Catalytic reaction method, method for producing organic compound, and catalyst composition

Abstract

The catalytic reaction method according to the present invention is a method for reacting a starting compound using a catalyst in the presence of a solvent. The solvent contains an organic solvent, an aqueous solvent, and an antioxidant. The reaction of the starting compound is carried out in a two-phase system in which an organic solvent and an aqueous solvent are separated. This method for producing an organic compound comprises reacting a starting compound using a catalyst in the presence of a solvent, and synthesizing an organic compound from the starting compound. The solvent contains an organic solvent, an aqueous solvent, and an antioxidant. The reaction of the starting compound is carried out in a two-phase system in which an organic solvent and an aqueous solvent are separated.

Description

Technical Field

[0001] The present invention relates to a catalytic reaction method, a method for producing an organic compound, and a catalyst composition. Background Art

[0002] In organic synthesis reactions, various reactions using various transition metal complexes composed of a transition metal and a ligand as a catalyst are known.

[0003] For example, in view of global warming, fossil fuel depletion problems, etc., hydrogen energy is expected to be a next-generation energy source, and a method for producing formic acid from carbon dioxide (CO2) and hydrogen (H2) in the presence of a catalyst has been studied.

[0004] Patent Document 1 describes a method for producing formic acid by reacting carbon dioxide with hydrogen in the presence of a catalyst containing an element from Group 8, 9 or 10 of the periodic table, a tertiary amine (I) and a polar solvent.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent No. 5734286 Summary of the invention

[0008] Problems to be solved by the invention

[0009] However, the conventional technology has a problem that even if the catalyst has excellent catalytic efficiency at the start of the reaction, the catalyst deteriorates as the catalytic reaction proceeds, thereby reducing the catalytic efficiency.

[0010] Therefore, an object of the present invention is to provide a catalytic reaction method, a method for producing an organic compound, and a catalyst composition suitable for suppressing a decrease in catalytic efficiency.

[0011] Means for solving problems

[0012] The inventors of the present application have conducted intensive studies and, as a result, have found for the first time that a decrease in catalytic efficiency can be suppressed by conducting a reaction in a two-phase system to which an antioxidant has been added, thereby completing the present invention.

[0013] The present invention provides a catalytic reaction method, which comprises reacting a starting compound using a catalyst in the presence of a solvent,

[0014] The aforementioned solvent includes an organic solvent, an aqueous solvent, and an antioxidant.

[0015] The above reaction is carried out in a two-phase system in which the above organic solvent and the above aqueous solvent are separated.

[0016] In addition, the present invention provides a method for producing an organic compound, which comprises reacting a starting compound using a catalyst in the presence of a solvent to synthesize an organic compound from the starting compound.

[0017] The aforementioned solvent includes an organic solvent, an aqueous solvent, and an antioxidant.

[0018] The above reaction is carried out in a two-phase system in which the above organic solvent and the above aqueous solvent are separated.

[0019] In addition, the present invention provides a catalyst composition comprising:

[0020] catalyst;

[0021] Antioxidants; and

[0022] Phase transfer catalyst.

[0023] Effects of the Invention

[0024] According to the present invention, a catalytic reaction method, a method for producing an organic compound, and a catalyst composition suitable for suppressing a decrease in catalytic efficiency can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] [ Figure 1 ] Figure 1 This is a schematic diagram showing an example of a three-chamber electrodialysis device.

[0026] [ Figure 2 ] Figure 2 This is a schematic diagram showing an example of a formic acid production system. DETAILED DESCRIPTION

[0027] The catalytic reaction method according to the first aspect of the present invention comprises reacting a starting compound using a catalyst in the presence of a solvent,

[0028] The aforementioned solvent includes an organic solvent, an aqueous solvent, and an antioxidant.

[0029] The above reaction is carried out in a two-phase system in which the above organic solvent and the above aqueous solvent are separated.

[0030] In the second aspect of the present invention, for example, in the catalytic reaction method according to the first aspect, the organic phase containing the organic solvent contains the catalyst, and the aqueous phase containing the aqueous solvent contains the starting compound.

[0031] In a third aspect of the present invention, for example, in the catalytic reaction method according to the first or second aspect, the organic phase containing the organic solvent contains the antioxidant.

[0032] In a fourth aspect of the present invention, for example, in the catalytic reaction method according to any one of the first to third aspects, the antioxidant includes at least one selected from the group consisting of phosphorus-based antioxidants, amine-based antioxidants, and phenol-based antioxidants.

[0033] In a fifth aspect of the present invention, for example, in the catalytic reaction method according to any one of the first to fourth aspects, the antioxidant includes a phosphorus-based antioxidant.

[0034] In a sixth aspect of the present invention, for example, in the catalytic reaction method according to the fifth aspect, the phosphorus-based antioxidant is a compound represented by the following chemical formula (1B).

[0035] [Chemical formula 1]

[0036]

[0037] (R 1 , R 2 , and R 3 Each independently represents a hydrogen atom or an optional substituent. )

[0038] In a seventh aspect of the present invention, for example, in the catalytic reaction method according to the fifth or sixth aspect, the phosphorus-based antioxidant is a compound represented by the following chemical formula (1C).

[0039] [Chemical formula 2]

[0040]

[0041] (R 4 , R 5 , and R 6 Each independently represents an optional substituent. )

[0042] In the eighth aspect of the present invention, for example, in the catalytic reaction method according to the seventh aspect, in the chemical formula (1C), R 4 , R 5 , and R 6 Each independently represents the following chemical formula (1D).

[0043] [Chemical formula 3]

[0044]

[0045] (* indicates a connection key. 1 , X 2 , X 3 , X 4 , and X 5 Each independently represents a hydrogen atom or a hydrocarbon group. )

[0046] In a ninth aspect of the present invention, for example, in the catalytic reaction method according to any one of the first to eighth aspects, the reaction is a hydrogenation reaction of the starting compound with hydrogen, and a hydride of the starting compound is obtained by the reaction.

[0047] In the tenth aspect of the present invention, for example, in the catalytic reaction method according to any one of the first to ninth aspects, the starting compound is at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate, and formate is obtained from the starting compound through the reaction.

[0048] In the 11th aspect of the present invention, for example, in the catalytic reaction method involved in any one of the 1st to 10th aspects, the above-mentioned catalyst is at least one selected from the group consisting of a metal complex represented by the following general formula (1A), its tautomers, stereoisomers, and salts thereof.

[0049] [Chemical formula 4]

[0050]

[0051] (In the general formula (1A),

[0052] X represents an atomic group containing a typical element of Groups 13 to 15 that can coordinate with M,

[0053] Q each independently represents a bridge structure including a typical element of Groups 14 to 16 that connects Y and X,

[0054] Y each independently represents an atomic group containing a typical element of Groups 14 to 16 that can coordinate with M, M represents a metal atom,

[0055] Z represents an anionic ligand,

[0056] n represents 0 to 3,

[0057] When there are multiple L, each L independently represents a neutral or anionic ligand.

[0058] In a twelfth aspect of the present invention, for example, in the catalytic reaction method according to the eleventh aspect, the metal complex represented by the general formula (1A) is a metal complex represented by the following general formula (2A).

[0059] [Chemical formula 5]

[0060]

[0061] (In general formula (2A),

[0062] X1 represents an aromatic heterocyclic ring formed together with a nitrogen atom and two carbon atoms, which may have a substituent or may be bonded to other substituents to form a ring.

[0063] Q1 each independently represents CH2, NH, or O, and CH2 and NH may further have a substituent,

[0064] Y1 each independently represents a phosphorus atom or a nitrogen atom,

[0065] R each independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have a substituent,

[0066] M represents a metal atom,

[0067] Z represents an anionic ligand,

[0068] n represents 0 to 3,

[0069] When there are multiple L, each L independently represents a neutral or anionic ligand.

[0070] In a thirteenth aspect of the present invention, for example, in the catalytic reaction method according to the twelfth aspect, the metal complex represented by the general formula (2A) is a metal complex represented by the following general formula (3A).

[0071] [Chemical formula 6]

[0072]

[0073] (In general formula (3A),

[0074] R0 represents a hydrogen atom or an alkyl group,

[0075] A each independently represents CH, CR5, or N, R5 represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxyl group, or an alkoxy group,

[0076] Q1 each independently represents CH2, NH, or O, and CH2 and NH may further have a substituent,

[0077] Y1 represents a phosphorus atom or a nitrogen atom,

[0078] R each independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have a substituent,

[0079] M represents a metal atom,

[0080] Z represents an anionic ligand,

[0081] n represents 0 to 3,

[0082] When there are multiple L, each L independently represents a neutral or anionic ligand.

[0083] In a fourteenth aspect of the present invention, for example, in the catalytic reaction method according to any one of the eleventh to thirteenth aspects, the metal atom represented by M is ruthenium.

[0084] In a fifteenth aspect of the present invention, for example, in the catalytic reaction method according to any one of the first to fourteenth aspects, the organic solvent contains toluene.

[0085] A sixteenth aspect of the present invention is a method for producing an organic compound, comprising synthesizing an organic compound from the starting compound by the catalytic reaction method according to any one of the first to fifteenth aspects.

[0086] A seventeenth aspect of the present invention is a catalyst composition comprising:

[0087] catalyst;

[0088] Antioxidants; and

[0089] Phase transfer catalyst.

[0090] In an eighteenth aspect of the present invention, for example, in the catalyst composition according to the seventeenth aspect, the antioxidant includes at least one selected from the group consisting of phosphorus-based antioxidants, amine-based antioxidants, and phenol-based antioxidants.

[0091] In a nineteenth aspect of the present invention, for example, in the catalyst composition according to the eighteenth aspect, the antioxidant includes a phosphorus-based antioxidant.

[0092] In the 20th aspect of the present invention, for example, in the catalyst composition according to any one of the 17th to 19th aspects, the catalyst is at least one selected from the group consisting of a metal complex represented by the following general formula (1A), its tautomers, stereoisomers, and salts thereof.

[0093] [Chemical formula 7]

[0094]

[0095] (In the general formula (1A),

[0096] X represents an atomic group containing a typical element of Groups 13 to 15 that can coordinate with M,

[0097] Q each independently represents a bridge structure including a typical element of Groups 14 to 16 that connects Y and X,

[0098] Y each independently represents an atomic group containing a typical element of Groups 14 to 16 that can coordinate with M, M represents a metal atom,

[0099] Z represents an anionic ligand,

[0100] n represents 0 to 3,

[0101] When there are multiple L, each L independently represents a neutral or anionic ligand.

[0102] In the 21st aspect of the present invention, for example, the catalyst composition according to any one of the 17th to 20th aspects is used for producing formate.

[0103] In the 22nd aspect of the present invention, for example, the catalyst composition according to any one of the 17th to 21st aspects is used for a hydrogenation reaction.

[0104] In a 23rd aspect of the present invention, for example, the catalyst composition according to any one of the 17th to 22nd aspects further contains a solvent.

[0105] In a 24th aspect of the present invention, for example, in the catalyst composition according to the 23rd aspect, the solvent is at least one selected from the group consisting of organic solvents and aqueous solvents.

[0106] Hereinafter, the present invention will be described in detail, but the following description is not intended to limit the present invention to specific embodiments.

[0107] [Catalytic reaction method]

[0108] The catalytic reaction method involved in the first embodiment of the present invention is a method for reacting a starting compound using a catalyst in the presence of a solvent. The above-mentioned solvent includes an organic solvent, an aqueous solvent, and an antioxidant. The reaction of the starting compound is carried out in a two-phase system in which the organic solvent and the aqueous solvent are separated. It should be noted that in this specification, in the two-phase system, the phase containing the organic solvent is sometimes referred to as the organic phase, and the phase containing the aqueous solvent is referred to as the aqueous phase. Sometimes the organic phase and the aqueous phase are collectively referred to as a reaction solution.

[0109] By making the solvent contain an antioxidant, it is possible to suppress oxidation of the catalyst due to oxygen contained in the system. Therefore, it is possible to suppress a decrease in catalytic efficiency. In addition, the catalyst can be reused thereby, and manufacturing costs can be reduced.

[0110] The organic phase may contain the catalyst and the aqueous phase may contain the starting compound. The product obtained by the catalytic reaction may be contained in the aqueous phase. Thus, the catalyst can be easily separated, so the catalyst can be easily reused and repeated reactions can be performed. In addition, in the reaction of the two-phase system, there is also the advantage of being able to easily produce a high concentration of the product in the aqueous phase. The organic phase may contain an antioxidant. The organic phase may contain a catalyst and an antioxidant, and the aqueous phase may contain the starting compound.

[0111] The catalytic reaction method according to the first embodiment of the present invention can be widely applied to various reaction methods.

[0112] Methods to which the catalytic reaction method of the first embodiment of the present invention can be applied include, for example, reduction reactions, dehydration condensation reactions, hydrolysis reactions, and the like. The catalytic reaction method of the embodiment of the present invention can be applied to the reduction reaction of inorganic compounds or organic compounds. The reduction reaction is, for example, a hydrogenation reaction. That is, the catalytic reaction method of the embodiment of the present invention can be a method for obtaining a hydride of a starting compound by a hydrogenation reaction of a starting compound. The hydrogenation reaction of an inorganic compound is, for example, a formate formation reaction. That is, the catalytic reaction method of the embodiment of the present invention can be a method in which the starting compound is at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate, and formate is obtained from the starting compound. When the catalytic reaction method of the first embodiment of the present invention is applied to the formate formation reaction, there is an advantage that formate can be generated efficiently at low cost.

