WO2010032770A1 - Catalyseur utilise dans une reaction de transfert d'hydrure d'alcool, procede de fabrication associe, et procede de fabrication d'un compose contenant un groupe carbonyle - Google Patents

Catalyseur utilise dans une reaction de transfert d'hydrure d'alcool, procede de fabrication associe, et procede de fabrication d'un compose contenant un groupe carbonyle Download PDF

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WO2010032770A1
WO2010032770A1 PCT/JP2009/066214 JP2009066214W WO2010032770A1 WO 2010032770 A1 WO2010032770 A1 WO 2010032770A1 JP 2009066214 W JP2009066214 W JP 2009066214W WO 2010032770 A1 WO2010032770 A1 WO 2010032770A1
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alcohol
ruthenium
catalyst
reaction
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哲孝 水野
和也 山口
範英 新井
勝行 辻
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昭和電工株式会社
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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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B55/00—Racemisation; Complete or partial inversion
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
    • C12C11/00—Fermentation processes for beer
    • C12C11/02—Pitching yeast
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a ruthenium-supported titania catalyst for hydrogen transfer reaction of alcohol and a method for producing the same, and a method for producing a carbonyl group-containing compound such as a ketone or an aldehyde by oxidizing alcohol with oxygen molecules using the catalyst. .
  • the present invention also relates to a method for racemizing a secondary alcohol, which is a hydrogen transfer reaction of alcohol using the catalyst, a method for producing a carbonyl compound by oxidation of the alcohol, and a method for producing an alcohol by reduction of the carbonyl compound. It is.
  • Examples of industrially important alcohol hydrogen transfer reactions include alcohol oxidation reactions, secondary alcohol racemization reactions, alcohol oxidation reactions using carbonyl compounds as oxidants, and carbonyl group-containing compounds using alcohol as reducing agents. There are reduction reactions and hydrogenation reactions of allyl alcohols using alcohol as a hydrogen source.
  • a method of contacting with oxygen molecules in the presence of a ruthenium supported catalyst is known.
  • a ruthenium catalyst such as ruthenium-carrying alumina or ruthenium-carrying carbon is present together with an oxygen activator such as dihydroxynaphthalene to carry out the above oxidation reaction.
  • an oxygen activator such as dihydroxynaphthalene
  • Patent Document 2 discloses ruthenium catalysts such as dichlorotris (triphenylphosphine) ruthenium, tetrapropylammonium perruthenate, ruthenium-supporting carbon, and dioxybenzenes. It has been proposed to carry out the oxidation reaction in the presence of an oxygen activator such as However, these methods require an oxygen activator and are not satisfactory in terms of oxidation product selectivity.
  • Patent Document 3 discloses a ruthenium-containing hydrotalcite catalyst
  • Patent Document 4 discloses a ruthenium-coordinated hydroxyapatite catalyst
  • Patent Document 5 presents a ruthenium-supported alumina catalyst
  • Patent Document 6 discloses a catalyst in which ruthenium oxide is supported on alumina, silica, zirconia, titania, tin oxide, and oxygen activity. It has been proposed to perform an oxidation reaction with oxygen molecules without using an agent. However, even in these methods, the activity of the ruthenium catalyst is not always sufficient, so that a desired alcohol conversion rate cannot be obtained and the productivity of the oxidized product may not be satisfied.
  • Non-patent Document 1 proposes that an anatase-type titania catalyst is present and a photo-oxidation reaction is carried out with oxygen molecules.
  • this method requires light, it is not easy to implement on an industrial scale, and the activity of the anatase-type titania catalyst is not sufficient, so that a desired alcohol conversion rate cannot be obtained, and the productivity of the oxidation product is not obtained. I was not satisfied with this point.
  • Enantiomerically high alcohol purity is extremely important in the pharmaceutical and agricultural fields.
  • One method for industrially producing an enantiomerically high-purity alcohol is a method of dividing a racemic mixture.
  • a major drawback of this method is that the yield is limited to a maximum of 50%.
  • One of the methods for recovering and reusing enantiomers that is not required is racemization, and in the pharmaceutical and agricultural fields, racemization under mild conditions using a solid catalyst is desired.
  • Oppenauer oxidation and Meerwein-Ponndorf-Verley reduction are inversely related and are equilibrium reactions.
  • a large amount of reducing agent alcohol or oxidizing agent carbonyl compound is used as a solvent to shift the equilibrium.
  • these reactions are homogeneous catalytic reactions and require complicated operations for separating the reaction product and the catalyst, so that solidification of the catalyst is desired.
  • An object of the present invention is to provide a ruthenium-supported catalyst having excellent hydrogen transfer reaction activity and a method for producing the same, and to oxidize alcohol to obtain a high selectivity and yield of carbonyl group-containing compounds such as ketones and aldehydes. Is to provide a method capable of producing a product with high productivity. Another object of the present invention is to provide a method for obtaining a racemic mixture by racemizing a secondary alcohol at a high conversion rate using the obtained catalyst. Another object of the present invention is to provide a method for producing a carbonyl compound with good productivity by oxidation of an alcohol using the above catalyst, and a method for producing an alcohol with high productivity by reducing the carbonyl compound. .
  • the present inventors obtained a ruthenium-supporting titania catalyst suitable as a catalyst for hydrogen transfer reaction of alcohol by supporting ruthenium on anatase-type titania with a specific formulation and achieved the above object.
  • the present inventors have found that this can be done and have completed the present invention.
  • a catalyst for hydrogen transfer reaction of alcohol characterized in that ruthenium hydroxide is supported on anatase type titania.
  • a base is added to adjust the pH of the solution to 8 or more, and the produced ruthenium-supporting titania is separated.
  • [4] A carbonyl group characterized in that an alcohol and oxygen molecules are brought into contact with each other in the presence of the alcohol hydrogen transfer reaction catalyst according to [1] or [2] above to perform the hydrogen transfer reaction of the alcohol. Production method of contained compound.
