WO2023080071A1 - Procédé de production d'aldéhyde 4-hydroxybutyle, procédé de production de gamma butyrolactone, procédé de production de n-méthyl-2-pyrrolidone et composé - Google Patents

Procédé de production d'aldéhyde 4-hydroxybutyle, procédé de production de gamma butyrolactone, procédé de production de n-méthyl-2-pyrrolidone et composé Download PDF

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WO2023080071A1
WO2023080071A1 PCT/JP2022/040335 JP2022040335W WO2023080071A1 WO 2023080071 A1 WO2023080071 A1 WO 2023080071A1 JP 2022040335 W JP2022040335 W JP 2022040335W WO 2023080071 A1 WO2023080071 A1 WO 2023080071A1
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producing
hba
reaction
mol
hydroxybutyraldehyde
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Japanese (ja)
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真也 塚本
尚平 西澤
和宏 北川
博 内田
英雄 宮田
ジュヨン シム
英治 山本
美乃 村山
信 徳永
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株式会社レゾナック
国立大学法人九州大学
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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
    • B01J31/24—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
    • 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
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • C07C47/19—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form

Definitions

  • the present invention is suitable for producing 4-hydroxybutyraldehyde, producing gamma-butyrolactone using the same, producing N-methyl-2-pyrrolidone, and producing 4-hydroxybutyraldehyde by hydroformylation of allyl alcohol. It relates to a ligand compound that constitutes a catalyst used in
  • 4-Hydroxybutyraldehyde (4-HBA) is a useful compound that can be used as a raw material for various compounds.
  • 1,4-butanediol (1,4-BDO) can be obtained by subjecting 4-HBA to a hydrogen reduction reaction.
  • 1,4-BDO is useful as a raw material for polybutylene terephthalate, urethane resin, and the like.
  • gamma-butyrolactone (GBL) can be produced by dehydrogenating 4-HBA or 1,4-BDO.
  • GBL is widely used industrially as a cleaning agent for electronic materials.
  • NMP N-methyl-2-pyrrolidone
  • NMP N-methyl-2-pyrrolidone
  • 4-HBA can be produced by hydroformylation of allyl alcohol.
  • an olefinic compound is hydroformylated using a rhodium catalyst and a ligand, the selectivity of linear and branched oxo compounds in the reaction product and the Yields are very different. This also applies to the hydroformylation reaction of allyl alcohol.
  • 4-HBA having a linear structure is produced, and 3-HBA having a branched structure is produced as a by-product.
  • Hydroxy-2-methylpropionaldehyde (HMPA) is produced, as well as low boiling by-products such as propionaldehyde.
  • Patent Document 1 discloses that allyl alcohol is reacted with carbon monoxide and hydrogen in the presence of a rhodium-containing hydroformylation catalyst to form hydroxybutyraldehydes, and the hydroxybutyraldehydes are hydrogenated to produce butanediols. A method for synthesizing is described.
  • Patent Document 2 describes a method for hydroformylating allyl alcohol in the presence of a rhodium complex compound and a trisubstituted phosphine. Specifically, it describes the hydroformylation of allyl alcohol using a rhodium complex, triphenylphosphine (monodentate ligand) and 1,4-bis(diphenylphosphino)butane (bidentate ligand). It is
  • Patent Document 3 describes the use of an optically active organic diphosphine compound and a specific organic diphosphine compound as ligands in a reaction to hydroformylate allyl alcohol in the presence of a rhodium complex catalyst.
  • Example 6 of Patent Document 3 rhodium-hydride(carbonyl)tri(triphenylphosphine) as a catalyst and trans-4,5-bis(diphenylphosphinomethyl)-2,2-dimethyl- Hydroformylations of allyl alcohols using 1,3-dioxolane (DIOP) and bis(diphenylphosphino)pentane, diphenylmethylphosphine have been described.
  • DIOP 1,3-dioxolane
  • Table 2 of Patent Document 3 describes that the 4-HBA selectivity in Example 6 was 84.8% and the HMPA selectivity was 13.8%.
  • Non-Patent Document 1 describes a calculation prediction when using a rhodium complex compound and a phosphine ligand having a xanthene skeleton as catalysts for the hydroformylation reaction.
  • Non-Patent Document 1 uses a simple olefin, 1-octene, as a model compound for hydroformylation.
  • Non-Patent Document 1 describes a prediction that when a phosphine ligand having a xanthene skeleton is used as a catalyst, the production ratio of linear compounds/branched compounds increases.
  • Non-Patent Document 1 describes the prediction that when a phosphine ligand having a xanthene skeleton is used as a catalyst for the hydroformylation reaction of 1-octene, the production ratio of linear compounds/branched compounds will increase. However, the hydroformylation reaction of a compound having a substituent such as allyl alcohol differs greatly from the hydroformylation reaction of a simple olefin such as 1-octene in the linear/branched compound selectivity. Non-Patent Document 1 does not describe predictions about the hydroformylation reaction of allyl alcohol.