[0113] (Antioxidant)

[0114] Examples of the antioxidant include a primary antioxidant that captures radicals and a secondary antioxidant that decomposes peroxides. The antioxidant is preferably a secondary antioxidant.

[0115] As the antioxidant, for example, phosphorus antioxidants, amine antioxidants, phenolic antioxidants, and sulfur antioxidants can be cited. The antioxidant may include at least one selected from the group consisting of phosphorus antioxidants, amine antioxidants, and phenolic antioxidants. The antioxidant may be one of the above, or two or more may be used in combination. For example, a phosphorus antioxidant and a phenolic antioxidant may be used in combination.

[0116] The phosphorus antioxidant is preferably a substance that is not easily decomposed by hydrolysis and has high stability, for example, preferably a compound having a bulky structure. The phosphorus antioxidant is, for example, a phosphorus compound. The phosphorus compound may be an organic phosphorus compound, and may be a phosphite, a hypophosphite, or a phosphonite. Phosphites are, for example, trialkyl phosphites, triaryl phosphites, alkylaryl phosphites, thiophosphites, etc.

[0117] The phosphorus-based antioxidant is, for example, a compound having an aryl group. Examples of the aryl group include substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, for example, substituted or unsubstituted phenyl groups, preferably phenyl groups having a tert-butyl group.

[0118] The phosphorus-based antioxidant may be a compound represented by chemical formula (1B).

[0119] [Chemical formula 8]

[0120]

[0121] In the chemical formula (1B), R 1 , R 2 , and R 3 Each independently represents a hydrogen atom or an optional substituent. The substituent is, for example, a hydrocarbon group, a group containing an oxygen atom together with a hydrocarbon, or a group containing a sulfur atom together with a hydrocarbon. The number of carbon atoms in the hydrocarbon group is not particularly limited, and may be, for example, 1 to 50, 6 to 50, and 6 to 30. The hydrocarbon group may be linear or branched. The hydrocarbon group may have a cyclic structure and may be an aryl group. Examples of aryl groups include the above-mentioned aryl groups. Examples of hydrocarbons that are groups containing oxygen atoms together with a hydrocarbon and groups containing sulfur atoms together with a hydrocarbon are hydrocarbons described above as hydrocarbon groups. Selected from R 1 , R 2 , and R 3 At least two of the groups consisting of may each independently have an aryl group, R 1 , R 2 , and R 3 Each independently may have an aryl group. Examples of the aryl group include the above-mentioned aryl groups.

[0122] The phosphorus-based antioxidant may be a compound represented by chemical formula (1C).

[0123] [Chemical formula 9]

[0124]

[0125] In the chemical formula (1C), R 4 , R 5 , and R 6 Each independently represents an optional substituent. Examples of the substituent include the substituents described above. In the chemical formula (1C), R 4 , R 5 , and R 6 Each independently may be represented by the following chemical formula (1D).

[0126] [Chemical formula 10]

[0127]

[0128] In the chemical formula (1D), * represents a connecting bond. 1 , X 2 , X 3 , X 4 , and X 5 Each independently represents a hydrogen atom or a hydrocarbon group. Examples of hydrocarbon groups include the above-mentioned hydrocarbon groups. 1, X 2 , X 3 , X 4 , and X 5 Each independently may be a hydrogen atom or an alkyl group, and may be a hydrogen atom or a tert-butyl group.

[0129] Examples of the phosphorus antioxidant include triphenyl phosphite, diisooctyl phosphite, heptathryl triphosphite, triisodecyl phosphite, diphenyl isooctyl phosphite, diisooctylphenyl phosphite, diphenyl tridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tri(dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, bis(tridecyl) phosphite, tri(isodecyl) phosphite, tri(tridecyl) phosphite, diphenyl decyl phosphite, dinonylphenyl bis(nonylphenyl) phosphite, poly(dipropylene glycol) phenyl phosphite, tetraphenyl dipropylene glycol diphosphite, and trinonylphenyl phosphite. 、Tris(2,4-di-tert-butylphenyl) phosphite, tris(2,4-di-tert-butyl-5-methylphenyl) phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tris(decyl) phosphite, octyl diphenyl phosphite, di(decyl) monophenyl phosphite, distearyl pentaerythritol diphosphite, mixture of distearyl pentaerythritol and calcium stearate, alkyl (C10) bisphenol A phosphite, di(tridecyl) pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Ester, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-diisopropylphenyl) pentaerythritol diphosphite, tetraphenyl-tetra(tridecyl) pentaerythritol tetraphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, tetra(tridecyl) isopropylidene diphenol diphosphite, tetra(tridecyl)-4,4'-n-butylidene bis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetra(2,4-di-tert-butylphenyl) biphenylene diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (1- 2,2'-Methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2'-Methylenebis(4,6-di-tert-butylphenyl)-octadecyl phosphite, 2,2'-Ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, 4,4'-butylenebis(3-methyl-6-tert-butylphenyl ditridecyl)phosphite, tris(2-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphoran-6-yl)oxy]ethyl)amine, 3,9-bis(4-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly-4,4'-isopropylidene diphenol C12-15 alcohol phosphite, tetraalkyl (C12-15)-4,4'-isopropylidene diphenyl diphosphite, etc.

[0130] The phosphorus-based antioxidant is preferably tris(2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, triisodecyl phosphite, tetraalkyl(C12-15)-4,4′-isopropylidene diphenyl diphosphite, or 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and particularly preferably tris(2,4-di-tert-butylphenyl) phosphite or triphenyl phosphite.

[0131] Examples of the amine antioxidant include 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N-phenyl-1-naphthylamine, p,p'-dioctyldiphenylamine, phenothiazine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-β-naphthyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, and aldol-α-naphthylamine.

[0132] Examples of the phenolic antioxidant include hindered phenolic antioxidants, such as 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-methoxyphenol, 2-tert-butyl-4-methoxyphenol, 3-tert-butyl-4-methoxyphenol, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, and 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)-mesitylene.

[0133] The phenolic antioxidant is not limited to the hindered phenolic antioxidants mentioned above. As other phenolic antioxidants other than the hindered phenolic antioxidants mentioned above, for example, 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-thiobis-(6-tert-butyl-4-methylphenol), 2,2'-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-methyl-4,6-bis(octylmercaptomethyl)phenol, 2,2'-isobutylenebis(4,6-dimethylphenol), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-diylbis[3-( 3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, 2,2'-oxalyl-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2-ethylhexyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 2,2'-ethylenebis(4,6-di-tert-butylphenol), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-phenylpropanoic acid and C13-15 alkyl esters, 2,5-di-tert-amylhydroquinone, hindered phenol polymers (trade name AO.OH998 manufactured by Adeka Palmarole Co., Ltd.), 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol], 2-tert-butyl-6-(3-tert-butyl-2 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 6-[3-(3-tert-butyl-4-hydroxy-5-methyl)propoxy]-2,4,8,10-tetra-tert-butylbenzo[d,f][1,3,2]-dioxaphosphatine, hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, bis[monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate calcium salt, 5,7-bis(1,1-dimethylethyl)-3-hydroxy-2(3H)-benzofuranone reaction product with o-xylene, 2,6-di-tert-butyl-4-(4,6-bis( 2,6-Diphenyl-4-octadecyloxyphenol, Stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, Distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, Tridecyl-3,5-tert-butyl-4-hydroxybenzyl thioacetate, Diethylene bis (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl-4-hydroxyphenoxy)-s-triazine, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]diol ester, 4,4'-butylenebis(2,6-di-tert-butylphenol), 4,4'-butylenebis(6-tert-butyl-3-methylphenol), 2,2'-ethylenebis(4,6-di-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butyl phenyl) butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxybenzyl) tert-butyl-4-hydroxyphenyl)propionyloxyethyl] isocyanurate, tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, 3,9-bis[2-(3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, tris[2-(3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 3-(3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives such as ethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], stearyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, palmityl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, myristyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, and lauryl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide.

[0134] Examples of the sulfur-based antioxidant include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl 3,3'-thiodipropionate.

[0135] The antioxidant may be a phosphorus-based antioxidant. In the catalytic reaction method according to the first embodiment, the phosphorus-based antioxidant can particularly suppress degradation of the catalyst and is particularly suitable for suppressing a decrease in catalytic efficiency.

[0136] From the viewpoint of fully exerting the function of the antioxidant, the amount of the antioxidant used is preferably 1 mmol or more relative to 1 L of the solvent. From the viewpoint of suppressing the cost of the antioxidant, the amount of the antioxidant used is preferably 100 mmol or less relative to 1 L of the solvent. The antioxidant can be used alone or in combination of two or more. The antioxidant can be added in full when preparing the reaction solution, or it can be added to the reaction solution in multiple portions during the reaction.

[0137] The amount of the antioxidant used is preferably 1 equivalent or more and 10000 equivalent or less relative to 1 equivalent of the catalyst, more preferably 10 equivalents or more and 10000 equivalents or less, further preferably 10 equivalents or more and 1000 equivalents or less, and particularly preferably 100 equivalents or more and 1000 equivalents or less.

[0138] (catalyst)

[0139] In the catalytic reaction method according to the first embodiment of the present invention, it is preferred to use as a catalyst at least one compound selected from the group consisting of a metal complex represented by the following general formula (1A), its tautomers, stereoisomers, and salts thereof.

[0140] [Chemical formula 11]

[0141]

[0142] (In the general formula (1A),

[0143] X represents an atomic group containing a typical element of Groups 13 to 15 that can coordinate with M,

[0144] Q each independently represents a bridge structure including a typical element of Groups 14 to 16 that connects Y and X,

[0145] Y each independently represents an atomic group containing a typical element of Groups 14 to 16 that can coordinate with M, M represents a metal atom,

[0146] Z represents an anionic ligand,

[0147] n represents 0 to 3,

[0148] When there are multiple L, each L independently represents a neutral or anionic ligand.

[0149] In this specification, "nth group" means "nth group of the periodic table".

[0150] Typical elements of Groups 13 to 15 of the periodic table in X include boron atoms, carbon atoms, silicon atoms, germanium atoms, tin atoms, nitrogen atoms, phosphorus atoms, arsenic atoms, oxygen atoms, sulfur atoms, and selenium atoms. Preferred elements are boron atoms, carbon atoms, silicon atoms, germanium atoms, tin atoms, nitrogen atoms, phosphorus atoms, and arsenic atoms. More preferred elements are carbon atoms, nitrogen atoms, phosphorus atoms, and sulfur atoms. Still more preferred are carbon atoms or nitrogen atoms.

[0151] X may be an atomic group having a valence of 0 to 1. Examples of the atomic group represented by X include an alkyl group, an alkenyl group, an alkoxy group, an aromatic ring, and a heterocyclic ring, and these may have a substituent or may be bonded to another substituent to form a ring.

[0152] As the alkyl group in X, there can be mentioned a linear, branched, cyclic substituted or unsubstituted alkyl group. As the alkyl group in X, there can be mentioned preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, eicosyl, 2-ethylhexyl, etc., preferably an alkyl group having 6 or less carbon atoms, preferably a methyl group.

[0153] As the alkenyl group in X, there can be mentioned a linear, branched, cyclic substituted or unsubstituted alkenyl group. As the alkenyl group in X, there can be mentioned preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, n-propenyl, isopropenyl, tert-butenyl, n-octenyl, etc., and preferably an alkenyl group having 6 or less carbon atoms.

[0154] Examples of the alkoxy group in X include linear, branched, cyclic substituted or unsubstituted alkoxy groups. Examples of the alkoxy group in X include preferably substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy, and the like.

[0155] Examples of the aromatic ring in X include a phenyl ring and a naphthyl ring.

[0156] Examples of the heterocyclic ring for X include a pyrrolidine ring, a piperidine ring, a pyrroline ring, an imidazoline ring, an imidazoline ring, a pyrrole ring, an imidazole ring, a pyridine ring, a pyrimidine ring, a triazine ring, a quinoline ring, and a quinazoline ring.

[0157] The 0- to 1-valent atomic group represented by X preferably represents an atomic group including an aromatic heterocyclic ring formed together with a nitrogen atom and two carbon atoms, and these atoms may have a substituent or may bond to other substituents to form a ring.

[0158] The 0- to 1-valent atomic group represented by X is preferably a pyrroline ring, a pyridine ring, an imidazoline ring, a pyrimidine ring, or a triazine ring, more preferably a pyridine ring or a triazine ring, and still more preferably a pyridine ring.

[0159] When the 0- to 1-valent atomic group represented by X has a substituent, examples of the substituent include the substituent group A, preferably an alkyl group, and more preferably a methyl group.

[0160] X may be an atomic group in which a hydrogen atom or an alkyl group is bonded to a nitrogen atom. The alkyl group is as described above, and is preferably a methyl group.