  • the alcohol is represented by the following formula (1) (Wherein R 1 and R 2 are each independently a hydrogen atom; or a hydrocarbon group, an aromatic group, which may be substituted with a halogeno group, a nitro group, an alkoxy group, a phenoxy group or an acyloxy group; Alternatively, it represents a heterocyclic group, and R 1 and R 2 may combine to form a ring.)
  • the carbonyl group-containing compound is represented by the following formula (2): (Wherein R 1 and R 2 represent the same meaning as described above.)
  • the method for producing a carbonyl group-containing compound according to [4], which is an aldehyde or a ketone represented by the formula: [6] A method for racemizing a secondary alcohol
  • the secondary alcohol is represented by the following formula (3) (In the formula, R 3 and R 4 are not the same and each independently represents a hydrocarbon group, an aromatic group, or a heterocyclic group that may be substituted with a halogeno group, a nitro group, an alkoxy group, a phenoxy group, or an acyloxy group.
  • the racemization method of the secondary alcohol according to the above item [6], which is a mixture having a high ratio of any of D-form, L-form, or D-form and L-form represented by [8] A carbonyl compound that oxidizes alcohol (A) using carbonyl compound (B) as an oxidizing agent in the presence of the catalyst for hydrogen transfer reaction of alcohol according to [1] or [2] above The manufacturing method of (A).
  • the alcohol (A) is represented by the following formula (4): Wherein R 5 and R 6 are each independently a hydrogen atom; or a hydrocarbon group, an aromatic group, which may be substituted with a halogeno group, a nitro group, an alkoxy group, a phenoxy group or an acyloxy group, Alternatively, it represents a heterocyclic group, and R 5 and R 6 may combine to form a ring.)
  • the carbonyl compound (B) is represented by the following formula (5): (Wherein R 7 and R 8 are each independently a hydrogen atom; or a hydrocarbon group, an aromatic group, which may be substituted with a halogeno group, a nitro group, an alkoxy group, a phenoxy group or an acyloxy group; Alternatively, it represents a heterocyclic group, and R 7 and R 8 may combine to form a ring.)
  • R 7 and R 8 are each independently a hydrogen atom; or a hydrocarbon group, an aromatic group, which may be substituted with a halogeno group, a nitro group, an alkoxy group, a phenoxy group or an acyloxy group; Alternatively, it represents a heterocyclic group, and R 7 and R 8 may combine to form a ring.
  • alcohol can be oxidized with oxygen molecules, and oxidation products such as ketones and aldehydes can be produced from alcohol with high productivity.
  • oxidation products such as ketones and aldehydes can be produced from alcohol with high productivity.
  • aldehydes and ketones can be produced in a high yield.
  • the ruthenium-supported titania of the present invention is used as a catalyst, secondary alcohols can be racemized at a high conversion rate under mild conditions. Therefore, unnecessary enantiomers generated by resolution of a racemic mixture are not required. Can be recovered and reused. Moreover, the production of a carbonyl compound by oxidation of an alcohol using a carbonyl compound as an oxidizing agent and the production of an alcohol by reduction of the carbonyl compound using an alcohol as a reducing agent can be performed with high productivity.
  • the solvent in the ruthenium solution water is usually used, but a mixed solvent of water and an organic solvent may be used as necessary, or an organic solvent may be used alone.
  • the organic solvent include methanol, ethanol, acetone, and the like. The amount of the solvent used is adjusted so that the ruthenium concentration in the ruthenium solution is usually 0.1 mM to 1 M, preferably 1 mM to 100 mM.
  • the anatase titania suspended in the ruthenium solution may include various titanias such as rutile titania and brookite titania as long as it is titania mainly composed of anatase titania. Among them, anatase type titania having an anatase ratio of 50% or more is preferable, and 75% or more is more preferable.
  • the amount of titania used is adjusted so that the ruthenium content in the obtained ruthenium-supported titania catalyst is usually 0.1 to 20% by mass, preferably 0.5 to 10% by mass.
  • the particle size of the anatase-type titania fine particles is not particularly limited as long as the suspension is stable, but 90% by mass or more is preferably in the range of about 0.001 to 3 ⁇ m. In terms of specific surface area, it is in the range of 0.5 to 1500 m 2 / g, and preferably in the range of 1 to 1000 m 2 / g.
  • the peak area refers to the area of the portion of the corresponding interference line of the X-ray diffraction spectrum that protrudes from the base line, and the calculation method may be performed by a known method, for example, by computer calculation, approximate triangulation, or the like. Desired.
  • the pH of the titania suspension thus obtained is usually about 2.
  • a base is added to this suspension, and the pH of the suspension is adjusted to usually 8 or higher, preferably 10 or higher, more preferably 12 to 14. It is not preferable to adjust the pH to 8 or more from the beginning when preparing the titania suspension. It is important to add the base from a state where the pH is less than 8. It seems that ruthenium in the solution is adsorbed and deposited on the surface of the titania particles in the process of changing the pH, thereby becoming a highly active catalyst. When no base is added, the activity of the resulting ruthenium-supported titania catalyst as a catalyst for hydrogen transfer reaction is not sufficient.
  • Examples of the base include metal hydroxides such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide; metal carbonates such as sodium carbonate, potassium carbonate, and magnesium carbonate; metals such as sodium acetate and potassium acetate. Examples thereof include acetates; metal silicates such as sodium silicate; ammonia and the like, and two or more of them can be used as necessary.
  • the ruthenium-supported titania catalyst can be separated from the suspension by subjecting the suspension after adding the base to a solid-liquid separation operation.
  • a solid-liquid separation operation filtration or decantation is usually employed.
  • the separated ruthenium-supporting titania catalyst is subjected to operations such as washing with water and drying as necessary.
  • ruthenium is ruthenium hydroxide (Ru (OH) 3 ).
  • Ru (OH) 3 ruthenium hydroxide
  • ruthenium itself is trivalent, a ruthenium atom may be bonded to titania, and in some cases, Ru (OH)... Ti, Ru (OH) 2. is there.