  • the present invention has been made in view of the above circumstances, and a reaction product is obtained in which the amount of HMPA produced is small and the ratio of the amount of 4-HBA produced to the amount of HMPA produced (4-HBA/HMPA) is large. It is an object of the present invention to provide a method for producing 4-HBA that can be obtained.
  • the present invention also provides a ligand compound that constitutes a catalyst capable of increasing the ratio of the amount of 4-HBA produced to the amount of HMPA produced (4-HBA/HMPA) in the hydroformylation reaction of allyl alcohol. With the goal.
  • the present invention provides a high yield of GBL even when the reaction product containing 4-HBA produced in the process of producing 4-HBA is directly used in a reaction for producing gamma-butyrolactone (GBL) without purification. It is an object of the present invention to provide a GBL manufacturing method capable of manufacturing a GBL efficiently. Another object of the present invention is to provide a method for producing NMP that can efficiently produce N-methyl-2-pyrrolidone (NMP) by including a step of efficiently producing GBL.
  • NMP N-methyl-2-pyrrolidone
  • a first aspect of the present invention provides the following method for producing 4-hydroxybutyraldehyde.
  • Ar represents an aryl group which may have a substituent.
  • the manufacturing method of the first aspect of the present invention preferably includes the features described in [2] to [10] below. Combinations of two or more of these features are also preferred. [2]
  • the bidentate phosphine ligand is represented by the formula (1), and Ar in the formula (1) is represented by any one of the formulas (a), (b), and (c).
  • the bidentate phosphine ligand is represented by the formula (3), and Ar in the formula (3) is any one of the formulas (a), (b), (d), and (e) A method for producing 4-hydroxybutyraldehyde according to any one of [1] to [3].
  • the pressure of the mixed gas containing carbon monoxide gas and hydrogen gas in the reaction vessel for the hydroformylation reaction is in the range of 0.1 to 10 MPaG (gauge pressure), According to any one of [1] to [8], wherein the partial pressure ratio of carbon monoxide gas and hydrogen gas (hydrogen gas/carbon monoxide gas) in the reaction vessel is in the range of 1/10 to 10/1.
  • a method for producing 4-hydroxybutyraldehyde [10] The 4-hydroxybutyraldehyde according to any one of [1] to [9], wherein the carbon monoxide gas and the hydrogen gas are generated by thermal decomposition of waste plastics and/or biomass. Production method.
  • a second aspect of the present invention provides the following method for producing gamma-butyrolactone.
  • the manufacturing method of the second aspect of the present invention preferably includes the features described in [11] below.
  • the method for producing gamma-butyrolactone according to [11] wherein the copper-containing catalyst further contains an oxide of at least one metal element selected from the group consisting of zinc, zirconium and aluminum.
  • a third aspect of the present invention provides the following method for producing N-methyl-2-pyrrolidone.
  • a fourth aspect of the present invention provides the following compounds. [14] A compound represented by the following formula (10).
  • the above compound can be preferably used as a catalyst in the above production method.
  • a fourth aspect of the present invention provides the following compounds. [15] A compound represented by the following formula (8).
  • the above compound can be preferably used as a catalyst in the above production method.
  • the amount of HMPA produced by the hydroformylation reaction is small, and the ratio of the amount of 4-HBA produced to the amount of HMPA produced (4-HBA/HMPA) is large. A product is obtained.
  • the compound of the present invention is a compound represented by the formula (10) or a compound represented by the formula (8), it can be used as a catalyst ligand in the hydroformylation reaction of allyl alcohol with a high yield.
  • 4-HBA can be produced, and a reaction product having a large ratio of 4-HBA to HMPA (4-HBA/HMPA) can be obtained.
  • the method for producing GBL of the present invention includes a step of producing 4-HBA by the method for producing 4-HBA of the present invention, and a step of contacting the produced 4-HBA with a copper-containing catalyst. Therefore, the reaction product containing 4-HBA produced in the process of producing 4-HBA has a large ratio of the amount of 4-HBA produced to the amount of HMPA produced (4-HBA/HMPA). Therefore, even if a reaction product containing 4-HBA is directly used in a reaction for producing GBL without purification, GBL can be produced at a high yield and GBL can be produced efficiently.
  • the method for producing NMP of the present invention includes a step of producing GBL by the method for producing GBL of the present invention, and a step of reacting the produced GBL with monomethylamine. Therefore, GBL can be efficiently produced, and the produced GBL can be used to efficiently produce NMP, which is an industrially useful compound.