[0161] The bridge structure including a typical element of Group 14 to Group 16 of the periodic table that connects Y and X and represented by Q may have a double bond, a monocyclic structure or a condensed ring structure, and may have a substituent.

[0162] As described above, various structures can be introduced into Q. For example, the number of atoms in the portion between Y and X is preferably 1 to 5, more preferably 1 to 4, further preferably 1 to 3, and particularly preferably 1 to 2.

[0163] The atoms in the portion between Y and X are not particularly limited, but are preferably carbon atoms, nitrogen atoms, phosphorus atoms, oxygen atoms, and sulfur atoms, more preferably carbon atoms, nitrogen atoms, and oxygen atoms, further preferably carbon atoms and oxygen atoms, and particularly preferably carbon atoms.

[0164] Q may have a single ring structure. In other words, the bridge structure represented by Q may also include a ring structure.

[0165] When Q has a monocyclic structure, the monocyclic structure and Y and X in the general formula (1A) may be directly bonded, and a divalent substituent may be interposed between the monocyclic structure and Y and / or Z in the general formula (1A). Examples of the divalent substituent include an alkylene group having 1 to 5 carbon atoms, an alkenylene group having 2 to 5 carbon atoms, an oxygen atom, a sulfur atom or other heteroatom, or a group formed by bonding these in series.

[0166] Q each independently represents preferably CH2, NH, or O. CH2 and NH may further have a substituent, and more preferably represents CH2 or NH.

[0167] Q may have a condensed ring structure. In other words, the bridge structure represented by Q may include a condensed ring structure.

[0168] When Q has a fused ring structure, the fused ring structure and Y and X in the general formula (1A) may be directly bonded, and a divalent substituent may be sandwiched between the fused ring structure and Y and / or X in the general formula (1A). The divalent substituent is the same as the group described above as a divalent substituent sandwiched between the monocyclic structure and Y and / or X in the general formula (1A).

[0169] Q may have a substituent. When Q does not have a monocyclic structure or a condensed ring structure, the substituent is a substituent of the Q portion in the ring structure composed of Q, Y, X, and M in the general formula (1A).

[0170] When Q has a monocyclic structure or a condensed ring structure, the substituent is a substituent of the monocyclic structure or the condensed ring structure, or a substituent of the Q portion in the ring structure composed of Q, Y, X, and M in the general formula (1A).

[0171] The substituent that Q may have may be, for example, a substituent having a heteroatom, or may be another atom or an atomic group.

[0172] Examples of the substituent having a hetero atom include an alkoxy group having 1 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an acyl group having 2 to 18 carbon atoms, an aroyl group having 7 to 18 carbon atoms, a dialkylamino group having 2 to 18 carbon atoms, an oxygen atom, a sulfur atom, and the like.

[0173] Examples of the other atoms or atomic groups include aromatic groups having 3 to 18 carbon atoms, alkyl groups having 1 to 18 carbon atoms, and halogen atoms. Examples of the aromatic group include aryl groups having 6 to 20 carbon atoms, such as phenyl, xylyl, naphthyl, and biphenyl.

[0174] The number of carbon atoms of Q is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.

[0175] Y can be a 0-1 valence atomic group. Y each independently represents a 0-1 valence atomic group containing a typical element of the 14th to 16th groups of the periodic table that can coordinate with M, and may further have a substituent. As typical elements of the 14th to 16th groups of the periodic table, preferably a carbon atom, a nitrogen atom, a phosphorus atom, an arsenic atom, an oxygen atom, a sulfur atom, a selenium atom, more preferably a carbon atom, a nitrogen atom, a phosphorus atom, an arsenic atom, further preferably a nitrogen atom, a phosphorus atom, and particularly preferably a phosphorus atom.

[0176] In the general formula (1A), it is preferred that both Ys represent a nitrogen atom or a phosphorus atom, or that one Y represents a phosphorus atom and the other Y represents a nitrogen atom.

[0177] When the 0- to 1-valent atomic group represented by Y has a substituent, examples of the substituent include the substituent group A, preferably an alkyl group or an aryl group, and more preferably an ethyl group, a tert-butyl group, or a phenyl group.

[0178] M represents a metal atom. M may include, for example, elements of Groups 7 to 11 of the periodic table, such as manganese, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, and gold, and may include elements of Groups 8 to 11 of the periodic table, such as iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, and gold. Among them, manganese, iron, ruthenium, cobalt, rhodium, iridium, nickel, palladium, or copper are preferred, manganese, ruthenium, rhodium, iridium, nickel, or palladium are more preferred, manganese, ruthenium, rhodium, iridium, or palladium are further preferred, and ruthenium (Ru) is particularly preferred. M may be ruthenium (Ru) or manganese (Mn).

[0179] As the anionic ligand represented by Z, for example, halide ion (halogen atom), hydride ion (hydrogen atom), nitrate ion, cyanide ion, etc. can be cited. Z preferably represents a halogen atom or a hydrogen atom, and more preferably represents a halogen atom. Z is further preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.

[0180] n represents an integer of 0 to 3, and indicates the number of ligands coordinated to the metal atom represented by M. From the viewpoint of catalyst stability, n is preferably 2 or 3.

[0181] When there are a plurality of L, each L independently represents a neutral or anionic ligand.

[0182] As the neutral ligand represented by L, for example, there can be mentioned ammonia, carbon monoxide, phosphines (for example, triphenylphosphine, tri(4-methoxyphenyl)phosphine), phosphine oxides (for example, triphenylphosphine oxide), sulfides (for example, dimethyl sulfide), sulfoxides (for example, dimethyl sulfoxide), ethers (for example, diethyl ether), nitriles (for example, p-methylbenzonitrile), heterocyclic compounds (for example, pyridine, N,N-dimethyl-4-aminopyridine, tetrahydrothiophene, tetrahydrofuran), etc., preferably triphenylphosphine and carbon monoxide, more preferably carbon monoxide.

[0183] Examples of the anionic ligand represented by L include hydride ions (hydrogen atoms), nitrate ions, and cyanide ions, and hydride ions (hydrogen atoms) are preferred.

[0184] In the general formula (1A), preferably, X represents a heterocycle, Q represents CH2, NH, or O, Y represents a phosphorus atom, and M represents ruthenium.

[0185] Preferably, Z represents a chlorine atom, n represents 1 to 3, and L each independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

[0186] Alternatively, in the general formula (1A), preferably, X represents an atomic group having a hydrogen atom or an alkyl group bonded to a nitrogen atom, Q represents CH2, NH, or O, Y represents a phosphorus atom, M represents manganese, preferably, Z represents a bromine atom, n represents 2 to 3, and L each independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

[0187] In the catalytic reaction method according to the first embodiment of the present invention, the metal complex represented by the general formula (1A) is preferably a metal complex represented by the following general formula (2A).

[0188] [Chemical formula 12]

[0189]

[0190] (In general formula (2A),

[0191] X1 represents an aromatic heterocyclic ring formed together with a nitrogen atom and two carbon atoms, which may have a substituent or may be bonded to other substituents to form a ring.

[0192] Q1 each independently represents CH2, NH, or O, and CH2 and NH may further have a substituent,

[0193] Y1 each independently represents a phosphorus atom or a nitrogen atom,

[0194] R each independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have a substituent,

[0195] M represents a metal atom,

[0196] Z represents an anionic ligand,

[0197] n represents 0 to 3,

[0198] When there are multiple L, each L independently represents a neutral or anionic ligand.

[0199] M, Q1, Z, n, and L in the general formula (2A) have the same meanings as M, Q, Z, n, and L in the general formula (1A), and the preferred ranges are also the same.

[0200] The aromatic heterocyclic ring formed together with the nitrogen atom and two carbon atoms represented by X1 is preferably a pyrroline ring, a pyridine ring, an imidazoline ring, a pyrimidine ring or a triazine ring, more preferably a pyridine ring or a triazine ring, and still more preferably a pyridine ring.

[0201] As the substituent which X1 may have, there are substituent group A, preferably an alkyl group, and more preferably a methyl group.

[0202] Y1 represents a phosphorus atom or a nitrogen atom, and both Y1 may represent a nitrogen atom or a phosphorus atom, or one Y1 may represent a phosphorus atom and the other Y1 may represent a nitrogen atom. Preferably, both Y1 are nitrogen atoms or phosphorus atoms, and more preferably, both Y1 are nitrogen atoms.

[0203] As the alkyl group represented by R, there can be mentioned a linear, branched, cyclic substituted or unsubstituted alkyl group. As the alkyl group represented by R, there can be mentioned preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an n-octyl group, an eicosyl group, a 2-ethylhexyl group, etc., and from the viewpoint of catalyst activity, an alkyl group having 12 or less carbon atoms is preferred, preferably an ethyl group or a tert-butyl group, and more preferably a tert-butyl group.

[0204] The aryl group represented by R includes substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, for example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl, etc., preferably an aryl group having 12 or less carbon atoms, more preferably phenyl.

[0205] When R further has a substituent, examples of the substituent include the substituent group A, preferably a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a phenyl group, and more preferably an ethyl group, an isopropyl group, or a tert-butyl group.

[0206] In the general formula (2A), preferably, X1 represents a pyridine ring or a triazine ring, Q1 represents CH2, NH, or O, Y1 represents a phosphorus atom, R represents an ethyl group, a tert-butyl group, or a phenyl group, and M represents ruthenium.

[0207] Preferably, Z represents a chlorine atom, n represents 1 to 3, and L each independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

[0208] In the catalytic reaction method according to the first embodiment of the present invention, the metal complex represented by the general formula (2A) is preferably a metal complex represented by the following general formula (3A).

[0209] [Chemical formula 13]

[0210]

[0211] (In general formula (3A),

[0212] R0 represents a hydrogen atom or an alkyl group,

[0213] A each independently represents CH, CR5, or N, R5 represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxyl group, or an alkoxy group,

[0214] Q1 each independently represents CH2, NH, or O, and CH2 and NH may further have a substituent,

[0215] Y1 represents a phosphorus atom or a nitrogen atom,

[0216] R each independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have a substituent,

[0217] M represents a metal atom,

[0218] Z represents an anionic ligand,

[0219] n represents 0 to 3,

[0220] When there are multiple L, each L independently represents a neutral or anionic ligand.

[0221] Y1, R, Q1, M, Z, n, and L in the general formula (3A) have the same meanings as Y1, R, Q1, M, Z, n, and L in the general formula (2A), and the preferred ranges are also the same.

[0222] R0 in the general formula (3A) represents a hydrogen atom or an alkyl group. As the alkyl group represented by R0, a linear, branched, cyclic substituted or unsubstituted alkyl group can be cited. As the alkyl group represented by R0, preferably an alkyl group having 1 to 30 carbon atoms can be cited, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, eicosyl, 2-ethylhexyl, etc., and from the viewpoint of ease of raw material procurement, an alkyl group having 6 or less carbon atoms is preferred, preferably a methyl group.

[0223] R0 in the general formula (3A) is preferably a hydrogen atom or a methyl group.

[0224] A each independently represents CH, CR5, or N, and R5 represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxyl group, or an alkoxy group.

[0225] As the alkyl group represented by R5, there can be mentioned a linear, branched, cyclic substituted or unsubstituted alkyl group. As the alkyl group represented by R5, there can be mentioned preferably an alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, eicosyl, 2-ethylhexyl, etc., and from the viewpoint of ease of raw material procurement, an alkyl group having 12 or less carbon atoms is preferred, and a methyl group is preferred.

[0226] The aryl group represented by R5 includes substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, for example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl, etc., preferably an aryl group having 12 or less carbon atoms, more preferably phenyl.

[0227] Examples of the aralkyl group represented by R5 include substituted or unsubstituted aralkyl groups having 30 or less carbon atoms, such as trityl, benzyl, phenethyl, tritylmethyl, diphenylmethyl, naphthylmethyl, etc., and preferably an aralkyl group having 12 or less carbon atoms.

[0228] Preferred examples of the alkoxy group represented by R5 include substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, and 2-methoxyethoxy groups.

[0229] In the general formula (3A), preferably, X1 represents a pyridine ring or a triazine ring, Q1 represents CH2, NH, or O, Y1 represents a phosphorus atom, R represents an ethyl group, a tert-butyl group, or a phenyl group, and M represents ruthenium.

[0230] Preferably, Z represents a chlorine atom, n represents 1 to 3, and L each independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

[0231] In the catalytic reaction method according to the embodiment of the present invention, the metal complex represented by the general formula (3A) is preferably a ruthenium complex represented by the following general formula (4A).

[0232] The ruthenium complex represented by the general formula (4A) is soluble in an organic solvent, insoluble in water, and is suitable as a catalyst in the manufacture of an organic compound. The ruthenium complex represented by the general formula (4A) is suitable as a catalyst in the manufacture of a formate, for example. The formate generated by the reaction is easily soluble in water, so it is easy to separate the catalyst from the formate through the reaction in a two-phase system, and it is easy to separate and recover the catalyst and formate from the reaction system, respectively, so that formate can be manufactured in high yield, and it is easy to reuse the expensive catalyst.

