problem that the catalyst life is short because the reactivity changes with time.
Furthermore, the palladium catalyst proposed in Patent Document 3 has a problem that the selectivity is still insufficient.
　本開示は、上記課題に鑑みてなされたものであり、官能基および／または不飽和結合を複数有する被水素化有機化合物を、水素化反応により、一部の官能基および／または不飽和結合のみを選択的に水素化することができ、且つ触媒耐久性にも優れる水素化反応用触媒を提供することを目的としている。 The present disclosure has been made in view of the above problems, and the organic compound to be hydrogenated, which has a plurality of functional groups and/or unsaturated bonds, is treated by a hydrogenation reaction with only some of the functional groups and/or unsaturated bonds. It is an object of the present invention to provide a hydrogenation reaction catalyst capable of selectively hydrogenating and having excellent catalyst durability.
　本開示者らは、上記課題を達成すべく鋭意研究を重ねた結果、水素化反応に使用されてきた従来のパラジウムカーボン触媒において、カーボン上に担持されたパラジウム粒子に、さらに銅を担持させることで、上記課題を解決できることを見出し、本開示を完成するに至った。即ち、本開示の要旨は、以下のとおりである。 As a result of intensive research to achieve the above problems, the present disclosure has found that in conventional palladium carbon catalysts that have been used in hydrogenation reactions, palladium particles supported on carbon are further supported with copper. Therefore, the inventors have found that the above problems can be solved, and have completed the present disclosure. That is, the gist of the present disclosure is as follows.
［１］　担体と、前記担体上に担持されたパラジウムと、前記パラジウム上に担持された銅と、を含んでなる、水素化反応用触媒。
［２］　前記担体が、カーボンである、［１］に記載の水素化反応用触媒。
［３］　前記パラジウム１００質量％に対して、前記銅を１０～２００質量％含んでなる、［１］または［２］に記載の水素化反応用触媒。
［４］　水素化が、水素化反応により水素化される複数の官能基において、ニトロ基および／または不飽和炭化水素基の選択的水素化である、［１］～［３］のいずれかに記載の水素化反応用触媒。
［５］　官能基および／または不飽和結合を２以上有する被水素化有機化合物の前記官能基および／または不飽和結合の一部を選択的に水素化して、水素化部位と非水素化部位とを有する水素化有機化合物を得ることができる、［１］～［３］のいずれかに記載の水素化反応用触媒。
［６］　前記水素化部位が、ニトロ基および／または不飽和炭化水素基を含む、［５］に記載の水素化反応用触媒。
［７］　前記非水素化部位が、芳香族ケトン、芳香族塩素原子、ベンジル保護基、ニトリル基、およびベンジル位水酸基からなる群から選択される少なくとも１種を含む、［５］または［６］に記載の水素化反応用触媒。
［８］　［１］～［７］のいずれかに記載の水素化反応用触媒の製造方法であって、Ｐｄ／Ｃを銅塩溶液に接触させ、昇温して撹拌した後、洗浄すること、を含む、製造方法。
［９］　洗浄した後、還元下で焼結することを実質的に含まない、［８］に記載の製造方法。
［１０］　官能基および／または不飽和結合を２以上有する被水素化有機化合物から、前記官能基および／または不飽和結合の一部を選択的に水素化して、水素化部位と非水素化部位とを有する水素化有機化合物を製造する方法であって、
　前記水素化反応を、［１］～［７］のいずれかに記載の水素化反応用触媒の存在下で実施する、方法。 [1] A hydrogenation reaction catalyst comprising a carrier, palladium supported on the carrier, and copper supported on the palladium.
[2] The hydrogenation reaction catalyst according to [1], wherein the carrier is carbon.
[3] The hydrogenation reaction catalyst according to [1] or [2], which contains 10 to 200% by mass of the copper with respect to 100% by mass of the palladium.
[4] Any one of [1] to [3], wherein the hydrogenation is selective hydrogenation of nitro groups and/or unsaturated hydrocarbon groups in a plurality of functional groups hydrogenated by a hydrogenation reaction. Catalysts for hydrogenation reactions as described.
[5] Selectively hydrogenating a portion of the functional groups and/or unsaturated bonds of an organic compound to be hydrogenated having two or more functional groups and/or unsaturated bonds to obtain a hydrogenated site and a non-hydrogenated site; The hydrogenation reaction catalyst according to any one of [1] to [3], which can obtain a hydrogenated organic compound having
[6] The hydrogenation reaction catalyst according to [5], wherein the hydrogenation site contains a nitro group and/or an unsaturated hydrocarbon group.
[7] The non-hydrogenated site contains at least one selected from the group consisting of aromatic ketones, aromatic chlorine atoms, benzyl protective groups, nitrile groups, and benzylic hydroxyl groups [5] or [6] The hydrogenation reaction catalyst according to .
[8] The method for producing a hydrogenation reaction catalyst according to any one of [1] to [7], wherein Pd/C is brought into contact with a copper salt solution, heated and stirred, and then washed. , including, manufacturing method.
[9] The manufacturing method according to [8], which does not substantially include sintering under reduction after washing.
[10] Selectively hydrogenating a part of the functional groups and/or unsaturated bonds from an organic compound to be hydrogenated having two or more functional groups and/or unsaturated bonds to obtain hydrogenated sites and non-hydrogenated sites A method for producing a hydrogenated organic compound having
A method, wherein the hydrogenation reaction is carried out in the presence of the hydrogenation reaction catalyst according to any one of [1] to [7].
　本開示の水素化反応用触媒は、官能基および／または不飽和結合を少なくとも２以上有する被水素化有機化合物を、官能基および／または不飽和結合の少なくとも１つを維持したまま、官能基および／または不飽和結合の一部を選択的に水素化することができる。
　特に、本開示の水素化反応用触媒は、ニトロ基および／または不飽和炭化水素基を水素化し、芳香族ケトン、芳香族塩素、ベンジル保護基、ニトリル基、およびベンジル位水酸基には水素化を生じさせない選択的水素化反応に好ましく用いることができる。 The hydrogenation reaction catalyst of the present disclosure is an organic compound to be hydrogenated having at least two functional groups and/or unsaturated bonds while maintaining at least one of the functional groups and/or unsaturated bonds. /or some of the unsaturated bonds can be selectively hydrogenated.
In particular, the hydrogenation reaction catalysts of the present disclosure hydrogenate nitro groups and/or unsaturated hydrocarbon groups, and hydrogenate aromatic ketones, aromatic chlorines, benzyl protecting groups, nitrile groups, and benzylic hydroxyl groups. It can be preferably used for a selective hydrogenation reaction that does not occur.
図１は、製造例１の水素化反応用触媒を走査透過型電子顕微鏡により撮影した電子顕微鏡写真である。FIG. 1 is an electron micrograph of the hydrogenation reaction catalyst of Production Example 1 taken with a scanning transmission electron microscope. 図２は、図１の局所を拡大し、金属組成を可視化したモノクロ写真である。FIG. 2 is a monochrome photograph in which a portion of FIG. 1 is enlarged and the metal composition is visualized.