  • the hydroformylation reaction of allyl alcohol with carbon monoxide gas and hydrogen gas involves the step of inserting allyl alcohol into a rhodium complex catalyst in which carbon monoxide and hydrogen atoms are coordinated to form an intermediate (olefin insertion ) and a step of reductive elimination of the rhodium complex catalyst from the intermediate to form hydroxyaldehyde (reductive elimination step).
  • All of the bidentate phosphine ligands represented by formulas (1) to (3) have a Xantphos skeleton and are electron-rich.
  • the method for producing 4-hydroxybutyraldehyde (4-HBA) of the present embodiment comprises a rhodium catalyst and a catalyst containing at least one bidentate phosphine ligand selected from the following formulas (1) to (3).
  • allyl alcohol is hydroformylated with carbon monoxide gas and hydrogen gas.
  • Ar represents an aryl group which may have a substituent.
  • allyl alcohol is hydroformylated with carbon monoxide gas and hydrogen gas.
  • the allyl alcohol and the catalyst are added into any selected reaction vessel, such as common or pressure-resistant vessels used in the field.
  • the gas containing carbon monoxide gas and the gas containing hydrogen gas may be separately supplied to the reaction vessel, or may be supplied to the reaction vessel in the state of a mixed gas of the gas containing carbon monoxide gas and the gas containing hydrogen gas. may be supplied to
  • the gas containing carbon monoxide gas supplied to the reaction vessel may be only carbon monoxide gas, or may contain nitrogen gas, an inert gas such as argon, etc., in addition to carbon monoxide gas. .
  • the gas containing hydrogen gas to be supplied to the reaction vessel may be hydrogen gas only, or may contain inert gas such as nitrogen gas and argon in addition to hydrogen gas.
  • the gas containing carbon monoxide gas and the gas containing hydrogen gas preferably do not contain oxidizing gases such as air and oxygen.
  • the carbon monoxide gas and hydrogen gas used in the hydroformylation reaction of allyl alcohol may be those generated by thermal decomposition of waste plastics and/or biomass.
  • the pressure of the mixed gas containing carbon monoxide gas and hydrogen gas in the reaction vessel for the hydroformylation reaction is not particularly limited, but is preferably in the range of 0.1 to 10 MPaG (gauge pressure). It is more preferably in the range of 1 to 5.0 MPaG (gauge pressure), more preferably in the range of 0.5 to 2.5 MPaG (gauge pressure).
  • the pressure of the mixed gas in the reaction vessel was consumed by the hydroformylation reaction so as to be maintained within the range of 0.5 to 2.5 MPaG from the start to the end of the hydroformylation reaction. It is particularly preferable to carry out while supplementing with carbon monoxide gas and hydrogen gas.
  • the pressure of the mixed gas in the reaction vessel during the hydroformylation reaction is 0.1 MPaG or more, the hydroformylation reaction proceeds easily.
  • the pressure of the mixed gas in the reaction vessel is preferably high in order to promote the hydroformylation reaction.
  • 4-HBA can be produced using an industrially suitable apparatus and method.
  • the catalyst promotes the hydroformylation reaction, so even if the pressure of the mixed gas is 10 MPaG or less, a sufficient reaction rate can be obtained and 4-HBA can be produced with a sufficient yield.
  • the partial pressure ratio of carbon monoxide gas and hydrogen gas (hydrogen gas/carbon monoxide gas) in the reaction vessel in which the hydroformylation reaction is carried out is preferably in the range of 1/10 to 10/1, preferably 1/5 to 5. /1, more preferably 1/2 to 2/1.
  • the partial pressure ratio (hydrogen gas/carbon monoxide gas) of carbon monoxide gas and hydrogen gas in the reaction vessel during the hydroformylation reaction is in the range of 1/10 to 10/1, the progress of the hydroformylation reaction A sufficient reaction rate is obtained by supplying the necessary hydrogen gas and carbon monoxide gas.
  • the partial pressure ratio (hydrogen gas/carbon monoxide gas) is 2/1 or less, it is possible to prevent the hydrogen reduction reaction from proceeding and lowering the yield of 4-HBA.
  • rhodium catalyst As the rhodium catalyst used in the method for producing 4-HBA of the present embodiment, one that can be used as an olefin hydroformylation catalyst can be used. Only one rhodium catalyst may be used, or two or more rhodium catalysts may be used.
  • rhodium catalysts include rhodium oxides such as RhO, Rh 2 O 3 and RhO 2 , rhodium salts such as rhodium nitrate, rhodium sulfate, rhodium chloride, rhodium bromide, rhodium iodide and rhodium acetate, and Rhodium complexes such as acetylacetonatodicarbonylrhodium, acetylacetonatocarbonyl(triphenylphosphine)rhodium, hydridocarbonyltris(triphenylphosphine)rhodium(I), and Rh4 (CO) 12 , Rh6 (CO) 16 , etc.
