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WO2008056768A1 - Catalyseur de métaux porteur de composites carbone/éthylénédiamine et son procédé de production - Google Patents

Catalyseur de métaux porteur de composites carbone/éthylénédiamine et son procédé de production Download PDF

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Publication number
WO2008056768A1
WO2008056768A1 PCT/JP2007/071788 JP2007071788W WO2008056768A1 WO 2008056768 A1 WO2008056768 A1 WO 2008056768A1 JP 2007071788 W JP2007071788 W JP 2007071788W WO 2008056768 A1 WO2008056768 A1 WO 2008056768A1
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Prior art keywords
group
ethylenediamine
catalyst
carbon
platinum
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PCT/JP2007/071788
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English (en)
Japanese (ja)
Inventor
Mutsumi Sato
Keiji Oono
Hironao Sajiki
Tomohiro Maegawa
Yasunari Monguchi
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Fujifilm Wako Pure Chemical Corp
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Wako Pure Chemical Industries Ltd
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Priority to JP2008543137A priority Critical patent/JP5212109B2/ja
Publication of WO2008056768A1 publication Critical patent/WO2008056768A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C227/04—Formation of amino groups in compounds containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
    • C07C239/08—Hydroxylamino compounds or their ethers or esters
    • C07C239/10—Hydroxylamino compounds or their ethers or esters having nitrogen atoms of hydroxylamino groups further bound to carbon atoms of unsubstituted hydrocarbon radicals or of hydrocarbon radicals substituted by halogen atoms or by nitro or nitroso groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/825—Osmium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/828—Platinum

Definitions

  • the present invention relates to a composite of a metal catalyst supported on carbon (metal catalyst-supported carbon) and ethylenediamine (metal catalyst-supported carbon / ethylenediamine complex) and a method for producing the same.
  • platinum catalyst-supporting compounds are known as platinum catalysts useful as reduction catalysts as described in WO 2004/072019. Since the platinum catalyst has a strong reducing power, for example, when a selective reduction reaction of nitrobenzene to phenylhydroxylamine is performed, a poisoning agent such as dimethylsulfoxide (DMSO) is used. It was considered preferable. Therefore, the post-reaction operation is complicated, for example, it is necessary to remove the poisoning agent after completion of the reaction. For this reason, it has been desired to develop a platinum catalyst that can be easily post-treated and can perform a selective reduction reaction.
  • DMSO dimethylsulfoxide
  • Osmium is a power that is widely used as an oxidation catalyst with a strong oxidizing action, but it is also useful as a reducing agent.
  • US Pat. No. 3,557,223 describes a method in which an alcohol compound is obtained by subjecting a carbonyl group-containing compound to a reduction reaction using a catalyst in which zero-valent osmium is supported on activated carbon as a catalyst.
  • osmium is useful as a reduction catalyst, and can be selectively reduced by being supported on an appropriate carrier such as activated carbon.
  • the activated carbon is supported on activated carbon as described in the document, since the activated carbon is a fine powder, the area where the osmium contacts with the reaction solvent is widened, and the catalyst has high reaction efficiency.
  • the osmium catalyst supported on the activated carbon has a problem in use such that there is a risk of ignition when left in a dry state. Therefore, the development of a catalyst supporting osmium that has high reaction efficiency and can be used safely has been desired.
  • Patent Literature l WO2004 / 072019
  • Patent Document 2 US Pat. No. 3,557,223
  • Non-Patent Document 1 Organic Square No.12 March 2004
  • the present invention provides a metal catalyst-supported carbon-ethylenediamine complex that can safely produce a metal-catalyst-supported carbon-ethylenediamine complex, which is different from the conventional method that has a risk of ignition. And a novel platinum-supported carbon-ethylenediamine complex (catalyst) and osmium-supported carbon ethylenediamine complex (catalyst) having excellent functions among those that can be efficiently obtained by such a manufacturing method. The issue is to provide.
  • the present inventors first aimed to reduce the risk of ignition. Specifically, an attempt was made to produce a metal catalyst-supported carbon ethylenediamine complex by reacting metal catalyst-supported carbon with ethylenediamine using an organic solvent that is difficult to ignite, such as black mouth form, as a solvent, but high reaction efficiency was not obtained. In addition, there were problems such as environmental pollution and it was not practical.
  • the solvent used is an organic solvent that easily dissolves the hydrophobic substance in order to increase the yield of the product.
  • water is not considered to be preferable as a solvent, and it has been thought that the use of water causes problems such as low product yield.
  • water is used as a solvent, water remains in the produced metal catalyst-supported carbon ethylenediamine complex, and when this is used as a catalyst for an oxidation reaction or a reduction reaction, catalytic activity is increased due to the presence of water. There were also concerns about a decline, increased by-product calorie, and substrate degradation.
  • the use of water as a solvent in the reaction between the metal catalyst-supporting carbon and ethylenediamine was avoided.
  • the present inventors have conducted intensive research, and even when water or a mixed solution of water and a water-soluble organic solvent is used as a solvent, the yield of a product resulting from the reaction of metal catalyst-supported carbon and ethylenediamine is higher than that of the conventional method. It is found that the method using water or a mixture of water and a water-soluble organic solvent is a method for producing an excellent metal catalyst-supported carbon ethylenediamine complex with a low risk of ignition.
  • the present invention has been completed.
  • the present inventors have also found that the metal catalyst-supported carbon ethylenediamine complex produced by this method has the same activity as that produced by the conventional method. Furthermore, as described above, by reacting metal catalyst-supported carbon with ethylenediamine using water or water and a water-soluble organic solvent as a solvent, a reaction with higher reaction efficiency than the conventional method becomes possible, and the amount of ethylenediamine used can be reduced. It has been found that a metal catalyst-supported carbon ethylenediamine complex can be obtained by reducing the reaction time.