　以下、本開示を実施する好ましい形態の一例について説明する。ただし、下記の実施形態は本開示を説明するための例示であり、本開示は下記の実施形態に何ら限定されるものではない。 An example of a preferred embodiment for implementing the present disclosure will be described below. However, the following embodiments are examples for explaining the present disclosure, and the present disclosure is not limited to the following embodiments.
［水素化反応用触媒］
　本開示による水素化反応用触媒は、担体と、担体上に担持されたパラジウムと、パラジウム上に担持された銅と、を含むものである。本開示による水素化反応用触媒は、パラジウムカーボン（Ｐｄ／Ｃ）触媒におけるパラジウム活性点に、銅を担持させることで、硫黄物質を用いることなく、水素化活性を適度に制御することができ、その結果、上記したように、被水素化有機化合物が有している複数の官能基および／または不飽和結合のうち、その一部を水素化せずに維持したまま、官能基および／または不飽和結合の一部を選択的に水素化することができるものと考えられる。
　特に、銅金属塩として、パラジウム活性点で分解・還元する材料を用いることで、パラジウム活性点上で銅に還元してパラジウム上に担持させることができ、上記効果が得られるものと考えられる。なお、本開示の水素化反応用触媒は、パラジウムの活性点上に銅が担持されていることが水素化活性制御に重要である。そのため、合金化は好ましくないと推測される。 [Catalyst for hydrogenation reaction]
A hydrogenation catalyst according to the present disclosure comprises a support, palladium supported on the support, and copper supported on the palladium. The hydrogenation reaction catalyst according to the present disclosure supports copper on the palladium active sites in the palladium carbon (Pd/C) catalyst, so that the hydrogenation activity can be appropriately controlled without using a sulfur substance. As a result, as described above, among the plurality of functional groups and/or unsaturated bonds possessed by the organic compound to be hydrogenated, some of the functional groups and/or unsaturated bonds are maintained without being hydrogenated. It is believed that some of the saturated bonds can be selectively hydrogenated.
In particular, by using a material that decomposes and reduces at the palladium active site as the copper metal salt, it is possible to reduce to copper on the palladium active site and support it on palladium, and it is thought that the above effects can be obtained. In the hydrogenation reaction catalyst of the present disclosure, it is important for hydrogenation activity control that copper is supported on the active sites of palladium. Therefore, alloying is presumed to be unfavorable.
　銅がパラジウム表面に担持されていることは、既存の装置を用いて確認することができる。このような装置としては、例えば、走査透過型電子顕微鏡（ＳＴＥＭ）が挙げられる。図１に、製造例１の水素化触媒を走査透過型電子顕微鏡により撮影した電子顕微鏡写真を示す。また、図１において、局所を拡大し、金属組成を可視化した写真を図２に示す。図２は、ＰｄとＣｕの存在位置をそれぞれ着色処理した画像のモノクロ写真であり、カラー写真では、Ｐｄ粒子の表面近傍にＣｕ粒子が担持されていることが示されている。 Existing equipment can be used to confirm that copper is supported on the palladium surface. Such devices include, for example, scanning transmission electron microscopes (STEM). FIG. 1 shows an electron micrograph of the hydrogenation catalyst of Production Example 1 taken with a scanning transmission electron microscope. Moreover, FIG. 2 shows a photograph in which a local area in FIG. 1 is enlarged and the metal composition is visualized. FIG. 2 is a monochrome photograph of an image obtained by coloring the positions of Pd and Cu. The color photograph shows that Cu particles are supported near the surface of Pd particles.
　また、銅が合金化されずにパラジウム表面に担持されていることは、サイクリックボルタンメトリー法によって判断することもできる。より詳細には、Ｐｄに銅が担持された触媒に銅のみが溶出される条件で、サイクリックボルタンメトリーを行なうと、サイクル数が増えるに従い銅由来のピークが消失し、パラジウムのみのピークが残る。このような傾向は、合金では生じ得ないことから、パラジウム表面に銅が担持していることの確認となる。 In addition, it can be determined by the cyclic voltammetry method that copper is supported on the palladium surface without being alloyed. More specifically, when cyclic voltammetry is performed under conditions in which only copper is eluted from a catalyst in which copper is supported on Pd, the copper-derived peak disappears as the number of cycles increases, leaving only the palladium peak. Since such a tendency cannot occur in an alloy, it confirms that copper is supported on the palladium surface.
　銅のみが溶出されるサイクリックボルタンメトリーの測定条件を以下に示す。
　測定：三電極式セル（作用極：電極材料／ＧＣ、対極：Ｐｔ、参照極：Ａｇ／ＡｇＣｌ）
　電解液：０．１ｍＭ　Ｋ２ＳＯ４（ｐＨ＝５．７５）
　測定電位範囲：０．０５～１．０８５Ｖ（可逆水素電極基準）
　走査速度：２０ｍＶ／ｓ
　測定温度：室温
　サイクル数：５０回 Measurement conditions for cyclic voltammetry under which only copper is eluted are shown below.
Measurement: Three-electrode cell (working electrode: electrode material/GC, counter electrode: Pt, reference electrode: Ag/AgCl)
Electrolyte: 0.1 mM K2SO4 ( pH = 5.75)
Measurement potential range: 0.05 to 1.085 V (based on reversible hydrogen electrode)
Scanning speed: 20mV/s
Measurement temperature: Room temperature Number of cycles: 50 times
　本開示の水素化反応用触媒を構成する担体としては、例えば、アルミナ、シリカ、シリカアルミナ、およびカーボン担体が挙げられる。これらの中でも、カーボン担体が好ましい。カーボン担体の由来は特に限定されないが、例えば、木材やヤシ殻炭の粉炭、石炭、オイルファーネス法、ランプブラック法、チャンネル法、ガスファーネス法、アセチレン分解法、サーマル法等の石油原料燃焼由来の炭素等挙げられる。これらの炭素は、水蒸気賦活あるいは薬品賦活を行ったものでもよい。 Examples of the carrier that constitutes the hydrogenation reaction catalyst of the present disclosure include alumina, silica, silica-alumina, and carbon carriers. Among these, carbon supports are preferred. Although the origin of the carbon carrier is not particularly limited, for example, wood or coconut charcoal pulverized coal, coal, oil furnace method, lamp black method, channel method, gas furnace method, acetylene decomposition method, thermal method, etc. carbon and the like. These carbons may be steam activated or chemically activated.
　カーボン担体は、転動造粒法や押し出し成型等の既知の方法を用いることにより、平均粒径が大きいカーボン担体を製造する、あるいは成型後に平均粒径が大きいカーボン担体をふるい分け等により選択することも可能である。 As for the carbon carrier, a known method such as tumbling granulation or extrusion molding is used to produce a carbon carrier having a large average particle diameter, or after molding, a carbon carrier having a large average particle diameter is selected by sieving or the like. is also possible.
