WO2024161880A1 - 有機化合物の製造方法、及びフローリアクター - Google Patents

有機化合物の製造方法、及びフローリアクター Download PDF

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WO2024161880A1
WO2024161880A1 PCT/JP2023/046825 JP2023046825W WO2024161880A1 WO 2024161880 A1 WO2024161880 A1 WO 2024161880A1 JP 2023046825 W JP2023046825 W JP 2023046825W WO 2024161880 A1 WO2024161880 A1 WO 2024161880A1
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phase
organic
flow reactor
organic compound
producing
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French (fr)
Japanese (ja)
Inventor
誠人 平野
一仁 和田
広和 松田
ガル アフリーン
アトゥール バンソード
篤 浦川
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Nitto Denko Corp
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Nitto Denko Corp
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
    • C07C53/02—Formic acid
    • C07C53/06—Salts thereof

Definitions

  • the present invention relates to a method for producing an organic compound and a flow reactor.
  • Patent Document 1 discloses a method for manufacturing an organic compound by contacting an aqueous medium containing a catalyst with an organic compound raw material using a microreactor.
  • the present invention relates to A method for producing an organic compound using a catalyst, comprising the steps of:
  • the manufacturing method includes:
  • the present invention provides a method for producing an organic compound, which comprises passing a gas phase, an aqueous phase, and an organic phase through a flow reactor to synthesize the organic compound from a starting compound contained in a raw material.
  • a flow reactor for producing an organic compound using a catalyst comprising: A flow reactor is provided through which a gas phase, an aqueous phase, and an organic phase pass during synthesis of the organic compound from a starting compound.
  • the present invention provides a new method for producing organic compounds using a flow reactor.
  • FIG. 1 is a schematic diagram showing an example of a flow reactor.
  • FIG. 2 is a schematic diagram showing a modified example of the flow reactor.
  • FIG. 3 is a schematic diagram showing an example of a system for producing an organic compound.
  • FIG. 4 is a schematic diagram showing another example of a system for producing an organic compound.
  • the method for producing an organic compound according to the first aspect of the present invention includes the steps of: A method for producing an organic compound using a catalyst, comprising the steps of: The manufacturing method includes: The method includes passing a gas phase, an aqueous phase, and an organic phase through a flow reactor to synthesize the organic compound from a starting compound contained in a raw material.
  • the raw material contains a gas capable of reacting with the starting compound, and the gas phase contains the gas.
  • the gas contains hydrogen, and the synthesis is carried out by a hydrogenation reaction of the starting compound with the hydrogen.
  • the starting compound is at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate, and a formate is synthesized from the starting compound by the reaction.
  • the organic phase contains the catalyst, and the aqueous phase contains the starting compound.
  • the flow reactor is a tubular reactor.
  • the flow reactor includes a portion filled with particles, and the gas phase, the aqueous phase, and the organic phase pass through the portion.
  • the particles contain silicon carbide.
  • the time during which the gas phase, the aqueous phase, and the organic phase pass through the flow reactor is 10 minutes or longer.
  • the method includes mixing the gas phase, the aqueous phase, and the organic phase before passing the gas phase, the aqueous phase, and the organic phase through the flow reactor.
  • the catalyst is a metal catalyst.
  • the metal catalyst contains ruthenium.
  • the organic phase contains toluene.
  • a flow reactor according to a fourteenth aspect of the present invention comprises: 1.
  • a flow reactor for producing an organic compound using a catalyst comprising: When the organic compound is synthesized from the starting compound, a gas phase, an aqueous phase, and an organic phase pass through the interior.
  • the flow reactor according to the fourteenth aspect is used in the production method according to any one of the first to thirteenth aspects.
  • the method for producing an organic compound according to this embodiment is a method for producing an organic compound using a catalyst.
  • the method for producing an organic compound according to this embodiment includes passing a gas phase, an aqueous phase, and an organic phase through a flow reactor to synthesize an organic compound from a starting compound contained in the raw materials.
  • the aqueous phase is a phase that contains an aqueous solvent
  • the organic phase is a phase that contains an organic solvent
  • the gas phase is a phase that contains a gas.
  • the aqueous solvent and the organic solvent may be collectively referred to as the solvent.
  • the organic phase and the aqueous phase may be collectively referred to as the reaction liquid.
  • a flow reactor is a flow reactor for synthesizing an organic compound from a starting compound using a catalyst, and a gas phase, an aqueous phase, and an organic phase pass through the inside of the flow reactor when an organic compound is synthesized from the starting compound contained in the raw material.
  • the flow reactor may be, for example, a plug flow reactor (PFR) or a continuous stirred tank reactor (CSTR).
  • the flow reactor may be a tubular reactor.
  • FIG. 1 is a schematic diagram showing an example of a flow reactor.
  • the flow reactor 1 is a tubular reactor equipped with an inlet 2 for supplying a gas phase, an aqueous phase, and an organic phase, a tubular reactor section 3 through which the gas phase, the aqueous phase, and the organic phase pass, and an outlet 4 for discharging the passed gas phase, the aqueous phase, and the organic phase.
  • the gas phase, the aqueous phase, and the organic phase may be supplied to the flow reactor 1 from one inlet.
  • the inlet 2 may include two inlets, for example, a gas phase supply port for supplying the gas phase and a reaction liquid supply port for supplying the aqueous phase and the organic phase, or may include three inlets, for example, a gas phase supply port for supplying the gas phase, an aqueous phase supply port for supplying the aqueous phase, and an organic phase supply port for supplying the organic phase.
  • the outlet 4 may be equipped with a back pressure regulator.
  • the flow reactor 1 may include a portion filled with particles.
  • the gas phase, aqueous phase, and organic phase passing through the flow reactor 1 may pass through the above-mentioned portion.
  • part or all of the reactor section 3 may be filled with particles. There may be multiple portions filled with particles.
  • the solvent mixes at the location where the particles are present, and the gas phase (gaseous raw material) is entrained in the solvent, resulting in a good mix of the gas phase, aqueous phase, and organic phase. This tends to increase the frequency of contact between the starting compound, catalyst, etc., and therefore allows for efficient synthesis of organic compounds.
  • the shape of the particles is not particularly limited and may be spherical, ellipsoidal, hollow cylindrical, scaly, fibrous, or irregular.
  • the particles are preferably an inert material that does not react with the catalyst.
  • the particle material are carbide, polytetrafluoroethylene (PTFE), glass, and aluminum oxide.
  • carbide are silicon carbide and calcium carbide.
  • the particle material may be silicon carbide. Silicon carbide tends to have a properly adjusted surface condition (e.g., degree of hydrophobicity and hydrophilicity). Therefore, it is presumed that silicon carbide is suitable for good mixing of a solvent containing an aqueous phase and an organic phase, and for contact of a gas phase, an aqueous phase, and an organic phase.
  • the specific surface area of the particles is, for example, 0.1 m 2 /g or more and 1500 m 2 /g or less.
  • the specific surface area is a BET specific surface area that can be measured by the BET method.
  • the average particle size of the particles is, for example, 100 ⁇ m or more, 200 ⁇ m or more, 500 ⁇ m or more, 600 ⁇ m or more, 1000 ⁇ m or more, or even 1100 ⁇ m or more.