  • the present inventors have made it possible to perform a reduction reaction without using a poisoning agent by using a platinum-supported carbon ethylenediamine complex. It was also found that the composite can be used repeatedly as a catalyst. In addition, the inventors have also disclosed the platinum-supported carbon ethylenediamine complex.
  • a nitro group can be selectively reduced to a hydroxyamino group to produce a hydroxylamine compound, and the platinum-supported carbon ethylenediamine It was also found that by using a complex as a catalyst and reacting a nitroaromatic compound having an unsaturated hydrocarbon group with hydrogen, only the nitro group can be selectively reduced without reducing the unsaturated hydrocarbon group. .
  • the present inventors have used an osmium-carrying carbon with ethylenediamine to form an osmium-carrying carbon ethylenediamine complex, which can be used without risk of ignition in a dry state, which has been a problem in the past. I found out that I can do it.
  • the inventors have also found that a carbonyl group in a compound having a double bond and a carbonyl group can be selectively reduced by using the osmium-supported carbon / ethylenediamine complex as a catalyst, thereby completing the present invention. It was.
  • the present invention specifically includes
  • a process for producing a metal catalyst-supported carbon ethylenediamine complex characterized by reacting metal catalyst-supported carbon and ethylenediamine in water or a mixed solution of water and a water-soluble organic solvent,
  • a method for producing an amino hydrocarbon compound having an unsaturated hydrocarbon group comprising reacting a nitro aromatic compound having an unsaturated hydrocarbon group with hydrogen in the presence of the platinum catalyst,
  • An osmium-carrying carbon ethylenediamine complex composed of osmium-carrying carbon and ethylenediamine.
  • the present invention relates to a method for selective reduction of a carbonyl group in a carbonyl compound.
  • the method for producing a metal catalyst-supported carbon ethylenediamine complex according to the present invention is capable of safely obtaining the target product with less risk of ignition and the like because the ethylenediamine complex reaction proceeds in water. . Furthermore, when the method of the present invention is used, the reaction proceeds with high efficiency, so that the target product can be obtained in a short time using a small amount of ethylenediamine. That is, according to the production method of the present invention, the target product can be efficiently obtained even if the reaction time is shortened compared to the conventional method.
  • the platinum-supported carbon ethylenediamine complex of the present invention when used as a catalyst, a selective reduction reaction can be performed without using a poisoning agent, so that the target product can be obtained by a post-treatment operation simpler than conventional methods. it can. Furthermore, the platinum-supported carbon ethylenediamine complex of the present invention can selectively reduce the nitro group of a nitro compound to hydroxylamine, and only the nitro group of a nitroaromatic compound having an unsaturated hydrocarbon group. Allows selective reduction. Furthermore, the osmium-supported carbon ethylenediamine complex of the present invention is safe and has a low risk of ignition, and can be used as an excellent catalyst that enables highly efficient reduction.
  • the method for producing the metal catalyst-supported carbon ethylenediamine complex of the present invention comprises the steps of: metal catalyst-supported carbon and ethylenediamine. It is made by reacting in water or a mixed solution of water and a water-soluble organic solvent.
  • the metal catalyst-supported carbon in the production method of the present invention is not particularly limited as long as the metal catalyst is supported on carbon.
  • the loading method may be based on physical bonding or chemical bonding, but the physical bonding method is particularly preferred, even though the physical bonding method is preferred. preferable.
  • the metal catalyst-supported carbon can be obtained by a method known per se, for example, by reacting the metal catalyst and the supported carbon with stirring in a solution in which the metal catalyst is dissolved. You may use things. In addition, what is carbon here is what is usually used in this field. Although activated carbon is preferred, activated carbon having micropores ⁇ to ⁇ A is preferred.
  • the metal catalyst for example, platinum, osmium, palladium, nickel, ruthenium, rhodium, iridium, gold, rhenium and the like are preferable. Among them, platinum, osmium, or palladium is preferable, and palladium is preferable.
  • the amount of the metal catalyst in the metal catalyst-supporting carbon is usually 0.1 to 20% by weight, preferably 1 to 20% by weight, more preferably 1 to 10% by weight. Further, the solution for dissolving the above metal catalyst is different from the preferred one depending on the metal used.
  • acidic solutions such as hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, acetic acid, caustic soda, potassium hydroxide
  • basic solutions such as barium hydroxide, calcium hydroxide, pyridine, and triethylamine
  • organic solvents such as acetone, methanol, ethanol, THF, chloroform, and ethyl acetate.
  • Examples of the water-soluble organic solvent in the method for producing a metal catalyst-supported C (en) composite of the present invention include methanol, ethanol, propanol, acetone, acetonitrile, tetrahydrofuran, and the like, such as methanol, ethanol, propanol, and the like. Lower alkyl alcohols are preferred, with methanol being particularly preferred.
  • the ratio of water in the mixed solution is usually 3% or more and less than 100%, preferably 5% or more and less than 100%.
  • water or a mixture of water and a water-soluble organic solvent can be used. Is preferred.
  • the reaction time between the metal catalyst-carrying carbon and ethylenediamine is usually;! To 100 hours, preferably 1 to 50 hours, more preferably. ! ⁇ 10 hours, more preferably 1-5 hours, and the reaction temperature is usually 5-70 ° C, preferably 5-40 ° C.
  • the pressure is usually normal pressure to lMpa, preferably normal pressure to 0.3 Mpa.
  • the reaction is preferably performed in a nitrogen atmosphere.
  • the amount of ethylenediamine used in this case is usually 1 to 200 mol, preferably 1 to 80 mol, more preferably;! To lOmol, relative to 1 mol of the metal catalyst in the metal catalyst-supported carbon.
