Method for producing n-methylated amine compounds

Abstract

To provide a novel production method for producing N-methylated amine compounds without the need for formaldehyde.SOLUTION: A method for producing N-methylated amine compounds includes a process in which, in the presence of a metal-supported catalyst, under an atmosphere containing introduced carbon dioxide at 0.1 to 10 MPa (gauge pressure) and hydrogen at 0.1 to 20 MPa (gauge pressure), an aliphatic amine compound having at least one intramolecular amino group is heated to 50 to 250°C to methylate the amino group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for producing an N-methylated amine compound. [Background technology]

[0002] One of the causes of global warming is the emission of greenhouse gases. Greenhouse gases include carbon dioxide (CO2), methane (CH4), and fluorocarbons (CFCs, etc.). Of all greenhouse gases, carbon dioxide has the greatest impact, and reducing carbon dioxide (such as that emitted from thermal power plants and steelworks) has become an urgent issue.

[0003] N-methylated amine compounds are industrially useful compounds with various applications such as urethane synthesis catalysts, surfactants, etc. A method for synthesizing N-methylated amine compounds by reacting them with formaldehyde and hydrogen in the presence of, for example, a nickel or metal catalyst, through a so-called reductive methylation reaction, has been reported as a publicly known technique (e.g., Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2000-159731 A Summary of the Invention [Problem to be solved by the invention]

[0005] The manufacturing method of N-methylated amine compounds described in Patent Document 1 above has a problem in that the raw material formaldehyde is highly toxic. If formaldehyde remains in the product during the manufacturing process, it can cause sick house syndrome and sick car syndrome. In addition, formaldehyde is suspected to be carcinogenic and poses a risk of health damage.

[0006] The present invention has been made in view of the above circumstances, and provides a method for producing an N-methylated amine compound that does not require formaldehyde. [Means for solving the problem]

[0007] The present inventors have investigated whether carbon dioxide discharged from plants or the like can be used to synthesize N-methylated amine compounds. As a result, they have found that the method for producing an N-methylated amine compound shown below does not require formaldehyde and can use carbon dioxide as a raw material, and have completed the present invention. That is, one aspect of the present invention relates to the method for producing an N-methylated amine compound shown below.

[0008] [1] A method for producing an N-methylated amine compound, comprising heating an aliphatic amine compound having at least one amino group in the molecule to 50 to 250°C in the presence of a metal-supported catalyst and in an atmosphere containing carbon dioxide at 0.1 to 10 MPa (gauge pressure) and hydrogen at 0.1 to 20 MPa (gauge pressure), thereby methylating the amino group. [2] The method for producing an N-methylated amine compound according to the above [1], wherein the aliphatic amine compound is an aliphatic amine compound represented by the following general formula (1), and the N-methylated amine compound is a methylated amine compound represented by the following general formula (3): [ka] [In the above general formula (1), R 1 ~R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; X represents a hydroxyl group or an amino group; n and m each independently represent an integer of 1 to 5; and a represents an integer of 0 to 4.] [ka] [In the above general formula (3), R 1 ~R 5 R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 12 , R13 each independently represents a hydrogen atom or a methyl group; Z represents a hydroxyl group or -NR 14 R 15 R represents an amino group represented by the formula: 14 , R 15 each independently represents a hydrogen atom or a methyl group; provided that when Z is a hydroxy group, R 3 , R 12 , and R 13 At least one of the groups is a methyl group, and Z is -NR 14 R 15 In the case of an amino group represented by R 3 , and R 12 ~R 15 at least one of them is a methyl group; n and m each independently represent an integer of 1 to 5; and a represents an integer of 0 to 4.] [3] The method for producing an N-methylated amine compound according to the above [2], wherein the aliphatic amine compound represented by the general formula (1) is an aliphatic amine compound represented by the following general formula (1-1), and the N-methylated amine compound is an N-methylated amine compound represented by the following general formula (3-1). [ka] [In the above general formula (1-1), R 1 , R 2 , R 4 , and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; X represents a hydroxyl group or an amino group; n and m each independently represent an integer of 1 to 5; and a represents an integer of 0 to 4.] [ka] [In the above general formula (3-1), R 1 ~R 2 , and R 4 ~R 5 R' each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 3 , R 12 , R 13 each independently represents a hydrogen atom or a methyl group; Z represents a hydroxyl group or -NR14 R 15 R represents an amino group represented by the formula: 14 , R 15 each independently represents a hydrogen atom or a methyl group, provided that when Z is a hydroxy group, R' 3 , R 12 , and R 13 At least one of the groups is a methyl group, and Z is -NR 14 R 15 In the case of an amino group represented by the formula: R' 3 , and R 12 ~R 15 at least one of them is a methyl group; n and m each independently represent an integer of 1 to 5; and a represents an integer of 0 to 4.] [4] R in the general formula (1-1) and the general formula (3-1) 1 ~R 2 , and R 4 ~R 5 are each independently a hydrogen atom or a methyl group. [5] R' in the general formula (3-1) 3 , and R 12 ~R 15 and each of them is a methyl group. [6] The aliphatic amine compound represented by the general formula (1) is ethylenediamine and the N-methylated amine compound represented by the general formula (3) is N,N,N',N'-tetramethylethylenediamine, or the amine compound represented by the general formula (1) is diethylenetriamine and the N-methylated amine compound represented by the general formula (3) is N,N,N',N'',N''-pentamethyldiethylenetriamine, or the aliphatic amine compound represented by the general formula (1) is triethylenetetramine and the N-methylated amine compound represented by the general formula (3) is N,N,N',N'',N''',N'''-hexamethyltriethylenetetramine, or the aliphatic amine compound represented by the general formula (1) is The method for producing an N-methylated amine compound according to any one of the above [2] to [5], wherein the N-methylated amine compound represented by the general formula (3) is N-(2-aminoethyl)ethanolamine and is N-[2-(dimethylamino)ethyl]-N-methylethanolamine, the aliphatic amine compound represented by the general formula (1) is 1,2-diaminopropane and is N,N,N',N'-tetramethyl-1,2-diaminopropane, or the aliphatic amine compound represented by the general formula (1) is propylenediamine and is N,N,N',N'-tetramethylpropylenediamine. [7] The method for producing an N-methylated amine compound according to the above item [1], wherein the aliphatic amine compound is an aliphatic amine compound represented by the following general formula (2), and the N-methylated amine compound is a methylated amine compound represented by the following general formula (4): [ka] [In the above general formula (2), R 6 ~R 11 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; X represents a hydroxyl group or an amino group; and n represents an integer of 1 to 5. [ka] [In the above general formula (4), R 6 ~R 11 R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 16 represents a hydrogen atom or a methyl group; Y represents a hydroxyl group or -NR 17 R 18 R represents an amino group represented by the formula: 17 , R 18 Each independently represents a hydrogen atom or a methyl group. However, when Y is a hydroxy group, R 16 is a methyl group and Y is -NR 17 R 18 In the case of an amino group represented by R 16 ~R 18 At least one of the groups is a methyl group. n represents an integer of 1 to 5.] [8] R in the general formula (2) and the general formula (4) 6 ~R 11 and each of them is a hydrogen atom. [9] R in the general formula (4) 16 ~R 18 and each of the N-methylated amine compounds is a methyl group.

[10] The method for producing an N-methylated amine compound according to any one of the above [7] to [9], wherein the aliphatic amine compound represented by the general formula (2) is N-(2-aminoethyl)piperazine, and the N-methylated amine compound represented by the general formula (4) is 1-[2-(dimethylamino)ethyl]-4-methylpiperazine.

[11] The method for producing an N-methylated amine compound according to any one of the above [1] to

[10] , wherein the metal-supported catalyst is a metal-supported catalyst carrying one or more metals selected from the group consisting of rhodium, platinum, iridium, ruthenium, palladium, molybdenum, rhenium, tungsten, gallium, zirconium, cesium, chromium, cobalt, vanadium, and rare earth elements.

[12] The method for producing an N-methylated amine compound according to any one of the above [1] to

[11] , wherein the metal-supported catalyst is a metal-supported catalyst having at least one support selected from the group consisting of activated alumina, cerium (IV) oxide, titanium (IV) oxide, magnesium oxide, zirconium oxide, silica, and activated carbon.

[13] The method for producing an N-methylated amine compound according to any one of the above [1] to

[12] , wherein the aliphatic amine compound is heated in a solvent, and the amount of the solvent is 0.1 to 100 parts by mass per 1 part by mass of the aliphatic amine compound. Effect of the Invention

[0009] According to the present invention, a novel technique for producing an N-methylated amine compound that does not require formaldehyde can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] An embodiment of the present invention will be described in detail below. In this specification, unless otherwise specified, "A to B" representing a numerical range means "A or more and B or less."

[0011] The present embodiment relates to a method for producing an N-methylated amine compound, characterized in that an aliphatic amine compound having at least one amino group in the molecule is heated to 50 to 250°C in the presence of a metal-supported catalyst and in an atmosphere containing carbon dioxide at 0.1 to 10 MPa (gauge pressure) and hydrogen at 0.1 to 20 MPa (gauge pressure), thereby methylating the amino group of the aliphatic amine compound.

[0012] In the production method of this embodiment, examples of the aliphatic amine compound used as a raw material include an aliphatic amine compound represented by the following general formula (1) (hereinafter also referred to as "aliphatic amine compound (1)") and an aliphatic amine compound represented by the following general formula (2) (hereinafter also referred to as "aliphatic amine compound (2)").

[0013] [ka] [In the above general formula (1), R 1 ~R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; X represents a hydroxyl group or an amino group; n and m each independently represent an integer of 1 to 5; and a represents an integer of 0 to 4.]

[0014] [ka] [In the above general formula (2), R 6 ~R 11 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; X represents a hydroxyl group or an amino group; and n represents an integer of 1 to 5.

[0015] In this specification, the alkyl group having 1 to 4 carbon atoms is a linear, branched, or cyclic alkyl group having 1 to 4 carbon atoms, and is not particularly limited, but examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, and a t-butyl group.