  • the average particle size of the particles is, for example, 10,000 ⁇ m or less, 5,000 ⁇ m or less, 3,000 ⁇ m or less, or even 2,300 ⁇ m or less.
  • the average particle size of the particles is, for example, 100 ⁇ m or more and 10,000 ⁇ m or less, preferably 200 ⁇ m or more and 3,000 ⁇ m or less, and more preferably 500 ⁇ m or more and 3,000 ⁇ m or less.
  • the size of the droplets of the aqueous phase and the organic phase and the size of the bubbles of the gas phase can be reduced, and it is presumed that this is more suitable for good stirring of the solvent containing the aqueous phase and the organic phase, and for contact of the gas phase, the aqueous phase, and the organic phase.
  • the particle diameter when the particle diameter is large within the above numerical range, it is considered that the effect of reducing the size of the droplets in the aqueous phase and the organic phase and the size of the bubbles in the gas phase is high, and it is presumed that it is more suitable for good stirring of the solvent containing the aqueous phase and the organic phase, and for contact of the gas phase, the aqueous phase, and the organic phase.
  • the "average particle diameter" can be determined, for example, by a laser diffraction scattering method.
  • the average particle diameter is the 50% cumulative value (median diameter) d50, which is determined, for example, by using a particle size distribution meter (Microtrac MT3300EXII) manufactured by Microtrac Bell Co., Ltd., from a particle size distribution curve in which the frequency is expressed as a volume-based fraction.
  • d50 50% cumulative value (median diameter) d50, which is determined, for example, by using a particle size distribution meter (Microtrac MT3300EXII) manufactured by Microtrac Bell Co., Ltd., from a particle size distribution curve in which the frequency is expressed as a volume-based fraction.
  • the material of the reactor section 3 can be selected from metal, ceramics, resin, etc.
  • the material of the reactor section 3 is, for example, metal, and may be stainless steel.
  • the internal volume of the reactor section 3 (i.e., the internal volume of the flow reactor 1) may be 1.0 mL or more and 100,000 mL or less.
  • the flow reactor 1 may be a tube with a length of 50.0 cm or more and 5,000 cm or less and an inner diameter of 0.1 cm or more and 20 cm or less.
  • the flow reactor 1 may be a bent tubular reactor.
  • FIG. 2 is a schematic diagram showing a modified example of a flow reactor.
  • the flow reactor 10 has an inlet 20, a reactor section 30, and an outlet 40.
  • the reactor section 30 is bent at a bent section 31.
  • the gas phase comprises a gas.
  • the gas phase may comprise at least a portion of the raw material.
  • the gas phase may comprise a gas capable of reacting with the starting compound.
  • the gas comprises, for example, hydrogen.
  • Hydrogen sources that can be used include, for example, hydrogen generated during the iron smelting process and hydrogen generated during the soda manufacturing process. Hydrogen generated from the electrolysis of water can also be used.
  • the gas phase may include the starting compound.
  • the starting compound is carbon dioxide
  • the gas phase may include the starting compound.
  • the carbon dioxide may be pure carbon dioxide gas or may be mixed with other components other than carbon dioxide.
  • components other than carbon dioxide include inert gases such as nitrogen and argon, water vapor, and any other components contained in exhaust gases.
  • the ratio of hydrogen and carbon dioxide used may be equal on a molar basis, but an excess of hydrogen is preferred.
  • the aqueous phase comprises an aqueous solvent and may further comprise a starting compound.
  • aqueous solvents examples include water, methanol, ethanol, ethylene glycol, glycerin, and mixtures of these, with water being preferred from the standpoint of low environmental impact.
  • the aqueous phase may include an aqueous solvent and a starting compound.
  • the starting compound is, for example, an inorganic substance.
  • the inorganic substance is, for example, carbon dioxide, bicarbonate, and carbonate. That is, the starting compound may be at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate.
  • bicarbonates and carbonates include carbonates or bicarbonates of alkali metals or alkaline earth metals.
  • bicarbonates include sodium bicarbonate, potassium bicarbonate, etc., with potassium bicarbonate being preferred from the viewpoint of high solubility in water. That is, in this embodiment, it is preferable that the starting compound contains potassium bicarbonate as the bicarbonate.
  • carbonates include sodium carbonate, potassium carbonate, potassium sodium carbonate, sodium sesquicarbonate, etc.
  • Bicarbonates and carbonates can be produced by the reaction of carbon dioxide with a base.
  • bicarbonates or carbonates may be produced by introducing carbon dioxide into a basic solution.
  • the solvent for the basic solution in the production of bicarbonates or carbonates is not particularly limited, but examples include water, methanol, ethanol, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, and mixed solvents of these, and preferably contains water, and more preferably is water.
  • the base used in the basic solution is not particularly limited as long as it can react with carbon dioxide to produce bicarbonates or carbonates, and is preferably a hydroxide. Examples include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, potassium hydroxide, sodium hydroxide, diazabicycloundecene, triethylamine, and the like. Of the above, hydroxides are preferred, potassium hydroxide and sodium hydroxide are more preferred, and potassium hydroxide is even more preferred.
  • the content of the base in the basic solution is not particularly limited as long as it is possible to produce bicarbonate and carbonate.
  • the content of the base is preferably 0.1 mol or more per 1 L of aqueous phase solvent, more preferably 0.5 mol or more, and even more preferably 1 mol or more.
  • the content of the base is preferably 30 mol or less, more preferably 20 mol or less, and even more preferably 15 mol or less. However, if the solubility of the aqueous phase is exceeded, the solution will become suspended.
  • the ratio of the amount of carbon dioxide and the amount of base used in the reaction of carbon dioxide and the base is preferably 0.1 or more in terms of generating carbonate from carbon dioxide, more preferably 0.5 or more, and even more preferably 1.0 or more in terms of molar ratio. In addition, from the viewpoint of the utilization efficiency of carbon dioxide, it is preferably 8.0 or less, more preferably 5.0 or less, and even more preferably 3.0 or less.
  • the ratio of the amount of carbon dioxide and the amount of base used is the molar amount (mol) of CO2 /molar amount (mol) of base.
  • the reaction temperature in the reaction of carbon dioxide with a base to produce bicarbonate or carbonate is not particularly limited, but in order to dissolve carbon dioxide in the aqueous phase, it is preferably 0°C or higher, more preferably 10°C or higher, and even more preferably 20°C or higher. It is also preferably 100°C or lower, more preferably 80°C or lower, and even more preferably 40°C or lower.
  • the reaction time in the reaction of carbon dioxide with a base to produce bicarbonate or carbonate is not particularly limited, but from the viewpoint of ensuring a sufficient amount of bicarbonate or carbonate produced, it is preferably 0.5 hours or more, more preferably 1 hour or more, and even more preferably 2 hours or more. From the viewpoint of cost, it is preferably 24 hours or less, more preferably 12 hours or less, and even more preferably 6 hours or less.
  • the organic phase contains an organic solvent.
  • the organic phase may further contain a catalyst.
  • the organic phase preferably contains a catalyst and a solvent that dissolves the catalyst to become homogeneous.
