Method for producing compounds

Abstract

To provide a manufacturing method that can efficiently produce hydrophilic compounds having two aminomethyl groups. [Solution] A method for producing a hydrophilic compound having two aminomethyl groups, comprising reacting a compound having a methyl halide group and a formyl group with hydrogen and ammonia in the presence of a hydrogenation catalyst and a hydrophobic solvent, and then separating the resulting hydrophilic compound having two aminomethyl groups with an aqueous solvent.

Description

Technical Field

[0001] The present invention relates to a method for producing a compound. In particular, it relates to a method for producing a hydrophilic compound having two aminomethyl groups using a hydrophobic solvent.

Background Art

[0002] Furan derivatives, which are compounds containing a furan ring, are useful as raw materials and intermediates for resins, pharmaceuticals, fragrances, etc. For example, 2,5-(hydroxymethyl)furfural (hereinafter also referred to as HMF), which is one of the furan derivatives, can be obtained from fructose, which is a sugar, as disclosed in Patent Document 1, and is a highly versatile intermediate that can be prepared from biomass raw materials such as naturally occurring carbohydrates. Biomass raw materials are inexpensive and available, and are superior to fossil fuels from the perspective of environmental protection, and thus are attracting attention as raw materials for resins and the like.

[0003] It has been studied to obtain highly versatile furan derivatives by further performing a functional group conversion reaction on HMF, and a method for producing 2,5-bis(aminomethyl)furan (hereinafter also referred to as BAF) is disclosed in, for example, Patent Document 2 and Non-Patent Document 1. Specifically, Non-Patent Document 1 discloses that BAF can be synthesized by oxidizing HMF to obtain 2,5-diformylfuran and then performing reductive amination using Raney nickel treated with hydrogen peroxide as a catalyst. Patent Document 2 also discloses that BAF can be synthesized using a catalyst such as Raney nickel, Mo-Raney nickel, Raney cobalt, copper, copper-nickel, ruthenium, etc. for 2,5-diformylfuran.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

[0005] [Non-Patent Document 1] Green and Sustainable Chemistry, 2015, 5, 115-127. [Overview of the project] [Problems that the invention aims to solve]

[0006] In the manufacturing methods described in Non-Patent Document 1 and Patent Document 2, when HMF is used as a starting material, the reaction from HMF to BAF requires two steps: an oxidation step of the hydroxyl group and a reductive amination step of the aldehyde. Furthermore, the formation of oligomers as by-products from the side reaction of amino and imino groups during BAF synthesis is a problem, so an efficient method for producing BAF is needed.

[0007] This invention has been made in view of the above circumstances, and aims to provide a manufacturing method that can efficiently produce a hydrophilic compound having two aminomethyl groups. [Means for solving the problem]

[0008] As a result of diligent research by the present inventors on methods for producing hydrophilic compounds having two aminomethyl groups, they discovered that by reacting a compound having a methyl halide group and a formyl group in a hydrophobic solvent and then separating the hydrophilic compound having two aminomethyl groups with an aqueous solvent, the hydrophilic compound having two aminomethyl groups can be efficiently separated from by-product oligomers, thus completing the present invention.