[0016] First, an embodiment in which the aliphatic amine compound (1) is used as the aliphatic amine compound (hereinafter also referred to as the "production method of the first embodiment") will be described.

[0017] The production method of the first embodiment is a production method in which an aliphatic amine compound (1) is heated to 50 to 250° C. in the presence of a metal-supported catalyst and in an atmosphere containing carbon dioxide at 0.1 to 10 MPa (gauge pressure) and hydrogen at 0.1 to 20 MPa (gauge pressure) to methylate (hereinafter also referred to as "N-methylation") the amino group of the aliphatic amine compound (1) to produce an N-methylated amine compound represented by the following general formula (3) (hereinafter also referred to as "N-methylated amine compound (3)").

[0018] [ka] [In the above general formula (3), R 1~R 5 R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 12 , R 13 each independently represents a hydrogen atom or a methyl group; Z represents a hydroxyl group or -NR 14 R 15 R represents an amino group represented by the formula: 14 , R 15 each independently represents a hydrogen atom or a methyl group; provided that when Z is a hydroxy group, R 3 , R 12 , and R 13 At least one of the groups is a methyl group, and Z is -NR 14 R 15 In the case of an amino group represented by R 3 , and R 12 ~R 15 at least one of them is a methyl group; n and m each independently represent an integer of 1 to 5; and a represents an integer of 0 to 4.]

[0019] In the production method of the first embodiment, it is preferable that the aliphatic amine compound (1) is an aliphatic amine compound represented by the following general formula (1-1) (hereinafter also referred to as "aliphatic amine compound (1-1)") and the N-methylated amine compound (3) is an N-methylated amine compound represented by the following general formula (3-1) (hereinafter also referred to as "N-methylated amine compound (3-1)"), in terms of excellent efficiency of N-methylation. That is, the production method of the first embodiment is preferably a production method in which the aliphatic amine compound (1-1) is heated to 50 to 250°C in an atmosphere in which carbon dioxide of 0.1 to 10 MPa (gauge pressure) and hydrogen of 0.1 to 20 MPa (gauge pressure) are introduced in the presence of a metal supported catalyst, to methylate the amino group of the aliphatic amine compound (1-1) and produce the N-methylated amine compound (3-1). [ka] [In the above general formula (1-1), R 1 , R 2 , R 4 , and R 5each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; X represents a hydroxyl group or an amino group; n and m each independently represent an integer of 1 to 5; and a represents an integer of 0 to 4.] [ka] [In the above general formula (3-1), R 1 ~R 2 , and R 4 ~R 5 R' each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 3 , R 12 , R 13 each independently represents a hydrogen atom or a methyl group; Z represents a hydroxyl group or -NR 14 R 15 R represents an amino group represented by the formula: 14 , R 15 each independently represents a hydrogen atom or a methyl group, provided that when Z is a hydroxy group, R' 3 , R 12 , and R 13 At least one of the groups is a methyl group, and Z is -NR 14 R 15 In the case of an amino group represented by the formula: R' 3 , and R 12 ~R 15 at least one of them is a methyl group; n and m each independently represent an integer of 1 to 5; and a represents an integer of 0 to 4.]

[0020] The aliphatic amine compound (1) used in the production method of the first embodiment has excellent efficiency in N-methylation, and therefore has a structure in which R 1 ~R 2 , and R 4 ~R 5 are each preferably independently a hydrogen atom, a methyl group, or an ethyl group, more preferably independently a hydrogen atom or a methyl group, and even more preferably all are a hydrogen atom. 1 ~R 2 , and R 4 ~R 5 respectively represent R in general formula (3).1 ~R 2 , and R 4 ~R 5 Similarly, n, m, and a in general formula (1) are the same integers as n, m, and a in general formula (3), respectively.

[0021] In the aliphatic amine compound (1) used in the production method of the first embodiment, n and m in the general formula (1) each independently represent an integer of 1 to 5. In terms of excellent efficiency of N-methylation, it is preferable that each independently be 1 or 2, and more preferably that both be 1.

[0022] In the aliphatic amine compound (1) used in the production method of the first embodiment, a in the general formula (1) represents an integer of 0 to 4, and is preferably 0, 1, or 2, more preferably 0 or 1, and more preferably 0, in terms of excellent efficiency of N-methylation.

[0023] Here, in the above general formula (1), when a is 0, the aliphatic amine compound (1) becomes an aliphatic amine compound represented by the following general formula (1') (hereinafter, also referred to as "aliphatic amine compound (1')"). When the aliphatic amine compound (1') is used as the aliphatic amine compound (1), an N-methylated amine compound represented by the following general formula (3') in which a in the above general formula (3) is 0 is produced as the N-methylated amine compound (3). [ka] [In general formula (1'), R 4 , R 5 In the general formula (3'), R 4 , R 5 , R 12 , R 13 and Z are defined as in general formula (3).

[0024] The aliphatic amine compound (1), which is a raw material in the production method of the first embodiment, is preferably ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-(2-aminoethyl)ethanolamine, 1,2-diaminopropane, propylenediamine (1,3-diaminopropane), tetramethylenediamine (1,4-diaminobutane), pentamethylenediamine (1,5-diaminopentane), or hexamethylenediamine (1,6-hexanediamine), from the viewpoint of excellent efficiency of N-methylation, and more preferably ethylenediamine, diethylenetriamine, triethylenetetramine, N-(2-aminoethyl)ethanolamine, 1,2-diaminopropane, or propylenediamine (1,3-diaminopropane).

[0025] In the manufacturing method of the first embodiment, the aliphatic amine compound (1) is heated under the above-mentioned predetermined conditions, whereby carbon dioxide (CO2) and hydrogen (H2) in the reaction atmosphere react with the aliphatic amine compound (1), and p hydrogen atoms bonded to the nitrogen atom in the aliphatic amine compound (1) are replaced with p methyl groups (N-methylation). As a result, an N-methylated amine compound (3) is produced in which p hydrogen atoms bonded to the nitrogen atom in the aliphatic amine compound (1) are replaced with p methyl groups. In other words, according to the manufacturing method of the first embodiment, an N-methylated amine compound (3) is produced in which at least one of the hydrogen atoms bonded to the nitrogen atom of the aliphatic amine compound (1) used as a raw material is replaced with a methyl group. Here, p represents an integer of 1 or more, and the upper limit is the number of hydrogen atoms bonded to the nitrogen atom in the aliphatic amine compound (1).

[0026] The N-methylated amine compound (3) produced by the production method of the first embodiment varies depending on the chemical structure of the aliphatic amine compound (1) used as a raw material, and can be, for example, N-methylethylenediamine, N,N'-dimethylethylenediamine, N,N-dimethylethylenediamine, N,N,N'-trimethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, N-methyldiethylenetriamine, N'-methyldiethylenetriamine, N,N-dimethyldiethylenetriamine, N,N'-dimethyldiethylenetriamine, N,N''-dimethyldiethylenetriamine, N,N,N'-trimethyldiethylenetriamine, N,N',N''-trimethyldiethylenetriamine, N,N,N''-tetramethyldiethylenetriamine, N,N,N'' ,N''-Tetramethyldiethylenetriamine, N,N,N',N'',N''-Pentamethyldiethylenetriamine, N-Methyltriethylenetetramine, N,N-Dimethyltriethylenetetramine, N,N'''-Dimethyltriethylenetetramine, N,N,N'''-Trimethyltriethylenetetramine, N,N',N''-Trimethyltriethylenetetramine, N,N,N''',N'''-Tetramethyltriethylenetetramine, N,N,N',N'',N'''-Tetramethyltriethylenetetramine, N,N,N',N'',N'''-Tetramethyltriethylenetetramine, N,N,N',N'',N''',N'''-Pentamethyltriethylenetetramine, N,N,N',N'',N''',N'''-Hexamethyltriethylenetetramine, N,N,N',N'',N'''',N'''',N''''-Heptamethyltetraethylenepentamine, N,N,N',N'',N'''',N'''',N'''',N'''''''-Octamethylpentaethylenehexamine, N-[2-(methylamino)ethyl]-N-ethanolamine, N-(2-aminoethyl)-N-methylethanolamine, N-[2-(dimethylamino)ethyl]-N-ethanolamine, N-[2-(methylamino)ethyl]-N-methylethanolamine, N-[2-(dimethylamino)ethyl]-N-methylethanolamine, 2-(methylamino)-propylamine, 2-amino-N-methylpropylamine, 2-(dimethylamino)-propylamine, 2-amino-N,N-dimethylpropylamine, 2-(methylamino)-N-methylpropylamine, 2-(dimethylamino)-N-methylpropylamine, 2-(methylamino)-N,N-dimethylpropylamine, N,N,N',N'-tetramethyl-1,2-diaminopropane, N-methylpropylenediamine, N,N'-dimethylpropylenediamine, N,N- Dimethylpropylenediamine, N,N,N'-trimethylpropylenediamine, N,N,N',N'-tetramethylpropylenediamine, N-methyltetramethylenediamine, N,N'-dimethyltetramethylenediamine, N,N-dimethyltetramethylenediamine, N,N,N'-trimethyltetramethylenediamine, N,N,N',N'-tetramethyltetramethylenediamine, N-methylpentamethylenediamine, N,N'-dimethylpentamethylenediamine Examples of the hexamethylene diamine include N,N-dimethylpentamethylene diamine, N,N,N'-trimethylpentamethylene diamine, N,N,N',N'-tetramethylpentamethylene diamine, N-methylhexamethylene diamine, N,N'-dimethylhexamethylene diamine, N,N-dimethylhexamethylene diamine, N,N,N'-trimethylhexamethylene diamine, and N,N,N',N'-tetramethylhexamethylene diamine.