[0233] [Chemical formula 14]

[0234]

[0235] (In the general formula (4A), R0 represents a hydrogen atom or an alkyl group,

[0236] Q1 each independently represents CH2, NH, or O, and CH2 and NH may further have a substituent,

[0237] R1 each independently represents an alkyl group or an aryl group (wherein, when Q1 represents NH or O, at least one of R1 represents an aryl group),

[0238] A each independently represents CH, CR5, or N, R5 represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxyl group, or an alkoxy group,

[0239] Z represents a halogen atom,

[0240] n represents 0 to 3,

[0241] When there are multiple L, each L independently represents a neutral or anionic ligand.

[0242] R0, A, Q1, Z, L, and n in the general formula (4A) have the same meanings as R0, A, Q1, Z, L, and n in the general formula (3A), and the preferred ranges are also the same.

[0243] The alkyl group and aryl group represented by R1 have the same meanings as the alkyl group and aryl group represented by R in the general formula (3A), respectively, and the preferred ranges are also the same.

[0244] The metal complexes represented by the general formula (1A) to the general formula (4A) may generate stereoisomers depending on the coordination mode and conformation of the ligands, and may be a mixture of these stereoisomers or a pure isomer.

[0245] The metal complexes represented by general formula (1A) to (4A) may be those produced by known methods, such as the method described in E. Pidko et al., Chem Cat Chem 2014, 6, 1526-1530.

[0246] Specific examples of the ruthenium complex represented by the general formula (4A) include the following compounds. In the compounds exemplified below, Et represents an ethyl group, tBu represents a tert-butyl group, and Ph represents a phenyl group.

[0247] [Chemical formula 15]

[0248]

[0249] [Chemical formula 16]

[0250]

[0251] [Chemical formula 17]

[0252]

[0253] The amount of the catalyst (preferably a ruthenium complex) used is not particularly limited. From the viewpoint of fully presenting the function of the catalyst, the amount of the catalyst used is preferably 0.1 μmol or more, more preferably 0.5 μmol or more, and further preferably 1 μmol or more relative to 1L of the solvent. In addition, from the viewpoint of cost, it is preferably 1 mol or less, more preferably 10 mmol or less, and further preferably 1 mmol or less relative to 1L of the solvent. In addition, from the viewpoint of suppressing the reduction in catalytic efficiency, it can be 100 μmol or less, or 10 μmol or less relative to 1L of the solvent. It should be noted that when using more than two catalysts, their total amount used can be within the above range.

[0254] (Phase transfer catalyst)

[0255] The catalytic reaction method that the first embodiment of the present invention is related to needs to react in a two-phase system, so a phase-transfer catalyst that makes the movement of the substance between the two phases smooth can be used. As a phase-transfer catalyst, for example, nitrogen-containing macrocyclic polyethers such as macrocyclic polyethers such as quaternary ammonium salts, quaternary phosphates, crown ethers, cryptands, nitrogen-containing macrocyclic polyethers, nitrogen-containing chain polyethers, polyethylene glycol and its alkyl ethers, etc. can be enumerated. Among them, from the viewpoint that the substance movement between the aqueous solvent and the organic solvent is also easy even under mild reaction conditions, preferably quaternary ammonium salts.

[0256] As the quaternary ammonium salt, for example, methyltrioctylammonium chloride, benzyltrimethylammonium chloride, trimethylphenylammonium bromide, tributylammonium tribromide, tetrahexylammonium hydrogen sulfate, decyltrimethylammonium bromide, diallyldimethylammonium chloride, dodecyltrimethylammonium bromide, dimethyldi(octadecyl)ammonium bromide, tetraethylammonium tetrafluoroborate, ethyltrimethylammonium iodide, tri(2-hydroxyethyl)methylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium bromide, tetraethylammonium iodide and the like can be mentioned, and methyltrioctylammonium chloride is preferred.

[0257] The usage amount of phase transfer catalyst is not particularly limited. Relative to 1L of solvent of organic phase and aqueous phase, the usage amount of phase transfer catalyst is preferably more than 0.1mmol, more preferably more than 0.5mmol, and further preferably more than 1mmol. In addition, from the viewpoint of cost, relative to 1L of solvent of organic phase and aqueous phase, it is preferably less than 1mol, more preferably less than 500mmol, and further preferably less than 100mmol. It should be noted that, when using more than two phase transfer catalysts, their total usage amount can be within the above range.

[0258] (Solvent)

[0259] The solvent is not particularly limited as long as it can form a two-phase system in which an organic solvent and an aqueous solvent exist separately, but it is preferred that the solvent contains a uniform solvent that dissolves the catalyst.

[0260] Examples of the aqueous solvent include water, methanol, ethanol, ethylene glycol, glycerin, and mixed solvents thereof. From the viewpoint of low environmental load, water is preferred.

[0261] As the organic solvent, for example, toluene, benzene, xylene, propylene carbonate, dioxane, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, methylcyclohexane, cyclopentyl methyl ether and mixed solvents thereof can be cited. From the viewpoint of separation from the aqueous solvent, it is preferred to contain toluene or dioxane, and more preferably toluene. For example, the organic solvent is toluene.

[0262] (Reaction Conditions)

[0263] The reaction conditions in the catalytic reaction method as an embodiment of the present invention are not particularly limited and can be appropriately selected according to the type of reaction. In addition, the reaction conditions can also be appropriately changed during the reaction. The form of the reaction vessel used in the reaction is not particularly limited.

[0264] The reaction temperature in the catalytic reaction method is not particularly limited, but is preferably 30° C. or higher, more preferably 40° C. or higher, and further preferably 50° C. or higher in order to efficiently carry out the reaction. In addition, from the viewpoint of energy efficiency, it is preferably 200° C. or lower, more preferably 150° C. or lower, and further preferably 100° C. or lower.

[0265] The reaction temperature can be adjusted by heating or cooling, preferably by heating. For example, in the reaction of hydrogen and carbon dioxide, the temperature can be increased by heating after introducing hydrogen and carbon dioxide into the reaction vessel, or carbon dioxide can be introduced into the reaction vessel and hydrogen can be introduced after the temperature is increased.

[0266] The reaction time in the catalytic reaction method is not particularly limited, for example, more than 0.5 hours, can be more than 1 hour, more than 2 hours, more than 6 hours, more than 12 hours, more than 24 hours, more than 36 hours, more than 48 hours, and more than 60 hours. The upper limit of the reaction time is not particularly limited, for example, less than 500 hours, less than 400 hours, less than 300 hours, less than 200 hours, less than 100 hours, and less than 80 hours.

[0267] It should be noted that the catalytic reaction method of the present invention is not limited to the above-mentioned embodiment. Depending on the situation, the catalytic reaction method of the present invention is not limited to a two-phase system. That is, the present invention provides a catalytic reaction method, which includes reacting the starting compound using a catalyst in the presence of a solvent, and the solvent includes an antioxidant. The solvent may, for example, include an organic solvent.

[0268] [Method for producing organic compound]

[0269] The method for producing an organic compound according to the second embodiment of the present invention comprises synthesizing an organic compound from a starting compound using the catalytic reaction method according to the first embodiment. That is, the method for producing an organic compound according to the second embodiment of the present invention comprises synthesizing an organic compound from the starting compound by reacting the starting compound using a catalyst in the presence of a solvent. The solvent comprises an organic solvent, an aqueous solvent, and an antioxidant. The reaction of the starting compound is carried out in a two-phase system in which the organic solvent and the aqueous solvent are separated.

[0270] By making the solvent contain an antioxidant, it is possible to suppress oxidation of the catalyst due to oxygen contained in the system. Therefore, it is possible to suppress a decrease in catalytic efficiency. In addition, the catalyst can be reused thereby, which is economically advantageous.

[0271] The organic phase may contain a catalyst and the aqueous phase may contain a starting compound. The organic phase may contain a catalyst and the aqueous phase may contain a synthesized organic compound. Thus, the catalyst can be easily separated, so that the catalyst can be easily reused and repeated reactions can be performed. In addition, in the reaction of the two-phase system, there is also the advantage of being able to easily produce an aqueous phase with a high concentration of the synthesized organic compound. The organic phase may contain an antioxidant. The organic phase may contain a catalyst and an antioxidant, and the aqueous phase may contain a starting compound.

[0272] The above reaction is a hydrogenation reaction of the above starting compound using hydrogen, and the above organic compound may be a hydride of the above starting compound.

[0273] The starting compound is at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate, and the organic compound may be formate. That is, the reaction is a hydrogenation reaction based on hydrogen of at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate, and the organic compound may be formate.

[0274] The antioxidant is, for example, the antioxidant described above as the antioxidant used in the catalytic reaction method according to the first embodiment. The antioxidant may include at least one selected from the group consisting of a phosphorus antioxidant, an amine antioxidant, a phenolic antioxidant, and a sulfur antioxidant. The antioxidant preferably includes at least one selected from the group consisting of a phosphorus antioxidant, an amine antioxidant, and a phenolic antioxidant, and more preferably includes a phosphorus antioxidant. The antioxidant may be a phosphorus antioxidant.

[0275] From the viewpoint of fully exerting the function of the antioxidant, the amount of the antioxidant used is preferably 1 mmol or more relative to 1 L of the solvent. From the viewpoint of suppressing the cost of the antioxidant, the amount of the antioxidant used is preferably 100 mmol or less relative to 1 L of the solvent. The antioxidant can be used alone or in combination of two or more. The antioxidant can be added in full when preparing the reaction solution, or it can be added to the reaction solution in multiple portions during the reaction.

[0276] The amount of the antioxidant used is preferably 1 equivalent or more and 10000 equivalent or less relative to 1 equivalent of the catalyst, more preferably 10 equivalents or more and 10000 equivalents or less, further preferably 10 equivalents or more and 1000 equivalents or less, and particularly preferably 100 equivalents or more and 1000 equivalents or less.

[0277] The catalyst is, for example, the compound described above as a catalyst used in the catalytic reaction method involved in the first embodiment. That is, the catalyst is, for example, at least one selected from the group consisting of metal complexes represented by the above-mentioned general formulas (1A) to (4A), their tautomers, stereoisomers, and their salts. The preferred range is also the same as that of the first embodiment. In the general formulas (1A) to (4A), M is preferably ruthenium.

[0278] The amount of the catalyst (preferably a ruthenium complex) used is not particularly limited. From the viewpoint of fully presenting the function of the catalyst, the amount of the catalyst used is preferably 0.1 μmol or more, more preferably 0.5 μmol or more, and further preferably 1 μmol or more relative to 1L of the solvent. In addition, from the viewpoint of cost, it is preferably 1 mol or less, more preferably 10 mmol or less, and further preferably 1 mmol or less relative to 1L of the solvent. In addition, from the viewpoint of suppressing the reduction in catalytic efficiency, it can be 100 μmol or less, or 10 μmol or less relative to 1L of the solvent. It should be noted that when using more than two catalysts, their total usage can be within the above range.

[0279] The manufacture method that the second embodiment of the present invention relates to needs to react in two-phase system, therefore can use the phase-transfer catalyst that makes the movement of interphase material smoothly.As phase-transfer catalyst, for example, can use the material recorded in the first embodiment.For example, in the reaction of at least one of hydrogen and the group selected from free carbonic acid gas, bicarbonate and carbonate composition, preferably also use quaternary ammonium salt as phase-transfer catalyst.As quaternary ammonium salt, can use the material recorded in the first embodiment, preferably methyl trioctyl ammonium chloride.

[0280] With regard to the usage amount of phase-transfer catalyst, as long as organic compound (for example, formate) can be manufactured, it is not particularly limited. For example, in order to play the role of efficiently assisting the movement of carbonate or bicarbonate, relative to the solvent 1L of organic phase and aqueous phase, the usage amount of phase-transfer catalyst is preferably more than 0.1mmol, more preferably more than 0.5mmol, and more preferably more than 1mmol. In addition, from the viewpoint of cost, relative to the solvent 1L of organic phase and aqueous phase, it is preferably less than 1mol, more preferably less than 500mmol, and more preferably less than 100mmol. It should be noted that, when using more than two phase-transfer catalysts, their total usage amount is within the above range.

[0281] (Solvent)

[0282] The solvent is not particularly limited as long as it can form a two-phase system in which an organic solvent and an aqueous solvent exist separately, but it is preferred that the solvent contains a uniform solvent that dissolves the catalyst.

[0283] As the aqueous solvent, for example, the solvents described in the first embodiment can be used. From the viewpoint of low environmental load, the aqueous solvent is preferably water.

[0284] As the organic solvent, for example, the organic solvent described in the first embodiment can be used. From the viewpoint of separation from the aqueous solvent, it is preferred that toluene or dioxane be contained, and it is more preferred that toluene be contained. An example of the organic solvent is toluene.

[0285] (Reaction Conditions)

[0286] The reaction conditions in the catalytic reaction method according to the embodiment of the present invention are not particularly limited, and the reaction conditions may be appropriately changed during the reaction. The form of the reaction container used in the reaction is not particularly limited.

[0287] The reaction temperature is not particularly limited, but is preferably 30°C or higher, more preferably 40°C or higher, and further preferably 50°C or higher in order to efficiently proceed the reaction. From the viewpoint of energy efficiency, it is preferably 200°C or lower, more preferably 150°C or lower, and further preferably 100°C or lower.