[0009] In other words, the present invention is as follows. <1> A method for producing a hydrophilic compound having two aminomethyl groups, comprising reacting a compound having a methyl halide group and a formyl group with hydrogen and ammonia in the presence of a hydrogenation catalyst and a hydrophobic solvent, and then separating the resulting hydrophilic compound having two aminomethyl groups with an aqueous solvent. <2> The hydrophilic compound having two aminomethyl groups is represented as X-(CH2NH2)2 (where X represents an aromatic ring or heterocycle), and the compound having a methyl halide group and a formyl group is represented as (Hr-CH2)-XC(=O)H (where X represents an aromatic ring or heterocycle, and Hr represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom). <1> The manufacturing method described above. <3> The hydrophilic compound having two aminomethyl groups is 2,5-bis(aminomethyl)furan, and the compound having a methyl halide group and a formyl group is 5-(methyl halide)furfural. <1> or <2> The manufacturing method described above. <4> The aforementioned methyl halogenated group is a chloromethyl group. <1> ~ <3> A manufacturing method described in any one of the following. <5> The hydrophilic compound having two aminomethyl groups is 2,5-bis(aminomethyl)furan, the compound having a methyl halogenated group and a formyl group is 5-(methyl halogenated)furfural, and the methyl halogenated group is a chloromethyl group. <1> ~ <4> A manufacturing method described in any one of the following. <6> The compound having the methyl halide group and the formyl group includes a compound derived from at least one selected from the group consisting of woody biomass, cellulose, and C6 sugars, which are sugars composed of six carbon atoms. <1> ~ <5> A manufacturing method described in any one of the following. <7> The hydrogenation catalyst is a catalyst comprising at least one selected from the group consisting of Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt, Re, and Os. <1> ~ <6> A manufacturing method described in any one of the following. <8> Furthermore, the process includes separating 2,5-bis(aminomethyl)furan from the catalyst. <1> ~ <7> A manufacturing method described in any one of the following. <9> The compound having a methyl halide group and a formyl group comprises a compound derived from at least one selected from the group consisting of woody biomass, cellulose, and C6 sugars, which are sugars composed of six carbon atoms, and the hydrogenation catalyst comprises at least one selected from the group consisting of Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt, Re, and Os, and further comprises a step of separating 2,5-bis(aminomethyl)furan from the catalyst. <1> ~ <8> A manufacturing method described in any one of the following. [Effects of the Invention]

[0010] The present invention provides a method for efficiently producing hydrophilic compounds having two aminomethyl groups. [Modes for carrying out the invention]

[0011] The following describes in detail an embodiment for carrying out the present invention (hereinafter referred to as "this embodiment"), but the present invention is not limited thereto, and various modifications are possible without departing from its essence. In this specification, "~" is used to mean that the numerical values ​​before and after it are included as the lower and upper limits. Furthermore, the upper and lower limits of the numerical values ​​in this specification are given as examples of this embodiment, regardless of the combination of upper and lower limits. In this specification, a preferred combination of embodiments is a more preferred embodiment. In this specification, all physical properties and characteristic values ​​shall be those at 23°C unless otherwise specified. In this specification, when groups (atomic groups) are not specified as substituted or unsubstituted, the notation includes both groups (atomic groups) with and without substituents. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. In this specification, when notation is not specified as substituted or unsubstituted, unsubstituted is preferred.

[0012] In this specification, the term "step" includes not only an independent step but also a step whose intended action is achieved even if it cannot be clearly distinguished from other steps. When measurement methods and the like described in the standards shown in this specification differ depending on the year, unless otherwise specified, they shall be based on the standards as of January 1, 2024.

[0013] The production method of this embodiment is a method for producing a hydrophilic compound having two aminomethyl groups, which comprises reacting a compound having a halomethyl group and a formyl group with hydrogen and ammonia in the presence of a hydrogenation catalyst and a hydrophobic solvent, and separating the obtained hydrophilic compound having two aminomethyl groups by an aqueous solvent. With such a configuration, a hydrophilic compound having two aminomethyl groups can be efficiently produced. More specifically, the following reaction will be described as an example.

Chemical formula

Chemical formula

[0014] When the above CMF (5-(chloromethyl)furfural) is reacted with hydrogen and ammonia in the presence of a hydrogenation catalyst and THF (a hydrophilic solvent), it is presumed that, as a by-product, the formyl group of CMF may react with ammonia to form an imine compound (a). Furthermore, it is presumed that the imine compounds (a) may polymerize to form a dimer (b) having a Schiff base. Furthermore, it is presumed that the dimer (b) having the Schiff base may polymerize to form an oligomer (c) having the Schiff base. Then, the yield of BAF will decrease. Under these circumstances, the inventors decided to carry out the amination reaction of a compound having a methyl halide group and a formyl group, such as CMF, under a hydrophobic solvent, and to separate the resulting hydrophilic compound having two aminomethyl groups, such as BAF, using an aqueous solvent. In this way, they found that by separating the hydrophilic compound having two aminomethyl groups from (a) to (c) above, they could efficiently produce the hydrophilic compound having two aminomethyl groups. That is, it is presumed that they were able to separate the aqueous layer in which the hydrophilic compound having two aminomethyl groups was dissolved from the hydrophobic solvent layer (oil layer) in which the by-products (a) to (c) were dissolved.

[0015] The manufacturing method of this embodiment allows for the production of a hydrophilic compound having two aminomethyl groups from a compound having a methyl halide group and a formyl group, for example, within a single reaction system. The details of this embodiment will be described below.