[0027] The N-methylated amine compound (3) produced by the production method of the first embodiment is a compound in which at least one of the hydrogen atoms bonded to the nitrogen atom in the aliphatic amine compound (1) used as a raw material has been substituted with a methyl group. The number of hydrogen atoms substituted with methyl groups may be one or more, but it is preferable that all hydrogen atoms bonded to the nitrogen atom have been substituted with methyl groups. That is, the N-methylated amine compound (3) produced by the production method of the first embodiment is a compound in which R 3 and R 12 ~R 15 are preferably N-methylated amine compounds (3), in which each of

[0028] R in general formula (3) 3 and R 12 ~R 15 Among the methods for producing the N-methylated amine compound (3) in which all of R are methyl groups, the production method of the first embodiment is preferably any one of the following production methods 1 to 11, and more preferably any one of the following production methods 1 to 3, 6, 7, and 11, in terms of excellent N-methylation efficiency. Note that in the following production methods 1 to 11, aliphatic amine compound (1) used as a raw material and N-methylated amine compound (3) (R 3 and R 12 ~R 15 The figure shows the N-methylated amine compound (3), in which all of the groups are methyl groups.

[0029] [Manufacturing method 1] Aliphatic amine compound (1): Ethylenediamine N-Methylated amine compound (3): N,N,N',N'-tetramethylethylenediamine [Manufacturing method 2] Aliphatic amine compound (1): Diethylenetriamine N-Methylated amine compound (3): N,N,N',N'',N''-Pentamethyldiethylenetriamine [Manufacturing method 3] Aliphatic amine compound (1): Triethylenetetramine N-Methylated amine compound (3): N,N,N',N'',N''',N'''-hexamethyltriethylenetetramine [Manufacturing method 4] Aliphatic amine compounds (1): Tetraethylenepentamine N-Methylated amine compound (3): N,N,N',N'',N''',N'''',N''''-heptamethyltetraethylenepentamine [Manufacturing method 5] Aliphatic amine compound (1): Pentaethylenehexamine N-Methylated amine compound (3): N,N,N',N'',N''',N'''',N'''''',N'''''-Octamethylpentaethylenehexamine [Manufacturing method 6] Aliphatic amine compound (1): N-(2-aminoethyl)ethanolamine N-Methylated amine compound (3): N-[2-(dimethylamino)ethyl]-N-methylethanolamine [Manufacturing method 7] Aliphatic amine compound (1): Propylenediamine (1,3-diaminopropane) N-Methylated amine compound (3): N,N,N',N'-tetramethylpropylenediamine [Manufacturing method 8] Aliphatic amine compound (1): Tetramethylenediamine (1,4-diaminobutane) N-Methylated amine compound (3): N,N,N',N'-tetramethyltetramethylenediamine [Manufacturing method 9] Aliphatic amine compound (1): Pentamethylenediamine (1,5-diaminopentane) N-Methylated amine compound (3): N,N,N',N'-tetramethylpentamethylenediamine [Manufacturing method 10] Aliphatic amine compound (1): Hexamethylenediamine (1,6-hexanediamine) N-Methylated amine compound (3): N,N,N',N'-tetramethylhexamethylenediamine [Manufacturing method 11] Aliphatic amine compound (1): 1,2-diaminopropane N-Methylated amine compound (3): N,N,N',N'-tetramethyl-1,2-diaminopropane

[0030] The aliphatic amine compound (1), which is a raw material used in the production method of the first embodiment, may be a commercially available product or may be synthesized by a known method, and is not particularly limited.

[0031] The purity of the aliphatic amine compound (1), which is the raw material used in the production method of the first embodiment, is not particularly limited. However, in consideration of ease of purification in the purification step after N-methylation, the purity is preferably 95% by mass or more, and more preferably 98% by mass or more.

[0032] In the production method of the first embodiment, n-methylation of the aliphatic amine compound (1) proceeds by heating the aliphatic amine compound (1) to 50 to 250° C. in the presence of a metal-supported catalyst in an atmosphere containing carbon dioxide at 0.1 to 10 MPa (gauge pressure) and hydrogen at 0.1 to 20 MPa (gauge pressure). To heat the aliphatic amine compound (1) in the presence of a metal-supported catalyst, for example, the aliphatic amine compound (1) may be heated in a state in which the aliphatic amine compound (1) is in contact with the supported metal catalyst.

[0033] The metal-supported catalyst used in the production method of the first embodiment is characterized in that it contains an arbitrary catalytically active metal and a carrier that holds the catalytically active metal, and the catalytically active metal is supported on the carrier.

[0034] The catalytically active metal is not particularly limited, but examples thereof include rhodium, platinum, iridium, ruthenium, palladium, molybdenum, rhenium, tungsten, gallium, zirconium, cesium, chromium, cobalt, vanadium, and rare earth elements. The metal-supported catalyst may contain one or more selected from the group of catalytically active metals.

[0035] Among these catalytically active metals, one or more selected from the group consisting of rhodium, platinum, iridium, ruthenium, molybdenum, rhenium, and tungsten are preferred in terms of shortening the production time of the N-methylated amine compound (3).

[0036] The amount of catalytically active metal supported can be 0.01 to 50 mass%, preferably 0.1 to 15 mass%, and particularly preferably 1 to 15 mass%, based on 100 mass% of the metal-supported catalyst. When the metal-supported catalyst contains two or more catalytically active metals, the amount of catalytically active metal supported as described above means the total amount of the two or more catalytically active metals supported.

[0037] The carrier is not particularly limited, and examples thereof include silica (including activated silica), alumina (including porous activated alumina), silica alumina, zeolite, zirconium oxide, magnesium oxide, calcia, cerium (IV) oxide, titanium (IV) oxide, activated carbon, apatite, monazite, and a composite of two or more of these. Activated alumina generally refers to porous aluminum oxide that exhibits strong substance adsorption power, and can be produced, for example, by calcining, pulverizing, forming, and firing aluminum hydroxide. In addition, for example, activated alumina may be produced by firing JRC-ALO-2 (γ-Al2O3), a reference catalyst of the Catalysis Society, as shown in the examples described later.

[0038] Among these supports, from the viewpoints of shortening the production time of the N-methylated amine compound (3) and achieving selectivity for the product N-methylated amine compound (3), at least one selected from the group consisting of activated alumina, cerium (IV) oxide, titanium (IV) oxide, magnesium oxide, zirconium oxide, silica, and activated carbon is preferred, and activated carbon is more preferred.

[0039] The shape of the carrier is not particularly limited, and examples of the shape include powder, beads, a cylinder, and a honeycomb.

[0040] The form of the metal-supported catalyst is preferably selected appropriately depending on the type of reaction. When the reaction in the production method of the first embodiment is carried out by a batch reaction, the metal-supported catalyst is preferably in the form of a powder obtained by supporting a catalytically active metal on a powdered carrier, in terms of excellent contact efficiency and stirring efficiency between the raw material aliphatic amine compound (1) and the metal-supported catalyst, and when the reaction in the production method of the first embodiment is carried out by a fixed-bed flow reaction, the metal-supported catalyst is preferably in the form of a molded body obtained by molding a powdered carrier supporting a catalytically active metal into any shape that can reduce pressure loss in order to prevent pressure loss.

[0041] Regarding the metal-supported catalyst, if a commercially available product is available, the commercially available product may be used as is, or a product produced according to a known production method may be used. The metal-supported catalyst can be produced, for example, by an impregnation method or a precipitation method.

[0042] An example of the impregnation method that can be used for producing a metal-supported catalyst is a method in which the support is impregnated with an aqueous solution containing a salt of the catalytically active metal, the water is evaporated, and then a reduction treatment is performed. For example, the catalytically active metal can be supported on the activated carbon by impregnating an aqueous solution containing a catalytically active metal salt, evaporating the water, and then performing a reduction treatment. Note that, as a method for the reduction treatment, for example, a method in which treatment is performed in a hydrogen atmosphere at 400 to 600°C for 0.5 to 5 hours can be mentioned.

[0043] An example of a precipitation method that can be used for producing a metal-supported catalyst is a method in which the support and a base are added to an aqueous solution containing a salt of the catalytically active metal, and an operation such as heating is performed as necessary to obtain a precipitate, which is then dried.

[0044] In the precipitation method, a carrier and a base may be added to an aqueous solution containing a salt of a catalytically active metal, and then the solution may be heated to generate a precipitate. The heating may be performed at atmospheric pressure, below the boiling point of water, or by reflux. The heating may be performed under pressurized conditions using a pressure-resistant vessel, but it is industrially preferable to heat the solution under atmospheric pressure.

[0045] For example, a supported rhodium catalyst can be obtained by adding a support and a base to an aqueous rhodium salt solution, filtering the resulting precipitate, drying it, and calcining it.

[0046] In the production method of the first embodiment, the amount of the metal-supported catalyst used is preferably adjusted according to the amount of the aliphatic amine compound (1) used as the raw material. The amount of the metal-supported catalyst used is not particularly limited, but for example, the amount of catalytically active metal atoms in the metal-supported catalyst is preferably in the range of 0.0005 to 0.2 mol, more preferably in the range of 0.001 to 0.1 mol, even more preferably in the range of 0.005 to 0.1 mol, and particularly preferably in the range of 0.005 to 0.05 mol, per 1 mol of the aliphatic amine compound (1). In addition, when the metal-supported catalyst contains two or more catalytically active metals, the amount of the catalytically active metal atoms described above means the total amount of the two or more catalytically active metals.

[0047] In the production method of the first embodiment, an aliphatic amine compound (1) is heated to 50 to 250°C in the presence of a metal-supported catalyst in an atmosphere into which carbon dioxide at 0.1 to 10 MPa (gauge pressure) and hydrogen at 0.1 to 20 MPa (gauge pressure) have been introduced (hereinafter also referred to as a "pressurized atmosphere").

[0048] The aliphatic amine compound (1) may be heated to a temperature of 50 to 250°C, but from the standpoints of reaction rate, selectivity, and energy cost, a temperature of 70 to 230°C is preferred, and a temperature of 100 to 200°C is more preferred.

