Method for producing aliphatic aldehydes

Abstract

This invention provides a method for producing aliphatic aldehydes in high yield by oxidizing aliphatic primary alcohols having four or more carbon atoms. [Solution] The present invention is a method for producing an aliphatic aldehyde, comprising the step of oxidizing an aliphatic primary alcohol having 4 or more carbon atoms with molecular oxygen in the presence of an amine compound and a metal-supported catalyst, wherein the metal-supported catalyst contains a metal supported on an inorganic carrier, and the amine compound is a compound represented by general formula (I). JPEG2026104782000016.jpg15159

Description

[Technical Field]

[0001] This invention relates to a method for producing aliphatic aldehydes. [Background technology]

[0002] Conventionally, a method for producing carbonyl compounds has been known in which alcohols are oxidized in the presence of a metal catalyst to obtain carbonyl compounds.

[0003] For example, Patent Document 1 discloses a paper catalyst structure containing metal oxide fibers, alumina, and ruthenium. In this paper catalyst structure, a coating layer containing γ-structured alumina is formed on the surface of the metal oxide fibers, and ruthenium is held by the coating layer containing γ-structured alumina. This paper catalyst structure has been reported to have high catalytic activity and be suitable as an oxidation catalyst for alcohols.

[0004] Patent Document 2 discloses a method for producing carbonyl compounds, characterized by oxidizing a specific alcohol in the presence of a catalyst in which at least one metal selected from ruthenium and platinum is supported on an activated carbon carrier, and oxygen, to produce a carbonyl compound consisting of an aldehyde compound or a ketone compound. It has been reported that this method allows for the production of carbonyl compounds from various alcohols in higher yields.

[0005] Patent Document 3 discloses a method for producing ruthenium-supported alumina, characterized by suspending alumina in a solution containing trivalent ruthenium, and then adding a base. It has been reported that this method of oxidizing alcohols using ruthenium-supported alumina can oxidize alcohols with a high conversion rate, enabling the productive production of ketones, aldehydes, carboxylic acids, and the like. Patent Document 4 discloses a method for producing a corresponding aldehyde from an alcohol using a ruthenium catalyst, comprising: (1) an oxidation step of oxidizing the alcohol by contacting it with molecular oxygen in the presence of the ruthenium catalyst; and (2) a separation step of separating and purifying the aldehyde produced from the reaction mixture by distillation or crystallization. It has been reported that this production method allows for the efficient production of the corresponding aldehyde from an alcohol. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2014-108393 [Patent Document 2] Japanese Patent Publication No. 2010-202555 [Patent Document 3] Japanese Patent Publication No. 2004-894 [Patent Document 4] Japanese Patent Publication No. 2001-48824 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, while the methods described in Patent Documents 1 and 2 are suitable for oxidizing aromatic alcohols and aliphatic secondary alcohols from a reactivity standpoint, they are not necessarily suitable for oxidizing aliphatic primary alcohols. Furthermore, the method described in Patent Document 3 requires a specific crosslinking polymer, which is not considered convenient.

[0008] Therefore, the present invention aims to provide a method for producing aliphatic aldehydes in high yield by oxidizing aliphatic primary alcohols. [Means for solving the problem]

[0009] The present invention relates to a method for producing an aliphatic aldehyde, comprising the step of oxidizing an aliphatic primary alcohol having 4 or more carbon atoms with molecular oxygen in the presence of an amine compound and a metal-supported catalyst, The metal-supported catalyst includes a metal supported on an inorganic support, This is a method for producing an aliphatic aldehyde, wherein the amine compound is a compound represented by general formula (I).

[0010] [ka]

[0011] [In the formula, R 1 and R 2 These are, independently of each other, an alkyl group or aryl group having 1 to 5 carbon atoms, or R 1 and R 2 Together with the nitrogen atom supporting the molecule, it is substituted with 1 to 4 functional groups independently selected from the group consisting of alkyl groups and alkoxy groups having 1 to 5 carbon atoms, forming a nitrogen-containing heterocyclic structure having 4 to 9 carbon atoms. R 3 [This is a hydrogen atom or a heteroaryl group.] [Effects of the Invention]

[0012] The method of the present invention has the advantage of being able to produce aliphatic aldehydes in good yield by oxidizing aliphatic primary alcohols having 4 or more carbon atoms (hereinafter also simply referred to as aliphatic primary alcohols). [Modes for carrying out the invention]

[0013] The inventors of the present invention have discovered that aliphatic aldehydes can be produced in high yield by oxidizing an aliphatic primary alcohol having 4 or more carbon atoms with molecular oxygen in the presence of an amine compound of a compound represented by general formula (I) and a metal-supported catalyst containing a metal supported on an inorganic support, thereby completing the present invention.

[0014] The reason why the aliphatic aldehyde can be produced with a high yield in this way is presumably that after the metal supported on the inorganic carrier is oxidized by oxygen, the metal combines with a specific amine compound and is activated, and then the aliphatic primary alcohol having 4 or more carbon atoms is oxidized to an aldehyde by the metal, and the amine compound can be quickly detached.

[0015] [Process for producing aliphatic aldehyde] The present invention relates to a process for producing an aliphatic aldehyde, comprising a step of oxidizing an aliphatic primary alcohol having 4 or more carbon atoms with molecular oxygen in the presence of an amine compound and a metal-supported catalyst, wherein the metal-supported catalyst contains a metal supported on an inorganic carrier, and the amine compound is a compound represented by the general formula (I), the process for producing an aliphatic aldehyde.

[0016] [Chemical formula]

[0017] [In the formula, R 1 and R 2 are each independently an alkyl group or an aryl group having 1 to 5 carbon atoms, or R 1 and R 2 together with the nitrogen atom carrying them, form a nitrogen-containing heterocyclic structure having 4 to 9 carbon atoms, which is substituted with 1 to 4 functional groups independently selected from the group consisting of an alkyl group and an alkoxy group having 1 to 5 carbon atoms, R 3 is a hydrogen atom or a heteroaryl group.]

[0018] [Aliphatic primary alcohol having >4 carbon atoms] In the present invention, the aliphatic primary alcohol having 4 or more carbon atoms may be linear or branched, and may be saturated or unsaturated. From the viewpoint of high reactivity in a short time, the aliphatic primary alcohol having 4 or more carbon atoms is preferably an aliphatic linear saturated primary alcohol having 4 or more carbon atoms.

