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

Abstract

A catalytic reaction method according to the present invention uses a catalyst so as to react starting compounds in the presence of a solvent. The solvent includes an organic solvent, an aqueous solvent, a first antioxidant, and a second antioxidant that is different from the first antioxidant. The reaction of the starting compounds is carried out in a two-phase system in which the organic solvent and the aqueous solvent are separated.

Description

[Technical Field]

[0001] The present invention relates to a catalytic reaction method, a method for producing organic compounds, and a catalytic composition. [Background technology]

[0002] In organic synthesis reactions, various reactions using various transition metal complexes, which consist of transition metals and ligands, as catalysts are known.

[0003] For example, due to issues such as global warming and the depletion of fossil fuels, hydrogen energy is attracting high expectations as a next-generation energy source, and methods for producing formic acid from carbon dioxide (CO2) and hydrogen (H2) in the presence of a catalyst are being investigated.

[0004] Patent Document 1 describes a method for producing formic acid by the reaction of carbon dioxide and 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. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Patent No. 5734286 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, in conventional technologies, even if a catalyst has high activity at the start of the reaction, it deteriorates as the catalytic reaction progresses, resulting in a decrease in the yield of the product, which has been a problem.

[0007] Therefore, the present invention aims to provide a catalytic reaction method, a method for producing organic compounds, and a catalytic composition suitable for reducing catalyst degradation. [Means for solving the problem]

[0008] The present invention includes reacting a starting compound using a catalyst in the presence of a solvent, where the solvent includes an organic solvent, an aqueous solvent, a first antioxidant, and a second antioxidant different from the first antioxidant, and the reaction is carried out in a two-phase system in which the organic solvent and the aqueous solvent are separated, and provides a catalytic reaction method.

[0009] Furthermore, the present invention provides a method for producing an organic compound, which includes producing an organic compound from the starting compound by the catalytic reaction method.

[0010] Furthermore, the present invention provides a catalyst composition including a catalyst, a first antioxidant, a second antioxidant different from the first antioxidant, and a phase transfer catalyst.

Advantages of the Invention

[0011] According to the present invention, it is possible to provide a catalytic reaction method, a method for producing an organic compound, and a catalyst composition suitable for reducing the deterioration of the catalyst.

Brief Description of the Drawings

[0012] [Figure 1] FIG. 1 is a schematic diagram showing an example of a three-chamber electrodialysis device. [Figure 2] FIG. 2 is a schematic diagram showing an example of a formic acid production system.

Modes for Carrying Out the Invention

[0013] The catalytic reaction method according to the first aspect of the present invention includes reacting a starting compound using a catalyst in the presence of a solvent, where the solvent includes an organic solvent, an aqueous solvent, a first antioxidant, and a second antioxidant different from the first antioxidant, The reaction is carried out in a two-phase system in which the organic solvent and the aqueous solvent are separated.

[0014] In a second embodiment of the present invention, for example, in the catalytic reaction method according to the first embodiment, the organic phase containing the organic solvent contains the catalyst, and the aqueous phase containing the aqueous solvent contains the starting compound.

[0015] In a third embodiment of the present invention, for example, in the catalytic reaction method according to the first or second embodiment, the organic phase containing the organic solvent contains the first antioxidant and the second antioxidant.

[0016] In a fourth aspect of the present invention, for example, in a catalytic reaction method according to any one of the first to third aspects, the first antioxidant is a phosphorus-based antioxidant.

[0017] In a fifth aspect of the present invention, for example, in the catalytic reaction method according to the fourth aspect, the phosphorus-based antioxidant is a compound represented by the following chemical formula (1B). [ka] (R 1 , R 2 , and R 3 Each of these independently represents a hydrogen atom or any substituent.

[0018] In a sixth aspect of the present invention, for example, in the catalytic reaction method according to the fourth or fifth aspect, the phosphorus-based antioxidant is a compound represented by the following chemical formula (1C). [ka] (R 4 , R 5 , and R 6 Each of these independently represents an arbitrary substituent.

[0019] In the seventh aspect of the present invention, for example, in the catalytic reaction method according to the sixth aspect, in chemical formula (1C), R 4 , R 5 , and R6 is, independently of each other, represented by the following chemical formula (1D). [Chemical formula] (* represents a bond. X 1 , X 2 , X 3 , X 4 , and X 5 each independently represents a hydrogen atom or a hydrocarbon group.)

[0020] In the eighth aspect of the present invention, for example, in the catalytic reaction method according to any one of the first to seventh aspects, the second antioxidant is at least one selected from the group consisting of an amine-based antioxidant, a phenol-based antioxidant, and a sulfur-based antioxidant.

[0021] In the ninth aspect of the present invention, for example, in the catalytic reaction method according to the eighth aspect, the second antioxidant is an amine-based antioxidant or a phenol-based antioxidant.

[0022] In the tenth aspect of the present invention, for example, in the catalytic reaction method according to the eighth or ninth aspect, the amine-based antioxidant is a hindered amine-based antioxidant.

[0023] In the eleventh aspect of the present invention, for example, in the catalytic reaction method according to any one of the first to tenth 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.

[0024] In the twelfth aspect of the present invention, for example, in the catalytic reaction method according to any one of the first to eleventh aspects, the starting compound is at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate, and a formate is obtained from the starting compound by the reaction.

[0025] In a thirteenth aspect of the present invention, for example, in a catalytic reaction method according to any one of the first to twelfth 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. [ka]

[0026] (In general formula (1A), X represents an atomic group containing typical elements from groups 13 to 15 that can coordinate with M. Each Q independently represents a bridging structure containing typical elements from groups 14 to 16 that connects Y and X. Each Y independently represents an atomic group containing typical elements from groups 14 to 16 that can coordinate with M. M represents a metal atom. Z represents an anionic ligand, n represents 0 to 3, If multiple Ls exist, each L independently represents a neutral or anionic ligand.

[0027] In the fourteenth aspect of the present invention, for example, in the catalytic reaction method according to the thirteenth aspect, the metal complex represented by the general formula (1A) is the metal complex represented by the following general formula (2A). [ka]

[0028] (In general formula (2A), X1 represents a heteroaromatic ring formed with two carbon atoms and a nitrogen atom, which may have substituents or be bonded to other substituents to form a ring. Q1 independently represents CH2, NH, or O, and CH2 and NH may further have substituents. Each Y1 independently represents either a phosphorus atom or a nitrogen atom. R independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have substituents. M represents a metal atom, Z represents an anionic ligand, n represents 0 to 3, When there are a plurality of Ls, each independently represents a neutral or anionic ligand.)

[0029] In the 15th aspect of the present invention, for example, in the catalytic reaction method according to the 14th aspect, the metal complex represented by the general formula (2A) is a metal complex represented by the following general formula (3A). [Chemical formula]

[0030] (In the general formula (3A), R0 represents a hydrogen atom or an alkyl group, Each A independently represents CH, CR5, or N, and R5 represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxy group, or an alkoxy group, Each Q1 independently represents CH2, NH, or O, and CH2 and NH may further have a substituent, Y1 represents a phosphorus atom or a nitrogen atom, Each R independently represents an alkyl group, an aryl group, or an aralkyl group, and these 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 Ls, each independently represents a neutral or anionic ligand.)

[0031] In the 16th aspect of the present invention, for example, in the catalytic reaction method according to any one of the 13th to 15th aspects, the metal atom represented by M is ruthenium.

[0032] In the 17th aspect of the present invention, for example, in the catalytic reaction method according to any one of the 1st to 16th aspects, the organic solvent contains toluene.

[0033] A method for producing an organic compound according to the 18th aspect of the present invention includes generating an organic compound from a starting compound by a catalytic reaction method according to any one of the 1st to 17th aspects.

[0034] The catalyst composition according to the 19th aspect of the present invention is Catalyst and The first antioxidant, A second antioxidant different from the first antioxidant, Phase-transfer catalyst and Includes.

[0035] In a 20th aspect of the present invention, for example, in the catalyst composition according to the 19th aspect, the first antioxidant is a phosphorus-based antioxidant.

[0036] In a 21st aspect of the present invention, for example, in a catalyst composition according to the 19th or 20th aspect, the second antioxidant is one selected from the group consisting of amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

[0037] In a 22nd aspect of the present invention, for example, in a catalyst composition according to any one of the 19th to 21st 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. [ka] (In general formula (1A), X represents an atomic group containing typical elements from groups 13 to 15 that can coordinate with M. Each Q independently represents a bridging structure containing typical elements from groups 14 to 16 that connects Y and X. Each Y independently represents an atomic group containing typical elements from groups 14 to 16 that can coordinate with M. M represents a metal atom. Z represents an anionic ligand, n represents 0 to 3, If multiple Ls exist, each L independently represents a neutral or anionic ligand.

[0038] In the 23rd aspect of the present invention, for example, the catalyst composition according to any one of the 19th to 22nd aspects is for formate production.

[0039] In the 24th aspect of the present invention, for example, the catalyst composition according to any one of the 19th to 23rd aspects is for a hydrogenation reaction.

[0040] In the 25th aspect of the present invention, for example, the catalyst composition according to any one of the 19th to 23rd aspects further comprises a solvent.

[0041] In a 26th embodiment of the present invention, for example, in the catalyst composition according to the 25th embodiment, the solvent is at least one selected from the group consisting of organic solvents and aqueous solvents.

[0042] The details of the present invention will be described below, but the following description is not intended to limit the present invention to any particular embodiment.

[0043] [Catalytic reaction method] A catalytic reaction method according to the first embodiment of the present invention is a method of reacting a starting compound with a catalyst in the presence of a solvent. The solvent includes an organic solvent, an aqueous solvent, a first antioxidant, and a second antioxidant different from the first 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. In this specification, in a two-phase system, the phase containing the organic solvent may be called the organic phase, and the phase containing the aqueous solvent may be called the aqueous phase. The organic phase and the aqueous phase may be collectively called the reaction solution.

[0044] By including a primary antioxidant and a secondary antioxidant in the solvent, oxidation of the catalyst by oxygen present in the system can be suppressed, thereby reducing catalyst degradation. Consequently, the activity retention rate can be improved. This allows for catalyst reuse, reducing manufacturing costs.

[0045] The organic phase may contain a catalyst, and the aqueous phase may contain a starting compound. The product obtained by the catalytic reaction may be contained in the aqueous phase. This allows for easy separation of the catalyst, making it easy to reuse the catalyst and repeat the reaction. In addition, two-phase reactions have the advantage of easily producing an aqueous phase with a high concentration of the product. The organic phase may contain a first antioxidant and a second antioxidant. The organic phase may contain a catalyst, a first antioxidant, and a second antioxidant, and the aqueous phase may contain a starting compound.

[0046] The catalytic reaction method according to the first embodiment of the present invention can be widely applied to various reaction methods.