  • the method for producing the metal catalyst-supported C (en) composite of the present invention is specifically as follows.
  • metal catalyst-supporting carbon containing 1 mol of the above metal catalyst and ethylenediamine usually 1 ⁇ 200 mol, preferably 1-80 mol, more preferably 1-10 mol, usually 1-50 hours, preferably;! -10 hours, more preferably 1-5 hours, usually 5-70 ° C, above It can be obtained by reacting in a water-soluble organic solvent or a mixed solution of water and a water-soluble organic solvent, if necessary, in an inert gas atmosphere such as nitrogen gas or argon gas.
  • the metal catalyst support C (en) of the present invention obtained as described above does not contain water. Therefore, it is desirable to further filter the target product and dry it.
  • the drying method in this case may be a method usually used in this field, and is usually 10 to 80 ° C, preferably 20 to 60 ° C, usually 100 Pa to 0.1 MPa, preferably 200 to 3000 Pa. Good! /
  • palladium-containing carbon containing 1 mol of palladium and ethylenediamine usually 1 to 200 mol, preferably 1 to 80 mol, more preferably 1 to 10 mol, water or methanol containing 3% or more and less than 100% water
  • a radium-supported carbon ethylenediamine complex By reacting at room temperature for 1 to 50 hours, preferably 1 to 10 hours, more preferably 1 to 5 hours in a medium nitrogen atmosphere, it is possible to obtain a radium-supported carbon ethylenediamine complex.
  • the obtained palladium-supported carbon ethylenediamine complex may be collected by filtration and dried at 200 to 3000 Pa and 10 to 80 ° C., if necessary.
  • the platinum-supported carbon ethylenediamine complex of the present invention (hereinafter sometimes abbreviated as the Pt / C (en) complex of the present invention) is formed from platinum-supported carbon and ethylenediamine.
  • the platinum-supported carbon according to the present invention is not particularly limited as long as platinum is supported on the carbon, and the support method may be based on physical bonding or chemical bonding. However, the method based on physical bonding by adsorption is particularly preferable, while the method based on physical bonding is preferable.
  • the platinum-supported carbon may be a commercially available one, or may be one obtained by a method known per se, for example, a reaction with stirring in a solution in which a metal catalyst is dissolved.
  • the carbon used here may be any carbon as long as it is usually used in this field, but activated carbon having fine pores of ⁇ to ⁇ is preferable among activated carbon.
  • platinum is not particularly limited as long as it is usually used in this field, but is usually 0 to 6, most preferably 0, 2, or 4 is preferable. Particularly preferred. Specifically, platinum oxide, platinum chloride, platinum bromide, platinum fluoride, ammonium hexachloroplatinum ammonium, tetrachloroplatinic acid ammonium, hexachloro potassium platinum, tetrachloroplatinic acid, tetrabromoplatinic acid Potassium, sodium hexachloroplatinate, sodium tetrachloroplatinate, platinum nitrate, platinum sulfate, platinum acetate Powers that are derived from platinum oxide, platinum chloride, hexachloroplatinum potassium Those derived from platinum chloride are particularly preferred.
  • the amount of platinum in the platinum-supported carbon according to the present invention is usually 0.1 to 20% by weight, preferably 1 to 20% by weight, more preferably 1 to 10% by weight.
  • the solution for dissolving the above metal catalyst has different power depending on the platinum used or the one from which the platinum is derived. For example, when platinum derived from platinum oxide, platinum chloride or potassium hexachloroplatinate is used, hydrochloric acid, sulfuric acid, nitrate excess Examples include acidic solutions such as chloric acid and acetic acid, with hydrochloric acid being preferred!
  • the amount of platinum in the Pt / C (en) of the present invention is usually 0.1 to 20% by weight, preferably as long as Pt / C (en) has a catalytic ability of platinum. Is 1 to 20% by weight, more preferably 1 to 10% by weight.
  • platinum-supported carbon and ethylenediamine are reacted in water or a mixed solution of water and a water-soluble organic solvent in the same manner as in the production method of the present invention. It is preferable to do so.
  • platinum-containing carbon containing 1 mol of platinum and ethylenediamine 1 to 200 mol, preferably 1 to 80 mol, more preferably;!
  • the platinum catalyst of the present invention contains the above-described Pt / C (en) of the present invention as a catalyst, and performs selective reduction without the coexistence of a poisoning agent such as dimethyl sulfoxide (DMSO). It is possible. In other words, if the catalyst is used in a selective reduction reaction, since the poisoning agent is not used, the step of removing the poisoning agent can also be reduced by the reaction solution force, and the target product obtained by the reduction reaction can be reduced by a simple operation method. Obtainable.
  • the platinum catalyst of the present invention used for the reaction can be repeatedly used as a catalyst for various reactions without reducing its activity if it is isolated from the reaction solution after completion of the reaction. Furthermore, in the platinum catalyst, platinum is supported on carbon, which is fine particles (fine powder), so that the area of platinum in contact with the reaction solution is increased, and as a result, high reaction efficiency is achieved.
  • the method for producing the hydroxylamine compound of the present invention is performed by reacting a nitro compound with hydrazines in the presence of the platinum catalyst of the present invention.
  • Examples of the nitro compound in the method for producing a hydroxylamine compound of the present invention include a compound represented by the general formula [1]
  • R may contain a hydrogen atom or a hetero atom and has a substituent.
  • And may represent an alkyl group, an aryl group or an aralkyl group.
  • the alkyl group represented by R is linear, branched, or
  • the number of carbon atoms which may be cyclic;! To 40, preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6, includes, for example, a methyl group or an ethyl group.