[0019] The carbon number of the aliphatic primary alcohol is preferably 4 or more, more preferably 6 or more, more preferably 8 or more, and from the same viewpoint, preferably 30 or less, more preferably 22 or less, and even more preferably 14 or less. The carbon number of the aliphatic primary alcohol is preferably 4 or more and 30 or less, more preferably 6 or more and 22 or less, even more preferably 6 or more and 14 or less, even more preferably 8 or more and 14 or less, and even more preferably 8 or more and 12 or less.

[0020] Specifically, the aliphatic primary alcohols include: C4 alcohols such as n-butyl alcohol and iso-butyl alcohol; C6 alcohols such as hexyl alcohol and isohexyl alcohol; C8 alcohols such as n-octyl alcohol (octanol), isooctyl alcohol, and 2-ethylhexyl alcohol; C9 alcohols such as n-nonyl alcohol, isononyl alcohol, and 3,5,5-trimethylhexyl alcohol; C10 alcohols such as n-decyl alcohol, 3,7-dimethyloctyl alcohol, and 2-propylheptyl alcohol; and n-undecyl alcohol. Examples include C11 alcohols such as kohl and 2-methyldecanol; C12 alcohols such as n-dodecyl alcohol (lauryl alcohol), 2-methylundecanol, and 2-butyloctanol; C14 alcohols such as myristyl alcohol (1-tetradecanol); C18 alcohols such as hexadecyl alcohols, oleyl alcohol, and stearyl alcohol; and behenyl alcohol, eicosyl alcohols, geraniol, nerol, citronellol, cyclopentylmethanol, cyclopentenylmethanol, cyclohexylmethanol, and cyclohexenylmethanol. The aliphatic primary alcohol is preferably aliphatic linear saturated primary alcohol having 4 to 30 carbon atoms, more preferably 6 to 22 carbon atoms, even more preferably 6 to 14 carbon atoms, even more preferably 8 to 14 carbon atoms, even more preferably 8 to 12 carbon atoms, and even more preferably 10 to 12 carbon atoms.

[0021] <Amine compounds> The amine compound used in the production method of the present invention is a compound represented by general formula (I).

[0022] [ka]

[0023] [In the formula, R 1 and R 2 These are, independently of each other, an alkyl group or aryl group having 1 to 5 carbon atoms, or R 1 and R 2 Together with the nitrogen atom supporting the molecule, it is substituted with 1 to 4 functional groups independently selected from the group consisting of alkyl groups and alkoxy groups having 1 to 5 carbon atoms, forming a nitrogen-containing heterocyclic structure having 4 to 9 carbon atoms. R 3 [This is a hydrogen atom or a heteroaryl group.]

[0024] In formula (I), the alkyl group having 1 to 5 carbon atoms is preferably 1 to 3 carbon atoms, and specifically, examples include a C1 alkyl group such as a methyl group; a C2 alkyl group such as an ethyl group; a C3 alkyl group such as an n-propyl group or an i-propyl group; a C4 alkyl group such as an n-butyl group, an i-butyl group, a sec-butyl group or a t-butyl group; and a C5 alkyl group such as an n-pentyl group, an i-pentyl group, a sec-pentyl group, a t-pentyl group or a 2-methylbutyl group.

[0025] Examples of alkyl groups having 1 to 3 carbon atoms include C1 alkyl groups such as methyl groups; C2 alkyl groups such as ethyl groups; and C3 alkyl groups such as n-propyl groups and i-propyl groups. In formula (I) above, the alkoxy group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably an alkoxy group having 1 to 3 carbon atoms, specifically including a methoxy group, an ethoxy group, a propoxy group, an iso-propoxy group, a butoxy group, and the like.

[0026] In formula (I) above, the aryl group is, for example, an aromatic group having 6 to 10 carbon atoms, and preferably includes a phenyl group, a naphthyl group, etc. When simply referred to as a naphthyl group, it includes 1-naphthyl groups and 2-naphthyl groups.

[0027] In formula (I) above, the heteroaryl group can be a saturated or unsaturated monocyclic or polycyclic heterocyclic group having at least one heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Examples of heteroaryl groups include, from the viewpoint of aliphatic aldehyde yield, unsaturated heteromonocyclic groups of 3 to 8 membered rings (preferably 5 or 6 membered rings) having 1 to 4 nitrogen atoms, such as pyrrolyl, pyrrolinyl, imidazolyl, pyrazolyl, pyridyl, dihydropyridyl, pyrimidyl, pyrazinyl, pyridadinyl, triazolyl, tetrazolyl, etc.; saturated heteromonocyclic groups of 3 to 8 membered rings (preferably 5 or 6 membered rings) having 1 to 4 nitrogen atoms, such as pyrrolidinyl, imidazolidinyl, piperidyl, piperazinyl, etc.; and unsaturated condensed heterocyclic groups having 1 to 4 nitrogen atoms, such as indolyl, isoindolyl, indolinyl, indolidinyl, benzimidazolyl, quinolyl, isoquinolyl, indazolyl, benzotriazolyl, etc. Among these, pyridyl groups are preferred as heteroaryl groups, and 4-pyridyl groups are more preferred.

[0028] In formula (I), the nitrogen-containing heterocyclic structure having 4 to 9 carbon atoms, which is substituted 1 to 4 times with functional groups independently selected from the group consisting of alkyl groups and alkoxy groups having 1 to 5 carbon atoms, preferably has 2 to 4 substitutions, more preferably 3 to 4 substitutions, and even more preferably 4 substitutions. It is believed that using a compound represented by general formula (I) having substituents can suppress the formation of aliphatic carboxylic acids by further oxidation of aliphatic aldehydes.

[0029] In formula (I), the nitrogen-containing heterocyclic structure having 4 to 9 carbon atoms, preferably 5 to 9 carbon atoms, is more preferably one or more selected from the group consisting of piperidine, pyridine, dihydropyridine, azepane, azepine, dihydroazepine, quinoline, dihydroquinoline, and tetrahydroquinoline.

