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WO2011111672A1 - Procédé de production d'un ester d'acide carboxylique, catalyseur et procédé de production associé - Google Patents

Procédé de production d'un ester d'acide carboxylique, catalyseur et procédé de production associé Download PDF

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Publication number
WO2011111672A1
WO2011111672A1 PCT/JP2011/055286 JP2011055286W WO2011111672A1 WO 2011111672 A1 WO2011111672 A1 WO 2011111672A1 JP 2011055286 W JP2011055286 W JP 2011055286W WO 2011111672 A1 WO2011111672 A1 WO 2011111672A1
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primary alcohol
gold
palladium
crosslinkable functional
producing
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Japanese (ja)
Inventor
修 小林
浩之 宮村
亙輔 貝塚
龍一 上野
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University of Tokyo NUC
Eneos Corp
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University of Tokyo NUC
JX Nippon Oil and Energy Corp
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Priority to JP2012504457A priority Critical patent/JP5776066B2/ja
Publication of WO2011111672A1 publication Critical patent/WO2011111672A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
    • C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
    • B01J37/0201—Impregnation
    • B01J37/0211—Impregnation using a colloidal suspension
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B01J31/30—Halides

Definitions

  • the present invention relates to a method for producing a carboxylic acid ester from a primary alcohol in a single step, a catalyst suitably used in the production method, and a method for producing the same.
  • Non-patent Document 1 The oxygen oxidation reaction using gold nanosize clusters as a catalyst was reported in 1989 by Haruta et al. As being very highly active in the low temperature carbon monoxide oxidation reaction (Non-patent Document 1).
  • Non-patent Document 2 As for the oxidation reaction of alcohol to aldehyde, ketone and carboxylic acid by a metal catalyst using oxygen as an oxidizing agent, many examples using ruthenium or palladium catalyst have been reported for both homogeneous and solid phase catalysts. In recent years, many examples using gold clusters as catalysts have been reported (Non-patent Document 2).
  • Non-Patent Documents 3 to 4, Patent Document 1 The inventors of the present application have found that a highly active catalyst can be produced in palladium or palladium by supporting a transition metal nanosize cluster on a styrenic polymer using a microencapsulation method. Further, it has been reported that a carbonyl compound is produced by an oxidation reaction for a gold catalyst (Patent Document 2).
  • the object of the present invention is to provide a method for producing a carboxylic acid ester from a primary alcohol in a single step with high selectivity and a high conversion rate, a catalyst suitably used in the production method, and a method for producing the same. .
  • the present invention relates to a support obtained by crosslinking the crosslinkable functional group of a styrenic polymer having a side chain containing a crosslinkable functional group, and a catalyst having a gold-palladium nanosize cluster and carbon black supported on the support.
  • a carboxylic acid comprising a step of oxidizing a part of the primary alcohol in the presence of the acid, further generating a hemiacetal from the aldehyde generated by the oxidation and the remainder of the primary alcohol, and further obtaining a carboxylic acid ester by oxidizing the generated hemiacetal.
  • a method for producing an ester is provided.
  • the present invention also provides a carrier obtained by crosslinking the crosslinkable functional group of a styrenic polymer having a side chain containing a crosslinkable functional group, and a gold-palladium nanosize cluster and carbon black supported on the carrier.
  • a carrier obtained by crosslinking the crosslinkable functional group of a styrenic polymer having a side chain containing a crosslinkable functional group, and a gold-palladium nanosize cluster and carbon black supported on the carrier.
  • a catalyst and a base a part of the primary alcohol is oxidized, and further, a hemiacetal is generated from the aldehyde generated by the oxidation and the remainder of the primary alcohol.
  • carboxylic acid ester provided with the process to obtain is provided.
  • the primary alcohol is selected from a first primary alcohol having 1 or more carbon atoms and a primary alcohol having 1 to 4 carbon atoms, and the first primary alcohol.
  • a mixture of a second primary alcohol which is a primary alcohol having a smaller carbon number, wherein the first step oxidizes the first primary alcohol and further oxidizes the second aldehyde formed by oxidation of the first primary alcohol and the second primary alcohol. It is preferable that a hemiacetal is produced from the primary alcohol and a carboxylic acid ester is obtained by oxidation of the produced hemiacetal.
  • the second primary alcohol is a raw material alcohol for esterification and may have a function as a solvent.