  • rhodium oxides such as RhO, Rh 2 O 3 and RhO 2
  • rhodium salts such as rhodium nitrate, rhodium sulfate, r
  • rhodium complexes are preferred, and hydridocarbonyltris(triphenylphosphine)rhodium (I) is particularly preferred, in terms of catalytic activity, solubility in solvents, and ease of handling as a catalyst.
  • the amount of the rhodium catalyst used is not particularly limited, but it is preferably an amount such that the ratio of rhodium atoms is 0.01 mol% to 5 mol%, and the amount is 0.05 mol% to 2 mol%, relative to allyl alcohol. is more preferable, and an amount of 0.1 mol % to 1 mol % is even more preferable. Sufficient hydroformylation activity can be obtained when the proportion of rhodium atoms is 0.01 mol % or more. Further, when the proportion of rhodium atoms is 5 mol % or less, it is economical because loss during recovery of the rhodium catalyst can be suppressed.
  • the bidentate phosphine ligand used in the method for producing 4-HBA of the present embodiment is at least one selected from the above formulas (1) to (3). Only one type of bidentate phosphine ligand may be used, or two or more types may be used.
  • the value (ratio) of 4-HBA/HMPA is arbitrarily selected as required. For example, it may be 10.0 or more, 11.0 or more, 12.0 or more, 13.0 or more, 14.0 or more, or 15.0 or more, but it is not limited to these examples.
  • trans-4,5-bis(diphenylphosphinomethyl)-2,2 a bidentate phosphine ligand without an Xantphos skeleton conventionally used in hydroformylation reactions of allyl alcohol
  • DIOP -dimethyl-1,3-dioxolane
  • Ar in formulas (1) to (3) is an aryl group which may have a substituent.
  • the aryl group which may have a substituent is not particularly limited as long as it is an aromatic hydrocarbon group. Therefore, the aryl group which may have a substituent may be a monocyclic aromatic group or a polycyclic aromatic group.
  • the aryl groups, which may have four substituents, contained in one molecule of the bidentate phosphine ligand may be different, or may be partially or wholly the same, which facilitates production. Therefore, it is preferable that all are the same.
  • An optionally substituted aryl group may have one substituent or two or more substituents. When an aryl group has two or more substituents, all those substituents may be different, or some or all of them may be the same. When the aryl group which may have a substituent has a substituent, the bonding position of the substituent in the aryl group is not particularly limited.
  • Substituents possessed by the optionally substituted aryl group include, for example, linear or branched alkyl groups, dialkylamino groups, cyano groups, nitro groups, amino groups, hydroxy groups, halogenated alkyl groups, and the like. is mentioned.
  • a linear or branched alkyl group and/or a dialkylamino group function as an electron-donating group and the stability of the aryl group, which may have a substituent, is improved. Especially preferred.
  • the linear or branched alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms.
  • Examples of linear or branched alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group and tert-butyl group. and a methyl group is preferred in terms of ease of production.
  • the dialkylamino group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms.
  • Specific examples of the dialkylamino group include a dimethylamino group, a diethylamino group, a methylethylamino group, and the like, and the dimethylamino group is preferred in terms of ease of production.
  • the aryl group which may have a substituent is preferably a phenyl group or a phenyl group having a substituent.
  • Ar in the formulas (1) to (3) gives a reaction product with a large ratio of the amount of 4-HBA to the amount of HMPA (4-HBA/HMPA), so the following formulas (a) to (e) is more preferred, and formula (b) is even more preferred because 4-HBA can be produced in high yield.
  • "---" in each formula means a bond with the P atom.
  • the bidentate phosphine ligand is the difference in activation energy between 1,2 insertion and 2,1 insertion in the hydroformylation reaction calculated by the density functional theory described later (hereinafter simply referred to as "activation energy difference" is preferably 4.2 kcal/mol or more, more preferably 4.5 kcal/mol or more, even more preferably 5.0 kcal/mol or more, Larger is better.
  • activation energy difference is preferably 4.2 kcal/mol or more, more preferably 4.5 kcal/mol or more, even more preferably 5.0 kcal/mol or more, Larger is better.
  • the bidentate phosphine ligand has a difference in activation energy of 4.2 kcal/mol or more, the selectivity of 4-HBA becomes higher, and the amount of 4-HBA produced and the amount of HMPA produced increase. A reaction product with a greater ratio of (4-HBA/HMPA) is obtained. Therefore, the yield and selectivity of 4-HBA in the method for producing 4-H
  • the 1,2-insertion in the hydroformylation reaction of allyl alcohol means that, as shown in the following reaction formula, allyl alcohol (olefin) is Rh- It is a reaction pathway in which 4-HBA is produced by inserting between H bonds to form a linear rhodium complex.
  • 2,1-insertion is a reaction in which allyl alcohol is inserted between the Rh—H bonds of a rhodium catalyst to form a branched rhodium complex, and as shown in the reaction formula below, it is a reaction pathway in which HMPA is produced. be.