[0016] (A hydrophilic compound having two aminomethyl groups) In this embodiment, the hydrophilic compound having two aminomethyl groups is preferably a compound represented as X-(CH2NH2)2 (where X represents an aromatic ring or heterocycle). Hydrophilic compounds are, for example, compounds that dissolve in water at 23°C in a proportion of 1% by mass or more.

[0017] X is preferably a heterocyclic ring. The aromatic ring in X is preferably a benzene ring, a naphthalene ring, or a biphenyl ring, with a benzene ring being preferred. The heteroring in X is preferably a 5-membered or 6-membered ring, with a 5-membered ring being preferred. The heteroatoms are preferably oxygen, nitrogen, or sulfur atoms, with oxygen being more preferred. X is preferably a furan ring. The aromatic ring and heterocycle may or may not have substituents. Examples of substituents include alkyl groups having 1 to 3 carbon atoms and hydroxyl groups.

[0018] In this embodiment, the hydrophilic compound having two aminomethyl groups is more preferably the compound represented by formula (1) (2,5-bis(aminomethyl)furan).

[0019] [ka]

[0020] The hydrophilic compound having two aminomethyl groups is not particularly limited to any other hydrophilic compound having two aminomethyl groups, and may include metaxylenediamine and isophoronediamine.

[0021] The molecular weight of the hydrophilic compound having two aminomethyl groups is preferably 100 or more, more preferably 110 or more, preferably 200 or less, and more preferably 190 or less.

[0022] (A compound containing a methyl halogenated group and a formyl group) In this embodiment, the compounds having a methyl halide group and a formyl group are preferably compounds represented as (Hr-CH2)-XC(=O)H (where X represents an aromatic ring or heterocycle, and Hr represents a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom). By using compounds with this structure as starting materials, hydrophilic compounds having two aminomethyl groups can be produced in fewer steps than when HMF is used as a starting material. Specifically, by subjecting a compound having a methyl halide group and a formyl group to a reductive amino reaction, a hydrophilic compound having two aminomethyl groups can be produced in a single step.

[0023] X is the same as X in the compound represented by X-(CH2NH2)2 as described above, and the preferred range is also the same. Hr is preferably a fluorine atom, a chlorine atom, or a bromine atom, more preferably a chlorine atom or a bromine atom, and even more preferably a chlorine atom.

[0024] In this embodiment, the compound having a methyl halide group and a formyl group is more preferably the compound represented by formula (2) (5-(methyl halide)furfural).

[0025] [ka]

[0026] In formula (2), X is equivalent to Hr in the compound represented by (Hr-CH2)-XC(=O)H above, and the preferred range is also the same. In this embodiment, the compound having a methyl halide group and a formyl group is preferably 5-(chloromethyl)furfural.

[0027] In this embodiment, the compound having a methyl halide group and a formyl group is preferably derived from at least one selected from the group consisting of woody biomass, cellulose, and C6 sugars, which are sugars composed of six carbon atoms. Furthermore, the compound having a methyl halide group and a formyl group is preferably obtained by derivatizing these raw materials. Thus, since compounds having a methyl halide group and a formyl group can be manufactured using natural materials of biological origin, such as biomass raw materials, the manufacturing method of the present invention can reduce the environmental burden.

[0028] Specifically, the compound having a methyl halide group and a formyl group in this embodiment can be obtained from a C6 sugar, which is a sugar composed of six carbon atoms, and a C6 sugar, which is a sugar composed of six carbon atoms, can be easily obtained from cellulose, which is a major component of woody biomass. Furthermore, in this embodiment, woody biomass refers to "biological resources consisting of wood," which are resources that are widely and abundantly available throughout the world.

[0029] In this embodiment, the compound having a methyl halide group and a formyl group is preferably obtained in a single reaction, for example, by hydrolysis of cellulose. Specifically, when obtaining a compound having a methyl halide group and a formyl group by hydrolysis of cellulose, such a compound can be obtained by reacting cellulose with a hydrogen halide such as hydrogen chloride, hydrogen bromide, or hydrogen iodide in an aqueous solvent. Furthermore, the compound having a methyl halide group and a formyl group in this embodiment may be a commercially available product. The compound having a methyl halide group and a formyl group in this embodiment can also be obtained in a single reaction by reacting woody biomass with a hydrogen halide such as hydrogen chloride, hydrogen bromide, or hydrogen iodide and performing hydrolysis.