  • primary alcohol (what consists only of 1 type of primary alcohol) can also be used as primary alcohol.
  • a part of the primary alcohol is subjected to oxidation to produce an aldehyde.
  • hemiacetal is generated from the aldehyde and the remainder of the primary alcohol, and further, by oxidation of the generated hemiacetal, a carboxylic acid ester having the same carbon number as the carboxyl group and the carbon number of the ester alkyl group is obtained.
  • the styrenic polymer preferably contains an epoxy group and a hydroxyl group as the crosslinkable functional group.
  • the styrene polymer is a polymerizable monomer represented by the following formula (1), a polymerizable monomer represented by the following formula (2), and the following formula: It is preferable that it is a polymer with the polymerizable monomer represented by (3).
  • the present invention provides a carrier obtained by crosslinking the crosslinkable functional group of a styrene polymer having a side chain containing a crosslinkable functional group, a gold-palladium nanosize cluster and carbon black supported on the carrier.
  • a catalyst is provided.
  • the present invention provides a monovalent or trivalent gold compound and a divalent or tetravalent palladium compound with a reducing agent in a solution containing a styrene polymer having a side chain containing a crosslinkable functional group and carbon black.
  • a first step of reduction, and a second solvent for supporting the gold-palladium nano-sized clusters and the carbon black on the styrene polymer by adding a poor solvent for the styrene polymer to the solution to cause phase separation.
  • a catalyst production method for obtaining a catalyst comprising a support obtained by crosslinking a crosslinkable functional group, a gold-palladium nanosize cluster supported on the support, and carbon black.
  • the weight average molecular weight of the styrene polymer is preferably 10,000 to 150,000.
  • the crosslinkable functional group of the styrenic polymer is preferably crosslinked by heating.
  • the reducing agent is preferably a borohydride compound, an aluminum hydride compound, or a silicon hydride compound.
  • the gold compound is preferably a gold halide or a triphenylphosphine complex of gold halide.
  • the palladium compound is preferably palladium halide, palladium halide alkali metal salt, or palladium acetate.
  • the gold compound is preferably AuCl (PPh 3 ), and the palladium compound is preferably (CH 3 COO) 2 Pd.
  • FIG. 1 It is the schematic which shows the distribution system apparatus used for reaction in Example 5, 6.
  • FIG. 1 It is the schematic which shows the distribution system apparatus used for reaction in Example 5, 6.
  • the catalyst according to the first embodiment of the present invention comprises a support obtained by crosslinking the crosslinkable functional group of a styrene polymer having a side chain containing a crosslinkable functional group, and a gold-palladium supported on the support. Having nano-sized clusters and carbon black.
  • the method for producing a catalyst according to the first embodiment of the present invention includes a styrenic polymer having a side chain containing a crosslinkable functional group, a monovalent or trivalent gold compound and a divalent or tetravalent palladium compound.
  • a second step of supporting the styrenic polymer on the styrenic polymer and a third step of crosslinking the crosslinkable functional group of the styrenic polymer after the second step.
  • Styrenic polymer and carbon black are a) dissolved in a suitable polar good solvent and mixed with a reducing agent and then aggregated with a suitable nonpolar poor solvent, or b) a suitable nonpolar or low polarity good It is carried out by dissolving in a solvent, mixing with a reducing agent, and then aggregating with a poor solvent having an appropriate polarity.
  • the gold-palladium cluster is supported by the interaction with the aromatic ring of the styrenic polymer.
  • Examples of good polar solvents include tetrahydrofuran (THF), dioxane, acetone, N, N-dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), and the like.
  • THF tetrahydrofuran
  • DMF dioxane
  • NMP N-methyl-2-pyrrolidone
  • toluene, dichloromethane, chloroform and the like can be used.
  • Examples of the polar poor solvent include methanol, ethanol, butanol, and amyl alcohol
  • examples of the nonpolar poor solvent include hexane, heptane, and octane.
  • the polymer concentration when the gold-palladium cluster is supported on the crosslinkable polymer varies depending on the solvent used and the molecular weight of the polymer, but is about 5.0 to 200 mg / mL, preferably 10 to 100 mg / ml.
  • the monovalent or trivalent gold compound is used in an amount of 0.01 to 0.5 mmol, preferably 0.03 to 0.2 mmol, relative to 1 g of the polymer.
  • the divalent or tetravalent palladium compound is used in an amount of 0.01 to 0.5 mmol, preferably 0.05 to 0.2 mmol, relative to 1 g of the polymer.