[0288] The reaction temperature can be adjusted by heating or cooling, preferably by heating. For example, in the reaction of hydrogen and carbon dioxide, the temperature can be increased by heating after introducing hydrogen and carbon dioxide into the reaction vessel, or carbon dioxide can be introduced into the reaction vessel and hydrogen can be introduced after the temperature is increased.

[0289] The reaction time is not particularly limited, for example, from the viewpoint of fully ensuring the amount of organic compound generated and suppressing the reduction of catalytic efficiency, it is more than 0.5 hour, and can be more than 1 hour, more than 2 hours, more than 6 hours, more than 12 hours, more than 24 hours, more than 36 hours, more than 48 hours, and more than 60 hours. The upper limit of the reaction time is not particularly limited, for example, less than 500 hours, less than 400 hours, less than 300 hours, less than 200 hours, less than 100 hours, and less than 80 hours.

[0290] The manufacturing method involved in the second embodiment is suitable for suppressing the degradation of catalytic efficiency. The suppression of catalytic efficiency degradation can be evaluated, for example, by the change in the catalyst turnover number (TON) when the reaction of the starting compound is repeatedly carried out using the catalyst. TON is calculated by the mathematical formula: (amount of the organic compound generated) / (amount of the catalyst used in the reaction).

[0291] For example, the ratio of the TON of the catalyst in the second reaction (TON(2)) to the TON of the catalyst in the first reaction (TON(1)) is 0.7 or more, preferably 0.8 or more, more preferably 0.9 or more, and further preferably 1.0 or more. The upper limit value is not limited, for example, it is 1.2 or less. For example, the ratio of the TON of the catalyst in the third reaction (TON(3)) to TON(1) is 0.4 or more, preferably 0.7 or more, more preferably 0.8 or more, and further preferably 1.0 or more. The upper limit value is not limited, for example, it is 1.2 or less. The ratio of the TON of the catalyst in the nth reaction to the TON of the catalyst in the first reaction is calculated by the mathematical formula: TON(n) / TON(1).

[0292] As for the manufacturing method involved in the second embodiment, in the reaction of the starting compound, it is preferred to have a sufficient yield in practical terms. For example, the yield of the first reaction is 10% or more, preferably 30% or more, and more preferably 50% or more. The yield of the second reaction when the reaction of the starting compound is repeated using a catalyst is, for example, 10% or more, preferably 30% or more, and more preferably 50% or more. The yield of the third reaction is, for example, 10% or more, preferably 30% or more, and more preferably 50% or more. The upper limit of the yield is not particularly limited, for example, 99% or less.

[0293] It should be noted that the method for producing an organic compound of the present invention is not limited to the above-mentioned embodiments. Depending on the circumstances, the reaction in the method for producing an organic compound of the present invention is not limited to a two-phase system. That is, the present invention provides a method for producing an organic compound, which comprises reacting a starting compound using a catalyst in the presence of a solvent to synthesize an organic compound from the starting compound, wherein the solvent comprises an antioxidant. The solvent may, for example, comprise an organic solvent.

[0294] The method for producing the organic compound of the present invention may be a batch method or a continuous method. The continuous method uses, for example, a continuous stirred tank reactor (CSTR) or a plug flow reactor (PFR) to react the starting compounds.

[0295] Hereinafter, a case where the organic compound is a formate in the method for producing an organic compound according to the second embodiment of the present invention, that is, a case where the method for producing a formate is described in detail.

[0296] (Method for producing formate)

[0297] The method for producing formate, for example, includes the following steps: in the presence of a solvent to which an antioxidant is added, a catalyst is used to react hydrogen with at least one selected from the group consisting of carbon dioxide, bicarbonate and carbonate, and formate is generated in the reaction solution. In this specification, this step is sometimes referred to as the first step. In the first step, as described above, the solvent contains an antioxidant. Thus, the catalyst can be inhibited from being oxidized by oxygen contained in the system. By inhibiting the oxidation of the catalyst, the catalytic efficiency can be inhibited from being reduced. In addition, it is possible to reuse the catalyst without deteriorating it. In addition, in the first step, the reaction of hydrogen with at least one selected from the group consisting of carbon dioxide, bicarbonate and carbonate is carried out in a two-phase system in which an organic solvent and an aqueous solvent are separated as described above. In this reaction, the catalyst and the antioxidant are, for example, dissolved in the organic phase. The formate generated by the reaction is dissolved in the aqueous phase. Thus, the formate generation reaction can be inhibited from stopping due to equilibrium, and formate can be generated at a high yield. In addition, the aqueous phase and the organic phase can be separated by a simple method, so there is a tendency for the expensive metal catalyst to be able to be reused without losing its catalytic activity. By reusing the catalyst, high productivity can be achieved.

[0298] Through the first step, hydrogen and carbon dioxide can be stored in the form of formate (e.g., alkali metal formate). Formate has a high hydrogen storage density and is safe, and is stable as a chemical substance, so it can be easily handled, and has the advantage of being able to store hydrogen and carbon dioxide for a long time. Formate has a high solubility in an aqueous solvent and can be separated as a high-concentration formate aqueous solution. The formate aqueous solution can be supplied to the formic acid production process described later after adjusting the concentration of the formate as needed.

[0299] The first step can be carried out as follows, for example. First, a reaction vessel equipped with a stirring device is prepared, and a solvent is introduced into the reaction vessel. A phase transfer catalyst can be further added as needed. A catalyst is added to the reaction vessel, dissolved in the solvent, and a catalyst solution is prepared. An antioxidant is added to the catalyst solution in the reaction vessel. Then, hydrogen and at least one selected from the group consisting of carbon dioxide, bicarbonate and carbonate are introduced into the reaction vessel to react. The order of adding the catalyst to the reaction vessel and the antioxidant to the reaction vessel is not particularly limited. The antioxidant can be added in full when preparing the reaction solution, or it can be added to the reaction solution in multiple portions during the reaction.

[0300] The reaction conditions in the method for producing formate (reaction conditions in the first step) are not particularly limited, and the reaction conditions may be appropriately changed during the reaction, but are preferably not changed. The form of the reaction vessel used in the reaction is not particularly limited.

[0301] In the first step, for example, the reaction solution is stirred. The stirring conditions of the reaction solution are not particularly limited, but the stirring power is preferably 0.2 kW / m 3 More preferably 0.5 kW / m 3 The greater the stirring power, the more the dispersibility of the gas in the aqueous phase and the organic phase tends to be improved. If the reaction solution is stirred, the gas (for example, hydrogen of the gas) is drawn into the reaction solution from the upper liquid surface of the reaction solution, thereby filling the aqueous phase and the organic phase with gas. However, the method of filling the aqueous phase and the organic phase with gas is not limited to the above method, and a bubbler can be used.

[0302] The shape of the stirring blade utilized in the stirring of the reaction solution is not particularly limited. As the stirring blade, for example, an anchor blade, a turbine blade, a paddle blade, etc. and stirring blades collectively referred to as large blades, such as FULLZONE (registered trademark) blade (Kobelco Eco-solutions Co., Ltd.), MAXBLEND (registered trademark) blade (Sumitomo Heavy Industries, Ltd.) can be used.

[0303] In the method for producing formate, there are mentioned the reaction of hydrogen and carbon dioxide, the reaction of hydrogen and bicarbonate, and the reaction of hydrogen and carbonate. In the reaction of hydrogen and carbon dioxide, for example, the reaction of carbon dioxide to form carbonate and the reaction of carbonate and hydrogen to form formate are carried out simultaneously.

[0304] There is no particular restriction on the method and order of introduction of hydrogen and at least one selected from the group consisting of carbon dioxide, bicarbonate and carbonate into the reaction vessel. For example, in the reaction of hydrogen and carbon dioxide, it is preferred to simultaneously introduce hydrogen and carbon dioxide. Hydrogen and carbon dioxide can be introduced separately or as a mixed gas. In addition, with respect to the introduction of hydrogen and carbon dioxide, the introduction of one or both can be carried out continuously or intermittently. In the reaction of hydrogen and bicarbonate and the reaction of hydrogen and carbonate, it is preferred to introduce hydrogen after bicarbonate or carbonate is introduced into the reaction vessel. With respect to the introduction of hydrogen and bicarbonate or carbonate, the introduction of one or both can be carried out continuously or intermittently.

[0305] The reaction temperature in the reaction of hydrogen, carbon dioxide, bicarbonate or carbonate is not particularly limited. In order to make the reaction proceed efficiently, it is preferably above 30°C, more preferably above 40°C, and further preferably above 50°C. In addition, from the viewpoint of energy efficiency, it is preferably below 200°C, more preferably below 150°C, and further preferably below 100°C. The adjustment of the reaction temperature can be carried out by heating or cooling, preferably based on heating. In addition, in the reaction of hydrogen and carbon dioxide, for example, the temperature can be increased by heating after hydrogen and carbon dioxide are introduced into the reaction vessel, carbon dioxide can also be introduced into the reaction vessel, and hydrogen is introduced after the temperature is increased. In the reaction of hydrogen and bicarbonate or carbonate, for example, it is preferred to introduce hydrogen after (generating) bicarbonate or carbonate into the reaction vessel, and the temperature is increased.

[0306] The reaction pressure (pressure of the gas in the reaction vessel) of hydrogen and at least one of the reaction selected from the group consisting of carbon dioxide, bicarbonate, and carbonate is not particularly limited, and from the viewpoint of improving the TON of the metal catalyst, for example, more than 0.1MPa, more than 0.2MPa, more than 0.5MPa, more than 1MPa, more than 4MPa, more than 4.5MPa, and more than 5MPa. The upper limit of the reaction pressure is not particularly limited, for example, 50MPa, 20MPa, or 10MPa.

[0307] In order to produce formate with high yield and excellent productivity, the concentration of the formate produced by the first step (the concentration of the formate in the aqueous phase) is preferably 1 mol / L or more, more preferably 2.5 mol / L or more, and even more preferably 5 mol / L or more. In order to simplify the production process by producing the formate in a dissolved state, the concentration is preferably 30 mol / L or less, more preferably 25 mol / L or less, and even more preferably 20 mol / L or less.

[0308] (Carbon dioxide and hydrogen)

[0309] As hydrogen used in the second embodiment, any of gaseous hydrogen from a gas cylinder and liquid hydrogen can be used. As a hydrogen supply source, for example, hydrogen generated in a steelmaking process, hydrogen generated in a soda ash manufacturing process, etc. can be used. In addition, hydrogen generated by the electrolysis of water can also be used.

[0310] The carbon dioxide used in this embodiment can be pure carbon dioxide gas, or it can be mixed with other components other than carbon dioxide. The mixed gas with other components can be prepared by respectively introducing carbon dioxide gas and other gases, or it can be prepared in advance before introduction. As components other than carbon dioxide, other arbitrary components contained in inert gases such as nitrogen and argon, water vapor, exhaust gas, etc. can be cited. As carbon dioxide, gaseous carbon dioxide from a gas cylinder, liquid carbon dioxide, supercritical carbon dioxide, dry ice, etc. can be used.

[0311] Hydrogen and carbon dioxide can be introduced into the reaction system separately or as a mixed gas. The ratio of hydrogen to carbon dioxide can be the same on a molar basis, preferably with excess hydrogen.

[0312] When using gaseous hydrogen from a gas cylinder as hydrogen, from the viewpoint of sufficiently ensuring reactivity, the pressure is, for example, 0.1 MPa or more, 0.2 MPa or more, 0.5 MPa or more, 1 MPa or more, 4 MPa or more, 4.5 MPa or more, and 5 MPa or more. In addition, since the equipment is likely to become larger, it is preferably 50 MPa or less, more preferably 20 MPa or less, and further preferably 10 MPa or less.

[0313] From the viewpoint of fully ensuring reactivity, the pressure of carbon dioxide is preferably 0.1 MPa or more, more preferably 0.2 MPa or more, and further preferably 0.5 MPa or more. In addition, because the equipment is easy to become larger, it is preferably 50 MPa or less, more preferably 20 MPa or less, and further preferably 10 MPa or less.

[0314] Hydrogen and carbon dioxide gas may be bubbled (blown) into the catalyst solution. In addition, after the introduction of the gas containing hydrogen and carbon dioxide, the catalyst solution and hydrogen and carbon dioxide gas may be stirred by stirring with a stirring device, rotating the reaction container, etc.

[0315] There is no particular restriction on the method for introducing the carbon dioxide, hydrogen, metal catalyst, solvent, etc. used in the reaction into the reaction vessel, and all raw materials can be introduced at once, a part or all of the raw materials can be introduced in stages, or a part or all of the raw materials can be introduced continuously. In addition, the introduction method combining these methods can also be used.

[0316] (Bicarbonate and Carbonate)

[0317] As the bicarbonate and carbonate used in the present embodiment, for example, carbonate or bicarbonate of alkali metal or alkaline earth metal can be mentioned. As the bicarbonate, for example, sodium bicarbonate, potassium bicarbonate, etc. can be mentioned. From the viewpoint of high solubility in water, potassium bicarbonate is preferred. That is, in the present embodiment, the starting compound preferably contains potassium bicarbonate as the bicarbonate. As the carbonate, for example, sodium carbonate, potassium carbonate, sodium potassium carbonate, sodium sesquicarbonate, etc. can be mentioned.