[0049] The carbon dioxide introduced to create a pressurized atmosphere can be any that is available by a commonly known method, and is not particularly limited, but examples that can be used include commercially available carbon dioxide gas, carbon dioxide separated from a steam reformed gas of a hydrocarbon, carbon dioxide separated from a combustion exhaust gas, carbon dioxide obtained in a lime kiln, etc. Of these, it is preferable to use carbon dioxide separated from a combustion exhaust gas in terms of reducing greenhouse gas emissions.

[0050] The purity of the carbon dioxide introduced to create a pressurized atmosphere is not particularly limited, but in consideration of ease of reaction, the purity is preferably 95% or more, and more preferably 98% or more.

[0051] The pressure (partial pressure) of carbon dioxide introduced into the pressurized atmosphere may be 0.1 to 10 MPa (gauge pressure), but from the viewpoints of reaction rate and energy cost, it is preferably 0.1 to 8 MPa (gauge pressure), and more preferably 0.5 to 2 MPa (gauge pressure). Note that the gauge pressure is a pressure with atmospheric pressure set to 0 MPa.

[0052] The pressure (partial pressure) of hydrogen introduced into the pressurized atmosphere may be 0.1 to 20 MPa (gauge pressure), but from the viewpoints of reaction rate and energy cost, it is preferably 0.3 to 15 MPa (gauge pressure), and more preferably 0.5 to 8 MPa (gauge pressure). The pressure (partial pressure) of hydrogen is preferably higher than the partial pressure of carbon dioxide.

[0053] The purity of the hydrogen introduced to create the pressurized atmosphere is not particularly limited, but in consideration of ease of reduction, the purity is preferably 95% or more, and more preferably 98% or more.

[0054] The pressurized atmosphere may contain other components (gas components) in addition to carbon dioxide and hydrogen, but is preferably composed of only carbon dioxide and hydrogen in terms of excellent efficiency of N-methylation. Note that "composed of only carbon dioxide and hydrogen" does not exclude substances other than carbon dioxide and hydrogen that may be unintentionally mixed in.

[0055] The pressurized atmosphere can be created by introducing carbon dioxide in an amount such that the pressure (partial pressure) after introduction is 0.1 to 10 MPa (gauge pressure) and hydrogen in an amount such that the pressure (partial pressure) after introduction is 0.1 to 20 MPa (gauge pressure) into an atmosphere at atmospheric pressure (hereinafter also referred to as "atmospheric pressure atmosphere"). The atmospheric pressure atmosphere into which carbon dioxide and hydrogen are introduced may be any atmosphere at atmospheric pressure, and may be an air atmosphere at atmospheric pressure, but in order to obtain a pressurized atmosphere consisting only of carbon dioxide and hydrogen, it is preferable that the atmosphere be a carbon dioxide atmosphere at atmospheric pressure (an atmosphere consisting of carbon dioxide) or a hydrogen atmosphere at atmospheric pressure (an atmosphere consisting of hydrogen).

[0056] The pressure (partial pressure) of carbon dioxide and hydrogen introduced into the pressurized atmosphere is the pressure (partial pressure) at 25°C (298 [K]) before heating the aliphatic amine compound (1), and can be calculated from the gas state equation (I) shown below. P = nRT / V (I) In the above formula (I), P represents the pressure (gauge pressure) [Pa] of the gas introduced into the pressurized atmosphere, n represents the amount of gas substance [mol] introduced into the atmospheric pressure atmosphere, and R represents the gas constant (8.31 × 10 3 ) [Pa L / (mol K)], T is 298 [K], and V is the volume of the pressurized atmosphere [L].

[0057] The total pressure (gauge pressure) of the pressurized atmosphere is not particularly limited, but is preferably the sum of the pressures (gauge pressures) of carbon dioxide and hydrogen introduced into the pressurized atmosphere.

[0058] In the production method of the first embodiment, the reaction time, i.e., the heat treatment time of the aliphatic amine compound (1), is preferably 6 to 300 hours, more preferably 12 to 250 hours, and particularly preferably 48 to 250 hours, in terms of the reaction yield and the facility operation cost.

[0059] In the production method of the first embodiment, the reaction method for producing the N-methylated amine compound (3) from the aliphatic amine compound (1) may be either a flow method (a method in which raw materials are continuously charged, the reaction is continuously carried out, and the product is continuously recovered) or a batch method (a method in which the steps of charging raw materials, reaction, and product recovery are carried out in sequence). For example, when the batch method is adopted, a mixture of the aliphatic amine compound (1) and the metal-supported catalyst is charged into a sealed container (sealed pressure-resistant container) and sealed so that the inside is at atmospheric pressure, and carbon dioxide at 0.1 to 10 MPa (gauge pressure) and hydrogen at 0.1 to 20 MPa (gauge pressure) are introduced into the sealed container and heated to 50 to 250°C to react.

[0060] In the production method of the first embodiment, the aliphatic amine compound (1) may be heated in a solvent. The solvent is not particularly limited, but examples thereof include water, methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, diethylene glycol, glycerin, tetrahydrofuran, dioxane, acetonitrile, methoxyethanol, dimethoxyethane, DMF, DMSO, benzene, toluene, and xylene. These solvents may be used alone or in combination of two or more as necessary.

[0061] Among these solvents, in terms of excellent reaction efficiency, the heating of the aliphatic amine compound (1) is preferably carried out in one or more solvents selected from the group consisting of water, methanol, ethanol, tetrahydrofuran, dioxane, acetonitrile, and dimethoxyethane, and more preferably in at least one of water and tetrahydrofuran.

[0062] The amount of the solvent used is preferably 0.1 to 100 parts by mass, and more preferably 0.5 to 50 parts by mass, per part by mass of the aliphatic amine compound (1), in terms of excellent reaction efficiency.

[0063] According to the production method of the first embodiment described above, it is possible to provide a production method of the N-methylated amine compound (3) that does not necessarily require formaldehyde and can use carbon dioxide as a raw material.

[0064] Next, an embodiment in which the aliphatic amine compound (2) is used as the aliphatic amine compound (hereinafter, also referred to as the "production method of the second embodiment") will be described.

[0065] The production method of the second embodiment is a production method in which an aliphatic amine compound (2) is heated to 50 to 250° C. in the presence of a metal-supported catalyst and in an atmosphere containing carbon dioxide at 0.1 to 10 MPa (gauge pressure) and hydrogen at 0.1 to 20 MPa (gauge pressure) to methylate (hereinafter also referred to as "N-methylation") the amino group of the aliphatic amine compound (2) to produce an N-methylated amine compound represented by the following general formula (4) (hereinafter also referred to as "N-methylated amine compound (4)").

[0066] [ka] [In the above general formula (4), R 6 ~R 11 R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 16 represents a hydrogen atom or a methyl group; Y represents a hydroxyl group or -NR 17 R 18 R represents an amino group represented by the formula: 17 , R 18 Each independently represents a hydrogen atom or a methyl group. However, when Y is a hydroxy group, R 16 is a methyl group and Y is -NR 17 R 18 In the case of an amino group represented by R 16 ~R 18 At least one of the groups is a methyl group. n represents an integer of 1 to 5.]

[0067] In addition, the production method of the second embodiment is the same as the production method of the first embodiment in all other conditions except for the aliphatic amine compound (aliphatic amine compound (2)) used and the N-methylated amine compound (N-methylated amine compound (4)) produced (including the preferred conditions). Therefore, the production method of the second embodiment will be described with reference to the aliphatic amine compound (aliphatic amine compound (2)) used and the N-methylated amine compound (N-methylated amine compound (4)) produced, and the description of the other conditions will be omitted.

[0068] In the aliphatic amine compound (2) used in the production method according to the second embodiment, R 6 ~R 11 In terms of excellent efficiency of N-methylation, each of R is preferably a hydrogen atom, a methyl group, or an ethyl group, and more preferably each is a hydrogen atom. 6 ~R 11 respectively represent R in general formula (4). 6 ~R 11 Similarly, n in general formula (2) is the same integer as n in general formula (4).

[0069] In the aliphatic amine compound (2) used in the production method of the second embodiment, n in the general formula (2) represents an integer of 1 to 5, and is preferably 1 or 2, and more preferably 1, in terms of excellent efficiency of N-methylation.

[0070] The aliphatic amine compound (2), which is a raw material in the production method of the second embodiment, is preferably N-(2-aminoethyl)piperazine or N-(2-hydroxyethyl)piperazine, and more preferably N-(2-aminoethyl)piperazine, in terms of excellent efficiency of N-methylation.

[0071] In the manufacturing method of the second embodiment, the aliphatic amine compound (2) is heated under the above-mentioned predetermined conditions, whereby carbon dioxide (CO2) and hydrogen (H2) in the reaction atmosphere react with the aliphatic amine compound (2), and p hydrogen atoms bonded to nitrogen atoms in the aliphatic amine compound (2) are replaced with p methyl groups (N-methylation). As a result, an N-methylated amine compound (4) is produced in which p hydrogen atoms bonded to nitrogen atoms in the aliphatic amine compound (2) are replaced with p methyl groups. In other words, according to the manufacturing method of the second embodiment, an N-methylated amine compound (4) is produced in which at least one of the hydrogen atoms bonded to the nitrogen atoms of the aliphatic amine compound (2) used as a raw material is replaced with a methyl group. Here, p represents an integer of 1 or more, and the upper limit is the number of hydrogen atoms bonded to the nitrogen atoms in the aliphatic amine compound (2).

[0072] The N-methylated amine compound (4) produced by the production method of the second embodiment varies depending on the chemical structure of the aliphatic amine compound (2) used as a raw material, and examples thereof include 1-(2-aminoethyl)-4-methylpiperazine, 1-[2-(methylamino)ethyl]piperazine, 1-[2-(methylamino)ethyl]-4-methylpiperazine, 1-[2-(dimethylamino)ethyl]piperazine, 1-[2-(dimethylamino)ethyl]-4-methylpiperazine, and 1-(2-hydroxyethyl)-4-methylpiperazine.