  • the reducing agent is used in an amount of 1 to 10 equivalents necessary for the reduction.
  • the sodium borohydride is a gold compound and 0.5 to 5 moles of the palladium compound is preferred.
  • the temperature and time required for the reduction depend on the kind of gold compound, palladium compound and reducing agent, but are usually between 0 ° C. and 50 ° C., preferably at room temperature for 1 to 24 hours.
  • the poor solvent for phase separation is used in an amount of 1 to 10 (v / v), preferably 2 to 5 times the amount of the good solvent, and is added dropwise in about 0.5 to 5 hours.
  • a gold halide or a triphenylphosphine complex of gold halide is preferable.
  • AuCl (PPh 3 ) is preferable.
  • the divalent or tetravalent palladium compound palladium halide, palladium halide alkali metal salt, and palladium acetate are preferable.
  • (CH 3 COO) 2 Pd is preferable.
  • Examples of carbon black include ketjen black.
  • a borohydride compound an aluminum hydride compound or a silicon hydride compound, preferably sodium borohydride or borane can be used.
  • the styrene polymer has a side chain containing a crosslinkable functional group.
  • the crosslinkable functional group preferably contains an epoxy group and a hydroxyl group.
  • the side chain containing a crosslinkable functional group may be composed of only a crosslinkable functional group, or may be one in which a crosslinkable functional group is bonded to a divalent group.
  • the upper divalent group may be a relatively short alkylene group, for example, an alkylene group having about 1 to 6 carbon atoms, but —R 1 (OR 2 ) w —, —R 1 (COOR 2 ) x -, or -R 1 (COOR 2) y ( oR 2) z - ( wherein, R 1 represents a covalent bond or 1 to 6 carbon atoms, preferably represents a covalent bond or an alkylene group having 1 or 2 carbon atoms , R 2 each independently represents an alkylene group having 2 to 4 carbon atoms, preferably 2 carbon atoms, w, x and z are integers of 1 to 10 and y represents 1 or 2. Those having a main chain are preferred because they are hydrophilic. Examples of such a preferable divalent group include —CH 2 (OC 2 H 4 ) 4 — and —CO (OC 2 H 4 ) 4 —.
  • a styrenic polymer for example, the following formula (4): (Wherein X a represents an alkylene group or an alkylene group containing an ether bond) or the following formula (5): (Wherein X b represents an alkylene group or an alkylene group containing an ether bond), the monomer having a structure represented by the formula: (Wherein X c represents an alkylene group or an alkylene group containing an ether bond) or the following formula (7): (Wherein X d represents an alkylene group or an alkylene group containing an ether bond), the monomer having the structure represented by 10 to 60% is contained in all the monomers, and the total of these is 100% or less. In addition, when the total of these is less than 100%, a styrenic polymer obtained by copolymerizing a monomer mixture containing a styrene monomer as the balance may be mentioned.
  • a polymerizable monomer represented by the following formula (1) As a preferred styrenic polymer, a polymerizable monomer represented by the following formula (1), a polymerizable monomer represented by the following formula (2), and a polymerizable monomer represented by the following formula (3) And a polymer with a monomer.
  • the styrenic polymer preferably contains 5 to 60%, more preferably 10 to 50%, of the polymerizable monomer represented by the formula (2). Further, the polymerizable monomer represented by the formula (3) is preferably contained in an amount of 10 to 60%, more preferably 20 to 50%. Moreover, it is preferable to include so that the sum total of the polymerizable monomer represented by Formula (2) and (3) may be less than 100%, and to contain the styrene monomer represented by Formula (1) as a remainder.
  • the weight average molecular weight of the styrene polymer is preferably 10,000 to 150,000.
  • the weight average molecular weight can be measured by gel permeation chromatography (GPC).
  • the gold compound and palladium compound as described above are dissolved in a suitable solvent as described above together with a reducing agent, the gold compound and palladium compound are first reduced.
  • the ligand is detached at that time. Reduced gold and palladium are incorporated as a cluster into the hydrophobic portion of the polymer and are stabilized even in a microscopic state by receiving electrons from the aromatic ring of the polymer. Thereafter, by adding a poor solvent for the polymer, the styrenic polymer carrying the gold-palladium cluster and the carbon black can be phase-separated.