[0047] The catalytic reaction method according to the first embodiment of the present invention can be applied to, for example, reduction reactions, dehydration condensation reactions, hydrolysis reactions, and the like. The catalytic reaction method according to the embodiment of the present invention may be applied to reduction reactions of inorganic compounds or organic compounds. A reduction reaction is, for example, a hydrogenation reaction. That is, the catalytic reaction method according to the embodiment of the present invention may be a method for obtaining a hydride of a starting compound by hydrogenation of the starting compound with hydrogen. A hydrogenation reaction of an inorganic compound is, for example, a formate formation reaction. That is, the catalytic reaction method according to the embodiment of the present invention may be a method for obtaining a formate from a starting compound, where the starting compound is at least one selected from the group consisting of carbon dioxide, bicarbonates, and carbonates. When the catalytic reaction method according to the first embodiment of the present invention is applied to a formate formation reaction, there is the advantage that formate can be produced efficiently at low cost.

[0048] (Antioxidant) The first antioxidant and the second antioxidant are antioxidants having different compositions. Antioxidants generally refer to compounds that, when added to materials such as plastics, can prevent polymer degradation caused by chain reactions between radicals generated within the material and oxygen. Examples include primary antioxidants that capture radicals and secondary antioxidants that decompose peroxides. For example, the first antioxidant may be a secondary antioxidant, and the second antioxidant may be a primary antioxidant.

[0049] Examples of the first antioxidant include phosphorus-based antioxidants, amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants. The first antioxidant is preferably a phosphorus-based antioxidant.

[0050] The second antioxidant is preferably at least one selected from the group consisting of amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants, and more preferably an amine-based antioxidant or a phenol-based antioxidant.

[0051] Preferably, the first antioxidant is a phosphorus-based antioxidant, and the second antioxidant is an amine-based or phenol-based antioxidant. With this configuration, catalyst degradation can be particularly reduced, and it is suitable for improving the activity maintenance rate.

[0052] Phosphorus-based antioxidants are preferably those that are highly stable and resistant to decomposition such as hydrolysis, and are preferably compounds with a relatively bulky structure. Phosphorus-based antioxidants are, for example, phosphorus compounds. Phosphorus compounds may be organophosphorus compounds, and may be phosphites, hypophosphites, or phosphonites. Examples of phosphites include trialkyl phosphites, triaryl phosphites, alkylaryl phosphites, and thiophosphites.

[0053] Phosphorus-based antioxidants are, for example, compounds having an aryl group. Examples of aryl groups include substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, such as substituted or unsubstituted phenyl groups, and preferably phenyl groups having a t-butyl group.

[0054] The phosphorus-based antioxidant may be a compound represented by chemical formula (1B).

[0055] [ka]

[0056] In chemical formula (1B), R 1 , R 2 , and R 3 Each of these independently represents a hydrogen atom or any substituent. The substituents are, for example, a hydrocarbon group, a group containing an oxygen atom along with the hydrocarbon, or a group containing a sulfur atom along with the 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, or even 6 to 30. The hydrocarbon group may be linear or branched. The hydrocarbon group may have a cyclic structure or may be an aryl group. Examples of aryl groups are those described above. Hydrocarbons of groups containing an oxygen atom along with the hydrocarbon and groups containing a sulfur atom along with the hydrocarbon are, for example, those described above as hydrocarbon groups. 1 , R 2 , and R 3 At least two selected from the group consisting of may each independently have an aryl group, R 1 , R 2 , and R 3 However, each may independently have an aryl group. Examples of aryl groups are those mentioned above.

[0057] The phosphorus-based antioxidant may be a compound represented by the chemical formula (1C).

[0058] [ka]

[0059] In chemical formula (1C), R 4 , R 5 , and R 6 Each of these independently represents an arbitrary substituent. Examples of substituents include those mentioned above. In chemical formula (1C), R 4 , R 5 , and R 6 Each of these may independently represent the following chemical formula (1D).

[0060] [ka]

[0061] In chemical formula (1D), * represents a bond. 1 , X 2 , X 3 , X 4 , and X 5 Each of these independently represents either a hydrogen atom or a hydrocarbon group. Examples of hydrocarbon groups include those mentioned above. 1 , X 2 , X 3 , X 4 , and X 5 Each of these may independently be a hydrogen atom or an alkyl group, or a hydrogen atom or a tert-butyl group.

[0062] Examples of phosphorus-based antioxidants include triphenyl phosphite, diisooctyl phosphite, heptakis triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctylphenyl phosphite, diphenyltridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris(dipropylene glycol) phosphite, diisodecylpentaerythritol diphosphite, dioleylhydrogen phosphite, and trila Uryl trithiophosphite, bis(tridecyl)phosphite, tris(isodecyl)phosphite, tris(tridecyl)phosphite, diphenyldecyl phosphite, dinonylphenylbis(nonylphenyl)phosphite, poly(dipropylene glycol)phenyl phosphite, tetraphenyldipropyl glycol diphosphite, trisnonylphenyl 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, Tridecyl 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, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) 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-butylidenebis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl) biphenylene Diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, [(1-methyl-1-propanyl-3-ylidene)tris(1,1-dimethylethyl)-5-methyl-4,1-phenylene]hexatridecyl phosphite, 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'-Butylidenebis(3-methyl-6-tert-butylphenylditridecyl)phosphite, Tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphine-6-yl)oxy]ethyl)amine, 3,9-bis(4-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5 Examples include 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, poly4,4'-isopropylidenediphenol C12-15 alcohol phosphite, tetraalkyl(C12-15)-4,4'-isopropylidenediphenyl diphosphite, etc.

[0063] The phosphorus-based antioxidants are preferably tris(2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, triisodecyl phosphite, tetraalkyl(C12-15)-4,4′-isopropylidenediphenyl diphosphite, or 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, with tris(2,4-di-tert-butylphenyl) phosphite or triphenyl phosphite being particularly preferred.

[0064] Amine-based antioxidants are antioxidants that have an amino group. Examples of amine-based antioxidants 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, and N-phenyl-N'-isopropyl- Examples include p-phenylenediamine, aldol-α-naphthylamine, bis(1,2,2,6,6-pentamethyl-4-piperidyl) butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, N1,N3-bis(2,2,6,6-tetramethylpiperidine-4-yl)isophthalamide, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate. The amine-based antioxidant is preferably a hindered amine-based antioxidant such as butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonate bis(1,2,2,6,6-pentamethyl-4-piperidyl), N1,N3-bis(2,2,6,6-tetramethylpiperidine-4-yl)isophthalamide, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, or bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate.

[0065] Phenolic antioxidants are antioxidants that have a phenol group. Examples of phenolic antioxidants include hindered phenolic antioxidants. Examples of hindered phenolic antioxidants include 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-hydroxybenzoate hexadecyl, 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzyl)mesitylene, and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0066] Phenolic antioxidants are not limited to the hindered phenolic antioxidants described above. Other phenolic antioxidants besides those described above include, for example, 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrene phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-thiobis-(6-tert-butyl-4-methylphenol), and 2,2'-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. 2-methyl-4,6-bis(octylsulfanylmethyl)phenol, 2,2'-isobutylidenebis(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'-oxamide-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-ethyl Ihexyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 2,2'-ethylenebis(4,6-di-tert-butylphenol), 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid and C13-15 alkyl ester, 2,5-di-tert-amylhydroquinone, polymer of hindered phenol (brand name AO.OH998, Adeka Palmarol), 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-crezo [T-T-T-T-T-T-T-T-T-T-T-T-T-T-T-T-Pentylphenyl], 2-T-T-T-T-T-T-Pentylphenyl Acrylate, 2-[1-(2-Hydroxy-3,5-Di-T-T-Pentylphenyl)Ethyl]-4,6-Di-T-T-T-Pentylphenyl Acrylate, 6-[3-(3-T[5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate]calcium salt, reaction product of 5,7-bis(1,1-dimethylethyl)-3-hydroxy-2(3H)-benzofuranone and o-xylene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol, DL-α-tocopherol (vitamin E), 2,6-bis(α-methylbenzyl)-4-methylphenol Lu, bis[3,3-bis-(4'-hydroxy-3'-tert-butyl-phenyl)butanoic acid] glycol ester, 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-hydroxybenzylthioacetate, thiodiethylenebis[(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] glycol ester, 4,4'-butylidenebis(2,6-di-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 2,2'- Ethylidenebis(4,6-di-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)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-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3',5'-tert-tributyl-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[ Examples include 3-(3,5-dialkyl-4-hydroxyphenyl)propionic acid derivatives such as undecane, triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], stearyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, palmityl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, myristyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, lauryl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, phenol, etc.

[0067] Sulfur-based antioxidants are antioxidants that contain a sulfur atom (S). Examples of sulfur-based antioxidants include didodecyl 3,3'-thiodipropionate, pentaerythritol tetrakis[3-laurylthiopropionate], dimyristyl 3,3'-thiodipropionate, and distearyl 3,3'-thiodipropionate.

[0068] From the viewpoint of ensuring the antioxidants fully exert their function, the total amount of the first and second antioxidants used is preferably 1 mmol or more per liter of solvent. From the viewpoint of reducing the cost of antioxidants, the total amount of the first and second antioxidants used is preferably 100 mmol or less per liter of solvent. The first and second antioxidants may be added in their entirety when preparing the reaction solution, or they may be added to the reaction solution in multiple portions during the reaction.

[0069] The ratio of the amount of the first antioxidant to the amount of the second antioxidant is, for example, 1:5 to 5:1, preferably 3:7 to 7:3, more preferably 1:2 to 2:1, even more preferably 4:6 to 6:4, and particularly preferably 5:5.

[0070] The total amount of the first antioxidant and the second antioxidant used is preferably 1 equivalent or more and 10,000 equivalents or less per equivalent of catalyst. More preferably, the total amount of the first antioxidant and the second antioxidant used is 10 equivalents or more and 10,000 equivalents or less, even more preferably 10 equivalents or more and 1,000 equivalents or less, and particularly preferably 100 equivalents or more and 1,000 equivalents or less.

[0071] The solvent may or may not further contain a third antioxidant different from the first and second antioxidants.

[0072] (catalyst) In the catalytic reaction method according to the first embodiment of the present invention, it is preferable to use 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 as a catalyst.

[0073] [ka]

[0074] (In general formula (1A), X represents an atomic group containing typical elements from groups 13 to 15 that can coordinate with M. Each Q independently represents a bridging structure containing typical elements from groups 14 to 16 that connects Y and X. Each Y independently represents an atomic group containing typical elements from groups 14 to 16 that can coordinate with M. M represents a metal atom. Z represents an anionic ligand, n represents 0 to 3, If multiple Ls exist, each L independently represents a neutral or anionic ligand.

[0075] In this specification, "group n" means "group n of the periodic table."

[0076] Typical elements of groups 13 to 15 of the periodic table in X include boron, carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, oxygen, sulfur, and selenium. Boron, carbon, silicon, germanium, tin, nitrogen, phosphorus, arsenic, and sulfur atoms are preferred, carbon, nitrogen, phosphorus, and sulfur atoms are more preferred, and carbon or nitrogen atoms are even more preferred.