[0073] The N-methylated amine compound (4) produced by the production method of the second embodiment is a compound in which at least one of the hydrogen atoms bonded to the nitrogen atom in the aliphatic amine compound (2) used as a raw material has been substituted with a methyl group. The number of hydrogen atoms substituted with methyl groups may be one or more, but it is preferable that all of the hydrogen atoms bonded to the nitrogen atom have been substituted with methyl groups. That is, the N-methylated amine compound (4) produced by the production method of the second embodiment is a compound in which R 16 ~R 18 are preferably N-methylated amine compounds (4), in which each of

[0074] R in general formula (4) 16 ~R 18 Among the methods for producing the N-methylated amine compound (4) in which all of R are methyl groups, the production method of the second embodiment is preferably the following production method 12 in terms of excellent N-methylation efficiency. Note that in the following production method 12, aliphatic amine compound (2) used as a raw material and N-methylated amine compound (4) (R 16 ~R 18 The figure shows the N-methylated amine compound (4) in which all of the groups are methyl groups.

[0075] [Manufacturing method 12] Aliphatic amine compound (2): N-(2-aminoethyl)piperazine N-Methylated amine compound (4): 1-[2-(dimethylamino)ethyl]-4-methylpiperazine

[0076] The aliphatic amine compound (2), which is a raw material in the production method of the second embodiment, may be a commercially available product or may be one synthesized by a known method, and is not particularly limited.

[0077] The purity of the aliphatic amine compound (2), which is the raw material in the production method of the second embodiment, is not particularly limited. However, in consideration of ease of purification in the purification step after N-methylation, the purity is preferably 95% by mass or more, and more preferably 98% by mass or more.

[0078] According to the production method of the second embodiment described above, it is possible to provide a production method of the N-methylated amine compound (4) that does not necessarily require formaldehyde and can use carbon dioxide as a raw material. EXAMPLES

[0079] The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

[0080] The components used in the examples and comparative examples are abbreviated as follows: Ethylenediamine: EDA N-Methylethylenediamine: M-EDA N,N-Dimethylethylenediamine: N,N-DM-EDA N,N'-Dimethylethylenediamine: N,N'-DM-EDA N,N,N'-Trimethylethylenediamine: TriM-EDA N,N,N',N'-Tetramethylethylenediamine: TetraM-EDA 1,2-Diaminopropane: DAP Propylenediamine (1,3-diaminopropane): PDA N-(2-aminoethyl)ethanolamine: AEEA N-(2-aminoethyl)piperazine: AEP Diethylenetriamine:DETA Triethylenetetramine: TETA Tetrahydrofuran: THF

[0081] Production Example 1 [Production of catalyst (Rh / C)] A rhodium nitrate aqueous solution was prepared by diluting 140 mg of rhodium nitrate (Rh(NO3)3, manufactured by Sigma-Aldrich) with 10 mL of distilled water, and added to 0.95 g of activated carbon (manufactured by CABOT), and the aqueous solution was impregnated into the carrier. After drying at 110°C for 12 hours, the carrier was reduced at 500°C for 1 hour in a hydrogen atmosphere to obtain a catalyst made of activated carbon carrying rhodium (hereinafter also referred to as "Rh / C") (at this time, the amount of rhodium carried was 5% by mass relative to the total amount of the catalyst).

[0082] Production Example 2 [Production of catalyst (Pt / C)] A catalyst made of activated carbon carrying platinum (hereinafter also referred to as "Pt / C") was obtained in the same manner as in Production Example 1, except that 82 mg of diaminedinitroplatinum nitrate (Pt(NO2)2(NH3)2, manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) was used instead of 140 mg of rhodium nitrate (the amount of platinum carried was 5% by mass relative to the total amount of the catalyst).

[0083] Production Example 3 [Production of catalyst (Ir / C)] A catalyst made of activated carbon carrying iridium (hereinafter, also referred to as "Ir / C") was obtained in the same manner as in Production Example 1, except that 110 mg of iridium nitrate (Ir(NO3)4, manufactured by Furuya Metal Co., Ltd.) was used instead of 140 mg of rhodium nitrate (the amount of iridium carried was 5 mass% relative to the total amount of the catalyst).

[0084] Production Example 4 [Production of catalyst (Ru / C)] Instead of 140 mg of rhodium nitrate, use ruthenium nitrosyl nitrate (Ru(NO)(NO3) X (OH) y A catalyst made of activated carbon carrying ruthenium (hereinafter, also referred to as "Ru / C") was obtained in the same manner as in Production Example 1, except that 160 mg of ruthenium ion exchange catalyst (x+y=3, manufactured by Sigma-Aldrich) was used (the amount of ruthenium carried was 5 mass % relative to the total amount of the catalyst).

[0085] Production Example 5 [Production of catalyst (Pd / C)] A catalyst made of activated carbon carrying palladium (hereinafter also referred to as "Pd / C") was obtained in the same manner as in Production Example 1, except that 110 mg of palladium nitrate (Pd(NO3)2, manufactured by N.E. Chemcat Corporation) was used instead of 140 mg of rhodium nitrate (at this time, the amount of palladium carried was 5 mass% relative to the total amount of the catalyst).

[0086] Production Example 6 [Production of catalyst (Re / C)] A catalyst consisting of activated carbon carrying rhenium (hereinafter also referred to as "Re / C") was obtained in the same manner as in Production Example 1, except that 72 mg of ammonium perrhenate (NH4ReO4, manufactured by Mitsuwa Chemical Co., Ltd.) was used instead of 140 mg of rhodium nitrate (the amount of rhenium carried was 5 mass% relative to the total amount of the catalyst).

[0087] Production Example 7 [Production of catalyst (Rh / CeO2)] A catalyst made of cerium oxide (IV) carrying rhodium (hereinafter also referred to as "Rh / CeO") was obtained in the same manner as in Production Example 1, except that 0.95 g of cerium oxide (CeO, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) that had been pre-calcined at 600°C for 3 hours was used instead of 0.95 g of activated carbon (the amount of rhodium carried was 5% by mass relative to the total amount of the catalyst).

[0088] Production Example 8 [Production of catalyst (Rh / Al2O3)] A catalyst made of activated alumina carrying rhodium (hereinafter also referred to as "Rh / Al2O3") was obtained in the same manner as in Production Example 1, except that 0.95 g of aluminum oxide (activated alumina) (γ-Al2O3, sample name "JRC-ALO-2", Catalysis Society reference catalyst) that had been pre-calcined at 700°C for 3 hours was used instead of 0.95 g of activated carbon (the amount of rhodium carried was 5% by mass relative to the total amount of the catalyst).

[0089] Production Example 9 [Production of catalyst (Rh / TiO2)] A catalyst consisting of titanium oxide (IV) carrying rhodium (hereinafter also referred to as "Rh / Al2O3") was obtained in the same manner as in Production Example 1, except that 0.95 g of titanium oxide (TiO2, sample name "JRC-TIO-4", Catalysis Society reference catalyst) was used instead of 0.95 g of activated carbon (the amount of rhodium carried was 5 mass% of the total amount of the catalyst).

[0090] Production Example 10 [Production of catalyst (Rh-Re / C)] An aqueous solution of rhodium nitrate was prepared by diluting 140 mg of rhodium nitrate (Rh(NO3)3, manufactured by Sigma-Aldrich) with 10 mL of distilled water, and added to 0.90 g of activated carbon (manufactured by CABOT), and the aqueous solution was impregnated into the carrier. This was dried at 110°C for 12 hours. Next, the dried product was impregnated with an aqueous solution of ammonium perrhenate prepared by diluting 65 mg of ammonium perrhenate (NH4ReO4, manufactured by Mitsuwa Chemical Co., Ltd.) with 10 mL of distilled water. This was dried at 110°C for 12 hours, and then reduced in a hydrogen atmosphere at 500°C for 1 hour to obtain a catalyst consisting of activated carbon carrying rhodium and rhenium (hereinafter also referred to as "Rh-Re / C"). (At this time, the amount of supported metal rhodium (Rh) was 5 mass% of the total catalyst amount, the amount of supported rhenium (Re) was 4.52 mass% of the total catalyst amount, and the molar ratio of Rh to Re, i.e., [Rh] / [Re] (mol / mol), was 2.)

[0091] Production Example 11 [Production of catalyst (Rh-W / C)] Instead of 65 mg of ammonium perrhenate, use ammonium metatungstate hydrate ((NH4)6H2W 12 O 40 A catalyst made of activated carbon carrying rhodium and tungsten (hereinafter also referred to as "Rh-W / C") was obtained in the same manner as in Production Example 10, except that 59 mg of activated carbon (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used and the amount of activated carbon (manufactured by CABOT Corporation) to be impregnated was changed from 0.90 g to 0.91 g (at this time, the amount of supported metal rhodium (Rh) was 5 mass% with respect to the total amount of the catalyst, the amount of supported tungsten (W) was 4.47 mass% with respect to the total amount of the catalyst, and the molar ratio of Rh to W, i.e., [Rh] / [W] (mol / mol), was 2).

[0092] Production Example 12 [Production of catalyst (Rh-Mo / C)] Instead of 65 mg of ammonium perrhenate, use ammonium molybdate tetrahydrate ((NH4)6Mo7O 24A catalyst made of activated carbon carrying rhodium and molybdenum (hereinafter also referred to as "Rh-Mo / C") was obtained in the same manner as in Production Example 10, except that 42 mg of rhodium-4H2O (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used and the amount of activated carbon (manufactured by CABOT Corporation) to be impregnated was changed from 0.90 g to 0.93 g. (At this time, the amount of supported metal rhodium (Rh) was 5 mass % with respect to the total amount of the catalyst, the amount of supported molybdenum (Mo) was 2.33 mass % with respect to the total amount of the catalyst, and the molar ratio of Rh to Mo, i.e., [Rh] / [Mo] (mol / mol), was 2.)