  • Ru (OH) 3 ruthenium hydroxide
  • Ru (OH) 3 ruthenium hydroxide
  • Ru (OH) 3 ruthenium hydroxide
  • Ru (OH) 3 ruthenium hydroxide
  • the hydrogen transfer reaction of alcohol in the present invention refers to a catalytic reaction involving transfer of hydrogen atoms from carbon having an alcoholic hydroxyl group, as shown in FIG.
  • the carbonyl group-containing compound is generated by the elimination reaction from the elimination of the catalyst as ruthenium hydride following the transfer of the hydrogen atom from the carbon having the OH group of the alcohol to the ruthenium catalyst.
  • carbonyl group-containing compounds refer to aldehydes and ketones.
  • the catalyst is regenerated to a ruthenium hydroxide catalyst by oxygen molecules. When oxygen molecules are not present in the system, the produced carbonyl group-containing compound is consumed in the regeneration reaction from ruthenium hydride to ruthenium hydroxide, and the yield is reduced. If the alcohol is an optical isomer, the reaction itself can be confirmed because the product (alcohol) is racemized.
  • alcohol (A) is ethanol and carbonyl compound (B) is acetone
  • Substrate alcohol (A) (ethanol) ⁇ carbonyl compound (A) (acetaldehyde)
  • Solvent (oxidant) carbonyl compound (B) (acetone) ⁇ alcohol (B) (isopropyl alcohol).
  • [2] Reduction of carbonyl compound (B) (Meerwein-Ponndorf-Verley reduction)
  • an alcohol such as isopropyl alcohol (referred to as “alcohol (A)”
  • the alcohol (A) is oxidized by a ruthenium hydroxide catalyst to produce ruthenium hydride.
  • the ruthenium hydride reduces the carbonyl compound (B) as a substrate to synthesize the alcohol (B). Since there is a large amount of alcohol (A), the production of ruthenium hydride is mainly carried out with alcohol (A).
  • the alcohol (A) as a solvent acts as a reducing agent.
  • the carbonyl compound (B) is acetophenone and the alcohol (A) is isopropyl alcohol
  • Substrate carbonyl compound (B) (acetophenone) ⁇ alcohol (B) (1-phenylethanol)
  • Solvent (reducing agent) alcohol (A) (isopropyl alcohol) ⁇ carbonyl compound (A) (acetone).
  • the oxidation reaction of alcohol (A) and the reduction reaction of carbonyl compound (B) are two sides of each other, and their names are determined depending on which one is regarded as a substrate and the other is regarded as a solvent.
  • the substrate alcohol may be a primary alcohol, a secondary alcohol, a monohydric alcohol or a polyhydric alcohol, and two or more of them may be used as necessary.
  • the alcohol of the substrate is preferably the following formula (1) The one shown in is used.
  • R 1 and R 2 are a hydrogen atom; a hydrocarbon group optionally substituted with a halogeno group, a nitro group, an alkoxy group, a phenoxy group or an acyloxy group; a halogeno group, a nitro group or an alkoxy group Represents an aromatic group optionally substituted with a phenoxy group or an acyloxy group; or a heterocyclic group optionally substituted with a halogeno group, a nitro group, an alkoxy group, a phenoxy group or an acyloxy group.
  • R 1 and R 2 may be bonded to each other to form a ring.
  • R 1 and R 2 may be the same or different.
  • the hydrocarbon group is preferably one having 1 to 30 carbon atoms.
  • an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group, an aryl group, an arylalkyl group, and an arylalkenyl group are preferable.
  • the halogeno group that may be bonded to a hydrocarbon group include a chlorine group, a fluorine group, a bromine group, and an iodine group.
  • the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a 2-ethoxy-ethoxy group.
  • the hydrocarbon group or aromatic group which may be substituted with a halogeno group, a nitro group, an alkoxy group, a phenoxy group or an acyloxy group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group.
  • methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group Group, cyclohexyl group, phenyl group and p-tolyl group are preferred.
  • the heterocyclic group preferably contains a heteroatom selected from oxygen, nitrogen and sulfur, and this heterocyclic ring is preferably a 5-membered ring or a 6-membered ring. Specific examples include a furan group, a thiophene group, and a pyridyl group.
  • this ring is preferably a monocyclic or polycyclic ring having 5 to 20 carbon atoms.
  • R 1 and R 2 being bonded to form a ring (expressed in a form including a carbon atom to which a hydroxyl group is bonded) include cyclopentane ring, 2-methylcyclopentane ring, cyclohexane Ring, 2-methylcyclohexane ring, cycloheptane ring, 2-methylcycloheptane ring, cyclooctane ring, 2-methylcyclooctane ring, cyclododecane ring, 2-methylcyclododecane ring, norbornene ring, 1-indane ring, 1 -Tetralin ring, fluorene ring and the like.
  • alcohol represented by the above formula (1) examples include methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 1-decanol, Dodecanol, 1-tetradecanol, 1-hexadecanol (palmitin alcohol), 1-octadecanol (stearyl alcohol), 1-eicosanol, 3-methyl-1-butanol, 3,3-dimethyl-1-butanol, 4-methyl-1-pentanol, 2-methyl-1-pentanol, 2,2-dimethyl-1-pentanol, 5-methyl-1-hexanol, 3-chloro-1-propanol, allyl alcohol, geraniol, Benzyl alcohol, p-methylbenzyl alcohol, p-methoxyben Alcohol, p-chlorobenzyl alcohol, p-nitrobenzyl alcohol,
  • methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 1-dodecanol, 1-tetradecane A linear aliphatic alcohol having a hydroxyl group bonded to the terminal, such as 1-hexadecanol (palmitine alcohol) and 1-octadecanol (stearyl alcohol), is preferable.
  • oxygen gas, air, or oxygen gas or air diluted with an inert gas such as nitrogen, carbon dioxide, or helium can be used.
  • the contact between the alcohol and the oxygen molecule may be performed, for example, by placing a liquid containing alcohol and the ruthenium-supported titania catalyst in an atmosphere of the oxygen molecule-containing gas, or blowing an oxygen molecule-containing gas into the liquid. It may be done by.