[0030] The compound represented by the general formula (I) is, from the viewpoint of the yield of aliphatic aldehydes, R 1 and R 2 These are, independently of each other, an alkyl group or aryl group having 1 to 3 carbon atoms, or R 1 and R 2 Together with the nitrogen atom supporting it, it is substituted with 1 to 4 functional groups independently selected from the group consisting of alkyl groups and alkoxy groups having 1 to 3 carbon atoms, forming a nitrogen-containing heterocyclic structure having 4 to 9 carbon atoms. R 3 It is preferably a hydrogen atom or a heteroaryl group. R 1 and R 2 These are, independently of each other, an alkyl group or phenol group having 1 to 3 carbon atoms, or R 1 and R 2 Together with the nitrogen atom supporting it, it forms a nitrogen-containing heterocyclic structure having 5 to 9 carbon atoms, which is substituted with 1 to 4 functional groups independently selected from the group consisting of alkyl groups and alkoxy groups having 1 to 3 carbon atoms. R 3 It is more preferable that this is a hydrogen atom or a pyridyl group.

[0031] Also, R 1 and R 2 However, if the alkyl group has 1 to 5 carbon atoms independently of each other, R 3 It is preferable to remove hydrogen atoms.

[0032] Specifically, from the viewpoint of the yield of aliphatic aldehydes, it is more preferable that the compound represented by the general formula (I) is one or more selected from (i) to (iii) below. (i)R 1 and R 2 These are aryl groups, independently of each other. R 3 It is preferable that it is a hydrogen atom. R 1 and R 2 These are, independently of each other, phenyl groups. R 3 It is more preferable that it be a hydrogen atom.

[0033] (ii)R 1 and R 2 These are alkyl groups having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and R 3 It is preferable that it is a pyridyl group. R 1 and R 2 It is a methyl group, and R 3 It is more preferable that it be a pyridyl group.

[0034] (iii)R 1 and R 2 R 1 and R 2 Together with the supporting nitrogen atom, it forms a nitrogen-containing heterocyclic structure having 4 to 9 carbon atoms, which is independently substituted with 1 to 4 alkyl groups and alkoxy groups having 1 to 5 carbon atoms. R 3 A hydrogen atom is preferred. R 1 and R 2 R 1 and R 2Together with the nitrogen atom supporting it, it is quadrisubstituted with a functional group independently selected from the group consisting of alkyl and alkoxy groups having 1 to 3 carbon atoms, forming a nitrogen-containing heterocyclic structure having 5 to 9 carbon atoms. R 3 A hydrogen atom is more preferable. Examples of the cyclic structure include those mentioned above.

[0035] Furthermore, the nitrogen-containing heterocyclic structure represented by the general formula (I) is preferably piperidine or dihydroquinoline from the viewpoint of aliphatic aldehyde yield.

[0036] The compound represented by the general formula (I) is more preferably one or more selected from diphenylamine (DPA), piperidine and dialkylaminopyridine substituted with four methyl groups, and dihydroquinoline substituted with three methyl groups and one ethoxy group, from the viewpoint of the yield of aliphatic aldehydes.

[0037] The compound represented by general formula (I) preferably contains one or more selected from diphenylamine, dimethylaminopyridine, tetramethylpiperidine, and ethoxyquin, and more preferably contains one or more selected from the group consisting of diphenylamine (DPA), 2,2,6,6-tetramethylpiperidine (TMP), 4-dimethylaminopyridine (DMAP), and ethoxyquin.

[0038] <Metal-supported catalyst> In the present invention, the metal-supported catalyst includes a metal supported on an inorganic support. From the viewpoint of aliphatic aldehyde yield, the metal can be a platinum group element such as ruthenium (Ru), palladium (Pd), rhodium (Rh), or platinum (Pt), with ruthenium being preferred. The inorganic support can be, for example, a porous oxide. The porous oxide can be one or more selected from the group consisting of alumina, titania, zirconia, silica, silica-alumina, magnesia, zeolite, and activated carbon. From the viewpoint of high activity and high selectivity, the support can be alumina, activated carbon, titania, silica-alumina, or zeolite, with alumina and activated carbon being more preferred. In the present invention, the porous oxide can be used alone or in combination of two or more types.

[0039] In the present invention, the metal-supported catalyst preferably has a surface area of ​​60 m² per unit mass of metal. 2 The value is 1 / g or more. A large surface area per unit mass of metal means that the particle size of the metal is small, and the metal is widely dispersed in the carrier, i.e., dispersed in a carrier with a large pore volume. The surface area per unit mass of metal can be measured by the pulse method, especially the CO pulse method.

[0040] When the metal in the metal-supported catalyst is ruthenium, the surface area per unit mass of the metal is preferably 60 m² from the viewpoint of increasing reactivity. 2 / g or more, comfortable 65m 2 / g or more, more preferably 70m 2 It is 250m or more / g, and from the same perspective, 2 Less than or equal to / g, preferably 200m 2 / g or less, more preferably 190m 2 / g or less, more preferably 180m 2 Less than or equal to / g, more preferably 170m 2 / g or less, more preferably 160m 2 It is less than / g. When the metal of the metal-supported catalyst is ruthenium, the surface area per unit mass of metal is preferably 60m from the viewpoint of increasing reactivity. 2 / g or more 250m 2 / g or less, more preferably 60m 2 / g or more 200m 2 / g or less, more preferably 60mg 2 / g or more 190m 2 / g or less, more preferably 65m 2 / g or more 190m 2 / g or less, more preferably 70m 2 / g or more 170m 2 It is less than / g.

[0041] The surface area per unit mass of a metal can be adjusted during catalyst preparation by increasing the amount of metal compound relative to the raw material carrier, or by using a carrier with a large surface area, i.e., a highly porous carrier. In this case, as will be described later, it is preferable to increase the mesopore volume by reducing the macropores of the carrier in order to increase both catalytic activity and the surface area per unit mass of the metal.

[0042] From the viewpoint of reactivity, the particle size of the metal is preferably 1 nm or larger, more preferably 2 nm or larger, and even more preferably 2.5 nm or larger. Similarly, from the same viewpoint, it is preferably 20 nm or smaller, more preferably 15 nm or smaller, and even more preferably 10 nm or smaller. This particle size can be determined by the method described in the examples.

[0043] The mesopore volume of the metal-supported catalyst can be measured by mercury porosimetry according to ASTM D4284-83. Specifically, the measurement is performed by filling a measurement cell containing the sample with mercury and pressurizing the inside of the cell. Then, the amount of mercury that enters is detected by a capacitance detector and the pore volume is measured. Alternatively, by modeling the pores as cylindrical, the pore distribution can be determined and the mesopore volume can be calculated. Catalysts having a mesopore volume of 0.15 mL / g or more are considered to have a pore size suitable for the reaction site of the oxidation reaction of aliphatic primary alcohols.