  • the aryl group represented by R includes those having usually 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms.
  • Specific examples include a phenyl group, a naphthyl group, and an anthryl group.
  • Examples of the aralkyl group represented by R include those usually having 7 to 10 carbon atoms.
  • Examples thereof include a benzyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, and the like.
  • ⁇ -10 preferably 1-3, more preferably 1 heteroatom.
  • hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom, and these include, for example, NH O S—, —NHR (in the formula, R
  • 5 5 represents an alkyl group, an aryl group or an aralkyl group.
  • the kill group is an alkyl group, aryl group or aralkyl group represented by R in the general formula [1].
  • the alkyl group represented by R is usually;! -10, preferably 1-5, more preferably May have 1 to 3 substituents.
  • substituents include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, a pentyloxy group, a hexyloxy group and the like;! -6 to alkoxy groups such as a chlorine atom, bromine atom, fluorine atom, iodine Halogen atoms such as atoms, hydroxyl groups, amino groups and the like can be mentioned.
  • the aryl group and aralkyl group represented by R are usually;! -10, preferably 1-5,
  • substituents include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec_butinole group, a tert-butinole group, an n-pentinole group, and an isopentinole group.
  • R is an aryl group
  • nitrobenzene derivatives such as nitrobenzene, nitrotonolene and nitroxylene are preferred, and nitrobenzene is particularly preferred.
  • hydrazine is preferred among hydrazine, methyl hydrazine, ethyl hydrazine, tert-butyl hydrazine, aryl hydrazine, phenyl hydrazine and the like.
  • the amount used is 1 to 100 moles, preferably 1 to 50 moles, more preferably 1 to 10 moles per mole of the nitroaromatic compound having an unsaturated hydrocarbon group.
  • the hydrazines may be used as they are in the method of the present invention, but may be used after being dissolved in water so that the concentration of hydrazines is usually 10 to 100% by weight, preferably 50 to 100% by weight. preferable. In addition, In this case, an amount is appropriately selected so that the weight excluding water is within the above range.
  • a reaction solvent is appropriately used as necessary when the nitro compound and / hydrazine are not liquid.
  • the reaction solvent include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, and t-butanol, ether solvents such as jet ether, tetrahydrofuran, and dioxane, n — Hydrocarbon solvents such as hexane, benzene, and toluene, water, etc., including methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, t-butanol, etc. Isopropanol and methanol are particularly preferred, which are preferred alcoholic solvents.
  • the reaction temperature during the reaction of the nitro compound and hydrazine is usually 10 to 150 ° C, preferably 15 to 130 ° C, more preferably 20 to 100 ° C. It is preferable that the reaction be performed with stirring as necessary.
  • the reaction time is usually;! To 24 hours, preferably 1 to 12 hours, more preferably 2 to 6 hours.
  • the hydroxyamino group of the target hydroxylamine compound represented by the general formula [2] may be further reduced to an amino group as in the conventional method.
  • the by-product formation rate is extremely low compared to the conventional method, so the reaction solution force can also reduce the step of removing the poisoning agent, and the purpose of the reduction reaction can be reduced.
  • the product can be obtained by a simple operation method.
  • the target hydroxylamine compound is usually 60% or more, preferably 70%, more preferably 80% or more, and still more preferably 90% in the reaction product. A reaction product containing at least% can be obtained.
  • the method for producing the hydroxylamine compound of the present invention is specifically as follows. It's good if you can.
  • hydrazine is usually added in an amount of 1 to 20 mol, preferably 1 to 10 mol, relative to 1 mol of a nitro compound, and Pt / C (en) of the present invention is added to the nitro compound in the reaction system.
  • Pt / C (en) of the present invention is added to the nitro compound in the reaction system.
  • 1.0 X 10- 5 ⁇ 1.0 X 10- 3 mol relative to I mol was preferably 1.0 X 10- 4 ⁇ 1 OX 10- 3 to mol presence, usually;.! ⁇ 24 hours, preferably 2 to 6 hours 10 to 150 ° C., preferably 30 to 80 ° C., if necessary, by reacting with stirring.
  • the platinum catalyst of the present invention described above is used. In the presence of hydrogen, by reacting a nitroaromatic compound having an unsaturated hydrocarbon group with hydrogen.
  • the nitroaromatic compound in the nitroaromatic compound having an unsaturated hydrocarbon group according to the present invention includes a nitrobenzene derivative, nitronaphthalene derivative, nitroanthracene derivative, nitroazulene derivative or nitrophenol having an unsaturated hydrocarbon group.
  • a nitrobenzene derivative nitronaphthalene derivative, nitroanthracene derivative, nitroazulene derivative or nitrophenol having an unsaturated hydrocarbon group.
  • nitrobenzene derivatives having an unsaturated hydrocarbon group and derivatives thereof are preferable.
  • R represents a bond, an alkylene group which may have a substituent and optionally have an oxygen atom in the chain, and a plurality of R's each independently represents a hydrogen atom or A compound having the following general formula [4]: an alkyl group having 1 to 6 carbon atoms, Ar represents an aryl group which may have a substituent, and n represents;! To 5)
  • R may have an oxygen atom in the chain
  • R is hydrogen or a group that may have a substituent.
  • An alkylene group represented by R may have a substituent! / And may have an oxygen atom in the chain.
  • the alkylene group in the case of having no oxygen includes, for example, those having a carbon number;! To 10, preferably 1 to 6, more preferably 2 to 6, which are linear or branched. It may be either a shape or a ring.
  • substituent may be, for example, an alkoxyl group having a carbon number of !! to 6, preferably 1 to 3 [straight, branched, or cyclic.