  • the difference between the activation energy of 1,2-insertion and the activation energy of 2,1-insertion (2,1-insertion - 1,2-insertion) is the ratio of the amount of 4-HBA produced to the amount of HMPA produced (4-
  • HBA/HMPA There is a correlation with HBA/HMPA.
  • 4-HBA/HMPA tends to increase as the activation energy for 1,2 insertion is smaller and the activation energy for 2,1 insertion is larger. Therefore, 4-HBA/HMPA can be predicted by obtaining the difference in activation energy between 1,2-insertion and 2,1-insertion in the hydroformylation reaction of allyl alcohol calculated by the density functional theory.
  • the difference in activation energy is a value that does not consider side reactions associated with isomerization of allyl alcohol.
  • the ratio of the amount of 4-HBA produced to the amount of HMPA produced (4-HBA/HMPA) may be slightly affected by side reactions associated with isomerization of allyl alcohol.
  • the activation energy for 1,2 insertion and the activation energy for 2,1 insertion in the hydroformylation reaction of allyl alcohol when a rhodium catalyst having an Rh—H bond is used is Change. Therefore, the difference in activation energy can be used as an index for selecting the bidentate phosphine ligand used in the hydroformylation reaction of allyl alcohol.
  • the bidentate phosphine ligand is used in an amount of 0.5 mol to 50 mol, preferably 1.5 mol to 20 mol, more preferably 2.5 mol to 50 mol, per 1 mol of rhodium atoms contained in the rhodium catalyst. It ranges from 0 mol to 10 mol.
  • the amount of the bidentate phosphine ligand to be used is 50 mol or less, a sufficient effect of improving the reaction rate of the hydroformylation reaction can be obtained, which is economically advantageous.
  • the selectivity of 4-HBA becomes higher, and the ratio of the amount of 4-HBA produced to the amount of HMPA produced (4-HBA/HMPA ) is obtained.
  • the bidentate phosphine ligand used in the method for producing 4-HBA of the present embodiment can be produced by appropriately combining known methods.
  • a bidentate phosphine ligand may be used by purchasing a commercially available product.
  • solvent In the method for producing 4-HBA of the present embodiment, it is preferable to carry out the hydroformylation reaction of allyl alcohol in a solvent.
  • the solvent it is preferable to use a solvent that is inert to the starting material, allyl alcohol, and the reaction product.
  • solvents tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, n-propyl acetate, n-butyl acetate, n-heptane, acetonitrile, benzene, toluene, xylene, N-methyl-2 -pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide and the like.
  • aromatic compounds such as benzene, toluene, and xylene are particularly preferable because they are highly separable from water.
  • water is added to the reaction solution after the hydroformylation reaction of allyl alcohol, and the desired 4-HBA is added to the aqueous layer side. can efficiently extract reaction products containing
  • the amount of the solvent to be used is 1 to 1 by weight with respect to allyl alcohol, since the separation of the organic layer and the aqueous layer is improved in the operation of adding water to the reaction solution after the hydroformylation reaction and separating the layers. It is preferably 50 times, more preferably 5 to 30 times, even more preferably 5 to 20 times.
  • reaction temperature in the hydroformylation reaction of allyl alcohol is preferably 40 to 100°C, more preferably 40 to 80°C, even more preferably 50 to 70°C.
  • reaction temperature is 40° C. or higher, 4-HBA can be efficiently produced without extremely slowing down the reaction rate. Further, when the reaction temperature is 100° C. or less, the selectivity of 4-HBA is not lowered due to excessively high reaction rate, and the stability of the catalyst is not impaired.
  • the reaction time in the hydroformylation reaction of allyl alcohol is preferably 0.5 to 10 hours, more preferably 0.5 to 5 hours, even more preferably 1 to 3 hours.
  • a reaction time of 0.5 to 10 hours ensures a high yield and good productivity.
  • a pressure-resistant reactor such as an autoclave can be used.
  • 4-HBA obtained in the hydroformylation step may be further purified. Alternatively, it may be stored as it is or used as a raw material for other production without purification.
  • the obtained 4-HBA may be used as it is in a method for producing gamma-butyrolactone and the like without being purified.
  • High yield may mean, for example, 70% or more, 80% or more, 85% or more, 90% or more, 95% or more, or 97% or more, but is limited to these examples only. not.
  • the method for producing gamma-butyrolactone (GBL) of the present embodiment includes the steps of producing 4-HBA by the method for producing 4-HBA of the present embodiment, and the steps of contacting the produced 4-HBA with a copper-containing catalyst. including.
  • 4-HBA is brought into contact with a copper-containing catalyst, and 4-HBA is dehydrogenated to produce GBL.