[0077] X may be an atomic group with a valency of 0 to 1. Examples of atomic groups represented by X include alkyl groups, alkenyl groups, alkoxy groups, aromatic rings, and heterocycles, which may have substituents or be bonded with other substituents to form a ring.

[0078] Examples of alkyl groups in X include linear, branched, cyclic, substituted, or unsubstituted alkyl groups. Preferably, the alkyl group in X is an alkyl group having 1 to 30 carbon atoms, such as a methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, n-octyl group, eicosyl group, or 2-ethylhexyl group, and is preferably an alkyl group having 6 or fewer carbon atoms, and is preferably a methyl group.

[0079] Examples of alkenyl groups in X include linear, branched, cyclic substituted, or unsubstituted alkenyl groups. Preferably, the alkenyl group in X is a C2 to C30 alkenyl group, such as a vinyl group, n-propenyl group, i-propenyl group, t-butenyl group, n-octenyl group, etc., and it is preferable that the alkenyl group has 6 or fewer carbon atoms.

[0080] Examples of alkoxy groups in X include linear, branched, cyclic substituted, or unsubstituted alkoxy groups. Preferably, examples of alkoxy groups in X include substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, and 2-methoxyethoxy groups.

[0081] Examples of aromatic rings in X include phenyl rings and naphthyl rings.

[0082] Examples of heterocyclic rings in X include pyrrolidine rings, piperidine rings, pyrroline rings, imidazoline rings, imidazolidine rings, pyrrole rings, imidazole rings, pyridine rings, pyrimidine rings, triazine rings, quinoline rings, and quinazoline rings.

[0083] The group of atoms represented by X, which has a valency of 0 to 1, preferably represents a group of atoms that includes a heteroaromatic ring formed with two carbon atoms and a nitrogen atom. These groups may have substituents, or they may bond with other substituents to form a ring.

[0084] The 0-1 valent atomic group represented by X is preferably a pyrroline ring, pyridine ring, imidazoline ring, pyrimidine ring, or triazine ring, more preferably a pyridine ring or triazine ring, and even more preferably a pyridine ring.

[0085] When the 0- to 1 valent atomic group represented by X has substituents, examples of substituents include substituent group A, where alkyl groups are preferred and methyl groups are more preferred.

[0086] 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.

[0087] The bridging structure between Y and X represented by Q, which includes typical elements from groups 14 to 16 of the periodic table, may have a double bond, a monocyclic or fused ring structure, or substituents.

[0088] Q can be made to have various structures, but for example, the number of atoms in the part between Y and X is preferably 1 to 5, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 1 to 2.

[0089] The atoms in the portion between Y and X described above are not particularly limited, but carbon atoms, nitrogen atoms, phosphorus atoms, oxygen atoms, and sulfur atoms are preferred, carbon atoms, nitrogen atoms, and oxygen atoms are more preferred, carbon atoms and oxygen atoms are even more preferred, and carbon atoms are particularly preferred.

[0090] Q may have a monocyclic structure. In other words, the bridging structure represented by Q may include a cyclic structure.

[0091] If Q has a monocyclic structure, the monocyclic structure may be directly bonded to Y and X in general formula (1A), or a divalent substituent may be sandwiched between the monocyclic structure and Y and / or Z in general formula (1A). Examples of the divalent substituent include alkylene groups having 1 to 5 carbon atoms, alkenylene groups having 2 to 5 carbon atoms, heteroatoms such as oxygen atoms and sulfur atoms, or these being bonded in series.

[0092] Q preferably represents CH2, NH, or O independently, and CH2 and NH may have further substituents, with CH2 or NH being more preferable.

[0093] Q may have a fused ring structure. In other words, the cross-linked structure represented by Q may include a fused ring structure.

[0094] If Q has a fused ring structure, the fused ring structure may be directly bonded to Y and X in general formula (1A), or a divalent substituent may be sandwiched between the fused ring structure and Y and / or X in general formula (1A). The above divalent substituent is the same as the divalent substituent sandwiched between the monocyclic structure and Y and / or X in general formula (1A) described above.

[0095] Q may have substituents. If Q does not have either a monocyclic or fused ring structure, the substituent is a substituent on the portion of Q in a ring structure comprising Q, Y, X, and M in general formula (1A).

[0096] If Q has a monocyclic or fused ring structure, the substituent is a substituent of the monocyclic or fused ring structure, or a substituent of the portion of Q in a ring structure composed of Q, Y, X, and M in general formula (1A).

[0097] The substituents that Q may have may, for example, have heteroatoms, or may be other atoms or groups of atoms.

[0098] Examples of substituents having the heteroatom include alkoxy groups having 1 to 18 carbon atoms, arylalkoxy groups having 7 to 18 carbon atoms, aryloxy groups having 6 to 18 carbon atoms, acyl groups having 2 to 18 carbon atoms, alloyl groups having 7 to 18 carbon atoms, dialkylamino groups having 2 to 18 carbon atoms, oxygen atoms, sulfur atoms, and the like.

[0099] Examples of other atoms or groups of atoms include aromatic groups having 3 to 18 carbon atoms, alkyl groups having 1 to 18 carbon atoms, halogen atoms, and the like. Examples of aromatic groups include aryl groups having 6 to 20 carbon atoms, such as phenyl, xylyl, naphthyl, and biphenyl.

[0100] The number of carbon atoms in Q is preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less.

[0101] Y may be a group of atoms with a valency of 0 to 1. Each Y independently represents a group of atoms with a valency of 0 to 1, containing typical elements from groups 14 to 16 of the periodic table that can coordinate to M, and may further have substituents. Preferred typical elements from groups 14 to 16 of the periodic table are carbon atoms, nitrogen atoms, phosphorus atoms, arsenic atoms, oxygen atoms, sulfur atoms, and selenium atoms; more preferably carbon atoms, nitrogen atoms, phosphorus atoms, and arsenic atoms; even more preferably nitrogen atoms and phosphorus atoms; and particularly preferably phosphorus atoms.

[0102] In general formula (1A), it is preferable that both Y atoms represent either a nitrogen atom or a phosphorus atom, or that one Y atom represents a phosphorus atom and the other Y atom represents a nitrogen atom.

[0103] When the 0-1 valent atomic group represented by Y has substituents, examples of substituents include substituent group A, which are preferably alkyl groups or aryl groups, and more preferably ethyl groups, t-butyl groups, or phenyl groups.

[0104] M represents a metal atom. M may include elements from groups 7 to 11 of the periodic table, such as manganese, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, and gold, or it may include elements from groups 8 to 11 of the periodic table, such as iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, and gold. Among these, 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 even more preferred, and ruthenium (Ru) is particularly preferred. M may also be ruthenium (Ru) or manganese (Mn).

[0105] Examples of anionic ligands represented by Z include halide ions (halogen atoms), hydride ions (hydrogen atoms), nitrate ions, and cyanide ions. Z preferably represents a halogen atom or a hydrogen atom, and more preferably a halogen atom. Z is even more preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.

[0106] n represents an integer between 0 and 3, and M represents the number of ligands coordinating to the metal atom. From the viewpoint of catalyst stability, n is preferably 2 or 3.

[0107] If multiple Ls exist, each L independently represents a neutral or anionic ligand.

[0108] Examples of neutral ligands represented by L include ammonia, carbon monoxide, phosphines (e.g., triphenylphosphine, tris(4-methoxyphenyl)phosphine), phosphine oxides (e.g., triphenylphosphine oxide), sulfides (e.g., dimethyl sulfide), sulfoxides (e.g., dimethyl sulfoxide), ethers (e.g., diethyl ether), nitriles (e.g., p-methylbenzonitrile), heterocyclic compounds (e.g., pyridine, N,N-dimethyl-4-aminopyridine, tetrahydrothiophene, tetrahydrofuran), and the like. Triphenylphosphine and carbon monoxide are preferred, and carbon monoxide is more preferred.

[0109] Examples of anionic ligands represented by L include hydride ions (hydrogen atoms), nitrate ions, cyanide ions, etc., with hydride ions (hydrogen atoms) being preferred.

[0110] In general formula (1A), it is preferable that X represents a heterocycle, Q represents CH2, NH, or O, Y represents a phosphorus atom, and M represents ruthenium.

[0111] Furthermore, it is preferable that Z represents a chlorine atom, n represents 1 to 3, and L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

[0112] Alternatively, in general formula (1A), it is preferable that X represents an atomic group in which a hydrogen atom or alkyl group is bonded to a nitrogen atom, Q represents CH2, NH, or O, Y represents a phosphorus atom, M represents manganese, Z represents a bromine atom, n represents 2 to 3, and L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

[0113] In the catalytic reaction method according to the first embodiment of the present invention, it is preferable that the metal complex represented by general formula (1A) is a metal complex represented by the following general formula (2A).

[0114] [ka]

[0115] (In general formula (2A), X1 represents a heteroaromatic ring formed with two carbon atoms and a nitrogen atom, which may have substituents or be bonded to other substituents to form a ring. Q1 independently represents CH2, NH, or O, and CH2 and NH may further have substituents. Each Y1 independently represents either a phosphorus atom or a nitrogen atom. R independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have substituents. M represents a metal atom. Z represents an anionic ligand, n represents 0 to 3, If multiple Ls exist, each L independently represents a neutral or anionic ligand.

[0116] In general formula (2A), M, Q1, Z, n, and L are equivalent to M, Q, Z, n, and L in general formula (1A), respectively, and the preferred ranges are also the same.

[0117] The heteroaromatic ring formed with the two carbon atoms and nitrogen atom 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 even more preferably a pyridine ring.

[0118] Substituents that X1 may have include the substituent group A, where alkyl groups are preferred and methyl groups are more preferred.

[0119] Y1 represents either a phosphorus atom or a nitrogen atom, and both Y1s may represent either a nitrogen atom or a phosphorus atom, or one Y1 may represent a phosphorus atom and the other Y1 may represent a nitrogen atom. It is preferable that both Y1s are nitrogen atoms or phosphorus atoms, and it is even more preferable that both Y1s are nitrogen atoms.

[0120] The alkyl group represented by R can be a linear, branched, cyclic, substituted, or unsubstituted alkyl group. Preferably, the alkyl group represented by R is an alkyl group having 1 to 30 carbon atoms, such as a methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, n-octyl group, eicosyl group, or 2-ethylhexyl group. From the viewpoint of catalytic activity, it is preferable that the alkyl group has 12 carbon atoms or less, preferably an ethyl group or a t-butyl group, and more preferably a t-butyl group.

[0121] The aryl group represented by R can be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, or an o-hexadecanoylaminophenyl group. Preferably, it is an aryl group having 12 carbon atoms or less, and more preferably a phenyl group.

[0122] If R has further substituents, examples of substituents include substituent group A, which preferably consists of a methyl group, an ethyl group, an i-propyl group, a t-butyl group, or a phenyl group, and more preferably an ethyl group, an i-propyl group, or a t-butyl group.