　担体の比表面積（ＢＥＴ値）については、限定されるものではないが、５０～３０００ｍ２／ｇが好ましく、１００～１５００ｍ２／ｇがより好ましい。上記範囲の比表面積を有する担体とすることで、触媒の製造時のシンタリングを抑制するとともに、パラジウム成分の分散性を良好にすることができる。その結果、触媒活性がより向上する。なお、比表面積値は、ＪＩＳ　Ｚ　８８３０：２０１３に記載の方法に準拠して測定された値を意味する。 Although the specific surface area (BET value) of the carrier is not limited, it is preferably 50 to 3000 m 2 /g, more preferably 100 to 1500 m 2 /g. By using a carrier having a specific surface area within the above range, sintering during catalyst production can be suppressed and the dispersibility of the palladium component can be improved. As a result, catalytic activity is further improved. In addition, a specific surface area value means the value measured based on the method of JISZ8830:2013.
　また、担体の粒径については、限定されるものではないが、そのメジアン径が０．５～５００μｍの範囲にあることが好ましく、５～５００μｍの範囲にあることがより好ましい。上記範囲とすることにより、触媒の製造時のシンタリングを抑制しつつ、触媒活性や耐毒性を向上させることができる。すなわち、粒径が小さすぎると、細孔容積が小さくなり、触媒活性の低下や耐毒性の低下をもたらす場合がある。また、粒径が大きすぎると、担体粒子の質量当たりの比表面積が小さくなるためシンタリングを起こしやすく、その結果、触媒が十分な活性を発揮しない場合がある。 The particle size of the carrier is not limited, but the median size is preferably in the range of 0.5 to 500 μm, more preferably in the range of 5 to 500 μm. By setting the content within the above range, it is possible to improve catalytic activity and toxicity resistance while suppressing sintering during the production of the catalyst. That is, if the particle size is too small, the pore volume becomes small, which may lead to a decrease in catalytic activity and a decrease in toxicity resistance. On the other hand, if the particle size is too large, the specific surface area per mass of the carrier particles becomes small, and sintering tends to occur, and as a result, the catalyst may not exhibit sufficient activity.
　カーボン担体の形状は、成型されている限り限定されないが、球状や円柱状、ペレット状でもよい。なかでも、球状が好ましい。このようなカーボン担体としては、上記のようにして製造されるものの他に、市販品であってもよい。市販品としては、例えば、株式会社クレハより販売されている、活性炭ビーズ（ＢＡＣ－ＭＰ、平均粒子径５００μｍ、比表面積値１２００ｍ２／ｇ、球状）が挙げられる。 The shape of the carbon support is not limited as long as it is shaped, and may be spherical, cylindrical, or pellet. Among them, a spherical shape is preferable. Such a carbon carrier may be a commercially available product in addition to the one produced as described above. Examples of commercially available products include activated carbon beads (BAC-MP, average particle diameter 500 μm, specific surface area value 1200 m 2 /g, spherical shape) sold by Kureha Corporation.
　パラジウムを担体に担持させる方法は、限定されるものではないが、例えば、パラジウム化合物を溶媒に溶解し、当該溶液中に担体を投入し、パラジウム化合物を吸着または含浸させることにより行うことができる。パラジウム化合物として、塩化パラジウム酸などの水溶性パラジウム化合物を用いる場合、水を溶媒として用いることができる。また、パラジウム化合物として、ビス（２，４－ペンタンジオナト）パラジウムなど非水溶性パラジウム化合物を用いる場合、当該パラジウム化合物を溶解する有機溶媒を溶媒として用いることができる。 The method for supporting palladium on a carrier is not limited, but can be carried out, for example, by dissolving a palladium compound in a solvent, introducing the carrier into the solution, and adsorbing or impregnating the palladium compound. When a water-soluble palladium compound such as chloropalladium acid is used as the palladium compound, water can be used as a solvent. When a water-insoluble palladium compound such as bis(2,4-pentanedionato)palladium is used as the palladium compound, an organic solvent that dissolves the palladium compound can be used as the solvent.
　なお、パラジウムを担持させたパラジウム担体としては、市販品を用いてもよい。このような市販品としては、例えば、「５重量％　Ｐｄ／Ｃ触媒　Ｋタイプ」（エヌ・イーケムキャット社製）が挙げられる。 A commercial product may be used as the palladium carrier on which palladium is supported. Examples of such commercial products include "5% by weight Pd/C catalyst K type" (manufactured by N E Chemcat).
　パラジウム上に銅を担持させる方法は、特に限定されるものではないが、例えば、パラジウムを担持させたカーボンを含む溶液に、銅化合物を投入し、銅化合物をパラジウムに担持させることにより行うことができる。パラジウム上に銅を担持させた後、必要に応じて還元処理を実施してもよい。湿式で還元する場合には、メタノール、ホルムアルデヒド、蟻酸などの還元剤のほか、ガス状水素を用いることもできる。乾式で還元する場合にはガス状水素を用いて行うが、水素ガスを窒素等の不活性ガスで希釈して使用することも可能である。 The method for supporting copper on palladium is not particularly limited. For example, a copper compound is added to a solution containing carbon on which palladium is supported, and the copper compound is supported on palladium. can. After supporting copper on palladium, reduction treatment may be performed as necessary. In the case of wet reduction, gaseous hydrogen can be used in addition to reducing agents such as methanol, formaldehyde and formic acid. In the case of dry reduction, gaseous hydrogen is used, but it is also possible to dilute hydrogen gas with an inert gas such as nitrogen and use it.
　銅化合物としては、例えば、ギ酸銅、酢酸銅、プロピオン酸銅、酪酸銅、吉草酸銅、カプロン酸銅、エナント酸銅、カプリル酸銅、ペラルゴン酸銅、カプリン酸銅、ウンデシル酸銅、ラウリン酸銅、トリデシル酸銅、ミリスチン酸銅、ペンタデシル酸銅、パルミチン酸銅、マルガリン酸銅、ステアリン酸銅、ノナデシル酸銅、アラキジン酸銅、ヘンイコシル酸銅、ベヘン酸銅、トリコシル酸銅、リグノセリン酸銅、セロチン酸銅、モンタン酸銅、メリシン酸銅、安息香酸銅、シュウ酸銅、マロン酸銅、コハク酸銅、テレフタル酸銅、イソフタル酸銅、フタル酸銅、サリチル酸銅、クエン酸銅、酒石酸銅等の有機銅塩；硫酸銅、炭酸銅、硝酸銅等の無機銅塩；ヨウ化銅、臭化銅、塩化銅等の銅ハロゲン化物；水酸化銅等の銅水酸化物；酸化銅等の銅酸化物が挙げられる。
　これらの銅化合物の銅の価数は、１価、２価のいずれでも良く、２種以上の銅塩を併用しても良い。これらの銅塩は、水和物であっても良い。 Copper compounds include, for example, copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper caprate, copper undecylate, lauric acid Copper, copper tridecylate, copper myristate, copper pentadecylate, copper palmitate, copper margarate, copper stearate, copper nonadesylate, copper arachidate, copper heneicosylate, copper behenate, copper tricosylate, copper lignocerate, Copper cerrotate, copper montanate, copper melisinate, copper benzoate, copper oxalate, copper malonate, copper succinate, copper terephthalate, copper isophthalate, copper phthalate, copper salicylate, copper citrate, copper tartrate, etc. Inorganic copper salts such as copper sulfate, copper carbonate, and copper nitrate; Copper halides such as copper iodide, copper bromide, and copper chloride; Copper hydroxides such as copper hydroxide; Copper such as copper oxide oxides.