  • the method for producing GBL of the present embodiment includes a step of producing 4-HBA by the method for producing 4-HBA of the present embodiment. Therefore, the reaction product containing 4-HBA produced in the process of producing 4-HBA has a low HMPA content, and the ratio of the amount of 4-HBA produced to the amount of HMPA produced (4-HBA/HMPA) is large. Therefore, even if a reaction product containing 4-HBA is directly used in a reaction for producing GBL without purification, GBL can be produced at a high yield and GBL can be produced efficiently.
  • High yield may mean, for example, 70% or more, 80% or more, 85% or more, 90% or more, 95% or more, or 97% or more, but is limited to these examples only. not.
  • highly pure 4-HBA obtained by further purifying the reaction product containing 4-HBA produced by the method for producing 4-HBA of the present embodiment It may be used in reactions to produce GBL.
  • the reaction product containing 4-HBA produced in the step of producing 4-HBA has a large ratio of 4-HBA/HMPA, so purification is easy.
  • a method for purifying the reaction product containing 4-HBA for example, a known method such as a method of separating each component by distillation utilizing the boiling point difference of each component contained in the reaction product can be used. .
  • the copper-containing catalyst that is contacted with 4-HBA contains copper as the active metal.
  • the copper-containing catalyst preferably further contains an oxide of at least one metal element selected from the group consisting of zinc, zirconium and aluminum.
  • the copper-containing catalyst may further contain other metal oxides in addition to copper and oxides of at least one metal element selected from the group consisting of zinc, zirconium and aluminum.
  • chromium oxides are preferable.
  • Dehydrogenation reaction of 4-HBA when the copper-containing catalyst contains an oxide of at least one metal element selected from the group consisting of zinc, zirconium and aluminum, and an oxide of chromium in addition to metallic copper. can be expected to activate the reaction that produces GBL by lowering the activation barrier of
  • the copper-containing catalyst contains chromium oxide, it suppresses the side reaction that produces 1,4-butanediol produced by the reduction of 4-HBA and other impurities, and improves the selectivity of GBL. An improvement effect can be expected.
  • the copper-containing catalyst used in the dehydrogenation reaction of 4-HBA more preferably contains chromium oxide.
  • the copper-containing catalyst preferably consists of copper, at least one selected from the group consisting of zinc, zirconium and aluminum, chromium, and oxygen.
  • copper-containing catalysts containing chromium oxides include catalysts containing zinc and chromium oxides and metallic copper (CuZnCrOx); catalysts containing zirconium and chromium oxides and metallic copper (CuZrCrOx); catalysts containing oxides of aluminum and chromium and copper metal (CuAlCrOx); catalysts containing oxides of zinc, zirconium and chromium and copper metal (CuZnZrCrOx); oxidation of zinc, aluminum and chromium oxides of zirconium, aluminum and chromium, and copper metal (CuZrAlCrOx); oxides of zinc, zirconium, aluminum, and chromium, and copper metal catalyst (CuZnZrAlCrOx) and the like.
  • x representing the proportion of
  • each metal of copper, zinc, zirconium, aluminum, and chromium in the catalyst containing copper can be arbitrarily selected. Since the content of each metal in the catalyst containing copper can further promote the reaction that produces GBL, it is 1.0 mol or less of zinc, 5.0 mol or less of zirconium, and 5.0 mol or less of aluminum per 1 mol of copper. mol or less, preferably 0.5 mol or less of chromium.
  • Zinc in the copper-containing catalyst is preferably 1.0 mol or less, more preferably 0.005 to 0.4 mol, and 0.01 to 0.3 mol, relative to 1 mol of copper. is more preferably 0.01 to 0.2 mol, and particularly preferably 0.05 to 0.1 mol.
  • Zirconium in the copper-containing catalyst is preferably 5.0 mol or less, more preferably 0.01 to 1.0 mol, and 0.05 to 0.4 mol, per 1 mol of copper. is more preferably 0.05 to 0.3 mol, and particularly preferably 0.1 to 0.2 mol.
  • Aluminum in the catalyst containing copper is preferably 5.0 mol or less, more preferably 0.01 to 3.0 mol, and 0.05 to 1.0 mol, per 1 mol of copper. is more preferably 0.1 to 0.8 mol, and particularly preferably 0.2 to 0.6 mol.
  • the amount of chromium in the catalyst containing copper is preferably 0.5 mol or less, more preferably 0.01 to 0.4 mol, more preferably 0.03 to 0.3 mol, per 1 mol of copper. more preferably 0.05 to 0.2 mol, more preferably 0.07 to 0.15 mol.
  • a method for producing a copper-containing catalyst a known method such as a coprecipitation method, a pore filling method, or a hydrothermal synthesis method can be used.
  • Step of producing gamma-butyrolactone In the step of producing GBL by contacting 4-HBA with a copper-containing catalyst in the method for producing GBL of the present embodiment (hereinafter sometimes referred to as “GBL production step”), an aqueous solution of 4-HBA is It is preferable to vaporize and bring the vaporized 4-HBA into contact with the copper-containing catalyst.