  • halogen atom more specifically, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like can be mentioned, and an ethylene group, a propylene group, a trimethylene group, a butylene group and the like are preferable.
  • the number of oxygen atoms is 1 to 5, preferably 1 to 3, more specifically, one (C H O) C H— (
  • n represents an integer of 1 to 5.
  • R substituent represented by R as described above! /
  • R may have an oxygen atom in the chain! /, May! /
  • alkylene groups an ethylene group, a propylene group More preferred are ethylene groups.
  • the particularly preferable one of the above R is a bond.
  • the alkyl group having 1 to 6 carbon atoms represented by R in the general formulas [3] to [6] may be linear, branched or cyclic. Specifically, for example, methyl Group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n butyl group, isobutyl group, sec-butyl group, tert butyl group, cyclobutyl group, n pentyl group, isopentyl group, sec pentyl group, tert pentyl group , Neopentyl group, 2-methylbutyl group, 1-ethynolepropyl group, cyclopentyl group, n hexyl group, isohexyl group, sec hexyl group, tert hexyl group, neohexyl group, 2-methylpentyl group, 1, Examples include 2-dimethylbutyl group, 1-ethyl group
  • the aryl group in the aryl group optionally having a substituent represented by Ar in the general formulas [3] to [6] is usually 6 to 14 carbon atoms, preferably 10 to 10 carbon atoms.
  • 14 aryl groups such as phenyl group, ⁇ naphthyl group, 2-naphthyl group, 1-azuleninole group, 2-azuleninole group, 4-azuleninole group, 5-azuleninole group, 6- Azleninole group, 1-anthrinole group, 2-anthrinole group, 9-anthrinole group, 1_phenanthrinol group, 2_phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, etc.
  • Examples of the substituent of the aryl group that may have a substituent include a halogen atom, a hydroxyl group, an alkyl group, and an alkoxyl group.
  • Specific examples of the halogen atom as a substituent here include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and examples of the alkyl group as a substituent include linear and branched.
  • any number of normal carbon numbers 1-6, preferably;!-3, more preferably Specific examples include those having 1 to 2 carbon atoms, such as methyl group, ethyl group, n-propylene group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, Examples thereof include an n-pentinole group, an isopentinole group, a sec-pentinole group, a tert-pentinole group, an n-hexinole group, an isohexyl group, a sec-hexyl group, and a tert-hexyl group.
  • alkoxyl group as a substituent examples include a linear or branched alkoxy group usually having carbon number;! To 6, preferably 1 to 3, more preferably 1 to 2, and specifically Examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, tert-butoxy group, n-pentyloxy group, n-hexyloxy group and the like. It is done.
  • n in the general formulas [3] to [6] is a force that represents the number of NO.
  • the force varies depending on the number of carbons and the structure of the aryl group represented by Ar. Usually;! To 5, preferably Is 1-3
  • m in the general formula [4] is a force representing the number of NO.
  • the force is represented by Ar.
  • the force S varies depending on the number of carbon atoms and the structure of the aryl group, usually 0 to 4, preferably 0 to 3.
  • R in the general formula [4] may have an oxygen atom in the chain and have a substituent.
  • the alkyl group of the alkyl group may be linear, branched, or cyclic, and usually has carbon number;! To 30, preferably 1 to 25. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, see-pentenole.
  • n_decyl group examples include n_dodecyl group, n-pentadecyl group, n-icosyl group, n-pentacosyl group, cyclopropyl group, cyclohexyl group, cyclopentyl group and the like.
  • the substituent may be, for example, an alkoxyl group having a carbon number of !!
  • alkoxy group represented by R in the general formula [2] is an alkyl group as described above.
  • a group in which a sulfur group is bonded to an oxygen atom is preferred. That is, the form -O-R (R is an alkyl group)
  • Examples of the kill group include those having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, which may be linear, branched or cyclic. Specific examples include a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n_pentinole group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group , Isohexyl group, sec-hexynole group, tert-hexyl group, n-heptyl group, n_octyl group, n_nonyl group, n-decyl group, cyclopropyl group, cyclohexyl group, cyclopentyl group Among them, a methyl group, an ethyl group, and
  • It may have a substituent and may be the same as the substituent of the alkyl group.
  • the amount of the platinum catalyst of the present invention used in the method for producing an amino aromatic compound of the present invention is such that the amount of platinum in the platinum catalyst is 1 mol of the nitroaromatic compound having an unsaturated hydrocarbon group as a substrate.
  • 1.0 X 10- 6 ⁇ 1.0mol Te preferably 1.0 X 10- 3 ⁇ 1.0mol, more preferably 1.0 X 10- 3 ⁇ 1 ⁇ 0 ⁇ 10- ol, more preferably 1.0 X 10- 3 ⁇ 1 ⁇ 0 chi may be an amount such that 10- 2 mol.
  • the amount of hydrogen used in the method for producing an amino aromatic compound of the present invention is usually 1 to 100 times mol, preferably 1 to 50 times mol, based on the nitro aromatic compound having an unsaturated hydrocarbon group. More preferably, it is 1 to 10 times mol.
  • a reaction solvent is appropriately used as necessary, for example, when the nitro aromatic compound having an unsaturated hydrocarbon group is not a liquid.
  • the reaction solvent include water, for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, such as dichloromethane, 1,2-dichloroethane, chlorine, and the like.
  • Halogenated hydrocarbons such as oral form and carbon tetrachloride, ethers such as jetyl ether, dimethoxyethane, diethoxyethane, and tetrahydrofuran, hydrocarbons such as n-hexane, n-heptane, and cyclohexane
  • organic solvents such as aromatic hydrocarbons such as benzene, toluene and xylene, for example esters such as ethyl acetate and butyl acetate, and methanol, ethyl acetate, tetrahydrofuran, etc. are preferred. Ethyl acetate is more preferred because it can perform the reduction efficiently. That's right.