  • the average diameter of one gold-palladium cluster supported on a styrene polymer together with carbon black is 20 nm or less, preferably 0.3 to 20 nm, more preferably 0.3 to 10 nm, still more preferably 0.3 to 5 nm. More preferably, the thickness is 0.3 to 2 nm, and most preferably 0.3 to 1 nm.
  • Many gold-palladium clusters are uniformly dispersed in the hydrophobic portion of the micelle (the aromatic ring of the styrenic polymer). It is considered to exist. Thus, since the metal is a minute cluster (minute metal lump), high catalytic activity can be exhibited.
  • the surrounding environment such as the diameter and valence of the gold-palladium cluster can be measured with a transmission electron microscope (TEM) or an extended X-ray absorption fine structure (EXAFS).
  • TEM transmission electron microscope
  • EXAFS extended X-ray absorption fine structure
  • the crosslinkable functional group of the styrenic polymer carrying the gold-palladium cluster and carbon black is crosslinked as described above.
  • the gold-palladium cluster is stabilized and insolubilized in various solvents, and leakage of the supported gold-palladium cluster can be prevented.
  • polymer chains carrying gold-palladium clusters can be bonded to each other, or can be bonded to an appropriate carrier such as a material having a crosslinking group.
  • the crosslinking reaction is carried out by reacting the crosslinkable functional group under heating and ultraviolet irradiation, preferably by heating, in a solvent-free condition.
  • the crosslinking reaction is a conventionally known method for crosslinking a linear organic polymer compound to be used.
  • a method using a crosslinking agent, a radical polymerization catalyst such as a peroxide or an azo compound This method can also be carried out according to a method of using an acid, a method of heating by adding an acid or a base, for example, a method of reacting by combining a dehydrating condensing agent such as carbodiimide and an appropriate crosslinking agent.
  • the temperature at which the crosslinkable functional group is crosslinked by heating is usually 50 to 200 ° C, preferably 70 to 180 ° C, more preferably 100 to 160 ° C.
  • the reaction time for the heat crosslinking reaction is usually 0.1 to 100 hours, preferably 1 to 50 hours, more preferably 2 to 10 hours.
  • the polymer-supported gold-palladium cluster produced as described above can be made into a lump or membrane, or fixed to a carrier.
  • a crosslinkable functional group for example, hydroxyl group or amino group
  • a carrier such as glass, silica gel, or resin
  • the polymer-supported gold-palladium cluster is It is firmly fixed on the surface.
  • the polymer-supported gold-palladium cluster composition is immobilized on the surface of a reaction vessel made of an appropriate resin or glass using the crosslinkable functional groups of micelles, the catalyst-supported reaction can be reused more easily. Can be used as a container.
  • cross-linked gold-palladium-containing polymer micelle has many pores and swells with an appropriate solvent to increase the surface area.
  • the supported gold and palladium form very small clusters of several nanometers or less.
  • the method for producing a carboxylic acid ester according to the second embodiment of the present invention includes a carrier obtained by crosslinking the crosslinkable functional group of a styrenic polymer having a side chain containing a crosslinkable functional group, and the carrier supported on the carrier.
  • a part of the primary alcohol is oxidized, and further, hemiacetal is generated from the aldehyde generated by the oxidation and the remainder of the primary alcohol, and the generated hemiacetal
  • a step of obtaining a carboxylic acid ester by oxidation of By using the above production method, a carboxylic acid ester of a carboxylic acid obtained from a primary alcohol and a solvent primary alcohol having the same or a small number of carbon atoms can be produced in a single step with high selectivity and high conversion.
  • the primary alcohol is selected from a first primary alcohol that is a primary alcohol having 2 or more carbon atoms and a primary alcohol having 1 to 4 carbon atoms, and the first primary alcohol.
  • the step is preferably a step of producing a hemiacetal from the second primary alcohol and further obtaining a carboxylic acid ester by oxidation of the produced hemiacetal.
  • the first primary alcohol is a substrate for the oxidation reaction.
  • the second primary alcohol is a substrate for the esterification reaction and may function as a solvent.
  • the second primary alcohol is selected from primary alcohols having 1 to 4 carbon atoms (so-called lower alcohols). The present inventors speculate that this is due to the fact that it functions effectively not only as a substrate for the esterification reaction but also as a solvent for the first primary alcohol.
  • R 3 represents an aliphatic group, an alicyclic aliphatic group, or an aromatic group, and R 3 includes a hetero atom. It may be.