The valence of copper in these copper compounds may be either monovalent or divalent, and two or more copper salts may be used in combination. These copper salts may be hydrates.
　銅化合物としては、銅原子を含有するものであれば特に制限はないが、水や極性溶媒への溶解度が高いという観点から、例えば、ギ酸銅、酢酸銅、硝酸銅、塩化銅、硫酸銅などの二価の有機もしくは無機銅イオンの塩または水和塩が好ましい。 The copper compound is not particularly limited as long as it contains a copper atom, but from the viewpoint of high solubility in water and polar solvents, for example, copper formate, copper acetate, copper nitrate, copper chloride, copper sulfate, etc. Salts or hydrated salts of divalent organic or inorganic copper ions of are preferred.
　溶液としては、水、極性溶媒、非極性溶媒のいずれでもよいが、水または極性溶媒が好ましく、水がより好ましい。 The solution may be water, a polar solvent, or a non-polar solvent, but water or a polar solvent is preferable, and water is more preferable.
　銅の担持量は、限定されるものではないが、パラジウム１００質量％に対して、１０～２００質量％含むことが好ましく、１５～１５０質量％含むことがより好ましく、２０～１００質量％含むことがさらに好ましい。銅の担持量を上記範囲とすることで、官能基選択性を維持しながら、水素化反応の反応速度を向上させることができる。すなわち、銅の担持量が少なすぎると官能基選択性が低下し、一方、銅の担持量が過剰になるとパラジウムの活性点を銅がすべて覆ってしまい水素化反応が起きない場合がある。 The amount of copper supported is not limited, but it preferably contains 10 to 200% by mass, more preferably 15 to 150% by mass, and 20 to 100% by mass with respect to 100% by mass of palladium. is more preferred. By setting the supported amount of copper within the above range, it is possible to improve the reaction rate of the hydrogenation reaction while maintaining the functional group selectivity. That is, if the supported amount of copper is too small, the functional group selectivity will decrease. On the other hand, if the supported amount of copper is excessive, copper may cover all the active sites of palladium, preventing the hydrogenation reaction from occurring.
　銅およびパラジウムの担持量は、次のようにして算出することができる。まず、対象物を王水に浸し、金属を溶解する。次いで、王水から不溶成分であるカーボンを除去する。その後、カーボンを除いた王水をＩＣＰ発光分析により解析することにより、銅およびパラジウムの担持量を算出することができる。 The supported amounts of copper and palladium can be calculated as follows. First, the object is immersed in aqua regia to dissolve the metal. Next, carbon, which is an insoluble component, is removed from the aqua regia. Thereafter, by analyzing the aqua regia from which the carbon has been removed by ICP emission spectrometry, the supported amounts of copper and palladium can be calculated.
　水素化反応用触媒における銅とパラジウムの担持量は、銅化合物の投入量を調整することにより調整することができる。 The amount of copper and palladium supported on the hydrogenation reaction catalyst can be adjusted by adjusting the amount of the copper compound added.
　本開示の水素化反応用触媒の一実施形態において、水素化は、水素化反応により水素化される複数の官能基における、ニトロ基および／または不飽和炭化水素基の選択的水素化であることが好ましい。 In one embodiment of the hydrogenation reaction catalyst of the present disclosure, hydrogenation is selective hydrogenation of nitro groups and/or unsaturated hydrocarbon groups in a plurality of functional groups hydrogenated by the hydrogenation reaction. is preferred.
　「水素化反応により水素化される複数の官能基」とは、例えば、ニトロ基、不飽和炭化水素基、芳香族ケトン、芳香族塩素原子、ベンジル保護基、ニトリル基、ベンジル位水酸基が挙げられる。 "Multiple functional groups hydrogenated by hydrogenation reaction" include, for example, a nitro group, an unsaturated hydrocarbon group, an aromatic ketone, an aromatic chlorine atom, a benzyl protective group, a nitrile group, and a benzylic hydroxyl group. .
　「ニトロ基」とは、脂肪族炭化水素基に結合したニトロ基、芳香環に結合したニトロ基、または複素環に結合したニトロ基をいう。 "Nitro group" refers to a nitro group bonded to an aliphatic hydrocarbon group, a nitro group bonded to an aromatic ring, or a nitro group bonded to a heterocyclic ring.
　「不飽和炭化水素基」とは、炭素－炭素二重結合、または炭素－炭素三重結合をいう。 "Unsaturated hydrocarbon group" refers to a carbon-carbon double bond or a carbon-carbon triple bond.
　「芳香族塩素原子」とは、芳香環または複素環と連結する塩素原子をいう。 "Aromatic chlorine atom" refers to a chlorine atom connected to an aromatic or heterocyclic ring.
　「ベンジル保護基」とは、水酸基やカルボン酸基の保護基として使用されるベンジル基をいう。 "Benzyl protecting group" refers to a benzyl group used as a protecting group for a hydroxyl group or a carboxylic acid group.
　「ベンジル位水酸基」とは、芳香環または複素環と連結する炭素原子と結合する水酸基をいう。 "Benzyl-position hydroxyl group" refers to a hydroxyl group that binds to a carbon atom that connects to an aromatic or heterocyclic ring.
　本開示の水素化反応用触媒は、従来のＰｄ／Ｃ触媒では、官能基および／または不飽和結合を２以上有する被水素化有機化合物の前記官能基および／または不飽和結合の一部のみを水素化することが困難であった水素化反応において、官能基および／または不飽和結合を残しながら（即ち、非水素化部位を維持しながら）、官能基および／または不飽和結合の一部（即ち、水素化部位）を選択的に水素化することができる。 In the conventional Pd/C catalyst, the hydrogenation reaction catalyst of the present disclosure has only a part of the functional groups and/or unsaturated bonds of the organic compound to be hydrogenated, which has two or more functional groups and/or unsaturated bonds. In hydrogenation reactions that have been difficult to hydrogenate, functional groups and/or some of the unsaturated bonds ( That is, the hydrogenation site) can be selectively hydrogenated.
　「水素化反応により水素化される、官能基および／または不飽和結合」としては、例えば、前述の「水素化反応により水素化される複数の官能基」が挙げられる。 "Functional groups and/or unsaturated bonds that are hydrogenated by a hydrogenation reaction" include, for example, the aforementioned "multiple functional groups that are hydrogenated by a hydrogenation reaction".
　被水素化有機化合物の非水素化部位（水素化反応により水素化されない部位）としては、例えば、芳香族ケトン、芳香族塩素原子、ベンジル保護基、ニトリル基、ベンジル位水酸基が挙げられる。また、被水素化有機化合物の水素化部位としては、例えば、ニトロ基、不飽和炭化水素基が挙げられる。 Examples of non-hydrogenated sites (sites not hydrogenated by the hydrogenation reaction) of the organic compound to be hydrogenated include aromatic ketones, aromatic chlorine atoms, benzyl protective groups, nitrile groups, and benzylic hydroxyl groups. Examples of the hydrogenation site of the organic compound to be hydrogenated include a nitro group and an unsaturated hydrocarbon group.