  • These reaction solvents can be used alone or in combination of two or more, and the reaction selectivity can be changed depending on the reaction solvent used or a combination thereof.
  • the reaction temperature of the reaction of the dihydroaromatic compound having an unsaturated hydrocarbon group with hydrogen is usually 20 to 110 ° C, preferably 40 to 100 ° C. More preferably, it is 60-100 degreeC, More preferably, it is 70-90 degreeC. Since the rate of selective reduction of the nitro group can be improved as the reaction temperature is increased, the reaction temperature is particularly preferably 70 to 90 ° C.
  • the reaction time for the above reaction is usually 1 to 24 hours, preferably 1 to 10 hours, more preferably 1 to 5 hours, and further preferably 2 to 3 hours. Moreover, you may pressurize as needed, In that case, what is necessary is just to make it react normally at 1-10atm, Preferably it is 1-5atm.
  • an amine compound is allowed to coexist at the time of reaction to allow reaction under milder conditions.
  • the reaction temperature is 20 to 60 ° C, preferably 20 to 40 ° C, the selectivity is higher and the reduction reaction is possible.
  • Examples of the amine compound according to the present invention include ammonia, dimethylamine, tritylamine, jetylamine, ethylenediamine, pyridine, dimethylaminopyridine, morpholine, 0-phenylenediamine, 8-aminoquinoline, 2, 2 '.
  • ethylenediamine is preferred, with pyridine and ethylenediamine being preferred.
  • the amount of that is, as the concentration of normal reaction solvent, usually 1 X 10- 4 ⁇ 1 X 10- mol / mL ⁇ favored properly so that 5 X 10- 3 ⁇ 5 X 10- 2 mmol / mL Added.
  • the target product, the aminoamino compound having an unsaturated hydrocarbon group is usually 60% or more, preferably 70%, more preferably 80% or more, and still more preferably in the reaction product. Can obtain a reaction product containing 90% or more.
  • the method for producing an amino amino compound of the present invention is as follows, for example. That is, a nitroaromatic compound having an unsaturated hydrocarbon group (hereinafter sometimes abbreviated as a substrate according to the present invention) in a solvent such as ethyl acetate or the like, and usually 1.0 X with respect to lmol of the substrate according to the present invention.
  • a nitroaromatic compound having an unsaturated hydrocarbon group hereinafter sometimes abbreviated as a substrate according to the present invention
  • a solvent such as ethyl acetate or the like
  • the aromatic amino compound in which the raw material and the unsaturated hydrocarbon group other than the aromatic amino compound having an unsaturated hydrocarbon group as the target product are also reduced by the substrate.
  • the aromatic amino compound having the desired unsaturated hydrocarbon group may be extracted and purified as appropriate by column purification or recrystallization method known per se.
  • the osmium-supported carbon-ethylenediamine complex of the present invention (hereinafter sometimes abbreviated as the Os / C (en) complex of the present invention) is composed of osmium-supported carbon and ethylenediamine.
  • the osmium-supported carbon according to the present invention is not particularly limited as long as osmium is supported on the carbon, and the support method is based on chemical bonding even if it is based on physical bonding.
  • the method based on physical bonding by adsorption is particularly preferable, while the method based on physical bonding is preferable.
  • the osmium-supporting carbon may be a commercially available carbon or a carbon obtained by a method known per se, for example, a reaction with stirring in a solution in which a metal catalyst is dissolved. .
  • the carbon used here may be any carbon as long as it is usually used in this field, but activated carbon having a fine pore of!
  • osmium 0-valent, 1-valent, 2-valent, and 4-valent osmium can be cited as S.
  • 0-valent, 1-valent, and 2-valent osmium are preferred, and 0-valent osmium is more preferable.
  • Specific examples include osmium halides such as osmium chloride, osmium dioxide, osmium tetroxide, potassium osmate (VI), and osmium derived from potassium oxalate hexium, and among them, those derived from osmium tetroxide. Is preferred.
  • the amount of osmium in the osmium-supporting carbon according to the present invention is usually 0.1 to 20% by weight, preferably 1 to 20% by weight, more preferably 1 to 10% by weight.
  • the solution for dissolving the above metal catalyst is different in strength depending on the osmium used or the one from which osmium is derived. For example, when using osmium tetroxide, acidic solution such as hydrochloric acid, sulfuric acid, nitric acid perchloric acid, acetic acid, acetone, Organic solvents such as methanol, ethanol, THF, black mouth form, and ethyl acetate.
  • the amount of osmium in Os / C (en) of the present invention may be such that Os / C (en) has the catalytic ability of osmium. Specifically, it is usually 0.1 to 20% by weight. Preferably from 1 to 20% by weight, more preferably from! To 10% by weight.
  • osmium-carrying carbon and ethylenediamine are reacted in water or a mixed solution of water and a water-soluble organic solvent. It is preferable to let it go.
  • osmium-supported carbon Imol and ethylenediamine. ; ⁇ 200 mol, preferably 1-80 mol, more preferably 1-10 mol in water or methanol containing 3% or more and less than 100% water, if necessary, inert gas atmosphere such as nitrogen gas or argon gas
  • the osmium-supported C (en) of the present invention can be obtained by reacting at room temperature;!
  • the obtained Os / C (en) of the present invention may be dried at 100 Pa to 0.1 MPa, preferably 200 to 3000 Pa, 10 to 80 ° C. after filtration, if necessary. .