[0044] When the metal of the metal-supported catalyst is ruthenium, the mesopore volume of the metal-supported catalyst is preferably 0.15 mL / g or more, preferably 0.2 mL / g or more, and more preferably 0.25 mL / g or more, from the viewpoint of increasing the reactivity of aliphatic primary alcohols and suppressing further oxidation of aldehydes to carboxylic acids, and from the viewpoint of catalyst preparation, preferably 0.5 mL / g or less, more preferably 0.45 mL / g or less, and even more preferably 0.4 mL / g or less. When the metal of the metal-supported catalyst is ruthenium, the mesopore volume of the catalyst is preferably 0.15 mL / g or more and 0.5 mL / g or less, more preferably 0.2 mL / g or more and 0.5 mL / g or less, even more preferably 0.25 mL / g or more and 0.5 mL / g or less, even more preferably 0.25 mL / g or more and 0.45 mL / g or less, and even more preferably 0.25 mL / g or more and 0.4 mL / g or less, from the viewpoint of increasing the reactivity of aliphatic primary alcohols and suppressing further oxidation of aldehydes to carboxylic acids, as well as from the viewpoint of catalyst adjustment.

[0045] The metal content in the metal-supported catalyst is, from the viewpoint of reactivity, preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and from the same viewpoint, preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 10% by mass or less, and even more preferably less than 10% by mass. The metal content in the metal-supported catalyst is, from the viewpoint of reactivity, preferably 1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 30% by mass or less, even more preferably 1% by mass or more and 10% by mass or less, even more preferably 1% by mass or more and less than 10% by mass, even more preferably 3% by mass or more and 30% by mass or less, even more preferably 3% by mass or more and 10% by mass or less, even more preferably 3% by mass or more and less than 10% by mass, even more preferably 5% by mass or more and 10% by mass or less, and even more preferably 5% by mass or more and less than 10% by mass.

[0046] <Method for manufacturing metal-supported catalysts> The metal-supported catalyst used in the present invention may be a commercially available metal-supported catalyst containing a metal supported on an inorganic support. Alternatively, such a metal-supported catalyst may be manufactured in accordance with known art or common technical knowledge. Examples of such manufacturing methods include impregnation methods in which a metal is impregnated into a support, and liquid-phase reduction methods in which a reducing agent is added.

[0047] An example of a method for producing a metal-supported catalyst used in the present invention, such as a ruthenium-supported catalyst, is described below. First, the porous oxide is added to a medium such as deionized water and suspended. Then, a solution of the ruthenium compound dissolved in an aqueous solvent such as deionized water is added to this suspension, and the mixture is heated while stirring as needed to adjust the temperature to about 20-95°C, preferably 40-80°C, to obtain a suspension containing the ruthenium compound. Examples of the ruthenium compound include ruthenium chloride, nitrate, formate, and ammonium salt.

[0048] Next, an alkali is added to the suspension containing the ruthenium compound to adjust the pH to 4-12, preferably 6-11, and hydrolysis is carried out, followed by aging to support the ruthenium component on a porous oxide. There are no particular restrictions on the type of alkali, but ammonia water, alkali metal carbonates such as sodium and potassium, hydroxides, etc., can be used. The time for adjusting the pH and aging is not particularly limited as long as sufficient time is provided for the ruthenium compound to hydrolyze.

[0049] Next, a reducing agent such as formaldehyde, hydrazine, or sodium borohydride is added to the reaction solution, and the mixture is heated as needed. After reduction treatment at a temperature of approximately 20-95°C, preferably 60-95°C, the solid-liquid mixture is separated by filtration or the like. The obtained solid is thoroughly washed with water and then dried at a temperature of preferably 140°C or lower under atmospheric pressure or reduced pressure. The reducing agent may be used alone or in combination of two or more types. In order to effectively reduce the supported ruthenium component, the reducing agent is usually used in a ratio of approximately 1 to 50 molars, preferably 15-40 molars, relative to the ruthenium. The duration of the reduction treatment described above is not particularly limited, as long as sufficient time is available for the reduction reaction to proceed to the desired extent. The reduction procedure described above is not necessarily required. After supporting the ruthenium component by hydrolysis, solid-liquid separation may be performed, and the resulting solid material may be thoroughly washed with water and dried.

[0050] When ruthenium components are supported on porous oxides by hydrolysis as described above, it is not necessarily required to perform operations such as high-temperature calcination or high-temperature reduction under an inert gas atmosphere, which are usually carried out in impregnation methods, and the preparation of the catalyst is simple. The ruthenium-supported catalyst obtained in this manner contains ruthenium as metal in a proportion of preferably 1 to 50% by mass, more preferably 3 to 30% by mass, based on the total amount of catalyst including porous oxides, from the viewpoint of sufficient catalytic activity, selectivity, and economic efficiency. The ruthenium content in the catalyst can be measured by ICP emission spectrometry after the catalyst has been melted with ammonium bisulfate.

[0051] <Method for producing aliphatic aldehydes> The present invention's manufacturing method includes the step of oxidizing an aliphatic primary alcohol with molecular oxygen in the presence of an amine compound and a metal-supported catalyst.

[0052] In this process, the molar ratio of the amine compound to the metal (amine compound (mmol) / metal (mmol)) is preferably 0.01 or more, more preferably 0.03 or more, even more preferably 0.1 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less, from the viewpoint of aldehyde yield. The molar ratio of the amine compound to the metal (amine compound (mmol) / metal (mmol)) is preferably 0.01 or more and 10 or less, more preferably 0.03 or more and 5 or less, and even more preferably 0.1 or more and 3 or less, from the viewpoint of aldehyde yield.

[0053] In this process, the molar ratio of the amine compound to the aliphatic primary alcohol (amine compound (mmol) / aliphatic primary alcohol (mmol)) is preferably 0.0001 or more, more preferably 0.001 or more, even more preferably 0.003 or more, preferably 0.5 or less, more preferably 0.3 or less, and even more preferably 0.1 or less, from the viewpoint of aldehyde yield.

[0054] In this process, the molar ratio of metal to aliphatic primary alcohol (metal (mmol) / aliphatic primary alcohol (mmol)) is preferably 0.001 or higher, more preferably 0.005 or higher, even more preferably 0.01 or higher, preferably 0.5 or lower, more preferably 0.2 or lower, even more preferably 0.07 or lower, even more preferably 0.04 or lower, preferably 0.001 or higher and 0.5 or lower, more preferably 0.001 or higher and 0.2 or lower, even more preferably 0.005 or higher and 0.07 or lower, and even more preferably 0.01 or higher and 0.04 or lower.