[0123] In the general formula (2A), it is preferable that 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 t-butyl group, or a phenyl group, and M represents ruthenium.

[0124] Also, it is preferable that Z represents a chlorine atom, n represents 1 to 3, and L each independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

[0125] In the catalytic reaction method according to the first embodiment of the present invention, it is preferable that the metal complex represented by the general formula (2A) is a metal complex represented by the following general formula (3A).

[0126] [Chemical formula]

[0127] (In the general formula (3A), R0 represents a hydrogen atom or an alkyl group, A each independently represents CH, CR5, or N, and R5 represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxy 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, and these may further have a substituent, M represents a metal atom, Z represents an anionic ligand, n represents 0 to 3, L, when there are a plurality of them, each independently represents a neutral or anionic ligand.)

[0128] Y1, R, Q1, M, Z, n, and L in the general formula (3A) are synonymous with Y1, R, Q1, M, Z, n, and L in the general formula (2A), respectively, and the preferred ranges are also the same.

[0129] In general formula (3A), R0 represents a hydrogen atom or an alkyl group. Examples of alkyl groups represented by R0 include linear, branched, cyclic, substituted, or unsubstituted alkyl groups. Preferably, the alkyl group represented by R0 is an alkyl group having 1 to 30 carbon atoms, such as a methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, n-octyl group, eicosyl group, or 2-ethylhexyl group. From the viewpoint of ease of raw material procurement, it is preferable that the alkyl group has 6 carbon atoms or less, and it is preferable that it is a methyl group.

[0130] In general formula (3A), R0 is preferably a hydrogen atom or a methyl group.

[0131] A independently represents CH, CR5, or N, and R5 represents an alkyl group, aryl group, aralkyl group, amino group, hydroxyl group, or alkoxy group.

[0132] The alkyl group represented by R5 can be a linear, branched, cyclic substituted, or unsubstituted alkyl group. Preferably, the alkyl group represented by R5 is an alkyl group having 1 to 30 carbon atoms, such as a methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, n-octyl group, eicosyl group, or 2-ethylhexyl group. From the viewpoint of ease of raw material procurement, it is preferable that the alkyl group has 12 carbon atoms or less, and is preferably a methyl group.

[0133] The aryl group represented by R5 can be a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, or an o-hexadecanoylaminophenyl group. Preferably, it is an aryl group having 12 carbon atoms or less, and more preferably a phenyl group.

[0134] The aralkyl group represented by R5 can be a substituted or unsubstituted aralkyl group having 30 or fewer carbon atoms, such as a trityl group, benzyl group, phenethyl group, tritylmethyl group, diphenylmethyl group, naphthylmethyl group, etc., and preferably an aralkyl group having 12 or fewer carbon atoms.

[0135] The alkoxy group represented by R5 is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, ethoxy group, isopropoxy group, t-butoxy group, n-octyloxy group, or 2-methoxyethoxy group.

[0136] In general formula (3A), it is preferable that 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 t-butyl group, or a phenyl group, and M represents ruthenium.

[0137] Furthermore, it is preferable that Z represents a chlorine atom, n represents 1 to 3, and L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

[0138] In the catalytic reaction method according to the embodiment of the present invention, it is preferable that the metal complex represented by general formula (3A) is a ruthenium complex represented by the following general formula (4A).

[0139] Ruthenium complexes represented by general formula (4A) are soluble in organic solvents and insoluble in water, making them suitable catalysts in the production of organic compounds. Ruthenium complexes represented by general formula (4A) are suitable, for example, in the production of formate. Since the formate produced by the reaction is readily soluble in water, the reaction can be easily separated from the catalyst in a two-phase system, making it easier to separate and recover the catalyst and formate from the reaction system, enabling the production of formate in high yield and facilitating the reuse of expensive catalysts.

[0140] [ka]

[0141] (In general formula (4A), R0 represents a hydrogen atom or an alkyl group, Each Q1 independently represents CH2, NH, or O, and CH2 and NH may have further substituents. Each R1 independently represents an alkyl group or an aryl group (however, if Q1 represents NH or O, at least one of R1 represents an aryl group). A independently represents CH, CR5, or N, and R5 represents an alkyl group, aryl group, aralkyl group, amino group, hydroxyl group, or alkoxy group. Z This represents a halogen atom, n represents 0 to 3, If multiple Ls exist, each L independently represents a neutral or anionic ligand.

[0142] In general formula (4A), R0, A, Q1, Z, L, and n are equivalent to R0, A, Q1, Z, L, and n in general formula (3A), respectively, and the preferred ranges are also the same.

[0143] The alkyl group and aryl group represented by R1 are equivalent to the alkyl group and aryl group represented by R in general formula (3A), respectively, and the preferred ranges are also the same.

[0144] Metal complexes represented by general formulas (1A) to (4A) may produce stereoisomers depending on the coordination mode and conformation of the ligands, but they may also be a mixture of these stereoisomers or a single pure isomer.

[0145] Metal complexes represented by general formulas (1A) to (4A) can also be used if they are prepared by known methods. Known methods include, for example, those described in E. Pidko et al., ChemCatChem 2014, 6, 1526-1530.

[0146] The following compounds are examples of ruthenium complexes represented by general formula (4A). In the compounds listed below, Et represents an ethyl group, tBu represents a tert-butyl group, and Ph represents a phenyl group.

[0147] [ka]

[0148] [ka]

[0149] [ka]

[0150] The amount of catalyst (preferably a ruthenium complex) used is not particularly limited. From the viewpoint of allowing the catalyst to fully exhibit its function, the amount of catalyst used is preferably 0.1 μmol or more, more preferably 0.5 μmol or more, and even more preferably 1 μmol or more per liter of solvent. From the viewpoint of cost, it is preferably 1 mol or less per liter of solvent, more preferably 10 mmol or less, and even more preferably 1 mmol or less. Furthermore, from the viewpoint of suppressing a decrease in catalytic efficiency, it may be 100 μmol or less, or 10 μmol or less per liter of solvent. When two or more catalysts are used, the total amount used is sufficient as long as it is within the above ranges.

[0151] (phase transfer catalyst) Since the catalytic reaction method according to the first embodiment of the present invention requires a two-phase system, a phase transfer catalyst may be used to facilitate the transfer of mass between the two phases. Examples of phase transfer catalysts include quaternary ammonium salts, quaternary phosphates, macrocyclic polyethers such as crown ethers, nitrogen-containing macrocyclic polyethers such as cryptands, nitrogen-containing linear polyethers, polyethylene glycol and its alkyl ethers. Among these, quaternary ammonium salts are preferred from the viewpoint that mass transfer between the aqueous solvent and the organic solvent is easy even under mild reaction conditions.

[0152] Examples of quaternary ammonium salts include methyltrioctylammonium chloride, benzyltrimethylammonium chloride, trimethylphenylammonium bromide, tributylammonium tribromide, tetrahexylammonium bisulfate, decyltrimethylammonium bromide, diallyldimethylammonium chloride, dodecyltrimethylammonium bromide, dimethyldioctadecylammonium bromide, tetraethylammonium tetrafluoroborane, ethyltrimethylammonium iodide, tris(2-hydroxyethyl)methylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium bromide, and tetraethylammonium iodide, with methyltrioctylammonium chloride being preferred.

[0153] The amount of phase transfer catalyst used is not particularly limited. Preferably, the amount of phase transfer catalyst used is 0.1 mmol or more, more preferably 0.5 mmol or more, and even more preferably 1 mmol or more, per liter of the organic and aqueous solvents. From a cost viewpoint, it is preferable that the amount is 1 mole or less, more preferably 500 mmol or less, and even more preferably 100 mmol or less, per liter of the organic and aqueous solvents. When using two or more types of phase transfer catalysts, the total amount used should not exceed the above range.

[0154] (solvent) 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 in separate states, but it is preferable that the solvent contains a solvent that dissolves the catalyst and becomes homogeneous.

[0155] Examples of aqueous solvents include water, methanol, ethanol, ethylene glycol, glycerin, and mixtures thereof, with water being preferred from the viewpoint of low environmental impact.

[0156] Examples of organic solvents include toluene, benzene, xylene, propylene carbonate, dioxane, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, methylcyclohexane, cyclopentyl methyl ether, and mixed solvents thereof. From the viewpoint of separation from aqueous solvents, it is preferable to include toluene or dioxane, and more preferable to include toluene. For example, the organic solvent is toluene.

[0157] (Reaction conditions) The reaction conditions in the catalytic reaction method according to the embodiment of the present invention are not particularly limited and can be appropriately selected depending on the type of reaction. Furthermore, the reaction conditions can be appropriately changed during the reaction process. The form of the reaction vessel used in the reaction is not particularly limited.

[0158] The reaction temperature in the catalytic reaction method is not particularly limited, but to ensure the reaction proceeds efficiently, it is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. Furthermore, from the viewpoint of energy efficiency, it is preferably 200°C or lower, more preferably 150°C or lower, and even more preferably 100°C or lower.

[0159] The reaction temperature can be adjusted by heating or cooling, with heating being preferred. For example, in the reaction between hydrogen and carbon dioxide, the reaction may be heated to raise the temperature after introducing hydrogen and carbon dioxide into the reaction vessel, or carbon dioxide may be introduced into the reaction vessel first, and then hydrogen may be introduced after the temperature has risen.

[0160] The reaction time in the catalytic reaction method is not particularly limited, but may be, for example, 0.5 hours or more, and may be 1 hour or more, 2 hours or more, 6 hours or more, 12 hours or more, 24 hours or more, 36 hours or more, 48 hours or more, or even 60 hours or more. The upper limit of the reaction time is not particularly limited, but may be, for example, 500 hours or less, 400 hours or less, 300 hours or less, 200 hours or less, 100 hours or less, or even 80 hours or less.

[0161] The catalytic reaction method of the present invention is not limited to the embodiments described above. In some cases, 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 that includes reacting a starting compound with a catalyst in the presence of a solvent, wherein the solvent includes an antioxidant. The solvent may include, for example, an organic solvent.

[0162] [Method for producing organic compounds] A method for producing an organic compound according to a second embodiment of the present invention includes producing an organic compound from a starting compound by a catalytic reaction method according to the first embodiment. That is, a method for producing an organic compound according to a second embodiment of the present invention includes reacting a starting compound with a catalyst in the presence of a solvent to produce an organic compound from the starting compound, wherein the solvent includes an organic solvent, an aqueous solvent, a first antioxidant, and a second 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.

[0163] By including a primary and secondary antioxidant in the solvent, oxidation of the catalyst by oxygen present in the system can be suppressed, thereby reducing catalyst degradation. Consequently, the activity retention rate can be improved. This allows for catalyst reuse, which is economically advantageous.