  • the osmium catalyst of the present invention contains the Os / C (en) complex of the present invention as described above as a catalyst, and such an Os / C (en) complex of the present invention. Because of the strong binding of osmium, there is little risk of ignition and a highly efficient reduction reaction is possible. In the Os / Cfen) composite, since osmium is supported on carbon, which is a fine particle (fine powder), the area of osmium in contact with the reaction solution is increased, resulting in high reaction efficiency.
  • the method for selectively reducing a carbonyl group in the carbonyl compound of the present invention is performed by reducing a compound having a double bond and a carbonyl group in the presence of the osmium catalyst of the present invention.
  • the carbonyl group in the compound having a double bond and a carbonyl group used in the selective reduction method include an aldehyde structure, a ketone structure, an ester structure, an amide structure, and the like.
  • a ketone structure is preferable, and an aldehyde structure is particularly preferable.
  • a specific example for example,
  • Examples include cinnamaldehyde, and among them cinnamaldehyde is preferable.
  • the solvent used in the reduction reaction in the method is not particularly limited as long as it can dissolve a compound having a double bond and a carbonyl group. What has a high production rate of a composition should just be selected suitably.
  • alcohol solvents such as methanol, ethanol, n propanol, isopropanol, n butanol, isobutyl alcohol, t-butanol, ether solvents such as jetyl ether, tetrahydrofuran and dioxane, n Hydrocarbon solvents such as hexane, benzene, and toluene, water, etc., among which methanol, ethanol, n propanol, isopropanol, n-butanol, isobutyl alcohol, t-butanol and other alcohol solvents are preferred Is particularly preferred.
  • the amount of the osmium catalyst of the present invention used at this time is such that the amount of osmium supported with respect to 1 mol of the compound having a double bond and a carbonyl group is usually 0.0005 to 0.5 mol, preferably 0.001 to 0.3 mol. May be appropriately selected and used.
  • the reaction temperature during the above reduction reaction is usually 10 to 100 ° C, preferably 50 to 100 ° C, more preferably 80 to 90 ° C, and it is preferable to pressurize as necessary.
  • the atmospheric pressure is usually 0.05 to 2 MPa, preferably 0.1 to 1 MPa.
  • the reaction time is usually 0.5 to 50 hours, preferably 1 to 40 hours, more preferably 6 to 30 hours.
  • cinnamaldehyde when used as a compound having a double bond and a carbonyl group, it may be performed as follows.
  • the Os / C (en) of the present invention is adjusted so that the amount of osmium supported on cinnamaldehyde and lmol of cinnamaldehyde is usually 0.005 to 0.5 mol, preferably 0.0001 to 0.3 mol in an isopropanol solution. ), And the reaction is carried out with stirring at 0.1 to 1 MPa at 10 to 100 ° C. for 0.5 to 50 hours in a hydrogen atmosphere. By filtering the obtained reaction solution and concentrating the filtrate, the corresponding cinnamaldehyde can be obtained.
  • Example 5 Synthesis of 5% white-carrying carbon ethylenediamine complex of the present invention (synthesis in a mixed solution of water-soluble organic medium and water)
  • Example 6 Synthesis of 5% osmium-supported carbon ethylenediamine complex of the present invention (water soluble ne ffi 7k ⁇ H ⁇ at night ⁇
  • Example 16 From the results of Example 16, it was found that various metal catalyst-supported carbon ethylenediamine complexes such as palladium, platinum, and osmium can be obtained by the method of the present invention. Further, according to this method, various metal catalyst-supported carbon ethylenediamine complexes can be obtained safely without the risk of ignition. Further, from Examples 3 and 4, even if the amount of ethylenediamine is reduced and the reaction time is shortened. It was also found that a palladium-supported carbon ethylenediamine complex was obtained.
  • various metal catalyst-supported carbon ethylenediamine complexes such as palladium, platinum, and osmium can be obtained by the method of the present invention. Further, according to this method, various metal catalyst-supported carbon ethylenediamine complexes can be obtained safely without the risk of ignition. Further, from Examples 3 and 4, even if the amount of ethylenediamine is reduced and the reaction time is shortened. It was also found that a palladium-supported carbon ethylenediamine complex was obtained.
  • Example 7 Carbon remaining carbon supported Hydrogenation reaction of nitro compound using ethylenediamine complex catalyst (Method for producing hydroxylamine)
  • phenylhydroxylamine can be obtained from nitrobenzene with a yield of 95% or more by using the platinum-supported carbon ethylenediamine complex catalyst of the present invention. That is, according to the platinum catalyst of the present invention, it is understood that a hydroxylamine compound can be synthesized from nitrobenzene with high efficiency without using a poisoning agent. Further, based on the results, the platinum-supported carbon ethylenediamine complex catalyst of the present invention has a hydroxylamine in spite of a small amount of catalyst as compared with the results of conventional platinum-supported ion exchange resins, for example, WO2004 / 072019. Is obtained in a high yield. That is, the platinum catalyst of the present invention has a higher reaction efficiency than the conventional platinum catalyst.
  • Example 8 Carbon remaining on carbon nitrostyrene hydrogen catalyst using ethylenediamine complex catalyst (Ethylene Z Mino Caro)
  • Example 2 The experiment was performed in the same manner as in Example 1 except that methanol was used as a solvent, platinum carbon (Pt / C) was used as a catalyst, and ethylenediamine was not added. N- (4-Burf obtained Table 2 shows the component ratios of (enyl) -hydroxylamine and 4-aminostyrene.
  • Example 13 Selective hydrogen reduction of 4-nitrostilbene using unsupported carbon ethylenediamine complex catalyst
  • a reduction reaction was carried out in the same manner as in Example 5 except that the amount of platinum-supported carbon ethylenediamine complex catalyst was 25 mg, the reaction time was 2 hours, and the reaction temperature was 80 ° C. The component ratio of enethylphenylamine was determined. The results are shown in Table 5.