  • organic solvents examples include toluene, benzene, xylene, propylene carbonate, dioxane, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, methylcyclohexane, cyclopentyl methyl ether, and mixed solvents thereof. From the viewpoint of separability from the aqueous solvent, it is preferable that the organic solvent contains toluene or dioxane, and it is more preferable that the organic solvent contains toluene.
  • the catalyst is, for example, a metal catalyst.
  • the metal catalyst includes, for example, ruthenium.
  • a catalyst at least one compound selected from the group consisting of a metal complex represented by the following general formula (1A), its tautomers, stereoisomers, and salts thereof.
  • X represents an atomic group containing a typical element of Groups 13 to 15 capable of coordinating to M;
  • Q independently represents a bridge structure connecting Y and X and containing a typical element of Group 14 to Group 16;
  • Each Y independently represents an atomic group containing a typical element of Group 14 to 16 capable of coordinating to M;
  • M represents a metal atom;
  • Z represents a halogen atom or a hydrogen atom;
  • n represents 0 to 3;
  • each L independently represents a neutral or anionic ligand.
  • Group n means “Group n of the periodic table.”
  • X is a typical element of Groups 13 to 15 of the periodic table, and examples thereof include a boron atom, a carbon atom, a silicon atom, a germanium atom, a tin atom, a nitrogen atom, a phosphorus atom, an arsenic atom, an oxygen atom, a sulfur atom, and a selenium atom.
  • a boron atom, a carbon atom, a silicon atom, a germanium atom, a tin atom, a nitrogen atom, a phosphorus atom, and an arsenic atom are preferred, a carbon atom, a nitrogen atom, a phosphorus atom, and a sulfur atom are more preferred, and a carbon atom or a nitrogen atom is even more preferred.
  • X may be an atomic group having a valence of 0 to 1.
  • Examples of the atomic group represented by X include an alkyl group, an alkenyl group, an alkoxy group, an aromatic ring, and a heterocyclic ring, which may have a substituent or may be bonded to another substituent to form a ring.
  • the alkyl group in X may be a linear, branched, or cyclic substituted or unsubstituted alkyl group.
  • the alkyl group in X is preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, an n-octyl group, an eicosyl group, or a 2-ethylhexyl group, and is preferably an alkyl group having 6 or less carbon atoms, and is preferably a methyl group.
  • the alkenyl group in X may be a linear, branched, or cyclic substituted or unsubstituted alkenyl group.
  • the alkenyl group in X is preferably an alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an n-propenyl group, an i-propenyl group, a t-butenyl group, or an n-octenyl group, and is preferably an alkenyl group having 6 or less carbon atoms.
  • the alkoxy group in X may be a linear, branched, or cyclic substituted or unsubstituted alkoxy group.
  • the alkoxy group in X may be a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, or a 2-methoxyethoxy group.
  • Examples of the aromatic ring in X include a phenyl ring and a naphthyl ring.
  • heterocyclic ring in X examples include a pyrrolidine ring, a piperidine ring, a pyrroline ring, an imidazoline ring, an imidazolidine ring, a pyrrole ring, an imidazole ring, a pyridine ring, a pyrimidine ring, a triazine ring, a quinoline ring, and a quinazoline ring.
  • the zero- to monovalent atomic group represented by X preferably represents an atomic group containing a heteroaromatic ring formed with two carbon atoms and a nitrogen atom, which may have a substituent or may combine with other substituents to form a ring.
  • the zero- to monovalent atomic group represented by X is preferably a pyrroline ring, a pyridine ring, an imidazoline ring, a pyrimidine ring, or a triazine ring, more preferably a pyridine ring or a triazine ring, and even more preferably a pyridine ring.
  • substituents include those in Substituent Group A, with alkyl groups being preferred and methyl groups being more preferred.
  • the bridge structure represented by Q that connects Y and X and contains a typical element from Groups 14 to 16 of the periodic table may have a double bond, a monocyclic structure or a condensed ring structure, or a substituent.
  • the number of atoms in the portion between Y and X is preferably 1 to 5, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 1 to 2.
  • the atom between Y and X is not particularly limited, but is preferably a carbon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom, more preferably a carbon atom, a nitrogen atom, or an oxygen atom, even more preferably a carbon atom or an oxygen atom, and particularly preferably a carbon atom.
  • Q may have a single ring structure.
  • the bridged structure represented by Q may contain a ring structure.
  • the monocyclic structure may be directly bonded to Y and X in general formula (1A), or a divalent substituent may be sandwiched between the monocyclic structure and Y and/or Z in general formula (1A).
  • the divalent substituent include an alkylene group having 1 to 5 carbon atoms, an alkenylene group having 2 to 5 carbon atoms, an oxygen atom, a heteroatom such as a sulfur atom, or a combination of these bonded in series.
  • Each Q preferably independently represents CH 2 , NH, or O, and CH 2 and NH may further have a substituent, more preferably CH 2 or NH.
  • Q may have a fused ring structure.
  • the bridged structure represented by Q may contain a fused ring structure.
  • the fused ring structure may be directly bonded to Y and X in general formula (1A), or a divalent substituent may be sandwiched between the fused ring structure and Y and/or X in general formula (1A).
  • the divalent substituent is the same as the divalent substituent sandwiched between the monocyclic structure and Y and/or X in general formula (1A) described above.
  • Q may have a substituent.
  • the substituent is a substituent of the Q portion of the ring structure that includes Q, Y, X, and M in general formula (1A).
  • the substituent is a substituent of the monocyclic or condensed ring structure, or a substituent of the Q portion of another ring structure including Q, Y, X, and M in general formula (1A).
  • the substituent that Q may have may, for example, have a heteroatom or may be another atom or atomic group.
  • Examples of the substituent having a heteroatom include an alkoxy group having 1 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an acyl group having 2 to 18 carbon atoms, an aroyl group having 7 to 18 carbon atoms, a dialkylamino group having 2 to 18 carbon atoms, an oxygen atom, a sulfur atom, etc.
  • the other atoms or atomic groups include, for example, aromatic groups having 3 to 18 carbon atoms, alkyl groups having 1 to 18 carbon atoms, halogen atoms, etc.
  • aromatic groups include aryl groups having 6 to 20 carbon atoms, such as phenyl, xylyl, naphthyl, and biphenyl.
  • the number of carbon atoms in Q is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.
  • Y may be an atomic group with a valence of 0 to 1.
  • Each Y independently represents an atomic group with a valence of 0 to 1, including a typical element of Groups 14 to 16 of the periodic table that can be coordinated to M, and may further have a substituent.
  • typical elements of Groups 14 to 16 of the periodic table carbon atom, nitrogen atom, phosphorus atom, arsenic atom, oxygen atom, sulfur atom, and selenium atom are preferred, carbon atom, nitrogen atom, phosphorus atom, and arsenic atom are more preferred, nitrogen atom and phosphorus atom are even more preferred, and phosphorus atom is particularly preferred.
  • both Y's represent a nitrogen atom or a phosphorus atom, or that one Y represents a phosphorus atom and the other Y represents a nitrogen atom.
  • examples of the substituent include those in the substituent group A, and an alkyl group or an aryl group is preferable, and an ethyl group, a t-butyl group, or a phenyl group is more preferable.
  • M represents a metal atom, and examples thereof include elements of Groups 8 to 11 of the periodic table, such as iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, and gold.
  • iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, and copper are preferred, ruthenium, rhodium, iridium, nickel, and palladium are more preferred, ruthenium, rhodium, iridium, and palladium are even more preferred, and ruthenium (Ru) is particularly preferred.
  • Z preferably represents a halogen atom, more preferably a chlorine atom.
  • n represents an integer from 0 to 3, and indicates the number of ligands coordinated to the metal atom represented by M. From the viewpoint of catalyst stability, n is preferably 2 or 3.
  • Examples of the neutral ligand represented by L include ammonia, carbon monoxide, phosphines (e.g., triphenylphosphine, tris(4-methoxyphenyl)phosphine), phosphine oxides (e.g., triphenylphosphine oxide), sulfides (e.g., dimethyl sulfide), sulfoxides (e.g., dimethyl sulfoxide), ethers (e.g., diethyl ether), nitriles (e.g., p-methylbenzonitrile), heterocyclic compounds (e.g., pyridine, N,N-dimethyl-4-aminopyridine, tetrahydrothiophene, tetrahydrofuran), etc., preferably triphenylphosphine.
  • phosphines e.g., triphenylphosphine, tris(4-methoxyphenyl)pho
  • anionic ligand represented by L examples include a hydride ion (hydrogen atom), a nitrate ion, a cyanide ion, etc., and preferably a hydride ion (hydrogen atom).
  • X represents a heterocycle
  • Q represents CH 2 , NH or O
  • Y represents a phosphorus atom
  • M represents ruthenium
  • Z represents a chlorine atom
  • n represents 1 to 3
  • each L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.
  • the metal complex represented by general formula (1A) is preferably a metal complex represented by the following general formula (2A).
  • X 1 represents a heteroaromatic ring formed together with two carbon atoms and a nitrogen atom, which may have a substituent or may be bonded to other substituents to form a ring;
  • Q1 's each independently represent CH2 , NH, or O, and CH2 and NH may further have a substituent;
  • Each Y independently represents a phosphorus atom or a nitrogen atom;
  • Each R independently represents an alkyl group, an aryl group, or an aralkyl group, each of which may further have a substituent;
  • M represents a metal atom;
  • Z represents a halogen atom or a hydrogen atom;
  • n represents 0 to 3;
  • M, Q1 , Z, n and L in formula (2A) have the same meanings as M, Q, Z, n and L in formula (1A), respectively, and the preferred ranges are also the same.
  • the heteroaromatic ring formed together with the two carbon atoms and the nitrogen atom represented by X 1 is preferably a pyrroline ring, a pyridine ring, an imidazoline ring, a pyrimidine ring, or a triazine ring, more preferably a pyridine ring or a triazine ring, and even more preferably a pyridine ring.
  • Examples of the substituent that X 1 may have include the substituent group A, and an alkyl group is preferable, and a methyl group is more preferable.
  • Y 1 represents a phosphorus atom or a nitrogen atom, and both Y 1 may represent a nitrogen atom or a phosphorus atom, or one Y 1 may represent a phosphorus atom and the other Y 1 may represent a nitrogen atom. It is preferable that both Y 1 are nitrogen atoms or phosphorus atoms, and it is more preferable that both Y 1 are nitrogen atoms.
  • the alkyl group represented by R may be a linear, branched, or cyclic substituted or unsubstituted alkyl group.
  • the alkyl group represented by R is preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, an n-octyl group, an eicosyl group, or a 2-ethylhexyl group. From the viewpoint of catalytic activity, an alkyl group having 12 or less carbon atoms is preferable, an ethyl group or a t-butyl group is preferable, and a t-butyl group is more preferable.
  • the aryl group represented by R includes substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, and o-hexadecanoylaminophenyl groups, and is preferably an aryl group having 12 or less carbon atoms, and more preferably a phenyl group.
  • R further has a substituent
  • substituents include those in the substituent group A, of which methyl, ethyl, i-propyl, t-butyl, and phenyl are preferred, and ethyl, i-propyl, and t-butyl are more preferred.
  • X1 represents a pyridine ring or a triazine ring
  • Q1 represents CH2 , NH or O
  • Y1 represents a phosphorus atom
  • R represents an ethyl group, a t-butyl group or a phenyl group
  • M represents ruthenium.
  • Z represents a chlorine atom
  • n represents 1 to 3
  • each L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.
  • the metal complex represented by general formula (2A) is preferably a metal complex represented by the following general formula (3A).
  • R represents a hydrogen atom or an alkyl group
  • Each A independently represents CH, CR5 , or N, where R5 represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxyl group, or an alkoxy group
  • Each Q1 independently represents CH2 , NH, or O, and CH2 and NH may further have a substituent
  • Y represents a phosphorus atom or a nitrogen atom
  • Each R independently represents an alkyl group, an aryl group, or an aralkyl group, each of which may further have a substituent
  • M represents a metal atom
  • Z represents a halogen atom or a hydrogen atom
  • n represents 0 to 3
  • each L independently represents a neutral or anionic ligand.
  • Y1 , R, Q1 , M, Z, n and L have the same meanings as Y1 , R, Q1 , M, Z, n and L in formula (2A), respectively, and the preferred ranges are also the same.
  • R 0 represents a hydrogen atom or an alkyl group.
  • the alkyl group represented by R 0 include linear, branched, and cyclic substituted or unsubstituted alkyl groups.
  • the alkyl group represented by R 0 include preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, an n-octyl group, an eicosyl group, and a 2-ethylhexyl group. From the viewpoint of ease of procurement of raw materials, an alkyl group having 6 or less carbon atoms is preferable, and a methyl group is preferable.
  • R 0 is preferably a hydrogen atom or a methyl group.
  • Each A independently represents CH, CR 5 , or N, and R 5 represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxyl group, or an alkoxy group.
  • Examples of the alkyl group represented by R5 include linear, branched, and cyclic substituted or unsubstituted alkyl groups.
  • Examples of the alkyl group represented by R5 include preferably alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, t-butyl, n-octyl, eicosyl, and 2-ethylhexyl groups, and from the viewpoint of ease of procurement of raw materials, alkyl groups having 12 or less carbon atoms are preferred, and methyl groups are preferred.
  • Examples of the aryl group represented by R5 include substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group, a m-chlorophenyl group, and an o-hexadecanoylaminophenyl group.
  • An aryl group having 12 or less carbon atoms is preferred, and a phenyl group is more preferred.
  • the aralkyl group represented by R5 includes a substituted or unsubstituted aralkyl group having 30 or less carbon atoms, such as a trityl group, a benzyl group, a phenethyl group, a tritylmethyl group, a diphenylmethyl group, a naphthylmethyl group, etc., and is preferably an aralkyl group having 12 or less carbon atoms.
  • the alkoxy group represented by R 5 is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, or a 2-methoxyethoxy group.
  • X1 represents a pyridine ring or a triazine ring
  • Q1 represents CH2 , NH or O
  • Y1 represents a phosphorus atom
  • R represents an ethyl group, a t-butyl group or a phenyl group
  • M represents ruthenium.
  • Z represents a chlorine atom
  • n represents 1 to 3
  • each L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.