[0030] Furthermore, the compounds having a methyl halide group and a formyl group in this embodiment can also be obtained by derivatization from C6 sugars, which are sugars composed of six carbon atoms. Examples of the above C6 sugars include glucose and fructose. Compounds having a methyl halide group and a formyl group can be obtained, for example, by a two-step reaction in which these C6 sugars are converted into HMF as described in International Publication No. 2003-024947, and a halogenation reaction such as the Appel reaction is carried out on the hydroxyl group in the HMF. Similarly, compounds having a methyl halide group and a formyl group can also be obtained in a one-step reaction by reacting a C6 sugar with a hydrogen halide such as hydrogen chloride, hydrogen bromide, or hydrogen iodide in an aqueous solvent.

[0031] (Hydrogenation catalyst) The hydrogenation catalyst in this embodiment is not particularly limited as long as it is one that is commonly used as a catalyst in catalytic hydrogenation reactions. The hydrogenation catalyst preferably contains at least one selected from the group consisting of Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt, Re, and Os, and more preferably contains Co. These metals may be used individually or in combination of two or more.

[0032] The metals mentioned above may be supported on a carrier. The carrier is not particularly limited as long as it is a carrier that is normally used as a catalyst carrier, and examples include inorganic oxides, activated carbon, and ion exchange resins. Specific examples of inorganic oxides include silica (SiO2), titania (TiO2), zirconia (ZrO2), alumina (Al2O3), magnesium oxide (MgO), and composites of two or more of these inorganic oxides (e.g., zeolites).

[0033] Specifically, hydrogenation catalysts include: iron (Fe) catalysts such as reduced iron; cobalt (Co) catalysts such as reduced cobalt and Raney cobalt (hereinafter also referred to as Raney-Co); nickel (Ni) catalysts such as reduced nickel, nickel oxide and Raney nickel (hereinafter also referred to as Raney-Ni); copper (Cu) catalysts such as copper(II) chloride, copper(I) chloride, copper(O), cuprous oxide (I), and copper(II) oxide; ruthenium (Ru) catalysts such as ruthenium / carbon and ruthenium / alumina; rhodium (Rh) catalysts such as rhodium / carbon and rhodium / alumina; and spongy palladium Examples of catalysts include palladium (Pd) catalysts such as palladium black, palladium oxide, palladium / carbon, palladium hydroxide, palladium / barium sulfate, and palladium / barium carbonate; iridium (Ir) catalysts such as chloro(cyclooctadinyl)iridium dimer; platinum (Pt) catalysts such as platinum plates, spongy platinum, platinum black, colloidal platinum, platinum oxide, and platinum wire; rhenium (Re) catalysts such as platinum-supported perrhenic acid; and osmium (Os) catalysts such as osmium / carbon. Cobalt (Co) catalysts are preferred, and Raney-Co catalysts are more preferred.

[0034] (Hydrophobic solvent) In this embodiment, the hydrophobic solvent refers to a solvent that is immiscible with water in any proportion, and examples include dichloromethane, chloroform, carbon tetrachloride, nitromethane, ethane, 1,2-dichloroethane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, pentane, cyclohexane, hexane, octane, heptane, benzene, toluene, o-xylene, m-xylene, p-xylene, cumene, nitrobenzene, phenol, s-butanol, cyclopentyl methyl ether, and cyclohexanone, with hexane, toluene, o-xylene, m-xylene, and p-xylene being particularly noteworthy. Among these, aromatic hydrocarbon solvents such as benzene, toluene, and m-xylene, and hydrocarbon solvents such as ethane, hexane, octane, and heptane are preferred, with aromatic hydrocarbon solvents being more preferred. By using aromatic hydrocarbon solvents, the solubility of hydrogen gas in the solvent is improved, and liquid-liquid separation with water after the reaction can be performed. In particular, the hydrophobic solvent is not particularly limited as long as the solubility of the hydrophilic compound having two aminomethyl groups is less than the solubility of the hydrophilic compound having two aminomethyl groups in water. That is, the hydrophobic solvent is not particularly limited as long as the partition coefficient K shown in the following formula for the hydrophilic compound having two aminomethyl groups when using a hydrophobic solvent and water is less than 1, it is preferably 0.7 or less, more preferably 0.5 or less, even more preferably 0.3 or less, and even more preferably 0.1 or less, with a practical lower limit of 0.001 or more. Partition coefficient K = (Concentration of hydrophilic compound with two aminomethyl groups in the hydrophobic solvent) / (Concentration of hydrophilic compound with two aminomethyl groups in the aqueous solvent) Here, dissolution means dissolving in a hydrophobic solvent at 23°C. These solvents may be used individually or in combination of two or more.