[0164] The organic phase may contain a catalyst, and the aqueous phase may contain the starting compound. The organic phase may contain a catalyst, and the aqueous phase may contain the generated organic compound. This allows for easy separation of the catalyst, making it easy to reuse the catalyst and repeat the reaction. In addition, in two-phase reactions, there is the advantage that an aqueous phase with a high concentration of the generated organic compound can be easily prepared. The organic phase may contain a first antioxidant and a second antioxidant. The organic phase may contain a catalyst, a first antioxidant, and a second antioxidant, and the aqueous phase may contain the starting compound.

[0165] The above reaction is a hydrogenation reaction of the starting compound with hydrogen, and the organic compound may be a hydride of the starting compound.

[0166] The above starting compound is at least one selected from the group consisting of carbon dioxide, bicarbonates, and carbonates, and the above organic compound may be a formate salt. That is, the above reaction is a hydrogenation reaction of at least one selected from the group consisting of carbon dioxide, bicarbonates, and carbonates with hydrogen, and the above organic compound may be a formate salt.

[0167] The first and second antioxidants can be those described above as antioxidants used in the catalytic reaction method according to the first embodiment. Preferably, the first antioxidant is a phosphorus-based antioxidant, and the second antioxidant is an amine-based or phenol-based antioxidant.

[0168] From the viewpoint of ensuring the antioxidants fully exert their function, the total amount of the first and second antioxidants used is preferably 1 mmol or more per liter of solvent. From the viewpoint of reducing the cost of antioxidants, the total amount of the first and second antioxidants used is preferably 100 mmol or less per liter of solvent. The first and second antioxidants may be added in their entirety when preparing the reaction solution, or they may be added to the reaction solution in multiple portions during the reaction.

[0169] The total amount of the first antioxidant and the second antioxidant used is preferably 1 equivalent or more and 10,000 equivalents or less per equivalent of catalyst. More preferably, the total amount of the first antioxidant and the second antioxidant used is 10 equivalents or more and 10,000 equivalents or less, even more preferably 10 equivalents or more and 1,000 equivalents or less, and particularly preferably 100 equivalents or more and 1,000 equivalents or less.

[0170] The catalyst is, for example, the compound described above used as a catalyst in the catalytic reaction method according to 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 general formulas (1A) to (4A), their tautomers, stereoisomers, and salts thereof. The preferred range is the same as in the first embodiment. In general formulas (1A) to (4A), M is preferably ruthenium.

[0171] The amount of catalyst (preferably a ruthenium complex) used is not particularly limited. From the viewpoint of allowing the catalyst to fully exhibit its function, the amount of catalyst used is preferably 0.1 μmol or more, more preferably 0.5 μmol or more, and even more preferably 1 μmol or more per liter of solvent. From the viewpoint of cost, it is preferably 1 mol or less per liter of solvent, more preferably 10 mmol or less, and even more preferably 1 mmol or less. Furthermore, from the viewpoint of suppressing a decrease in catalytic efficiency, it may be 100 μmol or less, or 10 μmol or less per liter of solvent. When two or more catalysts are used, the total amount used is sufficient as long as it is within the above ranges.

[0172] Since the production method according to the second embodiment of the present invention requires a two-phase reaction, a phase transfer catalyst may be used to facilitate the transfer of substances between the two phases. As the phase transfer catalyst, for example, those described above in the first embodiment can be used. For example, in the reaction between hydrogen and at least one selected from the group consisting of carbon dioxide, bicarbonates, and carbonates, it is preferable to further use a quaternary ammonium salt as the phase transfer catalyst. As the quaternary ammonium salt, those described above in the first embodiment can be used, and methyltrioctylammonium chloride is preferred.

[0173] The amount of phase transfer catalyst used is not particularly limited, as long as it can produce an organic compound (e.g., formate). The amount of phase transfer catalyst used is preferably 0.1 mmol or more, more preferably 0.5 mmol or more, and even more preferably 1 mmol or more, per liter of solvent in the organic and aqueous phases, for the purpose of efficiently assisting the transfer of carbonates or bicarbonates. Furthermore, from a cost viewpoint, it is preferably 1 mole or less, more preferably 500 mmol or less, and even more preferably 100 mmol or less, per liter of solvent in the organic and aqueous phases. When using two or more types of phase transfer catalysts, the total amount used should not exceed the above range.

[0174] (solvent) 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 in separate states, but it is preferable that the solvent contains a solvent that dissolves the catalyst and becomes homogeneous.

[0175] As an aqueous solvent, for example, those described above in the first embodiment can be used. From the viewpoint of low environmental impact, water is preferred as the aqueous solvent.

[0176] As the organic solvent, for example, those described above in the first embodiment can be used. From the viewpoint of separation from aqueous solvents, it is preferable to include toluene or dioxane, and more preferable to include toluene. The organic solvent is, for example, toluene.

[0177] (Reaction conditions) The reaction conditions in the catalytic reaction method according to the embodiment of the present invention are not particularly limited, and the reaction conditions can be appropriately changed during the reaction process. The form of the reaction vessel used in the reaction is not particularly limited.

[0178] The reaction temperature is not particularly limited, but to ensure the reaction proceeds efficiently, it is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. Furthermore, from the viewpoint of energy efficiency, it is preferably 200°C or lower, more preferably 150°C or lower, and even more preferably 100°C or lower.

[0179] The reaction temperature can be adjusted by heating or cooling, with heating being preferred. For example, in the reaction between hydrogen and carbon dioxide, the reaction may be heated to raise the temperature after introducing hydrogen and carbon dioxide into the reaction vessel, or carbon dioxide may be introduced into the reaction vessel first, and then hydrogen may be introduced after the temperature has risen.

[0180] The reaction time is not particularly limited, but from the viewpoint of ensuring a sufficient amount of organic compound produced and suppressing a decrease in catalytic efficiency, it should be 0.5 hours or more, and may be 1 hour or more, 2 hours or more, 6 hours or more, 12 hours or more, 24 hours or more, 36 hours or more, 48 hours or more, or even 60 hours or more. The upper limit of the reaction time is not particularly limited, and may be 500 hours or less, 400 hours or less, 300 hours or less, 200 hours or less, 100 hours or less, or even 80 hours or less.

[0181] The manufacturing method according to the second embodiment is suitable for reducing catalyst degradation. The reduction in catalyst degradation can be evaluated, for example, by the activity retention rate when the reaction of the starting compound is repeatedly carried out using the catalyst. The activity retention rate can be calculated, for example, from the ratio of the yield of the product in the second and subsequent reactions to the yield of the product in the first reaction.

[0182] In the production method according to the second embodiment, it is preferable that the reaction of the starting compound yields a practically sufficient yield. For example, the yield in the first reaction is 10% or more, preferably 20% or more, and more preferably 30% or more. When the reaction of the starting compound is repeated using a catalyst, the yield in the second reaction is, for example, 10% or more, preferably 15% or more, more preferably 20% or more, and even more preferably 25% or more.

[0183] The method for producing organic compounds of the present invention is not limited to the embodiments described above. In some cases, the reaction in the method for producing organic compounds of the present invention is not limited to a two-phase system. That is, the present invention provides a method for producing organic compounds, which involves reacting a starting compound with a catalyst in the presence of a solvent to produce an organic compound from the starting compound, wherein the solvent includes a first antioxidant and a second antioxidant. The solvent may include, for example, an organic solvent.

[0184] Furthermore, the method for producing the organic compound of the present invention may be batch-type or continuous-type. In the continuous-type method, for example, the reaction of the starting compound is carried out using a continuous stirred tank reactor (CSTR) or a plug flow reactor (PFR).

[0185] The following describes in detail the method for producing an organic compound according to the second embodiment of the present invention, specifically the case where the organic compound is a formate salt, i.e., the method for producing a formate salt.

[0186] (Method of manufacturing formate) A method for producing formate includes, for example, a step of reacting hydrogen with at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate, using a catalyst, in the presence of a solvent to which a first antioxidant and a second antioxidant have been added, to produce formate in a reaction solution. In this specification, this step may be referred to as the first step. In the first step, as described above, the solvent contains the first antioxidant and the second antioxidant. This suppresses oxidation of the catalyst by oxygen contained in the system. By suppressing oxidation of the catalyst, catalyst degradation is reduced, and the activity retention rate can be improved when the catalyst is reused. Furthermore, in the first step, the reaction between hydrogen and at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate is carried out in a two-phase system in which the organic solvent and the aqueous solvent are separated, as described above. In this reaction, the catalyst, the first antioxidant, and the second antioxidant are dissolved, for example, in the organic phase. The formate produced by the reaction dissolves in the aqueous phase. This prevents the formate formation reaction from stalling due to equilibrium, allowing for high yield production of formate. Furthermore, since the aqueous and organic phases can be separated by a simple method, expensive metal catalysts tend to be reused without losing their catalytic activity. By reusing the catalyst, high productivity can be achieved.

[0187] According to the first step, hydrogen and carbon dioxide can be stored as formate (e.g., alkali metal formate). Formate has the advantage of being easy to handle due to its high hydrogen storage density, safety, and chemical stability, and it is possible to store hydrogen and carbon dioxide for a long period of time. Formate has high solubility in aqueous solvents and can be separated as a highly concentrated aqueous solution of formate. The aqueous solution of formate can be used in the formic acid production process described later, after adjusting the concentration of formate as needed.

[0188] The first step can be carried out, for example, as follows: First, a reaction vessel equipped with a stirring device is prepared, and the solvent is introduced into the reaction vessel. A phase transfer catalyst may be added as needed. The catalyst is added to the reaction vessel and dissolved in the solvent to prepare a catalyst solution. The first antioxidant and the second antioxidant are added to the catalyst solution in the reaction vessel. Then, at least one selected from the group consisting of hydrogen, carbon dioxide, bicarbonates, and carbonates is introduced into the reaction vessel and the reaction is carried out. The order in which the catalyst, the first antioxidant, and the second antioxidant are added to the reaction vessel is not particularly limited. The first antioxidant and the second antioxidant may be added in their entirety when preparing the reaction solution, or they may be added to the reaction solution in multiple portions during the reaction.

[0189] 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 changed as appropriate during the reaction process, but it is preferable not to change them. The form of the reaction vessel used in the reaction is not particularly limited.

[0190] In the first step, for example, the reaction mixture is stirred. The stirring conditions for the reaction mixture are not particularly limited, but the stirring power is 0.2 kW / m². 3 Preferably, it is 0.5 kW / m 3 The above is more preferable. The greater the stirring power, the better the dispersibility of the gas in the aqueous and organic phases tends to be. When the reaction solution is stirred, the gas (e.g., gaseous hydrogen) is drawn into the reaction solution from above the liquid surface, thereby filling the aqueous and organic phases with gas. However, the method of filling the aqueous and organic phases with gas is not limited to the above, and a sparger may also be used.

[0191] The shape of the impeller used to stir the reaction liquid is not particularly limited. Examples of impellers include anchor impellers, turbine impellers, paddle impellers, and large impellers collectively known as "large impellers," such as Fullzone® impellers (Shinko Environmental Solutions Co., Ltd.) and Maxblend® impellers (Sumitomo Heavy Industries Process Equipment Co., Ltd.).