［水素化反応用触媒の製造方法］
　上記した水素化反応用触媒は、Ｐｄ／Ｃを銅塩溶液に接触させ、昇温して撹拌した後、洗浄することで製造することができる。Ｐｄ／Ｃを銅塩溶液に接触させる方法としては、前述のとおりである。 [Method for producing catalyst for hydrogenation reaction]
The hydrogenation reaction catalyst described above can be produced by bringing Pd/C into contact with a copper salt solution, raising the temperature and stirring, and then washing. The method of bringing Pd/C into contact with the copper salt solution is as described above.
　昇温温度は、銅化合物を溶解できる限り限定されるものではないが、２５～１００℃が好ましく、３５～９０℃がより好ましく、５０～８０℃がさらに好ましい。撹拌時間は、パラジウムに銅を担持できる限り限定されるものではないが、５～６０分が好ましく、１０～５０分がより好ましく、２０～４０分がさらに好ましい。 The elevated temperature is not limited as long as the copper compound can be dissolved, but is preferably 25 to 100°C, more preferably 35 to 90°C, and even more preferably 50 to 80°C. The stirring time is not limited as long as copper can be supported on palladium, but is preferably 5 to 60 minutes, more preferably 10 to 50 minutes, and even more preferably 20 to 40 minutes.
　パラジウム上に銅を担持させた後、必要に応じて還元処理を実施してもよい。湿式で還元する場合には、メタノール、ホルムアルデヒド、蟻酸などの還元剤のほか、ガス状水素を用いることもできる。乾式で還元する場合にはガス状水素を用いて行うが、水素ガスを窒素等の不活性ガスで希釈して使用することも可能である。 After copper is supported on palladium, reduction treatment may be performed as necessary. In the case of wet reduction, gaseous hydrogen can be used in addition to reducing agents such as methanol, formaldehyde and formic acid. In the case of dry reduction, gaseous hydrogen is used, but it is also possible to dilute hydrogen gas with an inert gas such as nitrogen and use it.
　洗浄は、限定されるものではないが、例えば、撹拌した溶液を濾別し、濾物に溶媒をかけることで行うことができる。洗浄に用いる溶媒は、０℃～２５℃程度で、１～３回実施することが好ましい。 Washing is not limited, but can be performed, for example, by filtering the stirred solution and applying a solvent to the filtrate. The solvent used for washing is preferably about 0° C. to 25° C., and washing is preferably performed 1 to 3 times.
　本開示の水素化反応用触媒の製造方法は、洗浄した後、還元下で焼結することを実質的に含まないことが好ましい。なお、本開示において「焼結」とは、洗浄物を、銅とパラジウムとが合金化する温度下に置くことをいい、例えば、１ａｔｍで、７００～１０００℃にすることをいうものとする。したがって、銅とパラジウムが合金化しない限り、例えば、乾燥のために加温してもよい。 The method for producing a hydrogenation reaction catalyst of the present disclosure preferably does not substantially include sintering under reduction after washing. In the present disclosure, "sintering" refers to subjecting the washed material to a temperature at which copper and palladium are alloyed, for example, 700 to 1000° C. at 1 atm. Thus, as long as the copper and palladium do not alloy, for example, they may be heated for drying.
［水素化有機化合物の製造方法］
　本開示の水素化反応用触媒を用いることにより、官能基および／または不飽和結合を少なくとも２以上有する被水素化有機化合物を、官能基および／または不飽和結合の少なくとも１つを維持したまま、官能基および／または不飽和結合の一部を選択的に水素化することができる。すなわち、官能基および／または不飽和結合を２種以上有する被水素化有機化合物の水素化反応を、本開示の水素化反応用触媒の存在下で実施することにより、官能基および／または不飽和結合の少なくとも１つを維持したまま（即ち、非水素化部位を残しながら）、官能基および／または不飽和結合の一部（即ち、水素化部位）を選択的に水素化することができる。
　選択的に水素化される官能基および／または不飽和結合としては、前述の通り、ニトロ基、不飽和炭化水素基が挙げられる。 [Method for producing hydrogenated organic compound]
By using the hydrogenation reaction catalyst of the present disclosure, an organic compound to be hydrogenated having at least two or more functional groups and/or unsaturated bonds, while maintaining at least one of the functional groups and/or unsaturated bonds, A portion of the functional groups and/or unsaturated bonds can be selectively hydrogenated. That is, by carrying out a hydrogenation reaction of an organic compound to be hydrogenated having two or more functional groups and/or unsaturated bonds in the presence of the hydrogenation reaction catalyst of the present disclosure, functional groups and/or unsaturated bonds A portion of the functional groups and/or unsaturated bonds (ie, hydrogenation sites) can be selectively hydrogenated while at least one of the bonds is maintained (ie, leaving unhydrogenated sites).
Functional groups and/or unsaturated bonds that are selectively hydrogenated include nitro groups and unsaturated hydrocarbon groups, as described above.
　したがって、本開示の水素化有機化合物の製造方法の一実施形態によれば、例えば、有機合成分野において、遺伝子導入剤の原料、医薬、農薬の中間体の他、インクジェットインキの画質の向上剤の原料、感光性高分子化合物原料などの機能性重合体の原料としての利用が検討されている芳香族ニトロ化合物の水素化により得られる種々の誘導体の合成方法として有用である。 Therefore, according to one embodiment of the method for producing a hydrogenated organic compound of the present disclosure, for example, in the field of organic synthesis, in addition to raw materials for gene introduction agents, intermediates for pharmaceuticals and agricultural chemicals, image quality improvers for inkjet inks It is useful as a method for synthesizing various derivatives obtained by hydrogenation of aromatic nitro compounds, which are being studied for use as raw materials for functional polymers such as raw materials for photosensitive polymer compounds.
　また、本開示の水素化反応用触媒は、パラジウム／銅をカーボン上に担持した触媒であるため、水素化反応終了後に、例えば、濾別することにより容易に回収することができ、洗浄、乾燥した後、再利用することができる。 In addition, since the hydrogenation reaction catalyst of the present disclosure is a catalyst in which palladium/copper is supported on carbon, it can be easily recovered by, for example, filtration after the completion of the hydrogenation reaction. After that, it can be reused.
　以下、実施例および比較例に基づいて本開示をより具体的に説明するが、本開示はその要旨を超えない限り、以下の実施例によって何ら限定されるものではない。すなわち、以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本開示の趣旨を逸脱しない限り、適宜変更することができる。また、下記の実施例中、特に記載がない限り、「％」は質量％を示すものとする。 Hereinafter, the present disclosure will be described more specifically based on examples and comparative examples, but the present disclosure is not limited by the following examples as long as it does not exceed the gist thereof. That is, materials, usage amounts, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present disclosure. Also, in the following examples, unless otherwise specified, "%" indicates % by mass.