[0035] (Reaction conditions) The manufacturing method of this embodiment specifically includes a method of mixing a compound having a methyl halide group and a formyl group, ammonia, a hydrophobic solvent, a hydrogenation catalyst, and hydrogen, and then reacting them. The order in which the compound having a methyl halide group and a formyl group, ammonia, hydrophobic solvent, hydrogenation catalyst, and hydrogen are mixed is arbitrary. From the viewpoint of work efficiency, in the manufacturing method of this embodiment, it is preferable to first mix the compound having a methyl halide group and a formyl group with the hydrophobic solvent and hydrogenation catalyst, then add ammonia, and then introduce hydrogen. The manufacturing method of this embodiment allows for the production of a hydrophilic compound having two aminomethyl groups from a compound having a methyl halide group and a formyl group, for example, within a single reaction system. A single reaction system includes a configuration in which the raw materials are reacted in a single reaction vessel. In the manufacturing method of this embodiment, it is preferable to react the compound having a methyl halide group and a formyl group with ammonia in a single reaction vessel. Furthermore, the addition of the aqueous solvent may also be carried out in a single reaction vessel. Furthermore, in the manufacturing method of this embodiment, it is preferable to add a compound having a methyl halide group and a formyl group, hydrogen, and ammonia to a reaction vessel and allow them to react.

[0036] In the manufacturing method of this embodiment, when adding the hydrogenation catalyst, depending on the hydrogenation catalyst used, the process may be carried out under an inert gas atmosphere such as nitrogen or argon to prevent ignition, or the hydrogenation catalyst may be suspended in water and added as a suspension.

[0037] In this embodiment, the manufacturing method is preferably carried out at a hydrogen pressure greater than 0 MPaG and 25 MPaG or less. The hydrogen pressure is more preferably 0.5 MPaG or more, and even more preferably 1.0 MPaG or more. The hydrogen pressure is also more preferably 15 MPaG or less, even more preferably 10 MPaG or less, even more preferably less than 9 MPaG, and even more preferably 8 MPaG or less. By keeping the hydrogen pressure below the above upper limit, the hydrogenation of the compound having a methyl halide group and a formyl group can be slowed down, and bis(aminomethyl)furan can be obtained more easily.

[0038] The ratio of ammonia to the compound having a methyl halide group and a formyl group is preferably in the range of 1 to 1000, more preferably in the range of 1 to 500, even more preferably in the range of 1 to 100, even more preferably in the range of 1 to 50, and even more preferably in the range of 1 to 20, in terms of molar ratio (compound having a methyl halide group and a formyl group / ammonia). By setting the ratio within this range, amination can be carried out more effectively.

[0039] The amount of hydrogenation catalyst relative to the compound having a methyl halide group and a formyl group can be appropriately adjusted depending on the type of substrate to be reacted, and is generally 1 to 200% by mass relative to the mass of the compound having the methyl halide group and the formyl group. Preferably, the amount of hydrogenation catalyst is 1 to 150% by mass, and more preferably 1 to 100% by mass, relative to the mass of the compound having the methyl halide group and the formyl group.

[0040] The amount of hydrophobic solvent used for compounds having methyl halogenated groups and formyl groups can be set appropriately considering other reaction conditions and is not particularly limited, but from the viewpoint of productivity and energy efficiency, it is preferably 0.5 to 100 times the mass of the compound having methyl halogenated groups and formyl groups, more preferably 1.0 to 50 times the mass, and even more preferably 1.0 to 20 times the mass.

[0041] The reaction temperature in this embodiment can be adjusted as appropriate depending on the type of substrate to be reacted, and is generally preferred to be 40°C or higher, more preferably 50°C, and more preferably 200°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The reaction time can be adjusted as appropriate by monitoring the progress of the reaction using GC-MS or the like, and is generally 1 minute to 24 hours, preferably 0.5 to 3 hours, and more preferably 0.5 to 2 hours.