[0055] The molecular oxygen (referring to elemental molecular oxygen (oxygen gas); the same applies hereinafter) functions as an oxidizing agent in this step. This molecular oxygen is present in the reaction system of the present invention and only needs to be in contact with the aliphatic primary alcohol. Specifically, this step can be carried out in an atmospheric environment. Furthermore, it is preferable to carry out this step in an oxygen atmosphere because the oxidation reaction of the aliphatic primary alcohol can be carried out in a higher yield. An oxygen atmosphere may include gases other than oxygen, such as air, and may be 100% oxygen, or it may include oxygen and an inert gas such as nitrogen, helium, or argon. In an oxygen atmosphere, the oxygen gas concentration is preferably 5% by volume or more, and more preferably 10% by volume or more. In an oxygen atmosphere, it is preferable to have a high concentration of oxygen, as a high concentration of oxygen can increase the reaction yield.

[0056] This step may be carried out in the presence of a solvent. The solvent is preferably one that can dissolve the aliphatic primary alcohol, such as water and organic solvents. Examples of such solvents include aromatic solvents such as toluene, liquid paraffin, and hydrocarbon solvents such as squalene. Among these, from the viewpoint of reaction efficiency, aromatic organic solvents having 6 to 40 carbon atoms are preferred. The solvent can be used alone or in combination of two or more.

[0057] In this process, the ratio of solvent (mL) to aliphatic primary alcohol (mmol), i.e., solvent (mL) / aliphatic primary alcohol (mmol), is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.1 or more, from the viewpoint of reactivity, and similarly, preferably 6 or less, more preferably 4 or less, and even more preferably 2 or less. The ratio of solvent to aliphatic primary alcohol is preferably 0.01 or more and 6 or less, more preferably 0.05 or more and 4 or less, and even more preferably 0.1 or more and 2 or less, from the viewpoint of reactivity.

[0058] The reaction temperature in this process is not particularly limited. When heating is used, the reaction temperature is preferably below the boiling point of the solvent used. From the viewpoint of reactivity, the reaction temperature is preferably 60°C or higher, more preferably 70°C or higher, and even more preferably 80°C or higher. From the viewpoint of productivity, it is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 170°C or lower. From the viewpoint of reactivity and productivity, the reaction temperature is preferably 60°C to 200°C, more preferably 70°C to 180°C, and even more preferably 80°C to 170°C.

[0059] The pressure used in this process is not limited, but it is preferable to perform it at atmospheric pressure or under reduced pressure.

[0060] The manufacturing method of the present invention is suitable not only for batch production but also for continuous flow production, as it can produce aldehydes in a short time and with high yield.

[0061] The present invention includes the following embodiments. [1] A method for producing an aliphatic aldehyde, comprising the step of oxidizing an aliphatic primary alcohol having 4 or more carbon atoms with molecular oxygen in the presence of an amine compound and a metal-supported catalyst, The metal-supported catalyst includes a metal supported on an inorganic support, A method for producing an aliphatic aldehyde, wherein the amine compound is a compound represented by the following general formula (I).

[0062] [ka]

[0063] [In the formula, R 1 and R 2 These are, independently of each other, an alkyl group or aryl group having 1 to 5 carbon atoms, or R 1 and R 2Together with the nitrogen atom supporting the molecule, it is substituted with 1 to 4 functional groups independently selected from the group consisting of alkyl groups and alkoxy groups having 1 to 5 carbon atoms, forming a nitrogen-containing heterocyclic structure having 4 to 9 carbon atoms. R 3 [This is a hydrogen atom or a heteroaryl group.]

[0064] [2] The manufacturing method according to [1], wherein the aryl group is an aromatic group having 6 to 10 carbon atoms, preferably a phenyl group.

[0065] [3] The manufacturing method according to [1] or [2], wherein the heteroaryl group is a saturated or unsaturated heteromonocyclic group of a 3- to 8-membered ring (preferably a 5 or 6-membered ring) having 1 to 4 nitrogen atoms, preferably a pyridyl group.

[0066] [4] The manufacturing method according to any one of [1] to [3], wherein the compound represented by the general formula (I) is one or more selected from (i) to (iii) below. (i)R 1 and R 2 These are aryl groups, independently of each other. R 3 It is preferable that it is a hydrogen atom. R 1 and R 2 These are, independently of each other, phenyl groups. R 3 is a hydrogen atom (ii)R 1 and R 2 These are alkyl groups having 1 to 5 carbon atoms, R 3 It is a pyridyl group. (iii)R 1 and R 2 R 1 and R 2 Together with the nitrogen atom supporting it, it forms a nitrogen-containing heterocyclic structure with 4 to 9 carbon atoms, which is substituted with 1 to 4 functional groups independently selected from the group consisting of alkyl groups and alkoxy groups having 1 to 5 carbon atoms, and R 3 is a hydrogen atom

[0067] [5] The nitrogen-containing heterocyclic structure contains one or more selected from the group consisting of piperidine, pyridine, dihydropyridine, azepane, azepine, dihydroazepine and dihydroquinoline, and the production method according to any one of [1] to [4].

[0068] [6] The compound represented by the general formula (I) preferably contains one or more selected from diphenylamine, dimethylaminopyridine, tetramethylpiperidine and ethoxyquin, and more preferably contains one or more selected from the group consisting of diphenylamine (DPA), 2,2,6,6-tetramethylpiperidine (TMP), 4-dimethylaminopyridine (DMAP) and ethoxyquin, and the production method according to any one of [1] to [5].

[0069] [7] The metal contains a platinum group element, and the production method according to any one of [1] to [6].

[0070] [8] The metal contains ruthenium, and the production method according to any one of [1] to [7].

[0071] [9] The surface area per unit mass of ruthenium metal is preferably 60 m 2 / g or more and 250 m 2 / g or less, and the production method according to [8].

[0072]

[10] The surface area per unit mass of ruthenium metal is more preferably 60 m 2 / g or more and 200 m 2 / g or less, and the production method according to [8] or [9].

[0073]

[11] The surface area per unit mass of ruthenium metal is still more preferably 60 m 2 / g or more and 190 m 2 / g or less, and the production method according to any one of [8] to

[10] .

[0074]

[12] The surface area per unit mass of ruthenium metal is even more preferably 70 m 2 / g or more and 170 m2 The production method according to any one of [8] to

[11] , which is below / g.