  • the metal complex represented by general formula (3A) is preferably a ruthenium complex represented by the following general formula (4A).
  • the ruthenium complex represented by the general formula (4A) is soluble in organic solvents and insoluble in water, and is suitable as a catalyst in the production of organic compounds.
  • the ruthenium complex represented by the general formula (4A) is suitable as a catalyst, for example, in the production of formate salts. Since the formate salt produced by the reaction is easily soluble in water, the reaction in a two-phase system makes it easy to separate the catalyst and formate salt, making it easy to separate and recover the catalyst and formate salt from the reaction system, making it possible to produce formate salts in high yields and making it easy to reuse expensive catalysts.
  • R 0 represents a hydrogen atom or an alkyl group
  • Each Q1 independently represents CH2 , NH, or O, and CH2 and NH may further have a substituent;
  • Each R1 independently represents an alkyl group or an aryl group (provided that when Q1 represents NH or O, at least one R1 represents an aryl group);
  • Each A independently represents CH, CR5 , or N, where R5 represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxyl group, or an alkoxy group;
  • X represents a halogen atom;
  • n represents 0 to 3;
  • each L independently represents a neutral or anionic ligand.
  • R 0 , A, Q1, Z, L and n in formula (4A) have the same meanings as R 0 , A, Q 1 , Z, L and n in formula (3A), respectively, and the preferred ranges are also the same.
  • the alkyl group and aryl group represented by R 1 have the same meanings as the alkyl group and aryl group represented by R in formula (3A), respectively, and the preferred ranges are also the same.
  • the metal complexes represented by general formulas (1A) to (4A) may produce stereoisomers depending on the coordination mode and conformation of the ligands, but may be a mixture of these stereoisomers or a single pure isomer.
  • the metal complexes represented by general formulas (1A) to (4A) may be produced by known methods. Examples of known methods include those described in E. Pidko et al., ChemCatChem 2014, 6, 1526-1530, etc.
  • ruthenium complexes represented by general formula (4A) include the compounds shown below.
  • Et represents an ethyl group
  • tBu represents a tertiary butyl group
  • Ph represents a phenyl group.
  • the amount of the catalyst (preferably a ruthenium complex) used is not particularly limited. From the viewpoint of fully expressing the function of the catalyst, the amount of the catalyst used is, for example, preferably 0.1 ⁇ mol or more per 1 L of the organic phase solvent, more preferably 0.5 ⁇ mol or more, and even more preferably 1 ⁇ mol or more. From the viewpoint of cost, the amount is preferably 1 mol or less per 1 L of the organic phase solvent, more preferably 10 mmol or less, and even more preferably 1 mmol or less. Furthermore, from the viewpoint of suppressing a decrease in catalyst efficiency, the amount may be 500 ⁇ mol or less per 1 L of the organic phase solvent, 400 ⁇ mol or less, or 100 ⁇ mol or less. When two or more types of catalysts are used, the total amount of the catalysts used may be within the above range.
  • the method for producing an organic compound according to the present embodiment may use a phase transfer catalyst that facilitates the transfer of substances between the aqueous phase and the organic phase.
  • the phase transfer catalyst include quaternary ammonium salts, quaternary phosphates, macrocyclic polyethers such as crown ethers, nitrogen-containing macrocyclic polyethers such as cryptands, nitrogen-containing linear polyethers, polyethylene glycols and their alkyl ethers.
  • quaternary ammonium salts are preferred from the viewpoint of facilitating the transfer of substances between the aqueous solvent and the organic solvent even under mild reaction conditions.
  • quaternary ammonium salts include methyltrioctylammonium chloride, benzyltrimethylammonium chloride, trimethylphenylammonium bromide, tributylammonium tribromide, tetrahexylammonium hydrogen sulfate, decyltrimethylammonium bromide, diallyldimethylammonium chloride, dodecyltrimethylammonium bromide, dimethyldioctadecylammonium bromide, tetraethylammonium tetrafluoroborate, ethyltrimethylammonium iodide, tris(2-hydroxyethyl)methylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium bromide, tetraethylammonium iodide, dimethyldioctylammonium bromide, methyltrioc
  • the amount of phase transfer catalyst used is not particularly limited.
  • the amount of phase transfer catalyst used is preferably 0.1 mmol or more per 1 L of organic and aqueous solvent, more preferably 0.5 mmol or more, and even more preferably 1 mmol or more. From the viewpoint of cost, the amount is preferably 1 mol or less per 1 L of organic and aqueous solvent, more preferably 500 mmol or less, and even more preferably 100 mmol or less. When two or more types of phase transfer catalysts are used, the total amount used may be within the above range.
  • an antioxidant may be added to the reaction liquid as necessary.
  • the antioxidant include phosphorus-based antioxidants, amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants. Examples of these antioxidants include those disclosed in JP-A-2016-44190.
  • additives such as ultraviolet absorbers and light stabilizers may be added to the reaction liquid in place of or together with the antioxidant. Examples of these additives include those disclosed in JP-A-2016-44190.
  • the organic phase may contain an antioxidant.
  • the amount used is adjusted, for example, to a range in which the antioxidant dissolves in the reaction liquid.
  • the amount of the antioxidant used is preferably 1 mmol or more per 1 L of solvent.
  • the amount of the antioxidant used is preferably 100 mmol or less per 1 L of solvent.
  • One type of antioxidant may be used alone, or two or more types may be used in combination.
  • a gas phase, an organic phase, and an aqueous phase are prepared.
  • the organic phase may contain a catalyst and the aqueous phase may contain a starting compound, and the gas phase may contain a gas that reacts with the starting compound.
  • the gas phase, organic phase, and aqueous phase are supplied to the inside of the reactor section 3 through the inlet 2 of the flow reactor 1.
  • the gas phase, organic phase, and aqueous phase may be mixed in advance.
  • the manufacturing method of this embodiment may further include mixing the gas phase, aqueous phase, and organic phase before passing them through the flow reactor 1.
  • the reaction of the starting compound progresses.
  • the starting compound reacts with the gas contained in the gas phase.
  • the reaction of the starting compound is typically a hydrogenation reaction.
  • the reaction of the starting compound is not limited to a hydrogenation reaction, and may be a reduction reaction other than the hydrogenation reaction, a dehydration condensation reaction, a hydrolysis reaction, etc.
  • the gas phase may contain hydrogen, and a hydrogenation reaction of the starting compound by hydrogen may progress.
  • the resulting organic compound dissolves, for example, in the aqueous phase. Since the organic phase contains the catalyst and the aqueous phase contains the organic compound, the catalyst can be easily separated and therefore easily reused.
  • the gas phase, the aqueous phase, and the organic phase may be heated while passing through the flow reactor 1. This promotes the synthesis reaction of the organic compounds.
  • the heating temperature is not particularly limited, but in order to efficiently proceed with the reaction, it is, for example, 30°C or higher, 40°C or higher, 50°C or higher, 60°C or higher, 70°C or higher, or even 80°C or higher. From the viewpoint of energy efficiency, the heating temperature is preferably 200°C or lower, more preferably 150°C or lower, and even more preferably 100°C or lower.
  • the gas phase, aqueous phase, and organic phase may be heated to 90°C.