  • the oxidation reaction may be performed in the presence of a solvent or may be solventless.
  • the solvent include halogenated aliphatic hydrocarbons such as dichloromethane, dichloroethane, and chloroform; esters such as isobutyl acetate and t-butyl acetate; nitriles such as acetonitrile; aromatics such as benzene and toluene.
  • Hydrocarbons Halogenated aromatic hydrocarbons such as chlorobenzene and trifluorotoluene, and the like, which are more inert than alcohol with respect to oxidation reactions.
  • the amount used is usually 1 to 100,000 parts by weight, preferably 10 to 10,000 parts by weight, per 100 parts by weight of alcohol.
  • the reaction temperature for the oxidation reaction is usually 20 to 300 ° C., preferably 50 to 200 ° C.
  • the reaction pressure is usually 0.1 to 10 MPa.
  • the oxidation reaction may be performed continuously or batchwise.
  • various carbonyl compounds can be produced as oxidation products from the substrate alcohol.
  • a primary alcohol is used as the alcohol
  • a secondary alcohol is used as the alcohol
  • a corresponding ketone can be produced.
  • the produced aldehyde and ketone may react with the raw material alcohol to be obtained as acetals and ketals.
  • polyhydric alcohol is used as alcohol, a corresponding polycarbonyl compound can be manufactured.
  • the oxidation product is represented by the following formula (2). (Wherein R 1 and R 2 represent the same meaning as described above.) Can be produced.
  • the oxidation product in the above oxidation reaction solution is oxidized by subjecting the oxidation reaction mixture to operations such as filtration, concentration, washing, alkali treatment, and acid treatment as necessary, and then purifying it by distillation, crystallization, etc. It can be separated from the reaction mixture.
  • Racemization reaction of secondary alcohol An example of a racemization reaction of a secondary alcohol is shown below as an alcohol hydrogen transfer reaction using a ruthenium-supported titania catalyst. This racemization reaction can be carried out in either the liquid phase or the gas phase, but is preferably carried out in the liquid phase.
  • the amount of the ruthenium-supported titania catalyst used is usually 0.000001 to 1 mol, preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.00 mol as ruthenium with respect to 1 mol of the secondary alcohol. 05 mol.
  • the secondary alcohol as the substrate is preferably a secondary alcohol having an optical isomer, and either the ratio of L-form or D-form may be high. Moreover, monohydric alcohol may be sufficient and polyhydric alcohol may be sufficient, and those 2 or more types can also be used as needed. Moreover, you may use together with alcohol which does not have an optical isomer.
  • R 3 and R 4 are not the same and are each independently a halogeno group, a nitro group, an alkoxy group, a hydrocarbon group optionally substituted with a phenoxy group or an acyloxy group, or a halogeno group, a nitro group, an alkoxy group, a phenoxy group Represents an aromatic group which may be substituted with a group or an acyloxy group, or a heterocyclic group which may be substituted with a halogeno group, a nitro group, an alkoxy group, a phenoxy group or an acyloxy group.
  • R 3 and R 4 may combine to form an asymmetric ring with respect to the optical center carbon atom.
  • the hydrocarbon group is preferably one having 1 to 30 carbon atoms.
  • the halogeno group that may be bonded to a hydrocarbon group include a chlorine group, a fluorine group, a bromine group, and an iodine group.
  • the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a 2-ethoxy-ethoxy group.
  • a hydrocarbon group or an aromatic group which may be substituted with a halogeno group, a nitro group, an alkoxy group, a phenoxy group or an acyloxy group is a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, Isobutyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, 2-ethyl-hexyl, heptyl, octyl, nonyl, decanyl, phenyl, o-tolyl, p-tolyl Group, 4-ethylphenyl group, 4-propylphenyl group, 4-isopropylphenyl group, benzyl group, naphthyl group, among which methyl group, ethyl group, propyl group, isopropyl group
  • heterocyclic group examples include a furan group, a thiophene group, and a pyridyl group.
  • Rings that are asymmetric with respect to the optical center by combining R 1 and R 2 include a 2-methylcyclopentane ring, a 2-methylcyclohexane ring, 2 -Methylcycloheptane ring, 2-methylcyclooctane ring, 2-methylcyclododecane ring, norbornene ring, 1-indane ring, 1-tetralin ring.
  • secondary alcohols having optical isomers include 2-butanol, 2-pentanol, 2-hexanol, 2-heptanol, 2-octanol, 2-decanol, 2-eicosanol, 3-hexanol, and 3-heptanol.
  • the racemization reaction is preferably performed in an oxygen-free atmosphere, and more preferably in an inert gas atmosphere or a hydrogen gas atmosphere.
  • hydrogen gas it is preferable to carry out most of the reaction in an inert gas atmosphere, and finally introduce hydrogen gas to complete the reaction. This is for returning the carbonyl remaining in the reaction under an inert gas atmosphere to the alcohol and increasing the yield of racemization.
  • the racemization reaction may be performed in the presence of a solvent.
  • the solvent needs to be more inert than the secondary alcohol for the racemization reaction of the present invention.
  • halogenated aliphatic hydrocarbons such as dichloromethane, dichloroethane and chloroform
  • esters such as isobutyl acetate and t-butyl acetate
  • nitriles such as acetonitrile
  • aromatic hydrocarbons such as benzene and toluene
  • halogenated aromatic hydrocarbons such as chlorobenzene and trifluorotoluene.
  • the amount used is usually 1 to 100,000 parts by weight, preferably 10 to 10,000 parts by weight, per 100 parts by weight of the secondary alcohol.
  • the reaction temperature of the racemization reaction is usually 20 to 300 ° C., preferably 50 to 200 ° C., and the reaction pressure is usually 0.1 to 10 MPa.
  • the racemization reaction may be performed continuously or batchwise.
  • a racemate By the racemization reaction, a racemate can be produced from a secondary alcohol as a substrate.