[0318] Bicarbonate and carbonate can be produced by the reaction of carbon dioxide and alkali. For example, bicarbonate or carbonate can be produced by introducing carbon dioxide into an alkaline solution.

[0319] As the solvent of the alkaline solution in the generation of bicarbonate or carbonate, there is no particular restriction, and water, methanol, ethanol, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, and their mixed solvents, etc. can be cited, preferably including water, more preferably water. As the alkali used in the alkaline solution, as long as it can react with carbon dioxide to generate bicarbonate or carbonate, there is no particular restriction, preferably hydroxide. For example, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, potassium hydroxide, sodium hydroxide, diazabicycloundecene, triethylamine, etc. can be cited. Among the above, it is preferably a hydroxide, more preferably potassium hydroxide, sodium hydroxide, and further preferably potassium hydroxide.

[0320] As for the content of the alkali in the alkaline solution, as long as bicarbonate and carbonate can be produced, there is no particular limitation. From the viewpoint of ensuring the production of formate, the content of the alkali is preferably more than 0.1 mol, more preferably more than 0.5 mol, and more preferably more than 1 mol relative to 1L of the aqueous phase solvent. In addition, from the viewpoint of reaction efficiency, it is preferably less than 30 mol, more preferably less than 20 mol, and more preferably less than 15 mol. However, when the solubility exceeds the aqueous phase, the solution is suspended.

[0321] From the viewpoint of generating carbonate by carbon dioxide, the ratio of the carbon dioxide used in the reaction of carbon dioxide and alkali to the usage amount of alkali is preferably more than 0.1 in molar ratio, more preferably more than 0.5, and more preferably more than 1.0. In addition, from the viewpoint of the utilization efficiency of carbon dioxide, it is preferably less than 8.0, more preferably less than 5.0, and more preferably less than 3.0. It should be noted that the ratio of the usage amount of carbon dioxide and alkali is the molar amount (mol) / molar amount (mol) of CO2 / alkali as long as it is the ratio of the molar amount of carbon dioxide and alkali introduced into the reaction vessel. By making the ratio of the usage amount of carbon dioxide and alkali within the above-mentioned range, it is possible to suppress the excessive input of carbon dioxide into the reaction vessel, suppress unreacted carbon dioxide to a minimum, and the conversion efficiency of final formic acid is easily improved. In addition, carbon dioxide can be hydrogenated via bicarbonate or carbonate in the same container by the reaction of carbon dioxide and alkali to generate formate. Unreacted carbon dioxide can be recovered from the reaction vessel and reused.

[0322] The method and the order of importing carbon dioxide and alkali in the reaction vessel are not particularly limited, preferably carbon dioxide is imported after the alkali is imported in the reaction vessel. In addition, with regard to the importing of carbon dioxide and alkali, the importing of one or both sides can be carried out continuously, or can be carried out intermittently.

[0323] The reaction temperature of the reaction of generating bicarbonate or carbonate by the reaction of carbon dioxide and alkali is not particularly limited, but is preferably 0° C. or higher, more preferably 10° C. or higher, and further preferably 20° C. or higher, in order to dissolve carbon dioxide in the aqueous phase. In addition, it is preferably 100° C. or lower, more preferably 80° C. or lower, and further preferably 40° C. or lower.

[0324] The reaction time of the reaction of generating bicarbonate or carbonate by the reaction of carbonic acid gas and alkali is not particularly limited, for example, from the viewpoint of fully ensuring the generation amount of bicarbonate or carbonate, preferably more than 0.5 hour, more preferably more than 1 hour, further preferably more than 2 hours. In addition, from the viewpoint of cost, preferably less than 24 hours, more preferably less than 12 hours, further preferably less than 6 hours.

[0325] The bicarbonate and carbonate generated by the reaction of carbon dioxide and alkali can be used in the reaction of hydrogen and bicarbonate or carbonate in the method for producing organic compounds according to the second embodiment of the present invention. In addition, bicarbonate or carbonate can be generated by reacting carbon dioxide and alkali in a reaction vessel, thereby introducing bicarbonate or carbonate into the reaction vessel.

[0326] [Method for producing formic acid]

[0327] The method for producing formic acid of the present embodiment includes: a step of producing a formate salt by the method for producing a formate salt described above; and a step of protonating at least a portion of the formate salt to produce formic acid. In this specification, the step of protonating at least a portion of the formate salt to produce formic acid is sometimes referred to as a second step. The method for producing formic acid of the present embodiment includes, for example, the first step and the second step described above.

[0328] In the first step, the generated formate is dissolved into the aqueous phase, so by separating the aqueous phase, an aqueous solution of the formate can be obtained. It is preferred to separate the aqueous phase in the first step, and treat the obtained aqueous solution in the second step, for example, using an electrodialysis device to generate formic acid. It should be noted that the aqueous phase to be separated is the aqueous phase after the first step.

[0329] In the second step, the aqueous solution of formate obtained in the first step can be used directly, or the concentration of formate in the aqueous solution can be adjusted by concentration or dilution as needed. As a method for diluting the aqueous solution of formate, a method of diluting by adding pure water can be cited. As a method for concentrating the aqueous solution of formate, a method of distilling water from the aqueous solution, a method of concentrating the aqueous solution using a separation membrane unit equipped with a reverse osmosis membrane, etc. can be cited. In the case of a treatment using an electrodialysis device, formate loss sometimes occurs due to a concentration diffusion phenomenon in the aqueous solution of a high concentration of formate. From the viewpoint of suppressing this, it is preferred to separate the aqueous phase in the first step, and use the aqueous solution after adjusting the concentration of formate by dilution in the second step. By preparing an aqueous solution of formate with a high concentration in the first step and using it in the second step after adjusting the concentration of the aqueous solution by dilution, formic acid can be produced with a higher yield and better productivity.

[0330] The degree of adjustment (preferably dilution) of the concentration of the aqueous solution of formate obtained in the first step is not particularly limited. The concentration of formate in the aqueous solution after the concentration adjustment is preferably a concentration suitable for electrodialysis, preferably 2.5 mol / L or more, more preferably 3 mol / L or more, further preferably 4.75 mol / L or more, and 5 mol / L or more. In addition, in the case of treatment using an electrodialysis device, from the viewpoint of suppressing the loss of formate caused by the concentration diffusion phenomenon, the concentration of formate is preferably 20 mol / L or less, more preferably 15 mol / L or less, and further preferably 10 mol / L or less.

[0331] Pure water can be used for dilution. In addition, the water generated by the second step can be used for dilution. When the water generated by the second step is reused for dilution, there are advantages such as being able to reduce the cost of wastewater treatment, environmental load, etc., so it is preferred.

[0332] In the manufacture method of formic acid related to the present embodiment, after adding acid to the aqueous solution of the formate obtained by the first operation and decarbonating, the aqueous solution can be used in the second operation. That is, the aqueous phase in the first operation can be separated, acid is added, and decarbonating is used in the second operation. In the aqueous solution of the formate obtained by the first operation, sometimes unreacted carbonate and bicarbonate generated by side reactions are contained. If the solution containing carbonate and bicarbonate is subjected to electrodialysis, carbon dioxide is sometimes produced and the dialysis efficiency is reduced. Therefore, by adding acid to the aqueous solution of the formate obtained by the first operation, electrodialysis is carried out after decarbonating, so that formic acid can be manufactured with higher yield and more excellent productivity.

[0333] Examples of the acid used in the decarbonation treatment include formic acid, citric acid, acetic acid, malic acid, lactic acid, succinic acid, tartaric acid, butyric acid, fumaric acid, propionic acid, hydrochloric acid, nitric acid and sulfuric acid, and formic acid is preferably used.

[0334] From the viewpoint of suppressing the amount of carbonic acid generated during electrodialysis treatment, the amount of acid used is preferably 50% or more, and more preferably 80% or more relative to the amount of carbonic acid present in the solution. In addition, by making the pH of the formate solution during electrodialysis treatment near neutral in advance, the degradation of the electrodialysis device can be suppressed, so the amount of acid used is preferably 150% or less, and more preferably 120% or less relative to the amount of carbonic acid present in the solution.

[0335] In the present embodiment, from the viewpoint of improving the purity of the aqueous solution of formic acid to be recovered, the ratio of the formate protonated by the second step is preferably 10% or more, more preferably 20% or more, and even more preferably 30% or more, relative to the initial molar amount of formate in the aqueous solution of formate.

[0336] Examples of the electrodialysis apparatus used in the second step include a two-chamber electrodialysis apparatus using a bipolar membrane and an anion exchange membrane or a cation exchange membrane; and a three-chamber electrodialysis apparatus using a bipolar membrane, an anion exchange membrane, and a cation exchange membrane.

[0337] Figure 1 This is a schematic diagram showing an example of a three-chamber electrodialysis device. Figure 1 The electrodialysis device shown is respectively equipped with a plurality of bipolar membranes, anion exchange membranes and cation exchange membranes. By arranging these bipolar membranes, anion exchange membranes and cation exchange membranes between the anode and the cathode, an alkali tank, a sample tank (salt tank) and an acid tank are formed. By circulated supply of an aqueous solution of formate to the sample tank while energizing the electrodialysis device, the formate can be converted into formic acid, the formic acid can be recovered from the acid tank, the water can be recovered from the sample tank, and the hydroxide can be recovered from the alkali tank.

[0338] The two-chamber electrodialysis device, for example, is provided with a plurality of bipolar membranes and cation exchange membranes. By alternately arranging these bipolar membranes and cation exchange membranes between the anode and the cathode, a salt chamber is formed between each bipolar membrane and the cation exchange membrane arranged on the cathode side thereof, and an alkali tank is formed between each bipolar membrane and the cation exchange membrane arranged on the anode side thereof. By circulating an aqueous solution of formate to the salt chamber while energizing the electrodialysis device, hydroxide is generated in the alkali tank, and the formate circulated to the salt chamber is converted into formic acid.

[0339] In the second step, by using an electrodialysis apparatus, the formate can be protonated by a simple method to obtain a formic acid solution.

[0340] [Formic acid production system]

[0341] like Figure 2 As shown, the formic acid production system 100 of the present embodiment includes, for example, a formate production device 10 and an electrodialysis device 30. The production system 100 may further include a dilution device 20 and a storage unit 40 for dilution water, and may further include a carbon dioxide cylinder 60 for introducing carbon dioxide into the production device 10, and a hydrogen cylinder 50 for introducing hydrogen into the production device 10. The concentration and pressure of carbon dioxide and hydrogen can be adjusted by valves 1 and 2 provided on the pipes L1 and L2.

[0342] The formate produced in the production device 10 is supplied to the electrodialysis device 30 as an aqueous solution of formate by separating the aqueous phase. Figure 2 As shown, the aqueous solution of formate can be sent to the diluting device 20 in advance through the flow path L3, and the concentration of the formate in the aqueous solution can be adjusted by dilution in the diluting device 20.

[0343] For the aqueous solution whose concentration of formate is adjusted by the diluting device 20, at least a part of the formate is protonated by the electrodialysis device 30. Thus, formic acid and water are generated from the formate. The generated formic acid can be taken out through the flow path L5. In addition, the generated water can be sent to the storage unit 40 through the flow path L7.

[0344] A portion of the formic acid generated by the electrodialysis device 30 can be sent to the storage unit 40 through the flow path L6. The storage unit 40 may further include a water supply unit 70 and a formic acid supply unit 80. The aqueous solution of formic acid prepared by the storage unit 40 can be supplied to the diluting device 20 through the flow path L9, thereby decarbonating the aqueous solution of formate. Each flow path of the manufacturing system 100 may be equipped with a valve for adjusting the pressure and the supply amount.

[0345] According to the production system 100 of the present embodiment, formic acid can be produced with a high yield and excellent productivity.

[0346] [Catalyst composition]

[0347] The catalyst composition according to the third embodiment of the present invention includes a catalyst and an antioxidant, and satisfies at least one selected from the group consisting of the following (A) to (D).

[0348] (A) further comprises a phase transfer catalyst.

[0349] (B) The catalyst is a compound represented by the general formula (1A) wherein Y is an atomic group having a phosphorus atom and a substituent, and the substituent is an alkyl group.

[0350] (C) The content of the antioxidant is 10 equivalents or more per 1 equivalent of the catalyst.

[0351] (D) The antioxidant contains a phosphorus-based antioxidant.

[0352] [Chemical formula 18]

[0353]

[0354] (In the general formula (1A),

[0355] X represents an atomic group containing a typical element of Groups 13 to 15 that can coordinate with M,

[0356] Q each independently represents a bridge structure including a typical element of Groups 14 to 16 that connects Y and X,

[0357] Y each independently represents an atomic group containing a typical element of Groups 14 to 16 that can coordinate with M, M represents a metal atom,

[0358] Z represents an anionic ligand,

[0359] n represents 0 to 3,

[0360] When there are multiple L, each L independently represents a neutral or anionic ligand.

[0361] By making the catalyst composition contain an antioxidant, it is possible to suppress a decrease in catalytic efficiency in the catalytic reaction.