[0075]

[13] The production method according to any one of [1] to [9], wherein the inorganic carrier contains a porous oxide.

[0076]

[14] The production method according to

[13] , wherein the porous oxide is one or more selected from the group consisting of alumina, titania, zirconia, silica, silica alumina, magnesia, zeolite, and activated carbon.

[0077]

[15] The production method according to any one of [1] to

[11] , wherein the aliphatic primary alcohol is an aliphatic straight-chain saturated primary alcohol.

[0078]

[16] The production method according to any one of [1] to

[15] , wherein the number of carbon atoms of the aliphatic primary alcohol is 4 or more and 30 or less.

[0079]

[17] The production method according to any one of [1] to

[16] , wherein the number of carbon atoms of the aliphatic primary alcohol is 8 or more and 14 or less.

[0080]

[18] The production method according to any one of [1] to

[17] , wherein the number of carbon atoms of the aliphatic primary alcohol is 10 or more and 12 or less.

[0081]

[19] The production method according to any one of [1] to

[18] , wherein the molar ratio of the amine compound to the metal (amine compound (mmol) / metal (mmol)) is 0.01 or more, preferably 0.01 or more and 10 or less.

[0082]

[20] The production method according to any one of [1] to

[19] , wherein the molar ratio of the amine compound to the metal (amine compound (mmol) / metal (mmol)) is 0.03 or more and 5 or less.

[0083]

[21] The manufacturing method according to any one of [1] to

[20] , wherein the molar ratio of the amine compound to the metal (amine compound (mmol) / the metal (mmol)) is 0.1 or more and 3 or less.

[0084]

[22] The production method according to any one of [1] to

[21] , wherein the molar ratio of the amine compound to the aliphatic primary alcohol (amine compound (mmol) / aliphatic primary alcohol (mmol)) is 0.0001 or more, preferably 0.0001 or more and 0.5 or less.

[0085]

[23] The production method according to any one of [1] to

[22] , wherein the molar ratio of the amine compound to the aliphatic primary alcohol (amine compound (mmol) / aliphatic primary alcohol (mmol)) is 0.001 or more and 0.3 or less.

[0086]

[24] The production method according to any one of [1] to

[23] , wherein the molar ratio of the amine compound to the aliphatic primary alcohol (amine compound (mmol) / aliphatic primary alcohol (mmol)) is 0.003 or more and 0.1 or less.

[0087]

[25] The manufacturing method according to any one of [1] to

[24] , wherein the molar ratio of the metal to the aliphatic primary alcohol (metal (mmol) / aliphatic primary alcohol (mmol)) is 0.001 or more and 0.5 or less.

[0088]

[26] The manufacturing method according to any one of [1] to

[25] , wherein the molar ratio of metal to aliphatic primary alcohol (metal (mmol) / aliphatic primary alcohol (mmol)) is 0.001 or more and 0.2 or less.

[0089]

[27] The manufacturing method according to any one of [1] to

[26] , wherein the molar ratio of the metal to the aliphatic primary alcohol (metal (mmol) / aliphatic primary alcohol (mmol)) is 0.005 or more and 0.07 or less.

[0090]

[28] The manufacturing method according to any one of [1] to

[27] , wherein the molar ratio of metal to aliphatic primary alcohol (metal (mmol) / aliphatic primary alcohol (mmol)) is 0.01 or more and 0.04 or less.

[0091]

[29] The manufacturing method according to any one of [1] to

[28] , wherein the temperature of the oxidation step is 60°C or more and 200°C or less.

[0092]

[30] The manufacturing method according to any one of [1] to

[29] , wherein the temperature of the oxidation step is 70°C or more and 180°C or less.

[0093]

[31] The manufacturing method according to any one of [1] to

[30] , wherein the temperature of the oxidation step is 80°C or more and 170°C or less.

[0094]

[32] The manufacturing method according to any one of [1] to

[31] , wherein the metal content in the metal-supported catalyst is 1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 30% by mass or less, even more preferably 1% by mass or more and 10% by mass or less, even more preferably 1% by mass or more and less than 10% by mass, even more preferably 3% by mass or more and 30% by mass or less, even more preferably 3% by mass or more and 10% by mass or less, even more preferably 3% by mass or more and less than 10% by mass, even more preferably 5% by mass or more and less than 10% by mass.

[0095] The present invention will be described in more detail below with reference to examples. In the following examples, the measurement and evaluation of each physical property was performed by the following methods.

[0096] <Method for measuring the surface area per unit mass and particle size of metals> The surface area per unit mass of the metal (ruthenium) was measured using the CO pulse method with a BELCAT-B manufactured by Nippon Bell. Pretreatment for the measurement involved reducing the active metal species (ruthenium) of the sample (catalyst) by passing helium gas through it at 200°C for 15 minutes, followed by passing hydrogen gas through it for 15 minutes. The measurement was performed using a 10% CO / He gas under conditions of 50°C, and the surface area of ​​the active metal species was calculated based on the number of moles of CO adsorbed onto the active metal species before equilibrium was reached. The stoichiometric ratio of the active metal species to CO was set to 1.

[0097] Using the obtained surface area per unit mass of ruthenium, the particle size of the active metal species (ruthenium) was calculated using the following formula based on the ratio of the volume (assuming the sample particles are perfectly spherical) to the surface area per unit mass of ruthenium. The density when ruthenium is used as the active metal species is 12.410 g / cm³. 3 That is the case.

[0098]

number

[0099] In the formula, X is the density (g / cm³) of ruthenium (an active metal species). 3 ) and Y is the surface area per unit mass of ruthenium (m²). 2 It is / g).

[0100] <Method for measuring the mesopore volume of a catalyst> The mesopore volume of the catalyst was measured by mercury intrusion porosimetry in accordance with ASTM standard ASTM D4284-83 (Standard method for measuring the pore volume distribution of catalysts by mercury intrusion porosimetry). Specifically, the mercury intrusion method was performed using Micromeritrics AutoPore IV. The measurement pressure was 1.5 to 60,000 psia, and the equilibrium time was 5 seconds. The mesopore capacity of a catalyst is defined as the cumulative volume of mercury introduced at pressures between 30 MPa and 400 MPa, corresponding to the volume contained in pores with apparent diameters between 2 and 50 nm.