[0192] Methods for producing formate include reactions between hydrogen and carbon dioxide, reactions between hydrogen and bicarbonate, and reactions between hydrogen and carbonate. In the reaction between hydrogen and carbon dioxide, for example, the reaction in which carbon dioxide forms a carbonate and the reaction in which the carbonate and hydrogen produce formate proceed simultaneously.

[0193] There are no particular restrictions on the method or 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 with carbon dioxide, it is preferable to introduce hydrogen and carbon dioxide simultaneously. Hydrogen and carbon dioxide may be introduced individually or as a mixed gas. Furthermore, the introduction of hydrogen and carbon dioxide may be carried out continuously or intermittently, with one or both being introduced at a time. In the reactions of hydrogen with bicarbonate and hydrogen with carbonate, it is preferable to introduce the bicarbonate or carbonate into the reaction vessel first, and then introduce hydrogen. The introduction of hydrogen and bicarbonate or carbonate may be carried out continuously or intermittently, with one or both being introduced at a time.

[0194] The reaction temperature in the reaction between hydrogen and carbon dioxide, bicarbonate, or carbonate is not particularly limited, but to allow the reaction to proceed efficiently, it is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher. Furthermore, from the viewpoint of energy efficiency, it is preferably 200°C or lower, more preferably 150°C or lower, and even more preferably 100°C or lower. The reaction temperature can be adjusted by heating or cooling, and heating is preferred. In the reaction between hydrogen and carbon dioxide, for example, the temperature may be raised by heating after introducing hydrogen and carbon dioxide into the reaction vessel, or carbon dioxide may be introduced into the reaction vessel, the temperature may be raised, and then hydrogen may be introduced. In the reaction between hydrogen and bicarbonate or carbonate, for example, it is preferable to introduce (produce) bicarbonate or carbonate into the reaction vessel, then introduce hydrogen, and then raise the temperature.

[0195] The reaction pressure (gas pressure in the reaction vessel) in the reaction between hydrogen and at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate is not particularly limited, but from the viewpoint of improving the catalyst's TON, it may be, for example, 0.1 MPa or higher, 0.2 MPa or higher, 0.5 MPa or higher, 1 MPa or higher, 4 MPa or higher, 4.5 MPa or higher, or even 5 MPa or higher. The upper limit of the reaction pressure is not particularly limited, and may be, for example, 50 MPa, 20 MPa or 10 MPa.

[0196] The concentration of formate produced in the first step (concentration of formate in the aqueous phase) is preferably 0.5 mol / L or higher, more preferably 1 mol / L or higher, even more preferably 2.5 mol / L or higher, and particularly preferably 5 mol / L or higher, in order to produce formate in high yield and with excellent productivity. Furthermore, in order to simplify the production process by producing the formate in a dissolved state, it is preferably 30 mol / L or lower, more preferably 25 mol / L or lower, even more preferably 20 mol / L or lower, and particularly preferably 10 mol / L or lower.

[0197] (Carbon dioxide and hydrogen) In the second embodiment, either gaseous hydrogen from a gas cylinder or liquid hydrogen can be used as the hydrogen source. As a hydrogen source, for example, hydrogen generated during the iron smelting process or hydrogen generated during the soda production process can be used. Furthermore, hydrogen generated from the electrolysis of water can also be utilized.

[0198] The carbon dioxide used in this embodiment may be pure carbon dioxide gas or a mixture with other components. The mixed gas with other components may be prepared by introducing carbon dioxide gas and the other gas separately, or it may be prepared in advance before introduction. Other components include inert gases such as nitrogen and argon, water vapor, and other arbitrary components contained in exhaust gas, etc. As carbon dioxide, gaseous carbon dioxide from a gas cylinder, liquid carbon dioxide, supercritical carbon dioxide, and dry ice can be used.

[0199] Hydrogen gas and carbon dioxide gas may be introduced into the reaction system individually or as a mixed gas. The ratio of hydrogen to carbon dioxide used may be equal in molar terms, but an excess of hydrogen is preferable.

[0200] When using gaseous hydrogen from a gas cylinder as the hydrogen source, the pressure should be, for example, 0.1 MPa or higher, but may also be 0.2 MPa or higher, 0.5 MPa or higher, 1 MPa or higher, 4 MPa or higher, 4.5 MPa or higher, or even 5 MPa or higher, from the viewpoint of ensuring sufficient reactivity. Furthermore, since the equipment tends to be large, the pressure should preferably be 50 MPa or lower, more preferably 20 MPa or lower, and even more preferably 10 MPa or lower.

[0201] From the viewpoint of ensuring sufficient reactivity, the pressure of carbon dioxide is preferably 0.1 MPa or higher, more preferably 0.2 MPa or higher, and even more preferably 0.5 MPa or higher. Furthermore, since the equipment tends to be large, it is preferably 50 MPa or lower, more preferably 20 MPa or lower, and even more preferably 10 MPa or lower.

[0202] Hydrogen gas and carbon dioxide gas may be bubbled into the catalyst solution. Alternatively, after introducing the gases containing hydrogen gas and carbon dioxide, the catalyst solution may be stirred with a stirring device or by rotating the reaction vessel.

[0203] There are no particular restrictions on the method of introducing carbon dioxide, hydrogen, catalyst, solvent, etc., used in the reaction into the reaction vessel. All raw materials may be introduced at once, some or all of the raw materials may be introduced in stages, or some or all of the raw materials may be introduced continuously. A combination of these methods is also acceptable.

[0204] (Bicarbonates and carbonates) Examples of bicarbonates and carbonates used in this embodiment include alkali metal and alkaline earth metal carbonates or bicarbonates. Examples of bicarbonates include sodium bicarbonate and potassium bicarbonate, with potassium bicarbonate being preferred from the viewpoint of high solubility in water. That is, in this embodiment, the starting compound preferably contains potassium bicarbonate as the bicarbonate. Examples of carbonates include sodium carbonate, potassium carbonate, sodium potassium carbonate, and sodium sesquicarbonate.

[0205] Bicarbonates and carbonates can be produced by the reaction of carbon dioxide with a base. For example, bicarbonates or carbonates may be produced by introducing carbon dioxide into a basic solution.

[0206] There are no particular restrictions on the solvent of the basic solution used in the production of bicarbonates or carbonates, but examples include water, methanol, ethanol, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, and mixed solvents thereof. It is preferable that the solvent contains water, and more preferably water. There are no particular restrictions on the base used in the basic solution, as long as it can react with carbon dioxide to produce bicarbonates or carbonates, and hydroxides are preferred. Examples include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, potassium hydroxide, sodium hydroxide, diazabicycloundecene, and triethylamine. Among the above, hydroxides are preferred, potassium hydroxide and sodium hydroxide are more preferred, and potassium hydroxide is even more preferred.

[0207] The base content in the basic solution is not particularly limited, as long as it is sufficient to produce bicarbonate and carbonate. From the viewpoint of ensuring the amount of formate produced, the base content is preferably 0.1 mol or more, more preferably 0.5 mol or more, and even more preferably 1 mol or more per liter of aqueous solvent. From the viewpoint of reaction efficiency, it is preferably 30 mol or less, more preferably 20 mol or less, and even more preferably 15 mol or less. However, if it exceeds the solubility of the aqueous phase, the solution will be suspended.

[0208] The ratio of carbon dioxide to base used in the reaction between carbon dioxide and a base is preferably 0.1 or higher in molar ratio, more preferably 0.5 or higher, and even more preferably 1.0 or higher, from the viewpoint of producing carbonate from carbon dioxide. Furthermore, from the viewpoint of carbon dioxide utilization efficiency, it is preferably 8.0 or lower, more preferably 5.0 or lower, and even more preferably 3.0 or lower. Note that the ratio of carbon dioxide to base used can be the ratio of the molar amounts of carbon dioxide to base introduced into the reaction vessel, which is molar amount of CO2 (mol) / molar amount of base (mol). By setting the ratio of carbon dioxide to base used within the above range, the excessive input of carbon dioxide into the reaction vessel can be suppressed, the amount of unreacted carbon dioxide can be minimized, and the final conversion efficiency of formic acid can be easily improved. In addition, within the same vessel, carbon dioxide can be hydrogenated via bicarbonate or carbonate from the reaction between carbon dioxide and a base to produce formate. Unreacted carbon dioxide can be recovered from the reaction vessel and reused.

[0209] There are no particular restrictions on the method or order of introducing carbon dioxide and the base into the reaction vessel, but it is preferable to introduce the base first, followed by the carbon dioxide. Furthermore, the introduction of carbon dioxide and the base may be carried out continuously or intermittently, either one or both at a time.

[0210] The reaction temperature in the reaction that produces a bicarbonate or carbonate by the reaction of carbon dioxide with a base is not particularly limited, but it is preferably 0°C or higher, more preferably 10°C or higher, and even more preferably 20°C or higher, in order to dissolve carbon dioxide in the aqueous phase. It is also preferably 100°C or lower, more preferably 80°C or lower, and even more preferably 40°C or lower.

[0211] The reaction time in the reaction between carbon dioxide and a base to produce a bicarbonate or carbonate is not particularly limited, but from the viewpoint of ensuring a sufficient amount of bicarbonate or carbonate produced, it is preferably 0.5 hours or more, more preferably 1 hour or more, and even more preferably 2 hours or more. Also from the viewpoint of cost, it is preferably 24 hours or less, more preferably 12 hours or less, and even more preferably 6 hours or less.

[0212] The bicarbonates and carbonates produced by the reaction of carbon dioxide with a base can be used in the reaction of hydrogen with the bicarbonate or carbonate in the method for producing an organic compound according to the second embodiment of the present invention. Alternatively, the bicarbonate or carbonate may be introduced into the reaction vessel by reacting carbon dioxide with a base in the reaction vessel to produce the bicarbonate or carbonate.

[0213] [Method for producing formic acid] The method for producing formic acid according to this embodiment includes the steps of producing a formate salt by the method for producing formate salt described above, and 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 may be referred to as the second step. The method for producing formic acid according to this embodiment includes, for example, the first step and the second step described above.

[0214] In the first step described above, the generated formate dissolves into the aqueous phase, and an aqueous solution of formate is obtained by separating the aqueous phase. It is preferable to separate the aqueous phase in the first step and treat the obtained aqueous solution in the second step, for example, using an electrodialysis apparatus, to produce formic acid. The aqueous phase to be separated is the aqueous phase after the completion of the first step.

[0215] In the second step, the aqueous solution of formate obtained in the first step may be used as is, or the concentration of formate in the aqueous solution may be adjusted by concentration or dilution as needed. Methods for diluting the aqueous solution of formate include adding pure water. Methods for concentrating the aqueous solution of formate include removing water by distillation, and concentrating the aqueous solution using a separation membrane unit equipped with a reverse osmosis membrane. When processing using an electrodialysis apparatus, loss of formate due to concentration diffusion may occur in high-concentration aqueous solutions of formate. From the viewpoint of suppressing this, it is preferable 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 a high-concentration aqueous solution of formate in the first step and adjusting the concentration of this aqueous solution by dilution before using it in the second step, formic acid can be produced in higher yield and with better productivity.