[0093] Production Example 13 [Production of catalyst (Rh-V / C)] A catalyst made of activated carbon carrying rhodium and vanadium (hereinafter also referred to as "Rh-V / C") was obtained in the same manner as in Production Example 10, except that 28 mg of ammonium vanadate (NH4VO3, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used instead of 65 mg of ammonium perrhenate, and the amount of activated carbon (manufactured by CABOT Corporation) to be impregnated was changed from 0.90 g to 0.94 g. (At this time, the amount of supported metal rhodium (Rh) was 5 mass% with respect to the total amount of catalyst, and the amount of supported vanadium (V) was 1.24 mass% with respect to the total amount of catalyst, and the molar ratio of Rh to V, i.e., [Rh] / [V] (mol / mol) was 2.)

[0094] Production Example 14 [Production of catalyst (Rh-Co / C)] A catalyst made of activated carbon carrying rhodium and cobalt (hereinafter also referred to as "Rh-Co / C") was obtained in the same manner as in Production Example 10, except that 71 mg of cobalt nitrate hexahydrate (Co(NO3)2·6H2O, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used instead of 65 mg of ammonium perrhenate, and the amount of activated carbon (manufactured by CABOT Corporation) to be impregnated was changed from 0.90 g to 0.94 g. (At this time, the amount of supported metal rhodium (Rh) was 5 mass% of the total amount of catalyst, the amount of supported cobalt (Co) was 1.43 mass% of the total amount of catalyst, and the molar ratio of Rh to Co, i.e., [Rh] / [Co] (mol / mol) was 2.)

[0095] Production Example 15 [Production of catalyst (Rh-Cr / C)] A catalyst made of activated carbon carrying rhodium and chromium (hereinafter also referred to as "Rh-Cr / C") was obtained in the same manner as in Production Example 10, except that 97 mg of chromium nitrate nonahydrate (Cr(NO3)3·9H2O, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used instead of 65 mg of ammonium perrhenate, and the amount of activated carbon (manufactured by CABOT Corporation) to be impregnated was changed from 0.90 g to 0.94 g. (At this time, the amount of supported metal rhodium (Rh) was 5 mass% of the total amount of catalyst, the amount of supported chromium (Cr) was 1.26 mass% of the total amount of catalyst, and the molar ratio of Rh to Cr, i.e., [Rh] / [Cr] (mol / mol), was 2.)

[0096] Production Example 16 [Production of catalyst (Rh-Cs / C)] A catalyst made of activated carbon carrying rhodium and cesium (hereinafter also referred to as "Rh-Cs / C") was obtained in the same manner as in Production Example 10, except that 47 mg of cesium nitrate (CsNO3, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used instead of 65 mg of ammonium perrhenate, and the amount of activated carbon (manufactured by CABOT Corporation) to be impregnated was changed from 0.90 g to 0.92 g. (At this time, the amount of supported metal rhodium (Rh) was 5 mass% with respect to the total amount of catalyst, the amount of supported cesium (Cs) was 3.23 mass% with respect to the total amount of catalyst, and the molar ratio of Rh to Cs, i.e., [Rh] / [Cs] (mol / mol), was 2.)

[0097] Production Example 17 [Production of catalyst (Rh-Zr / C)] A catalyst made of activated carbon carrying rhodium and zirconium (hereinafter also referred to as "Rh-Zr / C") was obtained in the same manner as in Production Example 10, except that 65 mg of zirconyl nitrate dihydrate (ZrO(NO3)·2H2O, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was used instead of 65 mg of ammonium perrhenate, and the amount of activated carbon (manufactured by CABOT Corporation) to be impregnated was changed from 0.90 g to 0.93 g. (At this time, the amount of supported metal rhodium (Rh) was 5 mass% of the total amount of catalyst, the amount of supported zirconium (Zr) was 2.22 mass% of the total amount of catalyst, and the molar ratio of Rh to Zr, i.e., [Rh] / [Zr] (mol / mol), was 2.)

[0098] Production Example 18 [Production of catalyst (Re-Ru / C)] 53 mg of ammonium perrhenate (NH4ReO4, Mitsuwa Chemical Co., Ltd.) was diluted with 10 mL of distilled water to prepare an aqueous solution of ammonium perrhenate, which was then added to 0.92 g of activated carbon (CABOT Co., Ltd.), and the aqueous solution was impregnated into the carrier. This was then dried at 110°C for 12 hours. Next, ruthenium nitrosyl nitrate (Ru(NO)(NO3) X (OH) y (x+y=3, Sigma-Aldrich) 125 mg was impregnated with an aqueous solution of nitrosyl ruthenium nitrate diluted with 10 mL of distilled water. After drying at 110°C for 12 hours, reduction treatment was performed under a hydrogen atmosphere at 500°C for 1 hour to obtain a catalyst (hereinafter also referred to as "Re-Ru / C") made of activated carbon carrying rhenium and ruthenium (at this time, the amount of metal rhenium (Re) supported was 3.7 mass% of the total catalyst amount, the amount of ruthenium (Ru) supported was 4.02 mass% of the total catalyst amount, and the molar ratio of Re to Ru, i.e., [Re] / [Ru] (mol / mol), was 0.5).

[0099] Production Example 19 [Production of catalyst (Re-Ir / C)] A catalyst consisting of activated carbon carrying rhenium and iridium (hereinafter also referred to as "Re-Ir / C") was obtained in the same manner as in Production Example 18, except that 91 mg of iridium nitrate (Ir(NO3)4, manufactured by Furuya Metal Co., Ltd.) was used instead of 125 mg of nitrosylruthenium nitrate. (At this time, the amount of supported metallic rhenium (Re) was 3.9 mass% with respect to the total amount of the catalyst, the amount of supported iridium (Ir) was 4.03 mass% with respect to the total amount of the catalyst, and the molar ratio of Re to Ir, i.e., [Re] / [Ir] (mol / mol), was 1.)

[0100] Production Example 20 [Production of catalyst (Re-Ir / C)] A catalyst consisting of activated carbon carrying rhenium and iridium (hereinafter also referred to as "Re-Ir / C") was obtained in the same manner as in Production Example 18, except that 46 mg of iridium nitrate (Ir(NO3)4, manufactured by Furuya Metal Co., Ltd.) was used instead of 125 mg of nitrosylruthenium nitrate. (At this time, the amount of supported metallic rhenium (Re) was 4.0 mass% relative to the total amount of the catalyst, the amount of supported iridium (Ir) was 2.06 mass% relative to the total amount of the catalyst, and the molar ratio of Re to Ir, i.e., [Re] / [Ir] (mol / mol), was 2.)

[0101] Example 1 In a 190 ml autoclave, 0.12 g of EDA (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 5.0 g of THF (manufactured by Kanto Chemical Co., Ltd.), and 0.30 g of the catalyst (Rh / C) obtained in Production Example 1 were charged so that rhodium was 0.071 mol per 1 mol of EDA, and after sealing, the atmosphere inside the autoclave was replaced with carbon dioxide at atmospheric pressure. Then, 1 MPa (gauge pressure) of carbon dioxide and 4 MPa (gauge pressure) of hydrogen were introduced into the atmosphere inside the autoclave, and the mixture was heated and stirred at 140°C for 24 hours. The autoclave was cooled to room temperature, and the contents were washed and collected using distilled water, and the obtained autoclave contents (liquid) were analyzed using a gas chromatography device. The analysis results are shown in Table 1. The pressure (partial pressure) of carbon dioxide and hydrogen introduced into the atmosphere inside the autoclave was calculated from the above-mentioned gas state equation (I).

[0102] Example 2 The same procedure as in Example 1 was repeated except that the solvent was changed from 5.0 g of THF to 5.0 g of water. The results are shown in Table 1.

[0103] Example 3 The same procedure as in Example 1 was carried out except that the catalyst (Rh / C) obtained in Production Example 1 was replaced with the catalyst (Pt / C) obtained in Production Example 2. At this time, the amount of catalyst charged was adjusted so that platinum was 0.071 mol per 1 mol of EDA. The analytical results are shown in Table 1.

[0104] Example 4 The same procedure as in Example 1 was carried out except that the catalyst (Rh / C) obtained in Production Example 1 was replaced with the catalyst (Ir / C) obtained in Production Example 3. At this time, the amount of catalyst charged was adjusted so that 0.071 mol of iridium was used per 1 mol of EDA. The analytical results are shown in Table 1.

[0105] Example 5 The same procedure as in Example 1 was carried out except that the catalyst (Rh / C) obtained in Production Example 1 was replaced with the catalyst (Ru / C) obtained in Production Example 4. At this time, the amount of catalyst charged was adjusted so that ruthenium was 0.071 mol per 1 mol of EDA. The analytical results are shown in Table 1.

[0106] Example 6 The same procedure as in Example 1 was carried out except that the catalyst (Rh / C) obtained in Production Example 1 was replaced with the catalyst (Pd / C) obtained in Production Example 5. The amount of catalyst charged was adjusted so that palladium was 0.071 mol per 1 mol of EDA. The analytical results are shown in Table 2.

[0107] Example 7 The same procedure as in Example 1 was carried out except that the catalyst (Rh / C) obtained in Production Example 1 was replaced with the catalyst (Re / C) obtained in Production Example 6, and the solvent was changed from 5.0 g of THF to 5.0 g of water. At this time, the amount of catalyst charged was adjusted so that 0.071 mol of rhenium was used per 1 mol of EDA. The analytical results are shown in Table 2.

[0108] Example 8 The same procedure as in Example 1 was carried out except that the reaction time was changed from 24 hours to 48 hours. The analytical results are shown in Table 2.

[0109] Example 9 The same procedure as in Example 1 was carried out except that the reaction time was changed from 24 hours to 72 hours. The analytical results are shown in Table 2.

[0110] Example 10 The same procedure as in Example 1 was carried out except that the reaction time was changed from 24 hours to 96 hours. The analytical results are shown in Table 2.

[0111] Example 11 The same procedure as in Example 1 was carried out except that the reaction temperature was changed from 140° C. to 130° C. The analytical results are shown in Table 3.