[0101] <Gas chromatography equipment and analytical conditions> GC system: Agilent Technologies, Inc. 7890B, flame ionization detector

[0102] A DB-1 column (capillary column, 100% dimethylpolysiloxane, inner diameter 0.25 mm, length 30 m, film thickness 0.25 μm, manufactured by Agilent Technologies, Inc.) was used. Carrier gas: Nitrogen, 1.5 mL / min Injection conditions: 280°C, split ratio 100 / 1 Injection volume: 1 μL Detection conditions: FID method, 280°C Column temperature conditions: Starting at 100°C, the temperature was held at 100°C for 2 minutes, then increased at a rate of 8°C / min to 180°C, and then increased at a rate of 10°C / min to 280°C. The temperature was then held at 280°C for 5 minutes.

[0103] [Examples, Comparative Examples] In the following examples and comparative examples, "%" refers to "mass%" unless otherwise specified. The following raw materials were used in the reaction. Octanol: Manufactured by Kao Corporation. Toluene: Manufactured by Fujifilm Wako Pure Chemical Corporation, Wako Special Grade. Tetradecane: Manufactured by Fujifilm Wako Pure Chemical Corporation, Wako Special Grade. Diethyl ether: Manufactured by Fujifilm Wako Pure Chemical Corporation, Wako Special Grade. DPA: Diphenylamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako Special Grade. DMAP: 4-dimethylaminopyridine, manufactured by Fujifilm Wako Chemical, Wako Special Grade. TMP: 2,2,6,6-tetramethylpiperidine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako Special Grade. Piperidine: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako Special Grade. Ethoxyquin: Manufactured by Fujifilm Wako Pure Chemical Corporation.

[0104] [Example 1] In a glass reaction tube with an inner diameter of 34 mm, a 5% alumina-supported ruthenium catalyst (N.E. Chemcat, HYAc-5E, N-type, surface area per unit mass of ruthenium 154 m²) is used as the catalyst. 2 The following were added: ruthenium (particle size 3.1 nm, mesopore volume 0.30 mL / g, dry mass 0.10 g, Ru 0.0495 mmol), diphenylamine (DPA) (0.017 g, 0.1 mmol), 1-octanol (0.26 g, 2.0 mmol), toluene (4.0 mL, 3.47 g), and tetradecane (GC internal standard, 0.026 g). An oxygen-filled balloon was connected to the reaction tube to purge the reaction tube with oxygen, and the mixture in the reaction tube was stirred at 90°C for 24 hours. After that, the reaction tube was cooled to 30°C to terminate the reaction.

[0105] The reaction results were obtained by quantitatively analyzing each component using the internal standard method with reaction solutions collected 2 hours and 24 hours after the start of heating and stirring, respectively, using GC (gas chromatography). Using the amounts of each component obtained in the reactant, the initial aldehyde activity (2h) and aldehyde yield (2h, 24h) were calculated according to the following formula. Tetradecane was used as the internal standard, and diethyl ether was used as the solvent. The obtained initial aldehyde activity, aldehyde yield, and the rate of carboxylic acid production as a by-product are shown in Table 1 below.

[0106] Specifically, 0.2 mL of the reaction solution was sampled, and the catalyst was removed by filtering the solution through a membrane filter (polytetrafluoroethylene (PTFE), 0.2 μm). The resulting filtrate was taken into a screw tube containing 2 mL of diethyl ether, diluted, and then subjected to GC analysis.

[0107] <Method for calculating aldehyde initial activity (2h)> The initial aldehyde activity was calculated using the mass of octanal in the reaction solution, obtained by GC analysis of the reaction solution collected 2 hours after the start of heating and stirring, according to the following formula. A higher initial aldehyde activity value indicates better initial activity.

[0108]

number

[0109] <Method for measuring aldehyde yield (2h)> The aldehyde yield (2h) was calculated using the mass of octanal in the reaction solution, obtained by GC analysis of the reaction solution collected 2 hours after the start of heating and stirring, according to the following formula. A higher aldehyde yield value indicates a better yield.

[0110]

number

[0111] <Method for calculating the alcohol conversion rate (24h)> The alcohol conversion rate (24h) was calculated using the mass of octanal in the reaction solution, obtained by GC analysis of the reaction solution collected 24 hours after the start of heating and stirring, according to the following formula.

[0112]

number

[0113] <Method for measuring carboxylic acid production rate (24h)> The carboxylic acid production rate (24h) was calculated using the mass of octanoic acid in the reaction solution, obtained by GC analysis of the reaction solution collected 24 hours after the start of heating and stirring, according to the following formula. A smaller carboxylic acid production rate indicates better suppression of carboxylic acid production.

[0114]

number

[0115] <Method for measuring aldehyde yield (24h)> The aldehyde yield (24h) was calculated using the mass of octanal in the reaction solution, obtained by GC analysis of the reaction solution collected 24 hours after the start of heating and stirring, according to the following formula. A higher aldehyde yield value indicates a better yield.

[0116]

number

[0117] <Method for measuring aldehyde selectivity (24h)> The aldehyde selectivity (24h) was calculated using the aldehyde yield and alcohol conversion rate after 24 hours, which were obtained from the reaction solution collected 24 hours after the start of heating and stirring by GC analysis, according to the following formula.

[0118]

number

[0119] [Examples 2-7] The procedure was carried out in the same manner as in Example 1, except that the amount of DPA (diphenylamine) was changed to the amount shown in Table 1.

[0120] [Table 1]

[0121] [Examples 8-10, Comparative Example 1] The procedure was the same as in Example 2, except that the amines listed in Table 2 were used instead of DPA.

[0122] [Example 11] As a catalyst, a 5% alumina-supported ruthenium catalyst (N.E. Chemcat, HYAc-5E, N-type, surface area per unit mass of ruthenium 154 m²) is used. 2Instead of using a 5% activated carbon-supported ruthenium catalyst (Johnson Matthey, Type 600, surface area per unit mass of ruthenium 197.3 m²) (ruthenium particle size 3.1 nm, mesopore volume 0.30 mL / g, dry mass 0.10 g), use a 5% activated carbon-supported ruthenium catalyst (Johnson Matthey, Type 600, surface area per unit mass of ruthenium 197.3 m²). 2 The procedure was carried out in the same manner as in Example 2, except that ruthenium (particle size 2.5 nm, mesopore volume 0.24 mL / g, dry mass 0.10 g) was used.