  • the racemate in the racemization reaction solution is subjected to operations such as filtration, concentration, washing, alkali treatment, acid treatment, etc. as necessary, and then purified by distillation, crystallization, etc. It can be separated from the racemization reaction mixture.
  • This oxidation reaction can be carried out in either the liquid phase or the gas phase, but is preferably carried out in the liquid phase.
  • the amount of the ruthenium-supported titania catalyst used is usually 0.000001 to 1 mol, preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0, as ruthenium with respect to 1 mol of the alcohol (A). 0.05 mole.
  • the substrate alcohol (A) may be, for example, a primary alcohol, a secondary alcohol, a monohydric alcohol or a polyhydric alcohol, and two or more of them are used as necessary. You can also.
  • R 5 and R 6 are each independently a hydrogen atom; or a hydrocarbon group, an aromatic group, which may be substituted with a halogeno group, a nitro group, an alkoxy group, a phenoxy group or an acyloxy group, Or, it represents a heterocyclic group, and R 5 and R 6 may be bonded to form a ring.
  • hydrocarbon group, aromatic group and heterocyclic group which may be substituted with a halogeno group, a nitro group, an alkoxy group, a phenoxy group or an acyloxy group are the same as those in the formula (3).
  • Examples where R 5 and R 6 are bonded to form a ring include cyclopentane ring, 2-methylcyclopentane ring, cyclohexane Ring, 2-methylcyclohexane ring, cycloheptane ring, 2-methylcycloheptane ring, cyclooctane ring, 2-methylcyclooctane ring, cyclododecane ring, 2-methylcyclododecane ring, norbornene ring, 1-indane ring, 1 -Tetralin ring, fluorene ring and the like.
  • alcohol (A) represented by the above formula (4) examples include methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol and 1-decanol.
  • the carbonyl compound (B) that is an oxidizing agent may be an aldehyde or a ketone. Moreover, not only a monocarbonyl compound but a polycarbonyl compound may be used. Two or more of these may be used as necessary. A compound represented by the formula (5) is preferable. Formula (5) will be specifically described in the section of carbonyl compound (B) as a substrate.
  • the amount of the carbonyl compound (B) used as the oxidizing agent is usually 1 mol or more, preferably 10 to 100 mol, per 1 mol of the alcohol (A).
  • the carbonyl compound (B) is preferably used as a solvent.
  • the oxidation reaction may be performed in the presence of a solvent.
  • the carbonyl compound (B) is preferably used as the solvent, but a solvent that is more inert than the alcohol may be used for the oxidation reaction.
  • halogenated aliphatic hydrocarbons such as dichloromethane, dichloroethane and chloroform
  • esters such as isobutyl acetate and t-butyl acetate
  • nitriles such as acetonitrile
  • aromatic carbonization such as benzene and toluene
  • Hydrogen Halogenated aromatic hydrocarbons such as chlorobenzene and trifluorotoluene.
  • the amount used is generally 1 to 100,000 parts by weight, preferably 10 to 10,000 parts by weight, per 100 parts by weight of the alcohol (A).
  • the reaction temperature of the oxidation reaction is usually 20 to 300 ° C., preferably 50 to 200 ° C., and the reaction pressure is usually 0.1 to 10 MPa. Moreover, the oxidation reaction may be performed continuously or batchwise.
  • various carbonyl compounds corresponding as oxidation products can be produced from the substrate alcohol (A).
  • a primary alcohol is used as the alcohol (A)
  • a secondary alcohol is used as the alcohol (A)
  • a corresponding ketone can be produced.
  • polyhydric alcohol is used as alcohol (A)
  • a corresponding polycarbonyl compound can be manufactured.
  • the oxidation product in the oxidation reaction solution is oxidized by subjecting the oxidation reaction mixture to operations such as filtration, concentration, washing, alkali treatment, and acid treatment as necessary, and then purifying it by distillation, crystallization, etc. It can be separated from the reaction mixture.
  • the amount of the ruthenium-supported titania catalyst used is usually 0.000001 to 1 mol, preferably 0.0001 to 0.1 mol, more preferably 0.001 to 1 mol of ruthenium with respect to 1 mol of the carbonyl compound (B). 0.05 mole.
  • the substrate carbonyl compound (B) may be an aldehyde or a ketone. Moreover, not only a monocarbonyl compound but a polycarbonyl compound may be used. Two or more of these may be used as necessary.
  • the substrate carbonyl compound (B) is preferably the following formula (5): (Wherein R 7 and R 8 are each independently a hydrogen atom; or a hydrocarbon group, an aromatic group, which may be substituted with a halogeno group, a nitro group, an alkoxy group, a phenoxy group or an acyloxy group; Alternatively, it represents a heterocyclic group, and R 7 and R 8 may combine to form a ring.) What is shown by is used.
  • hydrocarbon group, aromatic group and heterocyclic group which may be substituted with a halogeno group, a nitro group, an alkoxy group, a phenoxy group or an acyloxy group are the same as in the case of the formula (3).
  • R 7 and R 8 are combined to form a ring (expressed in a form containing a carbonyl carbon atom) include cyclopentane ring, 2-methylcyclopentane ring, cyclohexane ring, 2-methyl Cyclohexane ring, cycloheptane ring, 2-methylcycloheptane ring, cyclooctane ring, 2-methylcyclooctane ring, cyclododecane ring, 2-methylcyclododecane ring, norbornene ring, 1-indane ring, 1-tetralin ring, fluorene A ring is mentioned.
  • carbonyl compound (B) represented by the above formula (5) examples include formaldehyde, acetaldehyde, 1-propanal, 1-butanal, 1-pentanal, 1-hexanal, 1-heptanal, 1-octanal, 1- Decanal, 1-eicosanal, 3-methyl-1-butanal, 3,3-dimethyl-1-butanal, 4-methyl-1-pentanal, 2-methyl-1-pentanal, 2,2-dimethyl-1-pentanal, 5-methyl-1-hexanal, 3-chloro-1-propanal, acrolein, citral, benzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldehyde, p-chlorobenzaldehyde, p-nitrobenzaldehyde, 2-phenylethanal, 2 -(P-chlorophenyl Ethanal, cinnamaldehyde, furfural, 2-thiophen
  • the alcohol (A) as the reducing agent is not limited to monoalcohol but may be a polyol compound. Two or more of these may be used as necessary. Preferred is a compound represented by the formula (4) described above.