  • Platinum supported carbon A reduction reaction was performed in the same manner as in Example 5 except that a platinum carbon catalyst (Pt / C) was used instead of the ethylenediamine complex catalyst, and 4-aminostilbene and 4-phenylethylphenyl were used. The component ratio of the amount of amine was determined. The results are shown in Table 5.
  • a reduction reaction was carried out in the same manner as in Example 5 except that a palladium carbon catalyst (Pd / C) was used in place of the platinum-supported carbon ethylenediamine complex catalyst and the reaction time was 2 hours.
  • the component ratio of 4-phenylphenylamine was determined. The results are shown in Table 5.
  • Rhodium carbon catalyst instead of ethylenediamine complex catalyst
  • Example 5 According to the same method as in Example 5, except that a rhodium carbon catalyst (Rh / C) was used instead of the platinum-supported carbon-ethylenediamine complex catalyst, ethyl acetate was used as a solvent, and the reaction temperature was 80 ° C. A reduction reaction was performed, and the component ratio of 4-aminostilbene and 4-phenylethylphenylamine was determined. The results are shown in Table 5.
  • Example 15 Selective hydrogen reduction of ethyl 4-nitrocinnamate using white supported carbon ethylenediamine complex catalyst
  • a selective hydrogen reduction reaction was carried out in the same manner as in Example 8, except that methanol was used as the solvent, the reaction time was 2 hours, and the reaction temperature was 60 ° C.
  • the component ratios of the obtained 4-amino cinnamate ethyl and 3_ (4-nitrophenyl) propionate are shown in Table 6.
  • the platinum-supported carbon ethylenediamine complex catalyst selects only the nitro group of the nitroaromatic compound having an unsaturated hydrocarbon group, even when 4-nitrocinnamic acid ethyl is used as the substrate. It was found that it can be reduced. Also in this case, it was found that the selectivity was improved by raising the temperature. Furthermore, it was thought that selectivity was improved by using ethyl acetate over methanol.
  • Example 16 Reduction reaction by osmium-supported carbon ethylenediamine complex catalyst
  • This osmium-supported carbon ethylenediamine complex catalyst is capable of performing a selective reduction reaction of only the carbonyl group of a compound having a carbonyl group and a double bond with high efficiency.

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Abstract

La présente invention concerne un procédé pour la production d'un catalyseur de métaux porteur de composites carbone/éthylénédiamine, caractérisé par la réaction du carbone porteur d'un catalyseur de métaux avec l'éthylénédiamine dans l'eau ou un mélange liquide d'eau avec un solvant organique soluble dans l'eau ; un composite carbone/éthylénédiamine porteur de platine qui comprend un carbone porteur de platine et de l'éthylénédiamine ; des procédés pour la production d'hydroxylamines et de composés aminoaromatiques ayant des groupes hydrocarbures non saturés avec un catalyseur de platine contenant le composite ; un composite carbone/éthylénédiamine porteur d'osmium qui comprend du carbone porteur d'osmium et de l'éthylénédiamine ; et un procédé pour la réduction carbonyl-sélective de composés carbonylés avec un catalyseur contenant le composite.
PCT/JP2007/071788 2006-11-10 2007-11-09 Catalyseur de métaux porteur de composites carbone/éthylénédiamine et son procédé de production Ceased WO2008056768A1 (fr)

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WO2012101013A1 (fr) 2011-01-28 2012-08-02 Boehringer Ingelheim International Gmbh Pyridinyl-pyrimidines substituées et leur utilisation en tant que médicaments
CN105073700A (zh) * 2013-04-05 2015-11-18 三井化学株式会社 环己酮化合物的制造方法
CN109622050A (zh) * 2018-12-25 2019-04-16 万华化学集团股份有限公司 催化剂和利用该催化剂制备橙花醇和香叶醇的方法
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WO2005026190A1 (fr) * 2003-09-10 2005-03-24 Nihon University Procede de production d'amine cyclique
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Cited By (11)

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Publication number Priority date Publication date Assignee Title
WO2012101013A1 (fr) 2011-01-28 2012-08-02 Boehringer Ingelheim International Gmbh Pyridinyl-pyrimidines substituées et leur utilisation en tant que médicaments
CN105073700A (zh) * 2013-04-05 2015-11-18 三井化学株式会社 环己酮化合物的制造方法
US20160046553A1 (en) * 2013-04-05 2016-02-18 Mitsui Chemicals, Inc. Process for producing cyclohexanone compound
US9481625B2 (en) * 2013-04-05 2016-11-01 Mitsui Chemicals, Inc. Process for producing cyclohexanone compound
EP2982663A4 (fr) * 2013-04-05 2017-01-11 Mitsui Chemicals, Inc. Procédé de production d'un composé de cyclohexanone
JPWO2014163080A1 (ja) * 2013-04-05 2017-02-16 三井化学株式会社 シクロヘキサノン化合物の製造方法
TWI596084B (zh) * 2013-04-05 2017-08-21 Mitsui Chemicals Method for producing cyclohexanone compound
CN109622050A (zh) * 2018-12-25 2019-04-16 万华化学集团股份有限公司 催化剂和利用该催化剂制备橙花醇和香叶醇的方法
JP2022124454A (ja) * 2021-02-15 2022-08-25 エヌ・イーケムキャット株式会社 縮合多環芳香族化合物の製造方法および分子内環化反応用触媒
CN115504892A (zh) * 2022-11-09 2022-12-23 浙江工业大学 一种连续化催化加氢合成普鲁卡因的方法
CN115504892B (zh) * 2022-11-09 2023-04-07 浙江工业大学 一种连续化催化加氢合成普鲁卡因的方法

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