  • the aqueous solution of 4-HBA it is preferable to use an aqueous solution containing 1 to 30% by mass of 4-HBA, more preferably 5 to 25% by mass, still more preferably 10 to 20% by mass.
  • This step may include a step of preparing or adjusting an aqueous solution of 4-HBA having a preferred concentration as described above.
  • the liquid hourly space velocity (LHSV) in terms of raw materials is preferably 1.6 hr -1 or less in order to maintain the yield of GBL. It is more preferable to make it 0.4 hr ⁇ 1 or less.
  • the lower limit of the liquid hourly space velocity (LHSV) can be selected as required, and may be, for example, 0.1 hr ⁇ 1 or more, but is not limited to this.
  • reaction temperature is higher than 200° C.
  • 4-HBA exists in the gaseous phase during the reaction, promoting the reaction to produce GBL and producing GBL at a higher yield.
  • the reaction temperature is preferably 400° C. or lower because the safety of the reaction to generate GBL is further enhanced.
  • the reaction temperature is more preferably 210 to 370°C, even more preferably 230 to 360°C, and particularly preferably 260 to 350°C.
  • the GBL production process can be performed, for example, using a fixed-bed gas-phase reactor having a reaction vessel filled with a copper-containing catalyst.
  • GBL obtained in the GBL manufacturing process may be purified by a general method such as distillation under reduced pressure.
  • GBL obtained in the GBL production process can be preferably used as a raw material for N-methyl-2-pyrrolidone.
  • the method for producing N-methyl-2-pyrrolidone (NMP) of the present embodiment includes a step of producing GBL by the method for producing GBL of the present embodiment, and a step of reacting the produced GBL with monomethylamine. .
  • the step of reacting GBL and monomethylamine in the method for producing NMP of the present embodiment is, for example, a step of producing NMP by putting GBL, monomethylamine, and a solvent into a reaction vessel and causing a liquid phase reaction. be able to.
  • a reaction vessel a reaction vessel made of stainless steel can be preferably used.
  • Alcohols or water can be used as the solvent, preferably water.
  • the molar ratio of monomethylamine to 1 mol of GBL used as a raw material is preferably in the range of 1 to 10, more preferably in the range of 1 to 5, and even more preferably. It ranges from 1 to 1.5.
  • the molar ratio of monomethylamine to 1 mol of GBL is in the range of 1 to 10, NMP can be produced in high yield.
  • the reaction between GBL and monomethylamine may be carried out in the air or in an inert gas atmosphere such as a nitrogen gas atmosphere or an argon atmosphere, preferably in a nitrogen gas atmosphere.
  • the reaction between GBL and monomethylamine is preferably carried out at a reaction temperature of 100 to 400°C, more preferably 150 to 350°C, still more preferably 200 to 300°C.
  • the reaction temperature is 100 to 400° C.
  • the reaction time of GBL and monomethylamine is preferably 0.1 to 10 hours, more preferably 0.5 to 7 hours, still more preferably 1 to 5 hours.
  • a reaction time of 0.1 to 10 hours ensures a high yield and good productivity.
  • High yield may mean, for example, 70% or more, 80% or more, 85% or more, 90% or more, 95% or more, or 97% or more, but is limited to these examples only. not.
  • the reaction solution containing NMP produced in the step of reacting GBL and monomethylamine may be purified by a general method such as distillation under reduced pressure.
  • the NMP manufacturing method of this embodiment includes a step of manufacturing a GBL by the GBL manufacturing method of this embodiment. Therefore, GBL can be efficiently produced, and the produced GBL can be used to efficiently produce NMP, which is an industrially useful compound.
  • the reaction vessel is filled with a mixed gas of carbon monoxide gas and hydrogen gas and the pressure is 2.0 MPaG (gauge pressure) (carbon monoxide gas partial pressure 1.0 MPaG (gauge pressure), hydrogen gas partial pressure
  • the pressure was adjusted to 1.0 MPaG (gauge pressure), and the reaction was carried out at a reaction temperature of 65°C for 3 hours while stirring the inside of the reaction vessel.
  • 30 g of water was added to the reaction solution for extraction, and a liquid separation operation was performed to recover the aqueous layer, thereby obtaining an aqueous solution containing a reaction product containing 4-HBA.
  • Example 2 ⁇ Production of bidentate phosphine ligand> 4,6-Bis(diphenylphosphino)phenoxazine (1 g, 1.81 mmol) and 20 mL of dehydrated tetrahydrofuran were placed in a 200-mL two-necked flask purged with nitrogen, and 0.1 g of sodium hydride was added. It was refluxed for 1 hour at a temperature of °C. Further, a mixed solution of 0.62 g of benzyl chloride and 5 mL of tetrahydrofuran was added, and the mixture was refluxed at a temperature of 70° C. for 16 hours for reaction.