[0042] (Separation of reactants) The manufacturing method of this embodiment includes separating the obtained hydrophilic compound having two aminomethyl groups using an aqueous solvent. This allows for the separation of the aqueous layer of the hydrophilic compound having two aminomethyl groups, which dissolves in the aqueous solvent, from the hydrophobic solvent layer (oil layer) of the by-product oligomer, which dissolves in the hydrophobic solvent. Furthermore, using an aqueous solvent facilitates the formation of hydrogen bonds between water and the hydrophilic compound having two aminomethyl groups, making it easier to dissolve, thus tending to allow for the efficient production of the hydrophilic compound having two aminomethyl groups. The aqueous solvent in this embodiment is a solvent containing water, and may contain other components in amounts of 10% by mass or less (preferably 7% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and even more preferably 1% by mass or less), but it is preferable that it does not contain other components. The higher the proportion of water in the aqueous solvent, the easier it is for hydrogen bonds to form between water and the hydrophilic compound having two aminomethyl groups, and the easier it is for the compound to dissolve, so the hydrophilic compound having two aminomethyl groups tends to be produced more efficiently. Other components that may be included in the aqueous solvent include acids, bases, and salts. One embodiment of preparative separation using an aqueous solvent is, for example, a method in which an aqueous solvent is added to the reaction solution to form an aqueous layer in which a hydrophilic compound having two aminomethyl groups is dissolved and an oil layer in which the by-product oligomer is dissolved, and the aqueous layer is collected. In the first embodiment, after a hydrophilic compound having two aminomethyl groups is produced, separation with an aqueous solvent is preferably carried out within 5 minutes, more preferably within 3 minutes, even more preferably within 1 minute, even more preferably within 30 seconds, and even more preferably within 15 seconds. In the first embodiment, it is preferable to carry out the reaction in a reaction vessel such as a separatory funnel after the reaction is complete. In the first embodiment, the hydrophobic solvent may be removed before adding the aqueous solvent.

[0043] A second embodiment of preparative separation using an aqueous solvent is, for example, a method in which an aqueous solvent at a pressure greater than the reaction pressure is introduced into the reaction system to separate the hydrophilic compound having two aminomethyl groups from the by-product oligomer. In the second embodiment, the reaction pressure and the pressure of the reaction system and the supplied aqueous solvent may be the same, but it is preferable that the pressure of the reaction system and the supplied aqueous solvent is higher than the reaction pressure. In the second embodiment, the pressure difference between the reaction pressure and the pressure of the reaction system and the aqueous solvent being supplied is preferably 100 to 1000 Pa.

[0044] The manufacturing method of this embodiment preferably includes a step of separating the hydrophilic compound having two aminomethyl groups (preferably 2,5-bis(aminomethyl)furan) and the catalyst after the reaction is complete. The separation process can be carried out by common methods such as sedimentation, centrifugation, and filtration. Depending on the catalyst used, it is preferable to separate the catalyst under an inert gas atmosphere such as nitrogen or argon to prevent ignition. Furthermore, when a solvent is used in the above reaction, the reaction mixture may be concentrated as needed, and the residue may be used directly as a raw material or intermediate. Alternatively, the reaction mixture may be purified by appropriate post-treatment. Specific post-treatment methods include known purification methods such as extraction, distillation, and chromatography. Two or more of these purification methods may be combined. [Examples]

[0045] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or other reasons, measurements can be taken using other instruments with equivalent performance.

[0046] (Example 1) 0.12 g of 5-(chloromethyl)furfural, 12 g of m-xylene, and 0.028 g of Raney-Co as a hydrogenation catalyst were placed in a pressure-resistant autoclave, then 9.4 g of liquid ammonia was added, and the hydrogen pressure was increased to 1 MPaG. The reaction was then carried out while maintaining the temperature at 90°C for one hour, and the reaction was stopped by cooling the pressure-resistant autoclave with ice water. After evacuating the liquid ammonia, 0.72 mL of heavy water was added to 0.74 g of the reaction solution. This resulted in separation into an oil layer and an aqueous layer of m-xylene. The by-product oligomer component precipitated, and BAF could be isolated and extracted from the aqueous layer. Under argon gas flow, the catalyst and reaction mixture were filtered to remove the catalyst, and the filtrate was subjected to GC-FID measurement.