[0123] [Table 2]

[0124] [Example 12, Comparative Example 2] The procedure was carried out in the same manner as in Example 2, except that a 5% alumina-supported palladium catalyst (manufactured by Tokyo Chemical Industry Co., Ltd., dry weight 0.10 g) was used instead of a 5% alumina-supported ruthenium catalyst, and the amines listed in Table 3 were used. [Comparative Example 3] The procedure was the same as in Example 12, except that an amine compound was not used.

[0125] [Example 13] The procedure was carried out in the same manner as in Example 2, except that a 5% activated carbon-supported palladium catalyst (manufactured by Tokyo Chemical Industry Co., Ltd., dry weight 0.10 g) was used instead of a 5% alumina-supported ruthenium catalyst, and the amines listed in Table 3 were used.

[0126] [Table 3]

[0127] Tables 1-3 show the initial aldehyde activity, aldehyde yield, and carboxylic acid production rate obtained for Examples 1-13 and Comparative Examples 1-3. Specifically, Tables 1-3 show the type of metal-supported catalyst used (catalyst species, support, model number, manufacturer), the amount of metal-supported catalyst, additives, and results. In the term "catalyst," "g" represents the amount of metal-supported catalyst used (g), "Ru[mmol]" represents the amount of metal (Ru) in the metal-supported catalyst used (mmol), and "Pd[mmol]" represents the amount of metal (Pd) in the metal-supported catalyst used (mmol). In the context of "additives," "mmol" refers to the amount (mmol) of the amine compound used.

[0128] In the "Results," the "Method for Calculating Aldehyde Initial Activity (2h)" was obtained according to the "Method for Calculating Aldehyde Initial Activity (2h)," the "Aldehyde Yield (2h)" was obtained according to the "Method for Measuring Aldehyde Yield (2h)," the "Alcohol Conversion Rate (24h)" was obtained according to the "Method for Calculating Alcohol Conversion Rate (24h)," the "Aldehyde Selectivity (24h)" was obtained according to the "Method for Measuring Aldehyde Selectivity (24h)," the "Carboxylic Acid Production Rate (24h)" was obtained according to the "Method for Measuring Carboxylic Acid Production Rate (24h)," and the "Aldehyde Yield (24h)" was obtained according to the "Method for Measuring Aldehyde Yield (24h)."

[0129] In the table, DPA refers to diphenylamine, DMAP refers to 4-dimethylaminopyridine, and TMP refers to 2,2,6,6-tetramethylpiperidine (TMP).

[0130] As shown in Tables 1-3, it was confirmed that the method of the present invention can produce aliphatic aldehydes in good yield by oxidizing aliphatic primary alcohols.

[0131] On the other hand, in Comparative Example 3, which did not use an amine compound, the aliphatic aldehyde yield after 24 hours was significantly lower than the aliphatic aldehyde yield after 2 hours, indicating that carboxylic acids were being produced.

[0132] Furthermore, in the ruthenium-supported alumina catalyst, the aliphatic aldehyde yield after 24 hours was significantly higher than the aliphatic aldehyde yield after 2 hours.

[0133] Furthermore, it was found that the reaction using ruthenium-supported alumina catalyst and amine compounds exhibited high aldehyde selectivity.

Claims

1. A method for producing an aliphatic aldehyde, comprising the step of oxidizing an aliphatic primary alcohol having 4 or more carbon atoms with molecular oxygen in the presence of an amine compound and a metal-supported catalyst, The metal-supported catalyst includes a metal supported on an inorganic support, A method for producing an aliphatic aldehyde, wherein the amine compound is a compound represented by the following general formula (I). 【Transformation 5】 [In the formula, R 1 and R 2 These are, independently of each other, an alkyl group or aryl group having 1 to 5 carbon atoms, or R 1 and R 2 Together with the nitrogen atom supporting the molecule, it is substituted with 1 to 4 functional groups independently selected from the group consisting of alkyl groups and alkoxy groups having 1 to 5 carbon atoms, forming a nitrogen-containing heterocyclic structure having 4 to 9 carbon atoms. R 3 [This is a hydrogen atom or a heteroaryl group.]

2. The manufacturing method according to claim 1, wherein the metal includes a platinum group element.

3. The manufacturing method according to claim 1, wherein the metal includes ruthenium.

4. The surface area per unit mass of the ruthenium metal is 60 m². 2 / g or more 190m 2 The manufacturing method according to claim 3, wherein the amount is less than or equal to / g.

5. The manufacturing method according to claim 1, wherein the inorganic support comprises a porous oxide, one or more selected from the group consisting of alumina, titania, zirconia, silica, silicaalumina, magnesia, zeolite, and activated carbon.

6. The method for producing a product according to claim 1, wherein the aliphatic primary alcohol is an aliphatic linear saturated primary alcohol having 8 to 14 carbon atoms.

7. The manufacturing method according to claim 1, wherein the molar ratio of the amine compound to the metal is 0.01 or more.

8. The manufacturing method according to claim 1, wherein the molar ratio of the amine compound to the aliphatic primary alcohol is 0.0001 or more.

9. The manufacturing method according to claim 1, wherein the compound represented by the general formula (I) is one or more selected from (i) to (iii) below. (i) R 1 and R 2 are each independently an aryl group, and R 3 is a hydrogen atom (ii) R 1 and R 2 These are alkyl groups having 1 to 5 carbon atoms, R 3 It is a pyridyl group. (iii) R 1 and R 2 R 1 and R 2 Together with the nitrogen atom supporting it, it forms a nitrogen-containing heterocyclic structure with 4 to 9 carbon atoms, which is substituted with 1 to 4 functional groups independently selected from the group consisting of alkyl groups and alkoxy groups having 1 to 5 carbon atoms, R 3 is a hydrogen atom

10. The manufacturing method according to claim 1, wherein the nitrogen-containing heterocyclic structure comprises one or more selected from the group consisting of piperidine, pyridine, dihydropyridine, azepane, azepine, dihydroazepine, and dihydroquinoline.

11. The method for producing a compound according to claim 1, wherein the compound represented by the general formula (I) comprises one or more selected from diphenylamine, dimethylaminopyridine, tetramethylpiperidine, and ethoxyquin.

12. The manufacturing method according to claim 1, wherein the temperature of the oxidation step is 60°C or higher and 200°C or lower.

13. The manufacturing method according to claim 1, wherein the metal content in the metal-supported catalyst is 1% by mass or more and less than 10% by mass.

14. The method for producing a product according to claim 1, wherein the aliphatic primary alcohol includes an aliphatic linear saturated primary alcohol having 10 to 12 carbon atoms.

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