  • the method for producing a carboxylic acid ester according to this embodiment is particularly effective when R 3 represents an alkyl group having 1 to 7 carbon atoms.
  • the amount of the first primary alcohol is preferably selected so that the first primary alcohol concentration is 0.05 mol / l or more based on the total amount of the mixture of the first primary alcohol and the second primary alcohol. .
  • R 4 when the second primary alcohol is represented by R 4 CH 2 OH, R 4 may be linear or branched.
  • primary alcohol (what consists only of 1 type of primary alcohol) can also be used as primary alcohol.
  • a part of the primary alcohol is subjected to oxidation to produce an aldehyde.
  • hemiacetal is generated from the aldehyde and the remainder of the primary alcohol, and further, by oxidation of the generated hemiacetal, a carboxylic acid ester having the same carbon number as the carboxyl group and the carbon number of the ester alkyl group is obtained.
  • Examples of the oxidizing agent used in the method for producing a carboxylic acid ester according to this embodiment include oxygen gas and air.
  • reaction solvent inert to the reaction may be added.
  • the reaction solvent may be a single solvent or a mixed solvent as long as it can swell the polymer and dissolve the substrate alcohol.
  • a mixed solvent of water and an organic solvent may be effective.
  • the organic solvent include benzotrifluoride (BTF).
  • BTF benzotrifluoride
  • the mixing ratio of water and organic solvent is preferably 1: 1 to 1:10 (volume ratio).
  • the catalyst amount is preferably 0.1 to 10% (mol / mol) as gold and 0.1 to 10% (mol / mol) as palladium with respect to the substrate.
  • the concentration of the substrate is 0.01 to 1 mmol / ml, preferably 0.05 to 0.5 mmol / ml.
  • the reaction temperature is 0 to 80 ° C., preferably room temperature to 60 ° C., and the reaction time is 1 to 50 hours.
  • the method for producing a carboxylic acid ester according to the third embodiment of the present invention includes a carrier obtained by crosslinking the crosslinkable functional group of a styrene polymer having a side chain containing a crosslinkable functional group, and the carrier supported on the carrier.
  • a catalyst having gold-palladium nano-sized clusters and carbon black and a base a part of the primary alcohol is oxidized, and further, a hemiacetal is generated from the aldehyde generated by the oxidation and the remainder of the primary alcohol, A step of obtaining a carboxylic acid ester by oxidation of the produced hemiacetal.
  • the method for producing a carboxylic acid ester according to the third embodiment is different from the second embodiment in that a base is present in addition to the specific catalyst, but the others are the same as those in the second embodiment. Therefore, the overlapping description is omitted here.
  • the above step is performed in the presence of a base.
  • a base it is preferable to use an aqueous solution of an alkali metal carbonate, alkali metal carboxylate or hydroxide salt.
  • an alkali metal carbonate, alkali metal carboxylate or hydroxide salt for example, potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate, cesium carbonate, sodium acetate, potassium acetate, sodium hydroxide, potassium hydroxide and the like can be mentioned.
  • alkali metal carbonates such as potassium carbonate, sodium carbonate, cesium carbonate, and potassium carbonate is particularly preferred.
  • the amount of the base is preferably 0.01 to 20 equivalents relative to the substrate. More preferably, it is 0.05 to 15 equivalents.
  • the concentration of the aqueous solution is not particularly limited, but is preferably about 0.05 to 2.0 mol / l.
  • 4-vinylbenzyl glycidyl ether was synthesized according to the method described in Patent Document 1. As other compounds, commercially available products were purified as necessary. The yield of the carboxylic acid ester obtained by the oxidation reaction was quantified by gas chromatography using an internal standard. As a gas chromatograph, GC-2010 manufactured by Shimadzu Corporation was used.
  • a catalyst (PI-CB / Au-Pd) was produced as follows. 500.0 mg of Polymer A obtained in Production Example 2 was dissolved in 32 mL of diglyme (made by Wako Pure Chemical Industries, Ltd., special grade), cooled to 0 ° C., and then 500.0 mg of Ketjen Black (Lion Corporation, carbon ECP) was added. added. After the mixture was stirred at 0 ° C. for 15 minutes, a solution of 53 mg of sodium borohydride dissolved in 8 mL of diglyme was slowly added to the mixture. After stirring this mixed solution at 0 ° C.