[0112] Example 12 The same procedure as in Example 1 was carried out except that the reaction temperature was changed from 140° C. to 150° C. The analytical results are shown in Table 3.

[0113] Example 13 The same procedure as in Example 1 was carried out except that the reaction temperature was changed from 140° C. to 160° C. The analytical results are shown in Table 3.

[0114] Example 14 The same procedure as in Example 1 was repeated except that the amount of the catalyst (Rh / C) obtained in Production Example 1 was changed so that rhodium was 0.035 mol per 1 mol of EDA. The analytical results are shown in Table 3.

[0115] Example 15 The same procedure as in Example 1 was repeated except that the amount of the catalyst (Rh / C) obtained in Production Example 1 was changed so that rhodium was 0.024 mol per 1 mol of EDA. The analytical results are shown in Table 3.

[0116] Example 16 The same procedure as in Example 1 was repeated except that the amount of the catalyst (Rh / C) obtained in Production Example 1 was changed so that rhodium was 0.018 mol per 1 mol of EDA. The analytical results are shown in Table 4.

[0117] Example 17 The same procedure as in Example 1 was repeated except that the amount of the catalyst (Rh / C) obtained in Production Example 1 was changed so that rhodium was 0.014 mol per 1 mol of EDA. The analytical results are shown in Table 4.

[0118] Example 18 The same procedure as in Example 1 was carried out except that the catalyst (Rh / C) obtained in Production Example 1 was replaced with the catalyst (Rh / CeO2) obtained in Production Example 7. The amount of catalyst charged was adjusted so that rhodium was 0.071 mol per 1 mol of EDA. The analytical results are shown in Table 4.

[0119] Example 19 The same procedure as in Example 1 was carried out except that the catalyst (Rh / C) obtained in Production Example 1 was replaced with the catalyst (Rh / Al2O3) obtained in Production Example 8. The amount of catalyst charged was adjusted so that rhodium was 0.071 mol per 1 mol of EDA. The analytical results are shown in Table 4.

[0120] Example 20 The same procedure as in Example 1 was carried out except that the catalyst (Rh / C) obtained in Production Example 1 was replaced with the catalyst (Rh / TiO2) obtained in Production Example 9. The amount of catalyst charged was adjusted so that rhodium was 0.071 mol per 1 mol of EDA. The analytical results are shown in Table 4.

[0121] Example 21 In Example 1, the catalyst (Rh / C) obtained in Production Example 1 was changed to the catalyst (Rh-Re / C) obtained in Production Example 10, 5.0 g of THF was changed to 5.0 g of water, the reaction temperature was changed to 160°C, carbon dioxide was changed to 2 MPa (gauge pressure), and hydrogen was changed to 5 MPa (gauge pressure). The catalyst loading amount was adjusted so that rhodium was 0.024 mol and rhenium was 0.012 mol per mol of EDA. The analysis results are shown in Table 5.

[0122] Example 22 In Example 21, the same operation as in Example 21 was carried out except that the catalyst (Rh-Re / C) obtained in Production Example 10 was replaced with the catalyst (Rh-W / C) obtained in Production Example 11. At this time, the catalyst charge amount was adjusted so that rhodium was 0.024 mol and tungsten was 0.012 mol per mol of EDA. The analytical results are shown in Table 5.

[0123] Example 23 In Example 21, the same procedure as in Example 21 was carried out except that the catalyst (Rh-Re / C) obtained in Production Example 10 was replaced with the catalyst (Rh-Mo / C) obtained in Production Example 12. At this time, the catalyst charge amount was adjusted so that rhodium was 0.024 mol and molybdenum was 0.012 mol per mol of EDA. The analytical results are shown in Table 5.

[0124] Example 24 In Example 21, the same procedure as in Example 21 was carried out except that the catalyst (Rh-Re / C) obtained in Production Example 10 was replaced with the catalyst (Rh-V / C) obtained in Production Example 13. The catalyst loading amounts were adjusted so that rhodium was 0.024 mol and vanadium was 0.012 mol per mol of EDA. The analytical results are shown in Table 5.

[0125] Example 25 In Example 21, the same procedure as in Example 21 was carried out except that the catalyst (Rh-Re / C) obtained in Production Example 10 was replaced with the catalyst (Rh-Co / C) obtained in Production Example 14. At this time, the catalyst loading amounts were adjusted so that rhodium was 0.024 mol and cobalt was 0.012 mol per mol of EDA. The analytical results are shown in Table 5.

[0126] Example 26 In Example 21, the same procedure as in Example 21 was carried out except that the catalyst (Rh-Re / C) obtained in Production Example 10 was replaced with the catalyst (Rh-Cr / C) obtained in Production Example 15. The catalyst loading amounts were adjusted so that rhodium was 0.024 mol and chromium was 0.012 mol per mol of EDA. The analytical results are shown in Table 6.

[0127] Example 27 In Example 21, the same procedure as in Example 21 was carried out except that the catalyst (Rh-Re / C) obtained in Production Example 10 was replaced with the catalyst (Rh-Cs / C) obtained in Production Example 16. The catalyst loading amounts were adjusted so that rhodium was 0.024 mol and cesium was 0.012 mol per mol of EDA. The analytical results are shown in Table 6.

[0128] Example 28 In Example 21, the same procedure as in Example 21 was carried out except that the catalyst (Rh-Re / C) obtained in Production Example 10 was replaced with the catalyst (Rh-Zr / C) obtained in Production Example 17. At this time, the catalyst charge amount was adjusted so that rhodium was 0.024 mol and zirconium was 0.012 mol per mol of EDA. The analytical results are shown in Table 6.

[0129] Example 29 In Example 21, the catalyst (Rh-Re / C) obtained in Production Example 10 was changed to the catalyst (Re-Ru / C) obtained in Production Example 18, the reaction temperature was changed to 140°C, the reaction time was changed to 16 hours, carbon dioxide was changed to 1 MPa (gauge pressure), and hydrogen was changed to 4 MPa (gauge pressure). The catalyst charge amount was adjusted so that rhenium was 0.010 mol and ruthenium was 0.020 mol per 1 mol of EDA. The analysis results are shown in Table 6.

[0130] Example 30 In Example 29, the same procedure as in Example 29 was carried out except that the catalyst (Rh-Re / C) obtained in Production Example 18 was replaced with the catalyst (Re-Ir / C) obtained in Production Example 19. At this time, the amount of catalyst charged was adjusted so that rhenium was 0.010 mol and iridium was 0.010 mol per mol of EDA. The analytical results are shown in Table 6.

[0131] Example 31 The same procedure as in Example 2 was carried out except that the reaction temperature was changed to 130°C, the reaction time was changed to 192 hours, the carbon dioxide pressure was changed to 2 MPa (gauge pressure), the hydrogen pressure was changed to 6 MPa (gauge pressure), and the amount of the catalyst (Rh / C) obtained in Production Example 1 was changed so that rhodium was 0.036 mol per 1 mol of EDA. The analytical results are shown in Table 7.

[0132] Example 32 The same procedure as in Example 7 was carried out except that the reaction temperature was changed to 130°C, the reaction time was changed to 192 hours, the carbon dioxide pressure was changed to 2 MPa (gauge pressure), the hydrogen pressure was changed to 6 MPa (gauge pressure), and the amount of the catalyst (Re / C) obtained in Production Example 6 was changed so that rhenium was 0.020 mol per 1 mol of EDA. The analytical results are shown in Table 7.

[0133] Example 33 The same procedure as in Example 32 was carried out except that the reaction temperature was changed to 120° C. In this case, the amount of catalyst charged was adjusted so that rhenium was 0.020 mol per 1 mol of EDA. The analytical results are shown in Table 7.

[0134] Example 34 In Example 29, the catalyst (Re-Ru / C) obtained in Production Example 18 was replaced with the catalyst (Re-Ir / C) obtained in Production Example 20, and the reaction time was changed to 72 hours, but the same operation as in Example 29 was performed. At this time, the catalyst charging amount was adjusted so that rhenium was 0.0050 mol and iridium was 0.0026 mol per 1 mol of EDA. The analytical results are shown in Table 7.

[0135] Example 35 The same procedure as in Example 34 was carried out except that the reaction temperature was changed to 120°C and the reaction time was changed to 120 hours. At this time, the catalyst loading amount was adjusted so that rhenium was 0.015 mol and iridium was 0.0078 mol per mol of EDA. The analytical results are shown in Table 7.

[0136] Example 36 The same procedure as in Example 23 was repeated except that the reaction time was changed to 72 hours. The catalyst loading amounts were adjusted so that rhodium was 0.024 mol and molybdenum was 0.012 mol per mol of EDA. The analytical results are shown in Table 8.

[0137] Example 37 The same procedure as in Example 35 was carried out except that the reaction substrate was changed to DAP and the reaction time was changed to 192 hours. The catalyst loading amounts were adjusted so that rhenium was 0.0312 mol and iridium was 0.0156 mol per mol of DAP. The analysis results are shown in Table 9. In Table 9, the TetraM-substrate, which is the product of Example 37, represents N,N,N',N'-tetramethyl-1,2-diaminopropane.

[0138] Example 38 The same procedure as in Example 35 was carried out except that the reaction substrate was changed to PDA and the reaction time was changed to 192 hours. The catalyst loading amount was adjusted so that rhenium was 0.0312 mol and iridium was 0.0156 mol per mol of PDA. The analysis results are shown in Table 9. In Table 9, the TetraM-substrate, which is the product of Example 38, represents N,N,N',N'-tetramethylpropylenediamine.

[0139] Example 39 The same procedure as in Example 35 was carried out except that the reaction substrate was changed to AEEA. The catalyst loading amounts were adjusted so that rhenium was 0.0312 mol and iridium was 0.0156 mol per 1 mol of AEEA. The analysis results are shown in Table 9. In Table 9, the TriM-substrate, which is the product of Example 39, represents N-[2-(dimethylamino)ethyl]-N-methylethanolamine.