  • the amount of alcohol (A) used as a reducing agent is usually 1 mol or more, preferably 10 to 100 mol, per 1 mol of carbonyl compound (B).
  • the alcohol (A) is preferably used as a solvent.
  • the above reduction reaction may be performed in the presence of a solvent.
  • the solvent the alcohol (A) is preferably used, but a solvent which is more inert than the carbonyl compound may be used for the reduction reaction.
  • halogenated aliphatic hydrocarbons such as dichloromethane, dichloroethane and chloroform
  • esters such as isobutyl acetate and t-butyl acetate
  • nitriles such as acetonitrile
  • aromatic carbonization such as benzene and toluene
  • Halogenated aromatic hydrocarbons such as chlorobenzene and trifluorotoluene, and the like, which are more inactive than carbonyl compounds with respect to the reduction reaction.
  • the amount used is usually 1 to 100,000 parts by weight, preferably 10 to 10,000 parts by weight, per 100 parts by weight of the carbonyl compound (B).
  • the reaction temperature of the above reduction reaction is usually 20 to 300 ° C., preferably 50 to 200 ° C., and the reaction pressure is usually 0.1 to 10 MPa.
  • the said reduction reaction may be performed by a continuous type and may be performed by a batch type.
  • various corresponding alcohols can be produced as reduction products from the substrate carbonyl compound (B).
  • a corresponding primary alcohol can be produced
  • a ketone is used as the carbonyl compound (B)
  • a corresponding secondary alcohol can be produced.
  • a polycarbonyl compound is used as the carbonyl compound (B)
  • a corresponding polyhydric alcohol can be produced.
  • the reduction product in the reduction reaction solution is reduced by subjecting the reduction reaction mixture to operations such as filtration, concentration, washing, alkali treatment, and acid treatment as necessary, and then purifying by distillation, crystallization, etc. It can be separated from the reaction mixture.
  • the ruthenium content in the catalyst is measured by the IPC analysis method, the specific surface area of the catalyst and the support is measured by the BET method, the reaction mixture is analyzed by gas chromatography (DB-WAX capillary column), and the optical isomer is analyzed by liquid chromatography. Performed by chromatography (Chiralcel-OD column). The yield, reaction rate, enantiomeric excess (ee), and catalyst rotation speed of each product were calculated by the following formulas.
  • Example 1 Preparation of ruthenium-supported anatase titania catalyst (catalyst A) 8.3 mM an aqueous solution of ruthenium (III) chloride in 60 ml of anatase titania (manufactured by Ishihara Sangyo Co., Ltd., ST-01, particle size of about 4.9 nm, ratio) 2.0 g of surface area of 316 m 2 / g, anatase ratio ⁇ 100%) was added and suspended, and stirred at room temperature for 3 hours. At this time, the pH of the suspension was 2.0.
  • ruthenium-supported anatase-type titania catalyst A (ruthenium content 2.1 mass%, specific surface area 298 m 2 / g).
  • Example 2 Preparation of ruthenium-supported anatase-type titania catalyst (Catalyst B) Implementation was carried out except that the catalytic society reference catalyst JRC-TIO-1 (particle size of about 21 nm, specific surface area of 74 m 2 / g) was used as the anatase-type titania. The same operation as in Example 1 was performed to obtain a ruthenium-supported anatase-type titania catalyst B (ruthenium content 2.2 mass%, specific surface area 74 m 2 / g, anatase ratio ⁇ 100%).
  • the catalytic society reference catalyst JRC-TIO-1 particle size of about 21 nm, specific surface area of 74 m 2 / g
  • Comparative Example 1 Preparation of ruthenium-supported rutile-type titania catalyst (Comparative catalyst C) Instead of anatase-type titania, rutile-type titania (manufactured by Showa Denko KK, SUPER-TITANIA G-2, particle size of about 440 nm, specific surface area 3. The same operation as in Example 1 was carried out except that 2 m 2 / g and anatase ratio ⁇ 5%) were used, and a ruthenium-supported rutile-type titania catalyst (ruthenium content 2.2 mass%, specific surface area 7.0 m 2 / g) was obtained.
  • ruthenium-supported rutile-type titania catalyst ruthenium content 2.2 mass%, specific surface area 7.0 m 2 / g
  • Comparative Example 2 Preparation of Ruthenium-Supported ⁇ -Alumina Catalyst (Comparative Catalyst D) Instead of anatase-type titania, ⁇ -alumina (manufactured by Sumitomo Chemical Co., Ltd., KHS-24, particle size of about 9.4 nm, specific surface area of 160 m 2) Except for using / g), the same operation as in Example 1 was performed to obtain a ruthenium-supported ⁇ -alumina catalyst (ruthenium content 2.1 mass%, specific surface area 163 m 2 / g).
  • Example 3 Preparation of Ruthenium-Supported Anatase Type Titania Catalyst (Catalyst E)
  • Catalyst E As anatase type titania, AMT-600 (particle size: about 30 nm, specific surface area: 52 m 2 / g, anatase ratio ⁇ 100%) was used. Except for this, the same operation as in Example 1 was performed to obtain a ruthenium-supported anatase-type titania catalyst E (ruthenium content 2.2 mass%, specific surface area 51 m 2 / g).
  • Example 4 Preparation of ruthenium-supported anatase-type titania catalyst (catalyst F)
  • Catalyst F As anatase-type titania, P-25 (particle size of about 30 nm, specific surface area of 50 m 2 / g, anatase ratio ⁇ 80%) manufactured by Nippon Aerosil Co., Ltd. was used.