[0216] The degree to which the concentration of the aqueous solution of formate obtained in the first step is adjusted (preferably diluted) is not particularly limited. The concentration of formate in the aqueous solution after concentration adjustment is preferably a concentration suitable for electrodialysis, preferably 2.5 mol / L or more, more preferably 3 mol / L or more, 4.75 mol / L or more, and even more preferably 5 mol / L or more. Furthermore, when processing using an electrodialysis apparatus, from the viewpoint of suppressing the loss of formate due to concentration diffusion, the concentration of formate is preferably 20 mol / L or less, more preferably 15 mol / L or less, and even more preferably 10 mol / L or less.

[0217] Pure water can be used for dilution. Also, the water generated in the second step may be used for dilution. Reusing the water generated in the second step for dilution is preferable because it has advantages such as reducing the cost and environmental load associated with wastewater treatment.

[0218] In the method for producing formic acid according to this embodiment, an acid may be added to the aqueous solution of formate obtained in the first step, followed by decarboxylation treatment, and then the aqueous solution may be used in the second step. That is, the aqueous phase in the first step may be separated, an acid may be added, decarboxylation treatment may be performed, and then it may be used in the second step. The aqueous solution of formate obtained in the first step may contain unreacted carbonate or bicarbonate generated by side reactions. When a solution containing carbonate or bicarbonate is subjected to electrodialysis, carbon dioxide may be generated and the dialysis efficiency may decrease. Therefore, by adding an acid to the aqueous solution of formate obtained in the first step, performing decarboxylation treatment, and then performing electrodialysis, formic acid can be produced in a higher yield and with more excellent productivity.

[0219] Examples of the acid used for decarboxylation 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. It is preferable to use formic acid.

[0220] From the viewpoint of suppressing the amount of carbonic acid generated during electrodialysis treatment, the amount of acid used with respect to the amount of carbonic acid present in the solution is preferably 50% or more, and more preferably 80% or more. Also, by keeping the pH of the formate solution during electrodialysis treatment near neutral, deterioration of the electrodialysis device can be suppressed. Therefore, the amount of acid used with respect to the amount of carbonic acid present in the solution is preferably 150% or less, and more preferably 120% or less.

[0221] In the present embodiment, from the viewpoint of increasing the purity of the recovered aqueous solution of formic acid with respect to the molar amount of the initial formate in the aqueous solution of formate, the ratio at which the formate is protonated in the second step is preferably such that 10% or more is protonated, more preferably 20% or more is protonated, and even more preferably 30% or more is protonated.

[0222] Examples of the electrodialysis apparatus used in the second step include a two-chamber electrodialysis apparatus that uses a bipolar membrane and an anion exchange membrane or a cation exchange membrane, and a three-chamber electrodialysis apparatus that uses a bipolar membrane, an anion exchange membrane, and a cation exchange membrane.

[0223] FIG. 1 is a schematic diagram showing an example of a three-chamber electrodialysis apparatus. The electrodialysis apparatus shown in FIG. 1 includes a plurality of bipolar membranes, anion exchange membranes, and cation exchange membranes, respectively. By arranging these bipolar membranes, anion exchange membranes, and cation exchange membranes between the anode and the cathode, a base tank, a sample tank (salt tank), and an acid tank are formed. By circulating and supplying an aqueous solution of formate to the sample tank while applying an electric current to the electrodialysis apparatus, 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 base tank.

[0224] The two-chamber electrodialysis apparatus includes, for example, a plurality of bipolar membranes and cation exchange membranes, respectively. By alternately arranging these bipolar membranes and cation exchange membranes between the anode and the cathode, salt chambers are formed between each bipolar membrane and the cation exchange membrane disposed on the cathode side thereof, and base tanks are formed between each bipolar membrane and the cation exchange membrane disposed on the anode side thereof. By circulating and supplying an aqueous solution of formate to the salt chamber while applying an electric current to the electrodialysis apparatus, hydroxides are generated in the base tank, and the formate circulated and supplied to the salt chamber is converted into formic acid.

[0225] In the second step, by using an electrodialysis apparatus, the formate can be protonated by a simple method to obtain a solution of formic acid.

[0226] [Formic Acid Production System] As shown in Figure 2, the formic acid production system 100 of this embodiment includes, for example, a formate salt production apparatus 10 and an electrodialysis apparatus 30. The production system 100 may further include a dilution apparatus 20 and a dilution water storage unit 40, and may further include a carbon dioxide cylinder 60 for introducing carbon dioxide into the production apparatus 10 and a hydrogen cylinder 50 for introducing hydrogen into the production apparatus 10. The concentrations and pressures of carbon dioxide and hydrogen can be adjusted by valves 1 and 2 provided in piping L1 and piping L2.

[0227] The formate produced in the manufacturing apparatus 10 is supplied to the electrodialysis apparatus 30 as an aqueous solution of formate by separating the aqueous phase. At this time, as shown in Figure 2, the aqueous solution of formate may be pre-supplied to the dilution apparatus 20 via the flow path L3, and the concentration of formate in the aqueous solution may be adjusted by dilution in the dilution apparatus 20.

[0228] The aqueous solution, whose formate concentration has been adjusted by the dilution device 20, is sent to the electrodialysis device 30 via channel L4, where at least a portion of the formate is protonated. This produces formic acid and water from the formate. The produced formic acid can be removed via channel L5. Alternatively, the produced water may be sent to the storage unit 40 via channel L7.

[0229] A portion of the formic acid produced by the electrodialysis apparatus 30 may be supplied 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 in the storage unit 40 may be supplied to the dilution device 20 through the flow path L9 to perform decarboxylation treatment on the aqueous solution of formate. Each flow path of the manufacturing system 100 may be equipped with valves (for example, valves 3 and 5 in Figure 2) to adjust the pressure and supply amount.

[0230] According to the manufacturing system 100 of this embodiment, formic acid can be produced with high yield and excellent productivity.

[0231] The formate salts and formic acid obtained in this way have a wide range of applications in various fields, such as silage additives, feed preservatives, leather tanning agents, textile dyes, rubber coagulants, antifreeze agents, cleaning agents and neutralizing agents for precision machinery, heavy metal precipitants, de-icing agents, cutting fluids, heat conduction fluids, lubricants, hydride ion sources, and hydrogen sources.

[0232] [Catalyst composition] A catalyst composition according to a third embodiment of the present invention comprises a catalyst, a first antioxidant, and a second antioxidant different from the first antioxidant, and satisfies at least one selected from the group consisting of (A) to (D) below. (A) Further comprising a phase-transfer catalyst (B) The catalyst is a compound in which, in general formula (1A), Y is a group of atoms having a phosphorus atom and a substituent, and the substituent is an alkyl group. (C) The total amount of the first antioxidant and the second antioxidant is 10 equivalents or more per equivalent of the catalyst. (D) The first antioxidant includes a phosphorus-based antioxidant. [ka] (In general formula (1A), X represents an atomic group containing typical elements from groups 13 to 15 that can coordinate with M. Each Q independently represents a bridging structure containing typical elements from groups 14 to 16 that connects Y and X. Each Y independently represents an atomic group containing typical elements from groups 14 to 16 that can coordinate with M. M represents a metal atom. Z represents an anionic ligand, n represents 0 to 3, If multiple Ls exist, each L independently represents a neutral or anionic ligand.

[0233] The catalyst composition contains a first antioxidant and a second antioxidant, which can reduce catalyst degradation and improve the rate at which the catalytic reaction is maintained.

[0234] The catalyst composition of this embodiment may satisfy the above (A). That is, the present invention provides a catalyst composition including a catalyst, a first antioxidant, a second antioxidant, and a phase transfer catalyst. The phase transfer catalyst is, for example, the compound described above as the phase transfer catalyst used in the catalytic reaction method according to the first embodiment, and the preferable range is also the same as that of the first embodiment. Such a catalyst composition is useful for, for example, a two-phase reaction, and can more suppress the decrease in the catalytic efficiency in the catalytic reaction.

[0235] 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 preferable range is also the same as that of the first embodiment.

[0236] The catalyst composition of this embodiment may satisfy the above (B). That is, from another aspect of the present invention, there is provided a catalyst composition including a catalyst, a first antioxidant, and a second antioxidant, and wherein in the general formula (1A), Y is a phosphorus atom and an atomic group having a substituent, and the substituent is an alkyl group. The catalyst may 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 may be a compound in which R1 is an alkyl group in the general formula (4A).

[0237] The catalyst composition of this embodiment may satisfy the above (C). That is, from another aspect of the present invention, there is provided a catalyst composition including a catalyst, a first antioxidant, and a second antioxidant, and wherein the content of the antioxidant is 10 equivalents or more with respect 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, with respect to 1 equivalent of the catalyst.

[0238] The catalyst composition of this embodiment may satisfy the above (D).

[0239] The catalyst composition of this embodiment may satisfy at least two selected from the group consisting of (A) to (D) above. For example, the catalyst composition of this embodiment may satisfy (A) and at least one selected from the group consisting of (B) to (D).

[0240] The first antioxidant and the second antioxidant are the compounds described above used as the first antioxidant and the second antioxidant in the catalytic reaction method according to the first embodiment, and the preferred range is the same as in the first embodiment. The first antioxidant is preferably a phosphorus-based antioxidant. The second antioxidant is preferably at least one selected from the group consisting of amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants, and more preferably an amine-based antioxidant or a phenol-based antioxidant.

[0241] The catalyst composition of this embodiment is, for example, a catalyst composition for the production of organic compounds, and preferably a catalyst composition for the production of formate salts. Alternatively, the catalyst composition of this embodiment is, for example, a catalyst composition for hydrogenation reactions. The starting compound is, for example, at least one selected from the group consisting of carbon dioxide, bicarbonates, and carbonates.

[0242] An organic compound may be produced by contacting the catalyst composition of this embodiment with a starting compound. Contact between the catalyst composition and the starting compound can be 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.

[0243] The catalyst composition of this embodiment can be used, for example, in a catalytic reaction method according to the first embodiment of the present invention or in a method for producing an organic compound according to the second embodiment.

[0244] The catalyst composition of this embodiment may further contain a solvent. The solvent may be at least one selected from the group consisting of organic solvents and aqueous solvents. In one preferred embodiment of the present invention, the catalyst composition contains only an organic solvent. In another preferred embodiment of the present invention, the catalyst composition contains both an organic solvent and an aqueous solvent. As the organic solvent, for example, those described above in the first embodiment are used. The organic solvent is preferably toluene or dioxane, and more preferably toluene. As the aqueous solvent, for example, those described above in the first embodiment are used. [Examples]

[0245] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto. In the examples, formate salts were synthesized by hydrogenation reaction of the starting compound using a catalyst, and the effect of reducing catalyst degradation was evaluated.