  • the time of the synthesis reaction in the method for producing an organic compound is not particularly limited. That is, the time (residence time) for the gas phase, aqueous phase, and organic phase to pass through the flow reactor 1 is not particularly limited.
  • the residence time of the gas phase, aqueous phase, and organic phase in the flow reactor 1 may be, for example, 10 minutes or more, 30 minutes or more, 40 minutes or more, 45 minutes or more, 50 minutes or more, or even 70 minutes or more, from the viewpoint of ensuring sufficient reactivity.
  • the residence time may be 2000 minutes or less, or may be 100 minutes or less.
  • the residence time in the flow reactor 1 can be appropriately adjusted by the diameter and length of the flow path in the flow reactor 1, and the flow rate settings of the aqueous phase, organic phase, and gas phase.
  • the residence time (min) can be calculated by the following formula using the volume (mL) of the flow reactor 1, the flow rate (mL/min) of the aqueous phase passing through, the flow rate (mL/min) of the organic phase, and the flow rate (mL/min) of the gas phase under the reaction pressure.
  • Residence time (Volume of flow reactor) / ⁇ (Flow rate of gas phase under reaction pressure) + (Flow rate of aqueous phase) + (Flow rate of organic phase) ⁇
  • the reaction pressure is not particularly limited, but from the viewpoint of improving the catalyst turnover number (TON) of the metal catalyst, it may be, for example, 0.1 MPa or more, 0.2 MPa or more, 0.5 MPa or more, 1 MPa or more, 4 MPa or more, 4.5 MPa or more, or even 5 MPa or more.
  • the upper limit of the reaction pressure is not particularly limited, and may be, for example, 50 MPa, 20 MPa, or 10 MPa.
  • the gas phase, organic phase, and aqueous phase that have passed through the inside of the reactor section 3 are discharged from the reactor section 3 through the outlet 4.
  • the discharged organic phase and aqueous phase may be separated.
  • the aqueous phase and organic phase can be separated by a simple method, so that the organic compounds can be easily recovered.
  • expensive metal catalysts can be reused without losing their catalytic activity. By reusing the catalyst, high productivity can be achieved.
  • formate may be synthesized by a hydrogenation reaction between hydrogen and a starting compound that is at least one selected from the group consisting of carbon dioxide, hydrogen carbonate, and carbonate.
  • Formate has the advantage that it has a high hydrogen storage density, is safe, and is a stable chemical substance, making it easy to handle, and allows for the long-term storage of hydrogen and carbon dioxide.
  • At least a portion of the formate produced by the manufacturing method of an organic compound of this embodiment can be protonated to produce formic acid.
  • [Organic compound production system] 3 is a schematic diagram showing an example of a system for producing an organic compound.
  • the production system is not limited to the configuration shown in FIG. 3 as long as it includes the flow reactor of the present invention.
  • the manufacturing system 100 shown in FIG. 3 includes a flow reactor 1.
  • the manufacturing system 100 further includes a mixer 5 and a mixed phase supply path 36 before the flow reactor 1.
  • the mixer 5 is a device that mixes a gas phase, an aqueous phase, and an organic phase.
  • the mixer 5 is composed of a first mixer 6 and a second mixer 7. In the first mixer 6, the aqueous phase and the organic phase are mixed. In the second mixer 7, the organic phase and the aqueous phase (reaction liquid) mixed in the first mixer 6 are mixed with the gas phase.
  • a relief valve 19 is disposed in the reaction liquid supply path 35 for supplying the mixed reaction liquid from the first mixer 6 to the second mixer 7.
  • the gas phase, the aqueous phase, and the organic phase mixed by the mixer 5 are supplied to the flow reactor 1 through the mixed phase supply path 36.
  • a known mixer can be used as the mixer 5.
  • a mixer with three or more inlet systems and one outlet may be used, or a mixer with two inlet systems and one outlet may be used.
  • a mixer with two inlet systems and one outlet for example, a Y-shaped mixer can be used.
  • the mixer may have two mixers, and the organic phase and the aqueous phase may be mixed in the first mixer, and then the gas phase and the reaction liquid (organic phase and aqueous phase) may be mixed in the second mixer.
  • the aqueous phase and the organic phase mixed in the first Y-shaped mixer may be mixed with the gas phase in the second Y-shaped mixer and then supplied to the flow reactor 1.
  • the mixer may be a tank equipped with an agitating blade inside.
  • the manufacturing system 100 is connected to a container 11 containing an aqueous phase and a mixing device 5 (specifically, a first mixer 6), and includes an aqueous phase supply path 32 for supplying the aqueous phase from the container 11 to the mixing device 5.
  • the aqueous phase supply path 32 may be directly connected to the flow reactor 1.
  • a liquid delivery pump 13 for delivering the aqueous phase, a check valve 15, and a ball valve 17 are arranged in the aqueous phase supply path 32.
  • a known liquid delivery pump such as a syringe pump or a plunger pump can be used as the liquid delivery pump 13. By operating the liquid delivery pump 13, the aqueous phase can be passed through the flow reactor 1 at a desired flow rate.
  • the container 11 is, for example, a tank.
  • the manufacturing system 100 is connected to a container 12 containing an organic phase and a mixing device 5 (specifically, a first mixer 6), and includes an organic phase supply path 33 for supplying the organic phase from the container 12 to the mixing device 5.
  • the organic phase supply path 33 may be directly connected to the flow reactor 1.
  • a liquid delivery pump 14 for delivering the organic phase, a check valve 16, and a ball valve 18 are arranged in the organic phase supply path 33.
  • a known liquid delivery pump can be used as the liquid delivery pump 14, and the organic phase can be passed through the flow reactor 1 at a desired flow rate.
  • the container 12 is, for example, a tank.
  • the manufacturing system 100 is connected to a cylinder 21 containing a gas phase and a mixing device 5 (specifically, a second mixer 7), and includes a gas phase supply path 34 for supplying the gas phase from the cylinder 21 to the mixing device 5.
  • the gas phase supply path 34 may be directly connected to the flow reactor 1.
  • a diaphragm valve 22, a ball valve 23, a pressure regulator 24, a check valve 25, a relief valve 26, a mass flow controller 27, a check valve 28, and a ball valve 29 are arranged.
  • the residence time in the flow reactor 1 can be adjusted appropriately by adjusting the diameter and length of the flow path in the flow reactor 1, the flow rate settings of the liquid delivery pumps 13 and 14, and the flow rate settings of the gas (gas phase).
  • the manufacturing system 100 may further include a heating device (not shown) that heats the gas phase, aqueous phase, and organic phase passing through the flow reactor 1.
  • the heating device may be integrated with the flow reactor 1, or may be an oven or a thermostatic bath. A part of the flow reactor 1 may be located inside the oven.
  • the manufacturing system 100 may further include a separation device (not shown) that separates the gas phase and the reaction liquid discharged from the flow reactor 1.
  • the separation device may include a device that separates the reaction liquid into an aqueous phase and an organic phase. For example, if the synthesized organic compound dissolves into the aqueous phase, the organic compound can be recovered by separating the aqueous phase. Furthermore, if a catalyst is contained in the organic phase, the catalyst can be easily reused and the reaction can be repeated by separating the organic phase.