  • a bidentate phosphine ligand As a bidentate phosphine ligand, 0.1496 g of a bidentate phosphine ligand represented by formula (4) (4 mol per 1 mol of rhodium atoms contained in the rhodium catalyst) was used, and the reaction time was 2 hours. An aqueous solution containing a reaction product containing 4-HBA was obtained in the same manner as in Example 1, except that
  • chlorodiphenylphosphine (4.93 ml, 27.4 mmol) was added while maintaining the temperature at 0°C. Then, the mixture was stirred at room temperature for 3 hours or longer to react. Dichloromethane and water were added to the reaction solution to separate the layers. After the organic layer was washed with water and dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was washed with hexane. Then, by recrystallizing with dichloromethane and hexane, 2.5 g of the compound represented by the following formula (6) was obtained as a pale yellow solid. The yield of the compound represented by formula (6) was 47%.
  • bis(3,5-dimethylphenyl)chlorophosphine (excess amount) represented by the formula (7) was added while maintaining the temperature at 0°C. After that, the mixture was stirred at room temperature for 16 hours to react. Dichloromethane and water were added to the reaction solution to separate the layers. After the organic layer was washed with water and dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain a solid reaction product.
  • the calculation time for the activation energy of 1,2 insertion and the activation energy of 2,1 insertion varies depending on the type and molecular size of the bidentate phosphine ligand. Therefore, depending on the type and molecular size of the bidentate phosphine ligand, the computational cost may become enormous. For this reason, in the present invention, the Gibbs free energy of the transition state was calculated using the calculation technique described below while balancing the trade-off between calculation time and calculation accuracy.
  • the yield of 4-HBA shown in Table 1 is the sum of the yield of 4-HBA and the yield of 2-hydroxytetrahydrofuran. Since 4-HBA in the aqueous solution is in equilibrium with 2-hydroxytetrahydrofuran, the yield of 2-hydroxytetrahydrofuran contained in the aqueous solution containing the reaction product was also converted into the yield of 4-HBA.
  • the 1,2-insertion activation energy and the 2,1-insertion activation energy calculated by the density functional theory difference was 4.2 kcal/mol or more.
  • the difference in activation energy was less than 4.2 kcal/mol in spite of using a bidentate phosphine ligand. Therefore, the magnitude relationship of the calculated value of the activation energy difference in the 4-HBA production methods of Examples 1 to 5 and Comparative Example 2 is the same as that in the 4-HBA production methods of Examples 1 to 5 and Comparative Example 2. This coincided with the magnitude relationship of the experimental results for 4-HBA/HMPA. From this, it can be confirmed that 4-HBA/HMPA tends to increase as the difference in activation energy between 1,2 insertion and 2,1 insertion calculated by the density functional theory increases. The validity of the calculation method was confirmed.
  • GHSV gas hourly space velocity
  • LHSV liquid hourly space velocity in terms of raw material
  • the conversion of 4-HBA was 98.5%
  • the GBL yield was 97.5%
  • the GBL selectivity was 99.0%.
  • the reaction product containing 4-HBA produced in Example 1 can produce GBL at a high yield even if it is used as it is for the reaction for producing GBL without purification, and GBL can be produced efficiently. I have confirmed that it is possible. This is because the 4-HBA/HMPA of the reaction product containing 4-HBA produced in Example 1 is large.
  • NMP N-methyl-2-pyrrolidone
  • the resulting reaction solution containing NMP was analyzed using HPLC to determine the conversion rate of GBL and the yield of NMP. As a result, the conversion rate of GBL was 98.4% and the yield of NMP was 97.9%. From this, it was confirmed that NMP can be efficiently produced at a high yield using GBL produced using the reaction product containing 4-HBA produced in Example 1 as a starting material.
  • the present invention provides a method for producing 4-HBA that produces a small amount of HMPA and yields a large 4-HBA/HMPA reaction product.

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Abstract

La présente invention concerne un procédé de production de 4-hydroxybutyle aldéhyde, ledit procédé comprenant une étape dans laquelle un alcool allylique est soumis à une réaction d'hydroformylation conjointement avec un gaz monoxyde de carbone et un gaz hydrogène en présence d'un catalyseur au rhodium et d'un catalyseur qui contient au moins un ligand phosphine bidenté qui est choisi parmi les formules (1) à (3) (dans lesquelles Ar représente un groupe aryle éventuellement substitué).
PCT/JP2022/040335 2021-11-02 2022-10-28 Procédé de production d'aldéhyde 4-hydroxybutyle, procédé de production de gamma butyrolactone, procédé de production de n-méthyl-2-pyrrolidone et composé WO2023080071A1 (fr)

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