[0362] The catalyst composition of the present embodiment can satisfy the above (A). That is, the present invention provides a catalyst composition comprising a catalyst, an antioxidant and a phase transfer catalyst. The phase transfer catalyst is, for example, a compound described above as a phase transfer catalyst used in the catalytic reaction method involved in the first embodiment, and the preferred range is also the same as that of the first embodiment. Such a catalyst composition is useful for, for example, a reaction of a two-phase system, and can further suppress the reduction of catalytic efficiency in the catalytic reaction.

[0363] The catalyst is, for example, the compound described above as the catalyst used in the catalytic reaction method according to the first embodiment, and the preferred range is also the same as that of the first embodiment.

[0364] The catalyst composition of this embodiment can satisfy the above (B). That is, the present invention provides a catalyst composition from another aspect, which comprises a catalyst and an antioxidant, and the catalyst is a compound in which Y is an atomic group having a phosphorus atom and a substituent in the general formula (1A), and the substituent is an alkyl group. The catalyst can be a compound in which Y1 is a phosphorus atom and R is an alkyl group in the general formulas (2A) and (3A) described above for the first embodiment, or a compound in which R1 is an alkyl group in the general formula (4A).

[0365] The catalyst composition of this embodiment can satisfy the above (C). That is, the present invention provides a catalyst composition from another aspect, which comprises a catalyst and an antioxidant, and the content of the antioxidant is 10 equivalents or more relative to 1 equivalent of the catalyst. The content of the antioxidant is, for example, 10 equivalents or more and 10,000 equivalents or less, preferably 100 equivalents or more and 10,000 equivalents or less, and more preferably 100 equivalents or more and 1,000 equivalents or less relative to 1 equivalent of the catalyst.

[0366] The antioxidant is, for example, the substance described above as the antioxidant used in the catalytic reaction method according to the first embodiment. The antioxidant preferably includes at least one selected from the group consisting of phosphorus antioxidants, amine antioxidants, and phenolic antioxidants, and more preferably includes a phosphorus antioxidant.

[0367] The catalyst composition of the present embodiment may satisfy at least two selected from the group consisting of (A) to (D). The catalyst composition of the present embodiment satisfies, for example, (A) and at least one selected from the group consisting of (B) to (D).

[0368] The catalyst composition of the present embodiment is, for example, a catalyst composition for generating an organic compound, preferably a catalyst composition for generating a formate. In addition, the catalyst composition of the present embodiment is, for example, a catalyst composition for a hydrogenation reaction. The starting compound is, for example, at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate.

[0369] The starting compound can be contacted with the catalyst composition of the present embodiment to generate the organic compound. The contact of the catalyst composition with the starting compound is carried out, for example, by mixing the catalyst composition with a solution containing the starting compound; mixing the catalyst composition and the starting compound with a solvent; or mixing a solution containing the starting compound with a solution containing the catalyst composition; etc.

[0370] The catalyst composition of the present embodiment can be used, for example, in the catalytic reaction method according to the first embodiment of the present invention or the method for producing an organic compound according to the second embodiment.

[0371] The catalyst composition of the present embodiment may further include a solvent. The solvent may be at least one selected from the group consisting of an organic solvent and an aqueous solvent. In a preferred embodiment of the present invention, the catalyst composition includes only an organic solvent as a solvent. In another preferred embodiment of the present invention, the catalyst composition includes an organic solvent and an aqueous solvent. As an organic solvent, for example, the organic solvent described in the first embodiment can be used. The organic solvent is preferably toluene or dioxane, more preferably toluene. As an aqueous solvent, for example, the aqueous solvent described in the first embodiment can be used.

[0372] Example

[0373] The present invention is described in more detail below by way of examples and comparative examples, but the present invention is not limited thereto. In the examples, formate was synthesized by hydrogenation of the above-mentioned starting compounds with hydrogen using a catalyst, and the effect of suppressing the decrease in catalytic efficiency was evaluated.

[0374] [Synthesis of Catalyst]

[0375] (Catalyst 1)

[0376] Catalyst 1 was synthesized by the following operation. Under an inert atmosphere, 40 mg (0.1 mmol) of the following ligand A was added to a suspension of 95.3 mg (0.1 mmol) of [RuHCl(PPh3)3(CO)] in THF (tetrahydrofuran) (5 ml), the mixture was stirred, and heated at 65°C for 3 hours to react. Then, it was cooled to room temperature (25°C). The obtained yellow solution was filtered, and the filtrate was evaporated to dryness under vacuum. The obtained yellow residual oil was dissolved in a very small amount of THF (1 mL), and hexane (10 mL) was slowly added to precipitate a yellow solid, which was filtered. The filtrate was dried under vacuum to obtain the following catalyst 1 (55 mg, yield 97%) as yellow crystals. In the catalyst 1 and ligand A shown below, tBu represents tert-butyl.

[0377] [Chemical formula 19]

[0378]

[0379] 31 P{ 1 H}(C6D6):90.8(s), 1H (C6D6): -14.54 (t, 1H, J = 20.0Hz), 1.11 (t, 18H, J = 8.0Hz), 1.51 (t, 18H, J = 8.0Hz), 2.88 (dt, 2H, J = 16.0Hz, J=4.0Hz), 3.76 (dt, 2H, J=16.0Hz, J=4.0Hz), 6.45 (d, 2H, J=8.0Hz), 6.79 (t, 1H, J=8.0Hz). 13 C{ 1 H}NMR(C6D6): 29.8(s), 30.7(s), 35.2(t, J=9.5Hz), 37.7(t, J=6.0Hz), 37.9 (t, J=6.5Hz), 119.5 (t, J=4.5Hz), 136.4 (s), 163.4 (t, J=5.0Hz), 209.8 (s).

[0380] [Calculation of TON and yield]

[0381] In the following Examples and Comparative Examples, the TON of the catalyst and the yield of formate (potassium formate) were calculated by the following method.

[0382] First, the amount of formate contained in the aqueous phase was quantified in the following manner. 100 μL of the aqueous phase obtained after the reaction was taken out, 300 μL of dimethyl sulfoxide was added as a reference substance, and the mixture was dissolved in 500 μL of heavy water. In this way, a measurement sample was prepared. 1 H NMR measurement: From the obtained NMR spectrum, the integrated value Ia of the peak derived from potassium formate and the integrated value Ib of the peak derived from dimethyl sulfoxide were determined. The amount X (mol) of potassium formate was calculated by the following formula (1).

[0383] X=(W / M)×{Ia / (Ib / R)}×(A / B) (1)

[0384] (In formula (1), W is the weight (g) of dimethyl sulfoxide used in the quantitative determination of potassium formate,

[0385] M is the molecular weight of dimethyl sulfoxide,

[0386] R is the ratio of the number of protons in each molecule of dimethyl sulfoxide to the number of protons in each molecule of potassium formate,

[0387] Ia is the integrated value of the NMR peak derived from potassium formate,

[0388] Ib is the integrated value of the NMR peak derived from dimethyl sulfoxide,

[0389] A is the mass of the aqueous phase obtained after the reaction (g),

[0390] B is the mass (g) of the aqueous solution used in the quantitative determination of potassium formate.

[0391] Then, based on the amount X (mol) of the generated formate and the amount Y (mol) of the catalyst used in the reaction, the TON of the catalyst is calculated by the following formula (2).

[0392] TON of catalyst = X / Y (2)

[0393] Furthermore, based on the amount X (mol) of the generated formate and the total amount of carbon dioxide, bicarbonate and carbonate used in the reaction (in the following Examples and Comparative Examples, the amount of potassium bicarbonate) Z (mol), the yield (%) of formate was calculated by the following formula (3).

[0394] Yield of formate = 100 × X / Z (3)

[0395] [Example 1]

[0396] Under nitrogen atmosphere, 50 mL of water, 0.25 mol of potassium bicarbonate, 50 mL of toluene, 0.75 μmol of catalyst 1, 2.7 mmol of methyl trioctyl ammonium chloride, and 0.3 mmol of tris(2,4-di-tert-butylphenyl)phosphite as an antioxidant were placed in a reactor equipped with a U-shaped paddle stirring blade. Then, as the first reaction, hydrogen was added until it reached 5 MPa, the temperature was raised to 90°C, and stirred at 800 rpm for 16 hours. After stirring, it was cooled to room temperature, and the pressure was carefully released after cooling. The reactor was replaced with nitrogen.

[0397] The reaction solution was taken out from the reactor under a nitrogen atmosphere, and the organic phase and the aqueous phase were separated. The TON of the catalyst and the yield of the formate in the first reaction were calculated using the aqueous phase by the above-mentioned method.

[0398] Under nitrogen atmosphere, toluene was added to the separated organic phase and the volume was adjusted to 50 mL. Under nitrogen atmosphere, the entire amount of the organic phase (50 mL), 50 mL of water, and 0.25 mol of potassium bicarbonate were put into a reactor equipped with a U-shaped paddle stirring blade. Then, as the second reaction, hydrogen was added until 5 MPa was reached, the temperature was raised to 90 ° C, and stirred at 800 rpm for 16 hours. After stirring, it was cooled to room temperature and the pressure was carefully released after cooling. The reactor was replaced with nitrogen.

[0399] The reaction solution was taken out from the reactor under a nitrogen atmosphere, and the organic phase and the aqueous phase were separated. The TON of the catalyst and the yield of the formate in the second reaction were calculated by the above-mentioned method in the same manner as in the first reaction.

[0400] Under nitrogen atmosphere, toluene was added to the separated organic phase and the volume was adjusted to 50 mL. Under nitrogen atmosphere, the entire amount of the organic phase (50 mL), 50 mL of water, and 0.25 mol of potassium bicarbonate were put into a reactor equipped with a U-shaped paddle stirring blade. Then, as the third reaction, hydrogen was added until 5 MPa was reached, the temperature was raised to 90 ° C, and stirred at 800 rpm for 16 hours. After stirring, it was cooled to room temperature, and the pressure was carefully released after cooling. The reactor was replaced with nitrogen.

[0401] The reaction solution was taken out from the reactor under a nitrogen atmosphere, and the organic phase and the aqueous phase were separated. The TON of the catalyst and the yield of the formate in the third reaction were calculated by the above-mentioned method in the same manner as in the first and second reactions.

[0402] [Example 2]

[0403] The reaction was carried out in the same manner as in Example 1 except that the antioxidant was changed to 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane. The TON of the catalyst and the yield of the formate were calculated in the same manner as in Example 1 for each of the first to third reactions.

[0404] [Example 3]

[0405] Except that the antioxidant was changed to 2,6-di-tert-butyl-p-cresol, the reaction was carried out in the same manner as in Example 1. The TON of the catalyst and the yield of the formate in each of the first to third reactions were calculated in the same manner as in Example.

[0406] [Example 4]

[0407] The reaction was carried out in the same manner as in Example 1 except that the antioxidant was changed to 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline. The TON of the catalyst and the yield of the formate were calculated in the same manner as in Example 1 for each of the first to third reactions.

[0408] [Comparative Example 1]

[0409] Except that no antioxidant was added, the reaction was carried out in the same manner as in Example 1. In the same manner as in Example 1, the TON of the catalyst and the yield of the formate in each of the first to third reactions were calculated.

[0410] Table 1 shows the TON and yield of the catalysts in the reactions of Examples 1 to 4 and Comparative Example 1. The total TON shown in Table 1 means the ratio of the total amount of formate produced in the first to third reactions to the amount of the catalyst used.

[0411] [Table 1]

[0412]

[0413] As shown in Table 1, for Examples 1 to 4 in which the reaction is carried out in a two-phase system containing an antioxidant, compared with Comparative Example 1 which does not contain an antioxidant, even if the reaction is repeated more than 2 times, TON can be maintained. Therefore, in Examples 1 to 4, the reduction in catalytic efficiency is suppressed. As shown in Table 1, when a phosphorus antioxidant is used, it is particularly suitable for suppressing the reduction in catalytic efficiency. In addition, even if an antioxidant is added, the yield is a sufficient value in practical terms.

[0414] [Example 5]

[0415] The reaction was carried out in the same manner as in Example 1 except that the amount of the catalyst used was changed to 0.175 μmol. The TON of the catalyst and the yield of formate were calculated in the same manner as in Example 1 for each of the first to third reactions.

[0416] [Example 6]

[0417] A first reaction was carried out in the same manner as in Example 5 except that the antioxidant was changed to triphenyl phosphite, and the TON of the catalyst in the first reaction and the yield of the formate were calculated.

[0418] [Example 7]

[0419] The reaction was carried out in the same manner as in Example 6 except that the antioxidant was changed to tetraalkyl (C12-15)-4,4′-isopropylidene diphenyl diphosphite (Adekastab 1500), and the TON of the catalyst in the first reaction and the yield of the formate were calculated.

[0420] [Example 8]

[0421] The reaction was carried out in the same manner as in Example 6 except that the antioxidant was changed to triisodecyl phosphite, and the TON of the catalyst in the first reaction and the yield of the formate were calculated.

[0422] [Example 9]

[0423] The reaction was carried out in the same manner as in Example 6 except that the antioxidant was changed to 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and the TON of the first reaction catalyst and the yield of the formate were calculated.