  • the ruthenium-supported anatase-type titania catalyst F (ruthenium content 2.2% by mass, specific surface area 49 m 2 / g) was obtained in the same manner as in Example 1 except for the above.
  • Example 5 Ruthenium-supported anatase-type titania catalyst (Catalyst A; 0.001 g as ruthenium) was suspended in 3 ml of toluene and stirred at room temperature for 5 minutes. To this, 0.122 g of 1-phenylethanol was added and stirred, oxygen gas was passed through the gas phase, and the reaction was performed by stirring at 80 ° C. for 30 minutes. As a result of analyzing the reaction mixture, the yield of methyl phenyl ketone was 49%, and the reaction rate was 0.33 mol / h / L.
  • Catalyst A 0.001 g as ruthenium
  • Example 6 Comparative Examples 3-4: Ruthenium-supported anatase-type titania: Instead of catalyst A, ruthenium-supported anatase-type titania: catalyst B (Example 6), ruthenium-supported rutile-type titania: comparative catalyst C (Comparative Example 3), ruthenium-supported ⁇ -alumina: comparative catalyst D The same operation as in Example 1 was performed except that (Comparative Example 4) was used, and an oxidation reaction of 1-phenylethanol was performed. The results are shown in Table 1.
  • Comparative Example 5 An oxidation reaction of 1-phenylethanol was carried out in the same manner as in Example 6 except that argon gas was circulated instead of oxygen gas. The results are shown in Table 1. As a result of analyzing the reaction mixture, the yield of methyl phenyl ketone was 1%, and the reaction rate was 0.01 mol / h / L. In Comparative Example 5, although the reaction proceeds, the produced aldehyde returns to the original substrate by the reverse reaction, and as a result, the apparent reaction yield is lowered.
  • Example 7 Ruthenium-supported anatase-type titania catalyst B (0.001 g as ruthenium) was suspended in 3 ml of toluene and stirred at room temperature for 5 minutes. In this, 0.122 g of 1-phenylethanol was added and stirred, oxygen gas was passed through the gas phase, and the reaction was carried out at a reaction temperature of 80 ° C. and a reaction time of 2 hours. As a result of analyzing the reaction mixture, the yield of methyl phenyl ketone was 99% or more.
  • Examples 8 to 17 As shown in Table 2, the reaction was carried out in the same manner as in Example 7 while changing the catalyst amount, the alcohol type, and the reaction time. Table 2 shows the results of analysis of aldehyde or ketone which is a reaction product corresponding to the alcohol of the substrate. In the oxidation reaction of the present invention, almost no carboxylic acid was produced, and the target products, aldehyde and ketone, could be selectively produced.
  • Example 18 In a 50 ml stainless steel autoclave, 0.5 g of ruthenium-supported anatase titania: catalyst B and 9 ml of toluene were added, suspended, and stirred at room temperature for 5 minutes. To this, 0.46 g of ethanol was added, and the reaction was carried out at a pressure of 0.58 MPaG with oxygen gas, a reaction temperature of 75 ° C., and a reaction time of 1 hour. As a result of analysis of the reaction mixture and the reaction gas, the formation of acetaldehyde and acetaldehyde diethyl acetal was confirmed. The ethanol conversion was 24%, the acetaldehyde selectivity was 97%, and the yield was 23.3%.
  • Comparative Examples 6 to 8 Ruthenium-supported anatase titania: Instead of catalyst B, ruthenium-supported ⁇ -alumina catalyst (Comparative Example 6), ruthenium-supported hydroxyapatite (manufactured by Wako Pure Chemical Industries, Ltd.) (Comparative Example 7), 5% ruthenium-supported activated carbon (N -E-Chemcat Co., Ltd.) (Comparative Example 8) was used except that the same operation as in Example 18 was performed to carry out an oxidation reaction of ethanol. The results are shown in Table 3. In Example 18 and Comparative Examples 6 to 8, the reaction time was set to 1 hour. It can be seen that even in such a short reaction time, Example 18 has higher acetaldehyde selectivity and yield than the comparative example.
  • Example 19 Ruthenium-supported anatase-type titania: 0.5 g of catalyst B and 4.6 g of ethanol were added to a 50 ml stainless steel autoclave and stirred, then pressurized to 0.58 MPaG with oxygen gas, reaction temperature 75 ° C., reaction time 1 hour. went. As a result of analyzing the reaction mixture and the reaction gas, the formation of acetaldehyde and acetaldehyde diethyl acetal was confirmed. The ethanol conversion was 6.9%, the acetaldehyde selectivity was 95%, and the yield was 6.5%.
  • Example 20 Ruthenium-supported anatase-type titania: Instead of catalyst B, ruthenium-supported anatase-type titania: catalyst E was used in the same manner as in Example 19 to carry out an oxidation reaction of ethanol. As a result, the formation of acetaldehyde and acetaldehyde diethyl acetal was confirmed. The ethanol conversion was 8.9%, the acetaldehyde selectivity was 90%, and the yield was 8.0%.
  • Example 21 Ruthenium-supported anatase-type titania: Instead of catalyst B, ruthenium-supported anatase-type titania: catalyst F was used in the same manner as in Example 19 to carry out an oxidation reaction of ethanol. As a result, the formation of acetaldehyde and acetaldehyde diethyl acetal was confirmed. The ethanol conversion was 8.8%, the acetaldehyde selectivity was 89%, and the yield was 7.8%.
  • Comparative Examples 9 to 11 Ruthenium-supported anatase titania: Instead of catalyst B, ruthenium-supported ⁇ -alumina catalyst (Comparative Example 9), ruthenium-supported hydroxyapatite (manufactured by Wako Pure Chemical Industries, Ltd.) (Comparative Example 10), 5% ruthenium-supported activated carbon (N -E-Chemcat Co., Ltd.) (Comparative Example 11) was used, and the same operation as in Example 19 was performed to perform an ethanol oxidation reaction. The results are shown in Table 4.