  • PI-CB / Au-Pd a black powder
  • 10-20 mg of PI-CB / Au-Pd was heated in a mixture of sulfuric acid and nitric acid in a weight ratio of 1: 1 at 200 ° C. for 3 hours, and after returning to room temperature, aqua regia was added.
  • the contents of gold and palladium in the catalyst were measured by ICP analysis of this solution.
  • Au 0.1470 mmol / g
  • Pd 0.1377 mmol / g.
  • Example 1 1-octanol (Tokyo Kasei Co., Ltd., special grade) (32.6 mg, 0.25 mmol), PI-CB / Au—Pd obtained in Production Example 3 (17 mg, Au content 0.1470 mmol / g, 1 mol in terms of Au) %), Potassium carbonate (Wako Pure Chemicals / special grade) (103.7 mg, 0.75 mmol), water (2.0 mL), methanol (distilled and stored with Molecular Sieves 3A) (2.0 mL) Mix in bottom flask. After stirring for 24 hours at room temperature under an oxygen atmosphere, the catalyst was filtered and recovered by washing with ethyl acetate and water.
  • Example 2 Example 1 except that the amount of potassium carbonate was 345.6 mg, 2.5 mmol, and that ethanol (distilled and added with molecular sieves 3A) was used instead of methanol as the solvent. Then, an oxidation reaction was performed. The reaction results (aldehyde yield, carboxylic acid yield, ester yield, alcohol recovery rate) are shown in Table 1.
  • Example 3 The oxidation reaction was performed in the same manner as in Example 1 except that the substrate (0.25 mmol) shown in Table 1 was used instead of 1-octanol (0.25 mmol) in Example 1.
  • the reaction results (aldehyde yield, carboxylic acid yield, ester yield, alcohol recovery rate) are shown in Table 1.
  • Example 4 The oxidation reaction was performed in the same manner as in Example 2 except that the substrate (0.25 mmol) shown in Table 1 was used instead of 1-octanol (0.25 mmol) in Example 2.
  • the reaction results (aldehyde yield, carboxylic acid yield, ester yield, alcohol recovery rate) are shown in Table 1.
  • Example 5 the reaction was performed by the following procedure using the flow system apparatus shown in FIG.
  • lines L1, L2 and L3 are connected to the top (upstream side) of a glass column 1 (inner diameter 5 mm, total length 100 mm), and the other ends of the lines L1, L2 and L3 are connected.
  • a line L4 is connected to the bottom (downstream side) of the glass column 1, and a container 5 is connected to the other end of the line L4.
  • the column 1 was heated to 60 ° C., methanol in which 0.108 mmol / mL of 1-octanol (manufactured by Tokyo Chemical Industry Co., Ltd., special grade) from the container 3 was dissolved was 0.0070 mL / min, and potassium carbonate ( Wako Pure Chemicals / special grade) 0.335 mmol / L of dissolved water was introduced into column 1 using 0.0035 mL / min and oxygen gas from oxygen cylinder 2 at 2 mL / min using a pump and a mass flow controller, Oxidation reaction in the flow system was performed.
  • Example 6 An oxidation reaction was carried out in the same manner as in Example 5 except that ethanol in which 0.108 mmol / mL 1-octanol was dissolved was ethanol and the flow rate was 0.0035 mL / min.
  • the reaction results (aldehyde yield, carboxylic acid yield, ester yield, alcohol recovery rate) are shown in Table 2.
  • Example 7 PI-CB / Au-Pd obtained in Production Example 3 (17.0 mg, Au content 0.1470 mmol / g, 0.0025 mmol in terms of Au), potassium carbonate (Wako Pure Chemicals / special grade) (345.6 mg, 2 0.5 mmol), water (4.0 mL), and ethanol (stored by adding molecular sieves 3A after distillation) (2.0 mL) were mixed in a round bottom flask. After stirring for 72 hours at room temperature under an oxygen atmosphere, the catalyst was recovered by filtration. The yield of ethyl acetate was determined by gas chromatography using chloroform as an internal standard substance. At this time, the number of revolutions of the catalyst was 767. Further, regarding the selectivity, the reaction product detected by gas chromatography was 100% ethyl acetate, and no aldehyde was detected. This result suggests that all ethanol has been converted to ethyl acetate.