[0047] <Method for calculating the yield of the product and the yield> A calibration curve showing the relationship between GC-FID detection intensity (area value) and BAF concentration was created and compared with the BAF area value of the reaction solution. Specifically, the BAF concentration was calculated using the calibration curve described above from the GC-FID detection intensity (area value) obtained by GC-FID measurement of the reaction solution, and the BAF mass was determined from the reaction solution mass. The mass when 5-(chloromethyl)furfural used in the reaction was quantitatively converted to BAF was set to 100, and the yield was calculated to be 28%.

[0048] <Method for identifying the product ( 1 (H-NMR measurement results) 1 In 1H-NMR measurements, the chemical shift obtained from the aqueous layer of Example 1 matched the chemical shift of the BAF standard sample. GC-MS analysis revealed a molecular ion peak with the same molecular weight (126) as BAF. Furthermore, the fragment ion peak matched the molecular weight (96) of the compound obtained by removing one side of the methylamine from BAF. These results confirmed that BAF was obtained in Example 1. [Industrial applicability]

[0049] The hydrophilic compound having two aminomethyl groups obtained by the manufacturing method of the present invention is useful as a raw material or intermediate for resins, pharmaceuticals, and fragrances. Specifically, it is possible to provide 2,5-bis(aminomethyl)furan, which is useful as a monomer or epoxy resin curing agent, or as an intermediate raw material for compounds, and has industrial applicability in the manufacture of resins, pharmaceuticals, fragrances, etc. In particular, the hydrophilic compound having two aminomethyl groups obtained by the manufacturing method of the present invention can be used in the manufacture of H-BAF (2,5-bis(aminomethyl)tetrahydrofuran).

Claims

1. A method for producing a hydrophilic compound having two aminomethyl groups, A method for producing a compound having a methyl halide group and a formyl group, comprising reacting hydrogen and ammonia with a hydrogenation catalyst and a hydrophobic solvent, and then separating the resulting hydrophilic compound having two aminomethyl groups using an aqueous solvent.

2. The hydrophilic compound having two aminomethyl groups, X-(CH) ２ NH ２ ) ２ (Here, X represents an aromatic ring or heterocycle.) It is represented as, The compound having the methyl halogenated group and the formyl group, (Hr-CH ２ )-X-C(=O)H (Here, X represents an aromatic ring or heterocycle, and Hr represents a fluorine atom, chlorine atom, bromine atom, or iodine atom.) The manufacturing method according to claim 1, as represented by [the method described in claim 1].

3. The production method according to claim 1 or 2, wherein the hydrophilic compound having two aminomethyl groups is 2,5-bis(aminomethyl)furan, and the compound having a methyl halide group and a formyl group is 5-(methyl halide)furfural.

4. The manufacturing method according to any one of claims 1 to 3, wherein the methyl halogenated group is a chloromethyl group.

5. The hydrophilic compound having two aminomethyl groups is 2,5-bis(aminomethyl)furan, and the compound having a methyl halide group and a formyl group is 5-(methyl halide)furfural. The manufacturing method according to any one of claims 1 to 4, wherein the methyl halogenated group is a chloromethyl group.

6. The manufacturing method according to any one of claims 1 to 5, wherein the compound having a methyl halide group and a formyl group includes a compound selected from the group consisting of woody biomass, cellulose, and C6 sugars which are sugars composed of six carbon atoms.

7. The manufacturing method according to any one of claims 1 to 6, wherein the hydrogenation catalyst is a catalyst comprising at least one selected from the group consisting of Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt, Re, and Os.

8. Furthermore, the manufacturing method according to any one of claims 1 to 7, further comprising the step of separating 2,5-bis(aminomethyl)furan from the catalyst.

9. The compound having a methyl halide group and a formyl group includes a compound selected from at least one of the group consisting of woody biomass, cellulose, and C6 sugars, which are sugars composed of six carbon atoms. The hydrogenation catalyst is a catalyst comprising at least one selected from the group consisting of Fe, Co, Ni, Cu, Ru, Rh, Pd, Ir, Pt, Re, and Os. Furthermore, the manufacturing method according to any one of claims 1 to 8, further comprising the step of separating 2,5-bis(aminomethyl)furan from the catalyst.

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