  • FIG. 4 is a schematic diagram showing another example of a production system for an organic compound.
  • the production system is not limited to the configuration shown in FIG. 4 as long as it is equipped with the flow reactor of the present invention.
  • the production system 200 shown in FIG. 4 further includes a back pressure regulator 41 and a separation device 42 after the flow reactor 1.
  • the separation device 42 is a device that separates the gas phase, the aqueous phase, and the organic phase.
  • the separation device 42 is composed of a first separator 43 and a second separator 44.
  • the gas phase and the reaction liquid are separated.
  • the gas phase is discharged from the gas phase discharge path 45.
  • the gas phase and the reaction liquid may be completely separated, or the pressure of the gas phase in the first separator 43 may be adjusted to approximately the pressure of the surrounding environment (e.g., atmospheric pressure) by releasing the high-pressure gas phase.
  • the discharged gas phase may be recovered in a cylinder (not shown).
  • the recovered gas phase can be used again in a reaction using the flow reactor 1. In other words, the gas phase (gas) can be reused.
  • the separated reaction liquid is supplied to the second separator 44 through the reaction liquid recovery path 46.
  • the aqueous phase and the organic phase are separated.
  • the separated aqueous phase is collected in the aqueous phase recovery container 47.
  • the organic compound can be collected from the aqueous phase recovery container 47.
  • the separated organic phase is collected in the container 12 through the organic phase recovery path 48.
  • the organic phase recovery path 48 is provided with a liquid delivery pump 49 and a check valve 50 for delivering the organic phase.
  • the liquid delivery pump 49 can be a publicly known liquid delivery pump described above for the production system 100.
  • the organic phase collected in the container 12 can be used again for a reaction using the flow reactor 1. In this way, the separated organic phase can be easily reused. That is, the solvent and the catalyst can be reused.
  • the number of times of reuse is, for example, one or more times.
  • a known separator can be used as the separation device 42.
  • a gas-liquid separator that separates the gas phase from the reaction liquid, and a liquid-liquid separator that separates the aqueous phase from the organic phase may be used as the separator.
  • the first separator 43 is a gas-liquid separator
  • the second separator 44 is a liquid-liquid separator.
  • a known separator can be used as the gas-liquid separator.
  • a separator using a known separation method can be used as the liquid-liquid separator.
  • the separation method is, for example, static separation, centrifugation, and separation using an oil-water separation filter, and static separation is preferred from the viewpoint of simplicity. Separation using an oil-water separation filter is, for example, a coalescer method in which the reaction liquid is passed through a filter to coarsen water droplets and separate the aqueous phase and the organic phase due to the difference in specific gravity.
  • one end of a tube connected to the organic phase recovery path 48 may be immersed in the organic phase, and the organic phase may be sucked out using a pump. Also, for example, the organic phase may be recovered by overflowing from the top of the second separator 44 due to the difference in specific gravity.
  • the gas phase, aqueous phase, and organic phase are preferably separated under a non-oxygen atmosphere.
  • the non-oxygen atmosphere is an atmosphere in which the oxygen concentration is 1000 vol ppm or less.
  • the oxygen concentration in the non-oxygen atmosphere is preferably 100 vol ppm or less, and more preferably 10 vol ppm or less. This allows separation without degrading the catalyst.
  • the non-oxygen atmosphere may contain at least one selected from hydrogen and an inert gas.
  • the inert gas is, for example, nitrogen or argon.
  • the second separator 44 is in a non-oxygen atmosphere. If the gas phase is not completely separated in the first separator 43, the separation operation is performed in the second separator 44 under a gas phase (e.g., hydrogen) atmosphere.
  • the separation device 42 includes, in this order, a first separator 43 that separates the gas phase from the reaction liquid, and a second separator 44 that separates the aqueous phase from the organic phase.
  • This configuration can reduce the number of high-pressure resistant parts required for the manufacturing system 200, thereby reducing costs and size.
  • the order of the first separator 43 and the second separator 44 is not limited to this.
  • the aqueous phase and the organic phase may be separated in the presence of a gas phase, and then the gas phase may be separated from each of the aqueous phase and the organic phase.
  • the above-mentioned known liquid-liquid separator and gas-liquid separator can be used.
  • the manufacturing systems 100 and 200 can produce organic compounds in a flow system using various reactions, and can produce organic compounds with high yields and excellent productivity, for example. Furthermore, the manufacturing system 200 is suitable for reusing the organic phase, for example. This allows the catalyst to be easily reused and the reaction to be repeated. Furthermore, waste can be reduced.
  • the catalyst was synthesized by the following operation. First, under an inert atmosphere, 40 mg (0.1 mmol) of the ligand A below was added to a suspension of 95.3 mg (0.1 mmol) of [RuHCl(PPh 3 ) 3 (CO)] in 5 mL of THF (tetrahydrofuran), and the mixture was stirred and heated at 65° C. for 3 hours to carry out a reaction. Then, it was cooled to room temperature (25° C.). The obtained yellow solution was filtered, and the filtrate was evaporated to dryness under vacuum.
  • THF tetrahydrofuran
  • the amount of substance of the formate contained in the aqueous phase was quantified as follows. 100 ⁇ L of dimethyl sulfoxide was added as a reference substance to 100 ⁇ L of the aqueous phase discharged from the flow reactor, and dissolved in 500 ⁇ L of heavy water. In this manner, a measurement sample was prepared. NMR measurement was performed on this measurement sample. From the obtained NMR spectrum, the amount of substance X (mol) of the generated formate was calculated.
  • TON of catalyst X/Y (2)
  • the amount of substance Y (mol) of the catalyst used was calculated by the following formula (3) using the concentration of the catalyst in the organic phase supplied to the production system (mol/mL), the flow rate of the organic phase (mL/min), and the system operation time (Time on Stream: TOS) (min), and the concentration of the catalyst in the organic phase was calculated by the following formula (4).
  • Y (concentration of catalyst) x (flow rate of organic phase) x TOS (3)
  • Catalyst concentration Y/(volume of organic solvent used) (4)
  • Example 1 Preparation of flow reactor
  • SS tube stainless steel tube
  • SS tube manufactured by Sandvik
  • the above 4 cm tube and the connected tube were connected by compression fittings to prepare a flow reactor of Example 1.
  • the length of the flow reactor of Example 1 was 114 cm.
  • the above 4 cm tube was set as the inlet side of the flow reactor.
  • the part of the flow reactor other than the above 4 cm tube was installed inside an oven.
  • potassium bicarbonate was dissolved in degassed pure water and sonicated for 30 seconds to prepare the aqueous phase.
  • concentration of potassium bicarbonate was 1.5 M.
  • the manufacturing system is A vessel containing the organic phase, A vessel containing an aqueous phase; ⁇ Hydrogen gas cylinders, Mixing devices, and flow reactors, The mixer and the inlet of the flow reactor were connected to each other. The outlet of the flow reactor was equipped with a back pressure regulator.
  • reaction liquid After separating the reaction liquid and gas phase discharged from the outlet of the flow reactor, the reaction liquid was separated into an organic phase and an aqueous phase by static separation. 100 ⁇ L was taken from the separated aqueous phase, and the TON of the catalyst and the yield of formate were calculated using the method described above. The evaluation results are shown in Table 1.