  • a catalyst (PI-CB / Au-Pd) was produced as follows. 500.0 mg of Polymer A obtained in Production Example 2 was dissolved in 32 mL of diglyme (manufactured by Wako Pure Chemical Industries, Ltd., special grade), cooled to 0 ° C., stirred for 15 minutes, and then ketjen black (manufactured by Lion Corporation, carbon ECP). ) 500.0 mg was added and further stirred.
  • the solid was ground in a mortar to obtain 1.065 g of the target catalyst (PI-CB / Au-Pd).
  • concentrations of Au and Pd were measured by ICP.
  • the concentrations of Au and Pd in the catalyst were determined as Au: 0.107 mmol / g and Pd: 0.327 mmol / g.
  • reaction vessel was cooled in an ice bath, the inside of the test tube was returned to normal pressure, tetrachloroethane (32.0 mg, 190.6 ⁇ mol) was added as an internal standard, diluted with deuterated chloroform, and quantified by 1 H-NMR. It was. As a result, it was calculated as 0.14 mmol (0.41%) acetaldehyde, 5.0 mmol (14%) acetic acid, and 10.3 mmol (58%) ethyl acetate.

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Abstract

La présente invention concerne un procédé de production d'un ester d'acide carboxylique comprenant des procédés d'obtention d'un transporteur auquel sont réticulés les groupes fonctionnels réticulables d'un polymère du styrène ayant des chaînes latérales contenant des groupes fonctionnels réticulables, d'oxydation partielle d'un alcool primaire en présence d'un catalyseur comprenant des nano-agrégats d'or et de palladium supportés sur le transporteur et de noir de carbone, ainsi que la production d'un hémiacétal à partir de l'aldéhyde produit par oxydation et le reste de l'alcool primaire et pour finir l'obtention de l'ester d'acide carboxylique par le biais de l'oxydation de l'hémiacétal qui a été produit.
PCT/JP2011/055286 2010-03-10 2011-03-07 Procédé de production d'un ester d'acide carboxylique, catalyseur et procédé de production associé Ceased WO2011111672A1 (fr)

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JP2013067576A (ja) * 2011-09-21 2013-04-18 Jx Nippon Oil & Energy Corp アミド化合物の製造方法とその触媒
CN104292106A (zh) * 2013-07-17 2015-01-21 中国科学院大连化学物理研究所 一种一锅法制备有机羧酸酯的方法
CN110898831A (zh) * 2019-11-27 2020-03-24 中国科学院青岛生物能源与过程研究所 一种纳米金胶束催化剂及其制备方法与应用
WO2021235335A1 (fr) * 2020-05-18 2021-11-25 株式会社エーピーアイ コーポレーション Procédé de production d'acétaminophène

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JP5580613B2 (ja) * 2010-02-05 2014-08-27 独立行政法人科学技術振興機構 高分子担持金クラスター触媒を用いた非対称エステルの製法

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JP2007237116A (ja) * 2006-03-10 2007-09-20 Japan Science & Technology Agency 酸化反応用高分子担持金クラスター触媒
JP2009090204A (ja) * 2007-10-09 2009-04-30 Japan Science & Technology Agency 高分子担持二元金属クラスター触媒
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013067576A (ja) * 2011-09-21 2013-04-18 Jx Nippon Oil & Energy Corp アミド化合物の製造方法とその触媒
CN104292106A (zh) * 2013-07-17 2015-01-21 中国科学院大连化学物理研究所 一种一锅法制备有机羧酸酯的方法
CN104292106B (zh) * 2013-07-17 2016-09-28 中国科学院大连化学物理研究所 一种一锅法制备有机羧酸酯的方法
CN110898831A (zh) * 2019-11-27 2020-03-24 中国科学院青岛生物能源与过程研究所 一种纳米金胶束催化剂及其制备方法与应用
CN110898831B (zh) * 2019-11-27 2022-08-05 中国科学院青岛生物能源与过程研究所 一种纳米金胶束催化剂及其制备方法与应用
WO2021235335A1 (fr) * 2020-05-18 2021-11-25 株式会社エーピーアイ コーポレーション Procédé de production d'acétaminophène
JPWO2021235335A1 (fr) * 2020-05-18 2021-11-25
CN115397805A (zh) * 2020-05-18 2022-11-25 株式会社Api 乙酰氨基酚的制造方法
JP7690955B2 (ja) 2020-05-18 2025-06-11 Ｕｂｅ株式会社 アセトアミノフェンの製造方法

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