　＜製造例１：パラジウム－銅／カーボン触媒の製造＞
　ビーカーに、純水と５％　Ｐｄ／Ｃ触媒　Ｋタイプ（エヌ・イーケムキャット社製）を入れて撹拌した。このビーカーに銅化合物を投入して溶解させた後、７０℃に昇温して、３０分撹拌した。これをデカンテーションで濾別した後、純水で洗浄した。得られた固体を８０℃で終夜乾燥し、パラジウムを５質量％、銅を３質量％含むＰｄ－Ｃｕ／Ｃ触媒を得た。 <Production Example 1: Production of palladium-copper/carbon catalyst>
Pure water and 5% Pd/C catalyst K type (manufactured by N E Chemcat) were placed in a beaker and stirred. After the copper compound was put into this beaker and dissolved, the temperature was raised to 70° C. and the mixture was stirred for 30 minutes. After filtering this by decantation, it wash|cleaned with the pure water. The obtained solid was dried at 80° C. overnight to obtain a Pd—Cu/C catalyst containing 5% by mass of palladium and 3% by mass of copper.
　＜製造例２、３：パラジウム－銅／カーボン触媒の製造＞
　表１に記載の触媒となるように、投入する銅化合物の量を調整し、製造例１と同様にしてＰｄ－Ｃｕ／Ｃ触媒を得た。 <Production Examples 2 and 3: Production of palladium-copper/carbon catalyst>
A Pd—Cu/C catalyst was obtained in the same manner as in Production Example 1 by adjusting the amount of the copper compound to be added so as to obtain the catalyst shown in Table 1.
　＜製造例４：パラジウム－ニッケル／カーボン触媒の製造＞
　銅化合物に代えて、銅イオンをニッケルイオンに変更したニッケル化合物を用い、表１に記載の触媒となるように、投入するニッケル化合物の量を調整したこと以外は製造例１と同様としてＰｄ－Ｎｉ／Ｃ触媒を得た。 <Production Example 4: Production of palladium-nickel/carbon catalyst>
Pd- A Ni/C catalyst was obtained.
　＜製造例５：パラジウム－コバルト／カーボン触媒の製造＞
　銅化合物に代えて、銅イオンをコバルトイオンに変更したコバルト化合物を用い、表１に記載の触媒となるように、投入するコバルト化合物の量を調整したこと以外は製造例１と同様としてＰｄ－Ｃｏ／Ｃ触媒を得た。 <Production Example 5: Production of palladium-cobalt/carbon catalyst>
A Pd- A Co/C catalyst was obtained.
　製造例１～５で製造した触媒の一覧を下記の表１に示す。 A list of the catalysts produced in Production Examples 1 to 5 is shown in Table 1 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　＜実施例１＞
　製造例１で製造した水素化反応用触媒（５％Ｐｄ－３％Ｃｕ／Ｃ）を用いて、下記式に示す水素化反応を行った。具体的には、ｐ－ニトロアセトフェノンを、酢酸エチル１ｍｌに溶解し、製造例１で製造した水素化反応用触媒（５％Ｐｄ－３％Ｃｕ／Ｃ）１０ｍｇを添加し、水素０．２ＭＰａの雰囲気下、６０℃で２時間水素化反応を行った。
　得られた反応物をＧＣ－ＭＳで分析し、その転化率および選択性を算出した。その結果を表２に示す。
　なお、下記反応式中のその他化合物（３）は、原料（１）および目的物（２）以外の化合物の混合物である。 <Example 1>
Using the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, a hydrogenation reaction represented by the following formula was carried out. Specifically, p-nitroacetophenone was dissolved in 1 ml of ethyl acetate, 10 mg of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1 was added, and hydrogen was dissolved at 0.2 MPa. A hydrogenation reaction was carried out at 60° C. for 2 hours in an atmosphere.
The obtained reaction product was analyzed by GC-MS, and its conversion and selectivity were calculated. Table 2 shows the results.
The other compound (3) in the reaction formula below is a mixture of compounds other than the starting material (1) and the target compound (2).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　＜実施例２～３＞
　製造例１で製造した水素化反応用触媒（５％Ｐｄ－３％Ｃｕ／Ｃ）の代わりに、製造例２、３で製造した水素化反応用触媒（５％Ｐｄ－１．５％Ｃｕ／Ｃ）、水素化反応用触媒（５％Ｐｄ－４．５％Ｃｕ／Ｃ）を用いたこと以外は、実施例１と同様にして水素化反応を行った。
　得られた反応物をＧＣ－ＭＳで分析し、その転化率および選択性を算出した。その結果を表２に示す。 <Examples 2-3>
Instead of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, the hydrogenation reaction catalyst produced in Production Examples 2 and 3 (5% Pd-1.5% Cu/ C) A hydrogenation reaction was carried out in the same manner as in Example 1, except that a hydrogenation reaction catalyst (5% Pd-4.5% Cu/C) was used.
The obtained reaction product was analyzed by GC-MS, and its conversion and selectivity were calculated. Table 2 shows the results.
　＜比較例１＞
　製造例１で製造した水素化反応用触媒（５％Ｐｄ－３％Ｃｕ／Ｃ）の代わりに、５％　Ｐｄ／Ｃ触媒　Ｋタイプ（エヌ・イーケムキャット社製）を用いたこと以外は、実施例１と同様にして水素化反応を行った。
　得られた反応物をＧＣ－ＭＳで分析し、その転化率および選択性（上記の（１）、（２）および（３）の各化合物の割合）を算出した。その結果を表２に示す。 <Comparative Example 1>
Instead of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, 5% Pd/C catalyst K type (manufactured by N E Chemcat) was used, except that A hydrogenation reaction was carried out in the same manner as in Example 1.
The obtained reaction product was analyzed by GC-MS, and its conversion rate and selectivity (percentage of each compound of (1), (2) and (3) above) were calculated. Table 2 shows the results.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表２からわかるとおり、本開示の水素化反応用触媒によれば、従来のパラジウムカーボン（Ｐｄ／Ｃ）触媒を用いた場合（比較例１）に対して、官能基および／または不飽和結合を複数有する被水素化有機化合物の一部の官能基および／または不飽和結合のみを選択的に水素化できることがわかる（実施例１～３）。また、パラジウムとカーボンとのモル比（Ｐｄ：Ｃｕ）が１：１～１：１．５であると、ニトロ基を特に選択的に水素化できることがわかる。 As can be seen from Table 2, according to the hydrogenation reaction catalyst of the present disclosure, functional groups and/or unsaturated bonds are added to the conventional palladium carbon (Pd/C) catalyst (Comparative Example 1). It can be seen that only some of the functional groups and/or unsaturated bonds of the multiple organic compounds to be hydrogenated can be selectively hydrogenated (Examples 1 to 3). It is also found that nitro groups can be hydrogenated particularly selectively when the molar ratio of palladium to carbon (Pd:Cu) is 1:1 to 1:1.5.
　＜実施例１、４～１３＞
　製造例１で製造した水素化反応用触媒（５％Ｐｄ－３％Ｃｕ／Ｃ）を用いて、下記式に示す水素化反応を行った。具体的には、表３に示す原料を、表３に示す溶媒１ｍｌに溶解し、製造例１で製造した水素化反応用触媒（５％Ｐｄ－３％Ｃｕ／Ｃ）１０ｍｇを添加し、水素０．２ＭＰａの雰囲気下、表３に示す反応温度、反応時間で水素化反応を行った。
　得られた反応物をＧＣ－ＭＳで分析し、その転化率および選択性を算出した。その結果を表３に示す。 <Examples 1, 4 to 13>
Using the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, a hydrogenation reaction represented by the following formula was carried out. Specifically, the raw materials shown in Table 3 are dissolved in 1 ml of the solvent shown in Table 3, 10 mg of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1 is added, and hydrogen A hydrogenation reaction was carried out at the reaction temperature and reaction time shown in Table 3 under an atmosphere of 0.2 MPa.