  • Example 2 The evaluation was carried out in the same manner as in Example 1, except that the operating conditions were changed as shown in Table 1.
  • Example 3 (Preparation of flow reactor) The flow reactor of Example 3 was prepared in the same manner as in Example 1, except that particles were filled inside the 4 cm long SS tube and the 14 cm long SS tube constituting the flow reactor of Example 1.
  • the tube filled with particles was prepared by blocking one end of the tube with glass wool, filling the particles from the opening of the tube, and blocking the opening (the other end) with glass wool.
  • the particles used were silicon carbide (SiC) (Grit 60, manufactured by Boom) with an average particle size of 254 ⁇ m and irregular shape.
  • Example 4 (Preparation of flow reactor) The flow reactor of Example 4 was prepared in the same manner as Example 3, except that the particles were irregularly shaped SiC (Grit 24, manufactured by Boom) with an average particle size of 686 ⁇ m.
  • Example 5 (Preparation of flow reactor) The flow reactor of Example 5 was prepared in the same manner as Example 3, except that the particles were irregularly shaped SiC (Grit 12, manufactured by Boom) with an average particle size of 1600 ⁇ m.
  • Example 6 (Preparation of flow reactor) A flow reactor of Example 6 was prepared in the same manner as in Example 3, except that the particles were spherical glass beads (Sigma Aldrich (Merck)) with an average particle size of 2200 ⁇ m.
  • Example 7 A production system was constructed in the same manner as in Example 6, except that the catalyst concentration, the phase transfer catalyst concentration, and the potassium hydrogen carbonate concentration were changed as shown in Table 1. Evaluation was performed in the same manner as in Example 1, except that the operating conditions were changed as shown in Table 1.
  • Example 8 (Preparation of flow reactor) A flow reactor of Example 8 was prepared in the same manner as in Example 3, except that the particles were hollow cylindrical PTFE particles (manufactured by Da Vinci Europe) with an average particle size of 2000 ⁇ m.
  • Example 9 A production system was constructed and evaluated in the same manner as in Example 8, except that the catalyst concentration, phase transfer catalyst concentration, and potassium hydrogen carbonate concentration were changed as shown in Table 1.
  • Example 10 The evaluation was carried out in the same manner as in Example 8 except that the operating conditions were changed as shown in Table 1.
  • Example 11 (Preparation of flow reactor) One 1/4 inch SS tube with a length of 4 cm was prepared, and the inside was filled with hollow cylindrical PTFE particles with an average particle size of 2000 ⁇ m. Furthermore, a total of five tubes were prepared, including three 1/4 inch SS tubes with a length of 100 cm and two 1/4 inch SS tubes with a length of 14 cm, and the inside of the two 14 cm SS tubes was filled with hollow cylindrical PTFE particles with an average particle size of 2000 ⁇ m. The 100 cm SS tube and the 14 cm SS tube filled with particles were alternately connected by compression fittings. The 4 cm SS tube filled with particles and the connected tube were connected by compression fittings to prepare a flow reactor of Example 11. The length of the flow reactor of Example 11 was 332 cm. The 4 cm tube was the inlet side of the flow reactor. The part of the flow reactor other than the 4 cm tube was installed inside an oven.
  • Example 12 An organic phase and an aqueous phase were prepared in the same manner as in Example 1, except that the concentration of potassium hydrogen carbonate was changed as shown in Table 1. Then, a production system was constructed in the same manner as in Example 11, and evaluation was performed in the same manner as in Example 1, except that the operating conditions were changed as shown in Table 2.
  • Example 13 (Preparation of flow reactor) The flow reactor of Example 13 was prepared in the same manner as Example 11, except that the particles were irregularly shaped SiC (Grit 12, manufactured by Boom) with an average particle size of 1600 ⁇ m.
  • Example 14 Evaluation was carried out in the same manner as in Example 13 except that the operating conditions were changed as shown in Table 2.
  • Example 15 Evaluation was carried out in the same manner as in Example 13 except that the operating conditions were changed as shown in Table 2.
  • Example 16 The evaluation was carried out in the same manner as in Example 13, except that the catalyst concentration and the phase transfer catalyst concentration were changed as shown in Table 2.
  • Example 17 (Preparation of flow reactor) The flow reactor of Example 17 was prepared in the same manner as in Example 1, except that the insides of all of the tubes constituting the flow reactor of Example 1, namely, a 4 cm long SS tube, a 14 cm long SS tube, and two 48 cm long SS tubes, were filled with irregularly shaped SiC particles (Grit 12, manufactured by Boom) having an average particle size of 1600 ⁇ m.
  • SiC particles Grit 12, manufactured by Boom
  • Example 18 Evaluation was carried out in the same manner as in Example 17 except that the operating conditions were changed as shown in Table 2.
  • Example 19 (Preparation of flow reactor)
  • SS tube stainless steel tube
  • Grit 60 manufactured by Boom
  • two 1/8 inch SS tubes with a length of 48 cm were prepared, and a total of three tubes, one 14 cm tube and two 48 cm tubes, were alternately connected by compression fittings (manufactured by Swagelok).
  • the 4 cm tube and the connected tube were connected by compression fittings to prepare a flow reactor of Example 19.
  • the 4 cm tube was used as the inlet side of the flow reactor.
  • the part of the flow reactor other than the 4 cm tube was installed inside an oven. That is, the flow reactor of Example 19 corresponds to the flow reactor of Example 3 in which the diameters of all the tubes were changed to 1/8 inch.
  • Example 20 Evaluation was carried out in the same manner as in Example 17, except that the catalyst concentration and the phase transfer catalyst concentration were changed as shown in Table 2.
  • the tip of the tube was immersed in the separated organic phase and the organic phase was recovered using a pump.
  • Example 21 An organic phase and an aqueous phase were prepared in the same manner as in Example 1, except that the organic phase was changed to 39 mL of the organic phase recovered in Example 20, and evaluation was performed in the same manner as in Example 20. That is, in Example 21, the organic phase (catalyst, phase transfer catalyst, and toluene) used in Example 20 was reused.
  • Examples 3 to 21 in which the inside of the flow reactor was filled with particles, showed higher yields and TONs than Examples 1 and 2, in which the inside of the flow reactor was not filled with particles.
  • Examples 5, 6, and 8 when the particle material was SiC, higher yields and TONs were shown. Since the yields and TONs of Examples 20 and 21 were comparable, the organic compound production method and organic compound production system of this embodiment enable the reuse of the organic phase, and even when reused, a high yield and TON can be achieved.
  • the organic compound manufacturing method and organic compound manufacturing system of this embodiment can easily mass-produce the target organic compound.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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WO2025187654A1 (ja) * 2024-03-08 2025-09-12 日東電工株式会社 反応生成物の製造方法、及び反応生成物製造システム

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JPH0291038A (ja) * 1988-08-20 1990-03-30 Bp Chem Internatl Ltd 含窒素塩基の蟻酸塩の製造方法
JP2007209973A (ja) * 2006-01-13 2007-08-23 Ebara Corp 気液反応装置
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WO2025187654A1 (ja) * 2024-03-08 2025-09-12 日東電工株式会社 反応生成物の製造方法、及び反応生成物製造システム

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