  • Example 22 All operations were performed in a glove box substituted with argon gas. Ruthenium-supported anatase-type titania catalyst A (0.001 g as ruthenium) was suspended in 3 ml of toluene and stirred at room temperature for 5 minutes. To this, 0.122 g of (R) -1-phenylethanol (manufactured by Wako Pure Chemical Industries, Ltd.): 0.122 g was added, and the reaction was performed by stirring at 80 ° C. for 1 hour in an argon atmosphere. As a result of analyzing the reaction mixture, the yield of 1-phenylethanol was 92%, and the enantiomeric excess (ee) was 2%.
  • Example 23 Comparative Examples 12-13: Instead of ruthenium-supported anatase titania catalyst A, ruthenium-supported anatase-type titania catalyst B (Example 23), ruthenium-supported rutile-type titania comparative catalyst C (Comparative Example 12), ruthenium-supported ⁇ -alumina comparative catalyst D (Comparative Example 13) ) was used in the same manner as in Example 22 to carry out a racemization reaction of (R) -1-phenylethanol. The results (yield and ee) are shown in Table 5.
  • Examples 24-29 As shown in Table 6, the reaction was carried out in the same manner as in Example 22 while changing the catalyst amount, the alcohol of the substrate, and the reaction time. The results (yield and ee) of the analysis of the reaction mixture are shown in Table 6.
  • Example 30 All operations were performed in a glove box substituted with argon gas. Ruthenium-supported anatase-type titania catalyst A (0.001 g as ruthenium) was suspended in 3 ml of 2-propanol, and the mixture was stirred at room temperature for 5 minutes. To this, 0.120 g of acetophenone was added, and the reaction was performed by stirring at 90 ° C. for 0.5 hours under an argon atmosphere. As a result of analyzing the reaction mixture, it was confirmed that 1-phenylethanol and acetone were produced. The yield of 1-phenylethanol was 51%, and the catalyst rotation speed was 118 / h.
  • Example 31 Comparative Examples 14-15: Instead of ruthenium-supported anatase titania catalyst A, ruthenium-supported anatase-type titania catalyst B (Example 31), ruthenium-supported rutile-type titania comparative catalyst C (Comparative Example 14), ruthenium-supported ⁇ -alumina comparative catalyst D (Comparative Example 15) ) was used in the same manner as in Example 30, except that acetophenone was reduced. The results (1-phenylethanol yield and catalyst rotation speed) are shown in Table 7.
  • Examples 32 to 40 As shown in Table 8, the reaction was carried out in the same manner as in Example 30 except that the substrate carbonyl compound and the reaction time were changed. The results of analyzing the reaction mixture (the yield of the corresponding alcohol) are shown in Table 8.

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Abstract

L'invention concerne un catalyseur d'anhydride titanique supporté par du ruthénium obtenu par suspension de l'anhydride titanique anatase dans une solution contenant du ruthénium trivalent, après quoi, une base est ajoutée afin d'amener le pH de la solution à au moins 8, et le support de ruthénium produit est séparé, ainsi qu'un procédé de fabrication associé. En outre, l'invention concerne un procédé permettant de fabriquer un composé contenant un groupe carbonyle, un procédé de racémisation d'alcool secondaire, un procédé d'oxydation d'alcool, et un procédé permettant de réduire un composé carbonyle par une réaction de transfert d'hydrure qui utilise le catalyseur obtenu.
PCT/JP2009/066214 2008-09-19 2009-09-17 Catalyseur utilise dans une reaction de transfert d'hydrure d'alcool, procede de fabrication associe, et procede de fabrication d'un compose contenant un groupe carbonyle WO2010032770A1 (fr)

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Cited By (5)

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JP2010126448A (ja) * 2008-11-25 2010-06-10 Showa Denko Kk β，γ−不飽和アルコールの水素化反応による飽和アルコールの製造方法
JP2012041335A (ja) * 2010-07-21 2012-03-01 Hokkaido Univ 糖アルコールの製造方法
EP2597081A1 (fr) 2011-11-25 2013-05-29 Basf Se Procédé de préparation de 2-alcenals 3-substitués, en particulier le prenal
CN106905122A (zh) * 2017-01-19 2017-06-30 大连理工大学 一种脂环醇经Oppenauer氧化反应制备脂环酮的方法
KR101827034B1 (ko) * 2010-11-22 2018-03-22 미츠비시 가스 가가쿠 가부시키가이샤 아다만탄폴리올의 제조 방법

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FI3286270T3 (fi) * 2015-04-20 2024-04-23 Advansix Resins & Chemicals Llc Alkyylioksiimeja sisältävä päällystekoostumus

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JPS60190240A (ja) * 1984-03-09 1985-09-27 Jgc Corp 触媒調製方法
JP2007176891A (ja) * 2005-12-28 2007-07-12 Kao Corp 含窒素化合物の製造方法

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010126448A (ja) * 2008-11-25 2010-06-10 Showa Denko Kk β，γ−不飽和アルコールの水素化反応による飽和アルコールの製造方法
JP2012041335A (ja) * 2010-07-21 2012-03-01 Hokkaido Univ 糖アルコールの製造方法
KR101827034B1 (ko) * 2010-11-22 2018-03-22 미츠비시 가스 가가쿠 가부시키가이샤 아다만탄폴리올의 제조 방법
EP2597081A1 (fr) 2011-11-25 2013-05-29 Basf Se Procédé de préparation de 2-alcenals 3-substitués, en particulier le prenal
WO2013076226A1 (fr) 2011-11-25 2013-05-30 Basf Se Procédé pour la préparation de 2-alcénals 3-substitués, en particulier de prénal
US9000227B2 (en) 2011-11-25 2015-04-07 Basf Se Process for preparing 3-substituted 2-alkenals, in particular prenal
CN106905122A (zh) * 2017-01-19 2017-06-30 大连理工大学 一种脂环醇经Oppenauer氧化反应制备脂环酮的方法
CN106905122B (zh) * 2017-01-19 2020-07-14 大连理工大学 一种脂环醇经Oppenauer氧化反应制备脂环酮的方法

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