The obtained reaction product was analyzed by GC-MS, and its conversion and selectivity were calculated. Table 3 shows the results.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表３から、いずれの反応においても、原料化合物の官能基／二重結合のうち、ニトロ基または炭素－炭素二重結合が選択的に水素化されていることがわかる。一方で、芳香族ケトン、芳香族塩素原子、ベンジル保護基、およびニトリル基は水素化されずに維持されたままである。
　よって、本開示の水素化反応用触媒によれば、官能基および／または不飽和結合を少なくとも２以上有する被水素化有機化合物を、官能基および／または不飽和結合の少なくとも１つを維持したまま、官能基および／または不飽和結合の一部を選択的に水素化することができることがわかる。
　反応に用いた原料と目的物を以下に化学式で記載する。 From Table 3, it can be seen that the nitro group or the carbon-carbon double bond was selectively hydrogenated among the functional groups/double bonds of the raw material compounds in any reaction. On the other hand, aromatic ketones, aromatic chlorine atoms, benzyl protecting groups, and nitrile groups remain unhydrogenated.
Therefore, according to the hydrogenation reaction catalyst of the present disclosure, an organic compound to be hydrogenated having at least two functional groups and/or unsaturated bonds is treated while maintaining at least one of the functional groups and/or unsaturated bonds. , functional groups and/or some of the unsaturated bonds can be selectively hydrogenated.
Raw materials and target products used in the reaction are described below by chemical formulas.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　＜実施例６＞
　製造例１で製造した水素化反応用触媒（５％Ｐｄ－３％Ｃｕ／Ｃ）を用いて、下記反応式に示す水素化反応を行った。具体的には、ｏ－クロロニトロベンゼンを、酢酸エチル１ｍｌに溶解し、製造例１で製造した水素化反応用触媒（５％Ｐｄ－３％Ｃｕ／Ｃ）１０ｍｇを添加し、水素０．２ＭＰａの雰囲気下、６０℃で２時間水素化反応を行った。
　得られた反応物をＧＣ－ＭＳで分析し、その転化率および選択性を算出した。その結果を表４および表５に示す。なお、下記反応式中のその他化合物（３）は、原料（１）および目的物（２）以外の化合物の混合物である。 <Example 6>
Using the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, the hydrogenation reaction represented by the following reaction formula was carried out. Specifically, o-chloronitrobenzene is dissolved in 1 ml of ethyl acetate, 10 mg of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1 is added, and hydrogen is heated to 0.2 MPa. A hydrogenation reaction was carried out at 60° C. for 2 hours in an atmosphere.
The obtained reaction product was analyzed by GC-MS, and its conversion and selectivity were calculated. The results are shown in Tables 4 and 5. The other compound (3) in the reaction formula below is a mixture of compounds other than the starting material (1) and the target compound (2).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　＜試験例１～４＞
　実施例６で水素化反応を行った後、反応系から触媒をろ過・分離することにより触媒を回収した。回収した触媒を再度反応系に投入して、水素化反応に繰り返し使用した。具体的には、製造例１で製造した水素化反応用触媒（５％Ｐｄ－３％Ｃｕ／Ｃ）に代えて、回収した触媒を用いたこと、および反応時間を１時間に短縮したこと以外は、実施例６と同様にして水素化反応を１～４回繰り返し行った。
　１回目、２回目、３回目および４回目の水素化反応で得られた反応物をそれぞれＧＣ－ＭＳで分析し、その転化率および選択性を算出した。また、各水素化反応で回収した触媒をＩＣＰ－ＭＳ（Ａｇｉｌｅｎｔ社製）で分析して、溶媒に流出したパラジウムおよび銅の量を測定した。その結果を表４に示す。 <Test Examples 1 to 4>
After the hydrogenation reaction in Example 6, the catalyst was recovered by filtering and separating the catalyst from the reaction system. The recovered catalyst was put into the reaction system again and used repeatedly in the hydrogenation reaction. Specifically, instead of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, the recovered catalyst was used, and the reaction time was shortened to 1 hour. , the hydrogenation reaction was repeated 1 to 4 times in the same manner as in Example 6.
The reactants obtained in the first, second, third and fourth hydrogenation reactions were each analyzed by GC-MS, and their conversion and selectivity were calculated. In addition, the catalyst recovered from each hydrogenation reaction was analyzed by ICP-MS (manufactured by Agilent) to measure the amounts of palladium and copper that flowed out into the solvent. Table 4 shows the results.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　表４からわかるとおり、本開示の水素化反応用触媒によれば、パラジウムおよび銅の溶媒への流出がほとんどないと言える。また、本開示の水素化反応用触媒によれば、触媒を繰り返し使用しても、転化率および選択性に低下はみられない。よって、本開示の水素化反応用触媒は、触媒耐久性に優れるものといえる。 As can be seen from Table 4, according to the hydrogenation reaction catalyst of the present disclosure, it can be said that palladium and copper hardly flow out into the solvent. Further, according to the hydrogenation reaction catalyst of the present disclosure, even if the catalyst is repeatedly used, the conversion rate and selectivity do not decrease. Therefore, it can be said that the hydrogenation reaction catalyst of the present disclosure is excellent in catalyst durability.
　＜比較例２＞
　製造例１で製造した水素化反応用触媒（５％Ｐｄ－３％Ｃｕ／Ｃ）に代えて、５％　Ｐｄ／Ｃ　Ｋタイプ触媒（エヌ・イーケムキャット社製）を用いたこと以外は、実施例６と同様にして水素化反応を行った。
　得られた反応物をＧＣ－ＭＳで分析し、その転化率および選択性を算出した。その結果を表５に示す。 <Comparative Example 2>
Instead of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, except that a 5% Pd/CK type catalyst (manufactured by N E Chemcat) was used. A hydrogenation reaction was carried out in the same manner as in Example 6.
The obtained reaction product was analyzed by GC-MS, and its conversion and selectivity were calculated. Table 5 shows the results.
　＜比較例３＞
　製造例１で製造した水素化反応用触媒（５％Ｐｄ－３％Ｃｕ／Ｃ）に代えて、製造例４で製造した触媒（５％Ｐｄ－３．９％Ｎｉ／Ｃ）を用いたこと以外は、実施例６と同様にして水素化反応を行った。
　得られた反応物をＧＣ－ＭＳで分析し、その転化率および選択性を算出した。その結果を表５に示す。 <Comparative Example 3>
Instead of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, the catalyst (5% Pd-3.9% Ni/C) produced in Production Example 4 was used. A hydrogenation reaction was carried out in the same manner as in Example 6, except for this.
The obtained reaction product was analyzed by GC-MS, and its conversion and selectivity were calculated. Table 5 shows the results.