[0140] Example 40 In Example 35, the reaction substrate was changed to AEP, and the reaction time was changed to 132 hours, but the same operation as in Example 35 was performed. At this time, the catalyst charge amount was adjusted so that rhenium was 0.0312 mol and iridium was 0.0156 mol per mol of AEP. The analysis results are shown in Table 9. In Table 9, M-substrate, which is the product of Example 40, represents 1-(2-aminoethyl)-4-methylpiperazine and 1-[2-(methylamino)ethyl]piperazine, N,N-DM-substrate represents 1-[2-(methylamino)ethyl]-4-methylpiperazine and 1-[2-(dimethylamino)ethyl]piperazine, and TriM-substrate represents 1-[2-(dimethylamino)ethyl]-4-methylpiperazine.

[0141] Example 41 The same procedure as in Example 35 was carried out except that the reaction substrate was changed to DETA, the reaction temperature was changed to 110°C, and the reaction time was changed to 168 hours. The catalyst loading amounts were adjusted so that rhenium was 0.0312 mol and iridium was 0.0156 mol per mol of DETA. The analytical results are shown in Table 10. In Table 10, the PentaM-substrate, which is the product of Example 41, represents N,N,N',N'',N''-pentamethyldiethylenetriamine.

[0142] Example 42 The same procedure as in Example 35 was carried out except that the reaction substrate was changed to TETA, the reaction temperature was changed to 110°C, and the reaction time was changed to 168 hours. The catalyst loading amounts were adjusted so that rhenium was 0.0312 mol and iridium was 0.0156 mol per 1 mol of TETA. The analytical results are shown in Table 10. In Table 10, HexM-substrate, which is the product of Example 42, represents N,N,N',N'',N'',N'''-hexamethyltriethylenetetramine.

[0143] [Table 1]

[0144] [Table 2]

[0145] [Table 3]

[0146] [Table 4]

[0147] [Table 5]

[0148] [Table 6]

[0149] [Table 7]

[0150] [Table 8]

[0151] [Table 9] [Table 10]

[0152] In Tables 1 to 10, the conversion rate was calculated from the formula (II), and the yield was calculated from the formula (III). Conversion rate [%] = {(AB) / A} × 100 (II) [In the above formula (II), A represents the number of moles [mol] of the reaction substrate such as EDA in the reaction solution before the reaction, and B represents the number of moles [mol] of the reaction substrate such as EDA in the reaction solution after the reaction.] Yield [%] = {(X / (AB)} × 100 (III) [In the above formula (III), X represents the number of moles [mol] of the product obtained by the reaction, A represents the number of moles [mol] of the reaction substrate such as EDA in the reaction solution before the reaction, and B represents the number of moles [mol] of the reaction substrate such as EDA in the reaction solution after the reaction.]

[0153] As shown in Tables 1 to 8 above, according to the production methods of Examples 1 to 36, N-methylated amine compounds (M-EDA, N,N-DM-EDA, N,N'-DM-EDA, TriM-EDA, TetraM-EDA) in which at least one hydrogen atom bonded to a nitrogen atom in EDA was substituted with a methyl group could be produced from EDA. Also, as shown in Tables 9 to 10 above, according to the production methods of Examples 37 to 42, N-methylated amine compounds in which at least one hydrogen atom bonded to a nitrogen atom in each amine compound was substituted with a methyl group could be produced from DAP, PDA, AEEA, AEP, DETA, and TETA.

Claims

1. A method for producing an N-methylated amine compound, comprising heating an aliphatic amine compound having at least one amino group in the molecule to 50 to 250°C in the presence of a metal-supported catalyst and in an atmosphere containing carbon dioxide at 0.1 to 10 MPa (gauge pressure) and hydrogen at 0.1 to 20 MPa (gauge pressure), thereby methylating the amino group.

2. The aliphatic amine compound is an aliphatic amine compound represented by the following general formula (1): The method for producing an N-methylated amine compound according to claim 1, wherein the N-methylated amine compound is a methylated amine compound represented by the following general formula (3): 【Chemistry 1】 [In the above general formula (1), R １ ~R ５ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; X represents a hydroxyl group or an amino group; n and m each independently represent an integer of 1 to 5; and a represents an integer of 0 to 4.] 【Chemistry 2】 [In the above general formula (3), R １ ~R ５ R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. １２ , R １３ Each of Z independently represents a hydrogen atom or a methyl group. １４ R １５ R represents an amino group represented by the formula: １４ , R １５ Each independently represents a hydrogen atom or a methyl group. However, when Z is a hydroxy group, R ３ , R １２ , and R １３ At least one of the groups is a methyl group, and Z is -NR １４ R １５ In the case of an amino group represented by the formula: ３ , and R １２ ~R １５ At least one of the groups is a methyl group. n and m each independently represent an integer of 1 to 5. a represents an integer of 0 to 4.]

3. The method for producing an N-methylated amine compound according to claim 2, wherein the aliphatic amine compound represented by the general formula (1) is an aliphatic amine compound represented by the following general formula (1-1), and the N-methylated amine compound is an N-methylated amine compound represented by the following general formula (3-1): 【Chemistry 3】 [In the above general formula (1-1), R １ , R ２ , R ４ , and R ５ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; X represents a hydroxyl group or an amino group; n and m each independently represent an integer of 1 to 5; and a represents an integer of 0 to 4.] 【Chemistry 4】 [In the above general formula (3-1), R １ ~R ２ , and R ４ ~R ５ R' each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ３ , R １２ , R １３ Each of Z independently represents a hydrogen atom or a methyl group. １４ R １５ R represents an amino group represented by the formula: １４ , R １５ each independently represents a hydrogen atom or a methyl group, provided that when Z is a hydroxy group, R' ３ , R １２ , and R １３ At least one of the groups is a methyl group, and Z is -NR １４ R １５ In the case of an amino group represented by the formula: ３ , and R １２ ~R １５ At least one of the groups is a methyl group. n and m each independently represent an integer of 1 to 5. a represents an integer of 0 to 4.]

4. R in the general formula (1-1) and the general formula (3-1) １ ~R ２ and R ４ ~R ５ The method for producing an N-methylated amine compound according to claim 3, wherein each of the is independently a hydrogen atom or a methyl group.

5. R' in the general formula (3-1) ３ and R １２ ~R １５ The method for producing an N-methylated amine compound according to claim 3, wherein each of

6. The aliphatic amine compound represented by the general formula (1) is ethylenediamine, and the N-methylated amine compound represented by the general formula (3) is N,N,N',N'-tetramethylethylenediamine, The aliphatic amine compound represented by the general formula (1) is diethylenetriamine, and the N-methylated amine compound represented by the general formula (3) is N,N,N',N'',N''-pentamethyldiethylenetriamine, The aliphatic amine compound represented by the general formula (1) is triethylenetetramine, and the N-methylated amine compound represented by the general formula (3) is N,N,N',N'',N''',N'''-hexamethyltriethylenetetramine, The aliphatic amine compound represented by the general formula (1) is N-(2-aminoethyl)ethanolamine, and the N-methylated amine compound represented by the general formula (3) is N-[2-(dimethylamino)ethyl]-N-methylethanolamine, The aliphatic amine compound represented by the general formula (1) is 1,2-diaminopropane, and the N-methylated amine compound represented by the general formula (3) is N,N,N',N'-tetramethyl-1,2-diaminopropane, or The aliphatic amine compound represented by the general formula (1) is propylenediamine, and the N-methylated amine compound represented by the general formula (3) is N,N,N',N'-tetramethylpropylenediamine. The method for producing the N-methylated amine compound according to claim 2.

7. The aliphatic amine compound is an aliphatic amine compound represented by the following general formula (2): The method for producing an N-methylated amine compound according to claim 1, wherein the N-methylated amine compound is a methylated amine compound represented by the following general formula (4): 【Chemistry 5】 [In the above general formula (2), R ６ ~R １１ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; X represents a hydroxyl group or an amino group; and n represents an integer of 1 to 5. 【Chemistry 6】 [In the above general formula (4), R ６ ~R １１ R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. １６ represents a hydrogen atom or a methyl group; Y represents a hydroxy group or -NR １７ R １８ R represents an amino group represented by the formula: １７ , R １８ Each independently represents a hydrogen atom or a methyl group. However, when Y is a hydroxy group, R １６ is a methyl group, and Y is -NR １７ R １８ In the case of an amino group represented by the formula: １６ ~R １８ At least one of the groups is a methyl group. n represents an integer of 1 to 5.

8. R in the general formula (2) and the general formula (4) ６ ~R １１ The method for producing an N-methylated amine compound according to claim 7, wherein each of

9. R in the general formula (4) １６ ~R １８ The method for producing an N-methylated amine compound according to claim 7, wherein each of

10. The method for producing an N-methylated amine compound according to claim 7, wherein the aliphatic amine compound represented by the general formula (2) is N-(2-aminoethyl)piperazine, and the N-methylated amine compound represented by the general formula (4) is 1-[2-(dimethylamino)ethyl]-4-methylpiperazine.

11. The method for producing an N-methylated amine compound according to claim 2 or 7, wherein the supported metal catalyst is a supported metal catalyst on which one or more metals selected from the group consisting of rhodium, platinum, iridium, ruthenium, palladium, molybdenum, rhenium, tungsten, gallium, zirconium, cesium, chromium, cobalt, vanadium, and rare earth elements are supported.

12. The method for producing an N-methylated amine compound according to claim 2 or 7, wherein the metal-supported catalyst is a metal-supported catalyst having at least one support selected from the group consisting of activated alumina, cerium (IV) oxide, titanium (IV) oxide, magnesium oxide, zirconium oxide, silica, and activated carbon.

13. The heating of the aliphatic amine compound is carried out in a solvent, The method for producing an N-methylated amine compound according to claim 2 or 7, wherein the solvent is used in an amount of 0.1 to 100 parts by mass relative to 1 part by mass of the aliphatic amine compound.

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