[0424] [Comparative Example 2]

[0425] The reaction was carried out in the same manner as in Example 6 except that no antioxidant was added, and the TON of the catalyst and the yield of formate in the first reaction were calculated.

[0426] Table 2 shows the TON and yield of the catalysts in the reactions of Examples 5 to 9 and Comparative Example 2.

[0427] [Table 2]

[0428]

[0429] As shown in Table 2, Examples 5 to 9 showed high TON and yield compared to Comparative Example 2 which did not contain an antioxidant. In addition, Examples 5 to 9 showed higher TON than Examples 1 to 4, and in particular, Examples 5 and 6 showed high TON. In addition, in Example 5, even if the reaction was repeated more than 2 times, the TON was basically maintained. Therefore, in Examples 5 to 9, the TON of the catalyst can be further improved.

[0430] [Synthesis of Catalyst]

[0431] (Catalyst 2)

[0432] Catalyst 2 was synthesized by the following operation. 138 mg (0.3 mmol, 1.0 equivalent) of pentacarbonyl manganese bromide was added to a 50 mL Schlenk tube. Then, 10 mL of degassed toluene was added under an argon atmosphere. Furthermore, 300 mg (0.66 mmol, 1.3 equivalent) of the following ligand B was added. After reflux at 115°C for 18 hours, a yellow precipitate was filtered out. The filtrate was washed 3 times with hexane (10 mL) and extracted with dichloromethane. The solvent was evaporated from the extract to obtain the following catalyst 2 (300 mg, yield 92%) as a yellow powder. In the catalyst 2 and ligand B shown below, Ph represents phenyl.

[0433] [Chemical formula 20]

[0434]

[0435] (Catalyst 3)

[0436] Catalyst 3 was synthesized by the following operation. To a suspension of pentacarbonyl manganese bromide (1 mmol) in toluene (5 mL) was added bis(2-diethylphosphinoethyl)amine (1 mmol), and the mixture was stirred at 100° C. for 24 hours under an argon atmosphere to carry out the reaction. Then, the reaction mixture was cooled to room temperature and evaporated to dryness. The obtained yellow solid was washed several times with toluene. The washings were dried under vacuum to obtain the following catalyst 3 as a light yellow solid. In the catalyst 3 shown below, Et represents an ethyl group.

[0437] [Chemical formula 21]

[0438]

[0439] [Example 10]

[0440] Under an argon atmosphere, 1 mL of water, 2.0 mmol of potassium bicarbonate, 1 mL of toluene, 5.3 μmol of catalyst 2, 54 μmol of methyl trioctyl ammonium chloride, and 30 μmol of tris(2,4-di-tert-butylphenyl)phosphite as an antioxidant were added to a reactor equipped with a stirring rod. Then, hydrogen was added until it reached 5.5 MPa, the temperature was raised to 90°C, and stirred at 800 rpm for 20 hours. After stirring, it was cooled to room temperature, and the pressure was carefully released after cooling. The reaction solution was taken out from the reactor, and the organic phase was separated from the aqueous phase. Using the aqueous phase, the TON of the catalyst and the yield of formate were calculated using the above method.

[0441] [Comparative Example 3]

[0442] The reaction was carried out in the same manner as in Example 10 except that no antioxidant was added, and the TON of the catalyst in the first reaction and the yield of the formate were calculated.

[0443] [Example 11]

[0444] The reaction was carried out in the same manner as in Example 10 except that the amount of the catalyst used was changed to 12.6 μmol and toluene was changed to 1,4-dioxane, and the TON of the catalyst and the yield of the formate were calculated.

[0445] [Comparative Example 4]

[0446] The reaction was carried out in the same manner as in Example 11 except that no antioxidant was added, and the TON of the catalyst and the yield of the formate in the first reaction were calculated.

[0447] [Example 12]

[0448] The reaction was carried out in the same manner as in Example 11 except that the catalyst used was changed to 9.6 μmol of Catalyst 3, and the TON of the catalyst and the yield of the formate were calculated.

[0449] [Comparative Example 5]

[0450] The reaction was carried out in the same manner as in Example 12 except that no antioxidant was added, and the TON of the catalyst in the first reaction and the yield of the formate were calculated.

[0451] Table 3 shows the TON and yield of the catalysts in the reactions in Examples 10 to 12 and Comparative Examples 3 to 5.

[0452] [Table 3]

[0453]

[0454] As shown in Table 3, when a manganese catalyst is used, the hydrogenation reaction of the starting compound based on hydrogen also proceeds, and formate can be synthesized. As shown in Table 3, compared with Comparative Example 3 without an antioxidant, Example 10 shows a high TON and yield. Compared with Comparative Example 4 without an antioxidant, Example 11 shows a high TON and yield. Compared with Comparative Example 5 without an antioxidant, Example 12 shows a high TON and yield.

[0455] [Protonation of formate]

[0456] In the following Reference Examples 1 and 2, formate was protonated using an electrodialysis apparatus (ACILYZER-EX3B manufactured by ASTOM Corporation).

[0457] [Reference Example 1]

[0458] Into the alkali tank of the electrodialysis device, add a substance obtained by dissolving 165g of potassium hydroxide in 500mL of water. Into the salt tank, add 500mL of a 5mol / L aqueous solution of potassium formate. Into the acid tank, add 500mL of a 4.35mol / L aqueous solution of formic acid. Perform electrodialysis at a voltage of 28V for 80 minutes. After the dialysis is completed, take 100μL of the solution (acid solution) in the acid tank, dissolve it in 500μL of heavy water, add 300μL of dimethyl sulfoxide as an internal standard, and measure 1 H NMR was used to quantify the formic acid in the acid solution after the dialysis was completed.

[0459] [Reference Example 2]

[0460] Into the alkali tank of the electrodialysis device, add a substance prepared by dissolving 165g of potassium hydroxide in 500mL of water. Into the salt tank, add 500mL of an aqueous solution containing 4.75mol / L of potassium formate and 0.25mol / L of potassium bicarbonate. Into the acid tank, add 500mL of an aqueous solution of 4.81mol / L of formic acid. Perform electrodialysis at a voltage of 28V for 80 minutes. After the dialysis is completed, take 100μL of the solution (acid solution) in the acid tank, dissolve it in 500μL of heavy water, add 300μL of dimethyl sulfoxide as an internal standard, and measure 1 By using HNMR, the formic acid in the acid solution after the dialysis was quantified.

[0461] Reference Examples 1 and 2 are described in Table 4. In Table 4, the initial formate ratio is the percentage of the amount of substance X2 in the salt tank before electrodialysis relative to the total amount of formate (amount of substance X2) and the amount of substance of bicarbonate. The initial formate concentration is the molar concentration of formate in the salt tank before electrodialysis. The initial bicarbonate concentration is the molar concentration of bicarbonate in the salt tank before electrodialysis. The initial formic acid concentration is the molar concentration of formic acid in the acid tank before electrodialysis. The final formic acid concentration is the molar concentration of formic acid in the acid tank after the electrodialysis is completed. The formic acid yield is the percentage of the amount of substance (mol) of formic acid obtained by electrodialysis relative to the amount of substance (amount of substance X2) of formate used in the electrodialysis.

[0462] [Table 4]

[0463]

[0464] It is known from Table 4 that formic acid can be obtained from formate by electrodialysis. In Reference Example 2 in which the salt tank contained bicarbonate, formic acid can be obtained at a yield equivalent to that of Reference Example 1 in which the salt tank did not contain bicarbonate.

[0465] Industrial Applicability

[0466] According to the catalytic reaction method and the method for producing an organic compound of the present embodiment, for example, a target organic compound can be produced at low cost and efficiently.

Claims

1. A catalytic reaction method, which comprises reacting a starting compound using a catalyst in the presence of a solvent, The solvent includes an organic solvent, an aqueous solvent, and an antioxidant. The reaction is carried out in a two-phase system in which the organic solvent and the aqueous solvent are separated.

2. The catalytic reaction method according to claim 1, wherein: The organic phase including the organic solvent includes the catalyst, and the aqueous phase including the aqueous solvent includes the starting compound.

3. The catalytic reaction method according to claim 1, wherein: The organic phase including the organic solvent contains the antioxidant.

4. The catalytic reaction method according to claim 1, wherein: The antioxidant includes at least one selected from the group consisting of phosphorus-based antioxidants, amine-based antioxidants, and phenol-based antioxidants.

5. The catalytic reaction method according to claim 4, wherein: The antioxidant includes a phosphorus-based antioxidant.

6. The catalytic reaction method according to claim 5, wherein: The phosphorus-based antioxidant is a compound represented by the following chemical formula (1B): [Chemical formula 1] In the chemical formula (1B), R 1 , R 2 , and R 3 Each independently represents a hydrogen atom or an optional substituent.

7. The catalytic reaction method according to claim 5, wherein: The phosphorus-based antioxidant is a compound represented by the following chemical formula (1C): [Chemical formula 2] In the chemical formula (1C), R 4 , R 5 , and R 6 Each independently represents an optional substituent.

8. The catalytic reaction method according to claim 7, wherein: In the chemical formula (1C), R 4 , R 5 , and R 6 Each independently represents the following chemical formula (1D), [Chemical formula 3] In the chemical formula (1D), * represents a connecting bond; X 1 , X 2 , X 3 , X 4 , and X 5 Each independently represents a hydrogen atom or a hydrocarbon group.

9. The catalytic reaction method according to claim 1, wherein: The reaction is a hydrogenation reaction of the starting compound with hydrogen, and a hydride of the starting compound is obtained through the reaction.

10. The catalytic reaction method according to claim 9, wherein: The starting compound is at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate, and formate is obtained from the starting compound through the reaction.

11. The catalytic reaction method according to claim 1, wherein: The catalyst is at least one selected from the group consisting of a metal complex represented by the following general formula (1A), its tautomers, stereoisomers, and salts thereof, [Chemical formula 4] In the general formula (1A), X represents an atomic group containing a typical element of Groups 13 to 15 that can coordinate with M, Q each independently represents a bridge structure including a typical element of Groups 14 to 16 that connects Y and X, Y each independently represents an atomic group containing a typical element of Groups 14 to 16 that can coordinate with M, M represents a metal atom, Z represents an anionic ligand, n represents 0 to 3, When there are a plurality of L, each L independently represents a neutral or anionic ligand.

12. The catalytic reaction method according to claim 11, wherein: The metal complex represented by the general formula (1A) is a metal complex represented by the following general formula (2A), [Chemical formula 5] In the general formula (2A), X1 represents an aromatic heterocyclic ring formed together with a nitrogen atom and two carbon atoms, which may have a substituent or may be bonded to other substituents to form a ring. Q1 each independently represents CH2, NH, or O, and CH2 and NH may further have a substituent, Y1 each independently represents a phosphorus atom or a nitrogen atom, R each independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have a substituent, M represents a metal atom, Z represents an anionic ligand, n represents 0 to 3, When there are a plurality of L, each L independently represents a neutral or anionic ligand.

13. The catalytic reaction method according to claim 12, wherein: The metal complex represented by the general formula (2A) is a metal complex represented by the following general formula (3A), [Chemical formula 6] In the general formula (3A), R0 represents a hydrogen atom or an alkyl group, A each independently represents CH, CR5, or N, R5 represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxyl group, or an alkoxy group, Q1 each independently represents CH2, NH, or O, and CH2 and NH may further have a substituent, Y1 represents a phosphorus atom or a nitrogen atom, R each independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have a substituent, M represents a metal atom, Z represents an anionic ligand, n represents 0 to 3, When there are a plurality of L, each L independently represents a neutral or anionic ligand.

14. The catalytic reaction method according to claim 11, wherein: The metal atom represented by M is ruthenium.

15. The catalytic reaction method according to claim 1, wherein: The organic solvent comprises toluene.

16. A method for producing an organic compound, comprising synthesizing the organic compound from the starting compound by the catalytic reaction method according to any one of claims 1 to 15.

17. A catalyst composition comprising: catalyst; Antioxidants; and Phase transfer catalyst.

18. The catalyst composition according to claim 17, wherein The antioxidant includes at least one selected from the group consisting of a phosphorus-based antioxidant, an amine-based antioxidant, and a phenol-based antioxidant.

19. The catalyst composition according to claim 18, wherein The antioxidant includes a phosphorus-based antioxidant.

20. The catalyst composition of claim 17, wherein The catalyst is at least one selected from the group consisting of a metal complex represented by the following general formula (1A), its tautomers, stereoisomers, and salts thereof, [Chemical formula 7] In the general formula (1A), X represents an atomic group containing a typical element of Groups 13 to 15 that can coordinate with M, Q each independently represents a bridge structure including a typical element of Groups 14 to 16 that connects Y and X, Y each independently represents an atomic group containing a typical element of Groups 14 to 16 that can coordinate with M, M represents a metal atom, Z represents an anionic ligand, n represents 0 to 3, When there are a plurality of L, each L independently represents a neutral or anionic ligand.

21. The catalyst composition of claim 17, which is used to generate formate.

22. The catalyst composition of claim 17, which is used in a hydrogenation reaction.

23. The catalyst composition of claim 17, further comprising a solvent.

24. The catalyst composition of claim 23, wherein The solvent is at least one selected from the group consisting of organic solvents and aqueous solvents.

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