　＜比較例４＞
　製造例１で製造した水素化反応用触媒（５％Ｐｄ－３％Ｃｕ／Ｃ）に代えて、製造例５で製造した触媒（５％Ｐｄ－３．６％Ｃｏ／Ｃ）を用いたこと以外は、実施例６と同様にして水素化反応を行った。
　得られた反応物をＧＣ－ＭＳで分析し、その転化率および選択性を算出した。その結果を表５に示す。なお、表５中の選択性における１、２、３は、それぞれ前述の実施例６の反応式における（１）、（２）、（３）に対応する。 <Comparative Example 4>
Instead of the hydrogenation reaction catalyst (5% Pd-3% Cu/C) produced in Production Example 1, the catalyst (5% Pd-3.6% Co/C) produced in Production Example 5 was used. A hydrogenation reaction was carried out in the same manner as in Example 6, except for this.
The obtained reaction product was analyzed by GC-MS, and its conversion and selectivity were calculated. Table 5 shows the results. Note that 1, 2 and 3 in selectivity in Table 5 correspond to (1), (2) and (3) in the reaction formula of Example 6 above, respectively.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　表５からわかるとおり、Ｃｕ以外の金属をＰｄに担持させた触媒を用いた場合や、Ｃｕを担持させないＰｄ／Ｃ触媒を用いた場合には、選択的な水素化が困難であることがわかる。このことから、水素化反応における選択性の発現にはＣｕをＰｄに担持させることが必要であるとわかる。 As can be seen from Table 5, when using a catalyst in which Pd supports a metal other than Cu, or when using a Pd/C catalyst that does not support Cu, selective hydrogenation is difficult. . From this, it can be seen that it is necessary to support Cu on Pd for expression of selectivity in the hydrogenation reaction.

Claims (10)

  1. 　担体と、
    　前記担体上に担持されたパラジウムと、
    　前記パラジウム上に担持された銅と、を含んでなる、水素化反応用触媒。     a carrier;
    Palladium supported on the support;
    and copper supported on palladium.
  2. 　前記担体が、カーボンである、請求項１に記載の水素化反応用触媒。 The hydrogenation reaction catalyst according to claim 1, wherein the carrier is carbon.
  3. 　前記パラジウム１００質量％に対して、前記銅を１０～２００質量％含んでなる、請求項１に記載の水素化反応用触媒。 The hydrogenation reaction catalyst according to claim 1, comprising 10 to 200% by mass of said copper with respect to 100% by mass of said palladium.
  4. 　水素化が、水素化反応により水素化される複数の官能基において、ニトロ基および／または不飽和炭化水素基の選択的水素化である、請求項１に記載の水素化反応用触媒。 The hydrogenation catalyst according to claim 1, wherein the hydrogenation is selective hydrogenation of nitro groups and/or unsaturated hydrocarbon groups in a plurality of functional groups hydrogenated by the hydrogenation reaction.
  5. 　官能基および／または不飽和結合を２以上有する被水素化有機化合物の前記官能基および／または不飽和結合の一部を選択的に水素化して、水素化部位と非水素化部位とを有する水素化有機化合物を得ることができる、請求項１に記載の水素化反応用触媒。 Selectively hydrogenating a portion of the functional groups and/or unsaturated bonds of an organic compound to be hydrogenated having two or more functional groups and/or unsaturated bonds to produce hydrogen having hydrogenated sites and non-hydrogenated sites 2. The hydrogenation reaction catalyst according to claim 1, which is capable of obtaining a hydrogenated organic compound.
  6. 　前記水素化部位が、ニトロ基および／または不飽和炭化水素基を含む、請求項５に記載の水素化反応用触媒。 The hydrogenation reaction catalyst according to claim 5, wherein the hydrogenation site contains a nitro group and/or an unsaturated hydrocarbon group.
  7. 　前記非水素化部位が、芳香族ケトン、芳香族塩素原子、ベンジル保護基、ニトリル基、およびベンジル位水酸基からなる群から選択される少なくとも１種を含む、請求項５に記載の水素化反応用触媒。 6. The hydrogenation reaction according to claim 5, wherein the non-hydrogenation site contains at least one selected from the group consisting of aromatic ketones, aromatic chlorine atoms, benzyl protecting groups, nitrile groups, and benzylic hydroxyl groups. catalyst.
  8. 　請求項１に記載の水素化反応用触媒の製造方法であって、
    　Ｐｄ／Ｃを銅塩溶液に接触させ、昇温して撹拌した後、洗浄すること、を含む、製造方法。     A method for producing a hydrogenation reaction catalyst according to claim 1,
    A process comprising contacting Pd/C with a copper salt solution, heating and stirring, and then washing.
  9. 　洗浄した後、還元下で焼結することを実質的に含まない、請求項８に記載の製造方法。 The manufacturing method according to claim 8, which does not substantially include sintering under reduction after washing.
  10. 　官能基および／または不飽和結合を２以上有する被水素化有機化合物から、前記官能基および／または不飽和結合の一部を選択的に水素化して、水素化部位と非水素化部位とを有する水素化有機化合物を製造する方法であって、
    　前記水素化反応を、請求項１に記載の水素化反応用触媒の存在下で実施する、方法。     Selectively hydrogenating a portion of the functional groups and/or unsaturated bonds from an organic compound to be hydrogenated having two or more functional groups and/or unsaturated bonds to have hydrogenated sites and non-hydrogenated sites A method for producing a hydrogenated organic compound, comprising:
    A method, wherein the hydrogenation reaction is carried out in the presence of the hydrogenation reaction catalyst according to claim 1 .
PCT/JP2023/003674 2022-02-04 2023-02-03 Catalyst for hydrogenation reactions, method for producing same and method for producing hydrogenated organic compound WO2023149559A1 (en)

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JPH04288028A (en) * 1990-11-06 1992-10-13 Elf Atochem Sa Preparation of fluoroethylene and chlorofluoroethylene
WO1993025510A1 (en) * 1992-06-05 1993-12-23 Daikin Industries, Ltd. Processes for producing 1,1,1,2,3-pentafluoropropene and producing 1,1,1,2,3-pentafluoropropane
US20120111802A1 (en) * 2009-05-05 2012-05-10 Technion Research And Development Foundation Ltd. Activated carbon cloth-supported bimetallic pd-cu catalysts for nitrate removal from water
US20170342019A1 (en) * 2013-09-04 2017-11-30 Taminco Bvba Process for the reductive amination and selective hydrogenation of substrates containing a selected halogen

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62149635A (en) * 1985-12-24 1987-07-03 Mitsubishi Petrochem Co Ltd Purification of styrene-containing material by selective hydrogenation
JPH04288028A (en) * 1990-11-06 1992-10-13 Elf Atochem Sa Preparation of fluoroethylene and chlorofluoroethylene
WO1993025510A1 (en) * 1992-06-05 1993-12-23 Daikin Industries, Ltd. Processes for producing 1,1,1,2,3-pentafluoropropene and producing 1,1,1,2,3-pentafluoropropane
US20120111802A1 (en) * 2009-05-05 2012-05-10 Technion Research And Development Foundation Ltd. Activated carbon cloth-supported bimetallic pd-cu catalysts for nitrate removal from water
US20170342019A1 (en) * 2013-09-04 2017-11-30 Taminco Bvba Process for the reductive amination and selective hydrogenation of substrates containing a selected halogen

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