[0246] [Catalyst synthesis] (Catalyst 1) Catalyst 1 was synthesized by the following procedure. Under an inert atmosphere, 40 mg (0.1 mmol) of ligand A was added to a suspension of [RuHCl(PPh3)3(CO)] in 5 ml of THF (tetrahydrofuran), and the mixture was stirred and heated at 65°C for 3 hours to carry out the reaction. After that, it was cooled to room temperature (25°C). The resulting yellow solution was filtered, and the filtrate was evaporated to dryness under vacuum. The resulting 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 then filtered. The filtrate was dried under vacuum to obtain catalyst 1 (55 mg, yield 97%), which is a yellow crystal. In catalyst 1 and ligand A shown below, tBu represents a tertiary butyl group.

[0247] [ka]

[0248] 31 P{ 1H}(C6D6):90.8(s), 1 H(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).

[0249] [Calculation of yield] In the following examples and comparative examples, the yield of formate (potassium formate) was calculated by the following method.

[0250] First, the amount of formate contained in the aqueous phase was quantified as follows. 500 μL was taken from the aqueous phase obtained after the reaction, 100 μL of dimethyl sulfoxide was added as a reference substance, and the mixture was dissolved in 500 μL of heavy water. The measurement sample was prepared in this way. Regarding this measurement sample... 1 1H NMR measurements were performed. From the obtained NMR spectra, the integral value Ia of the peak originating from potassium formate and the integral value Ib of the peak originating from dimethyl sulfoxide were identified. The amount of substance X (mol) of potassium formate was calculated using the following formula (1). X=(W / M)×{Ia / (Ib / R)}×(A / B) (1) (In formula (1), W is the weight (g) of dimethyl sulfoxide used to quantify potassium formate. M is the molecular weight of dimethyl sulfoxide. R is the ratio of the number of protons per molecule of dimethyl sulfoxide to the number of protons per molecule of potassium formate. Ia is the integral value of the NMR peak originating from potassium formate. Ib is the integral value of the NMR peak derived from dimethyl sulfoxide. A is the mass (g) of the aqueous phase obtained after the reaction. B is the mass (g) of the aqueous solution used to quantify potassium formate.

[0251] Then, based on the amount of formate produced (X moles) and the total amount of carbon dioxide, bicarbonate, and carbonate used in the reaction (the amount of potassium bicarbonate in the following examples and comparative examples) (Z moles), the yield (%) of formate was calculated using the following formula (2). Formate yield = 100 × X / Z (2)

[0252] [Example 1] Under a nitrogen gas atmosphere, 3 mL of water, potassium bicarbonate, 3 mL of toluene, catalyst 1, methyltrioctylammonium chloride as a phase transfer catalyst, tris(2,4-di-tert-butylphenyl) phosphite as a primary antioxidant, and 2,6-di-tert-butyl-p-cresol as a secondary antioxidant were added to a pressure-resistant glass vial equipped with a stirring bar and introduced into a reactor. In the aqueous phase, the concentration of potassium bicarbonate was 2 mL / L. In the organic phase, the concentration of catalyst 1 was 0.12 mmol / L, the concentration of the phase transfer catalyst was 1 mmol / L, and the concentrations of the primary and secondary antioxidants were 6 mmol / L, respectively. Subsequently, as the first reaction, hydrogen gas was added to 0.6 MPa, the temperature was raised to 90°C, and the mixture was stirred at 800 rpm for 3 hours. After stirring, the mixture was cooled to room temperature, and the pressure was carefully released after cooling. The reactor was then purged with nitrogen gas.

[0253] Under a nitrogen gas atmosphere, the reaction mixture was removed from the reactor, and the organic phase and aqueous phase were separated. Using this aqueous phase, the yield of formate from the first reaction was calculated using the method described above.

[0254] Under a nitrogen gas atmosphere, 3 mL of water and potassium bicarbonate were added to the separated organic phase in a pressure-resistant glass vial equipped with a stirring bar, and then introduced into the reactor. At this time, the potassium bicarbonate concentration in the aqueous phase was adjusted to 2 mol / L. Subsequently, in the second reaction, hydrogen gas was added up to 0.6 MPa, the temperature was raised to 90°C, and the mixture was stirred at 800 rpm for 3 hours. After stirring, the mixture was cooled to room temperature, and the pressure was carefully released after cooling. The reactor was then purged with nitrogen gas.

[0255] Under a nitrogen gas atmosphere, the reaction mixture was removed from the reactor, and the organic phase and aqueous phase were separated. Similar to the first reaction, the yield of formate from the second reaction was calculated using the method described above.

[0256] [Example 2] The reaction was carried out in the same manner as in Example 1, except that the second antioxidant was changed to butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonate bis(1,2,2,6,6-pentamethyl-4-piperidyl). The yields of formate from the first and second reactions were calculated in the same manner as in Example 1.

[0257] [Example 3] The reaction was carried out in the same manner as in Example 1, except that the second antioxidant was changed to 2,6-di-tert-butyl-4-methoxyphenol. The yields of formate from the first and second reactions were calculated in the same manner as in Example 1.

[0258] [Example 4] The reaction was carried out in the same manner as in Example 1, except that the second antioxidant was changed to didodecyl 3,3'-thiodipropionate. The yields of formate from the first and second reactions were calculated in the same manner as in Example 1.

[0259] [Example 5] The reaction was carried out in the same manner as in Example 1, except that the second antioxidant was changed to pentaerythritol tetrakis[3-laurylthiopropionate]. The yields of formate from the first and second reactions were calculated in the same manner as in Example 1.

[0260] [Example 6] The reaction was carried out in the same manner as in Example 1, except that the second antioxidant was changed to hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate. The yields of formate from the first and second reactions were calculated in the same manner as in Example 1.

[0261] [Example 7] The reaction was carried out in the same manner as in Example 1, except that the second antioxidant was changed to N1,N3-bis(2,2,6,6-tetramethylpiperidine-4-yl)isophthalamide. The yields of formate from the first and second reactions were calculated in the same manner as in Example 1.

[0262] [Example 8] The reaction was carried out in the same manner as in Example 1, except that the second antioxidant was changed to phenothiazine. The yield of formate from the first and second reactions was calculated in the same manner as in Example 1.

[0263] [Example 9] The reaction was carried out in the same manner as in Example 1, except that the second antioxidant was changed to phenol. The yield of formate from the first and second reactions was calculated in the same manner as in Example 1.

[0264] [Example 10] The first reaction was carried out in the same manner as in Example 1, except that the concentrations of the first antioxidant and the second antioxidant were each changed to 1 mmol / L. The yield of formate from the first reaction was calculated in the same manner as in Example 1.

[0265] After the first reaction, the second reaction was carried out in the same manner as in Example 1, except that the stirring time was changed to 16 hours. The yield of formate from the second reaction was calculated as follows.

[0266] Based on the amount of formate produced (X moles), the total amount of carbon dioxide, bicarbonate, and carbonate used in the reaction (in this case, the amount of potassium bicarbonate) (Z moles), the amount of hydrogen consumed when the stirring time was 3 hours (α moles), and the amount of hydrogen consumed when the stirring time was 16 hours (β moles), the yield (%) of formate from the second reaction was calculated using the following formula (3). Formate yield = 100 × X / Z × α / β (3)

[0267] [Example 11] The first reaction was carried out in the same manner as in Example 1, except that the concentrations of the first antioxidant and the second antioxidant were each changed to 3 mmol / L. The yield of formate from the first reaction was calculated in the same manner as in Example 1. In addition, the second reaction was carried out in the same manner as in Example 10, and the yield of formate from the second reaction was calculated.

[0268] [Example 12] The first reaction was carried out in the same manner as in Example 1, except that the concentrations of the first antioxidant and the second antioxidant were each changed to 12 mmol / L. The yield of formate from the first reaction was calculated in the same manner as in Example 1. In addition, the second reaction was carried out in the same manner as in Example 10, and the yield of formate from the second reaction was calculated.

[0269] [Example 13] The first reaction was carried out in the same manner as in Example 1, except that the concentration of the first antioxidant was changed to 2 mmol / L and the concentration of the second antioxidant was changed to 10 mmol / L. The yield of formate from the first reaction was calculated in the same manner as in Example 1. In addition, the second reaction was carried out in the same manner as in Example 10, and the yield of formate from the second reaction was calculated.

[0270] [Example 14] The first reaction was carried out in the same manner as in Example 1, except that the concentration of the first antioxidant was changed to 4 mmol / L and the concentration of the second antioxidant was changed to 8 mmol / L. The yield of formate from the first reaction was calculated in the same manner as in Example 1. In addition, the second reaction was carried out in the same manner as in Example 10, and the yield of formate from the second reaction was calculated.

[0271] [Example 15] The first reaction was carried out in the same manner as in Example 1, except that the concentration of the first antioxidant was changed to 8 mmol / L and the concentration of the second antioxidant was changed to 4 mmol / L. The yield of formate from the first reaction was calculated in the same manner as in Example 1. In addition, the second reaction was carried out in the same manner as in Example 10, and the yield of formate from the second reaction was calculated.

[0272] [Example 16] The first reaction was carried out in the same manner as in Example 2, except that the concentrations of the first antioxidant and the second antioxidant were each changed to 3 mmol / L. The yield of formate from the first reaction was calculated in the same manner as in Example 1. In addition, the second reaction was carried out in the same manner as in Example 10, and the yield of formate from the second reaction was calculated.

[0273] [Example 17] The reaction was carried out in the same manner as in Example 2, except that the concentrations of the first antioxidant and the second antioxidant were changed to 12 mmol / L each. The yield of formate from the first and second reactions was calculated in the same manner as in Example 1.

[0274] [Example 18] The reaction was carried out in the same manner as in Example 2, except that the concentrations of the first antioxidant and the second antioxidant were changed to 24 mmol / L each. The yield of formate from the first and second reactions was calculated in the same manner as in Example 1.

[0275] [Example 19] The reaction was carried out in the same manner as in Example 1, except that the first antioxidant was changed to triphenylphosphite. The yields of formate from the first and second reactions were calculated in the same manner as in Example 1.

[0276] [Example 20] The reaction was carried out in the same manner as in Example 1, except that the first antioxidant was changed to 2,6-di-tert-butyl-4-methoxyphenol and the second antioxidant was changed to phenothiazine. The yields of formate from the first and second reactions were calculated in the same manner as in Example 1.

[0277] [Comparative Example 1] The reaction was carried out in the same manner as in Example 1, except that the concentration of the first antioxidant in the organic phase was set to 12 mmol / L and the second antioxidant was not added. The yield of formate from the first and second reactions was calculated in the same manner as in Example 1.

[0278] [Comparative Example 2] The reaction was carried out in the same manner as in Example 1, except that the second antioxidant was not added. The yield of formate from the first and second reactions was calculated in the same manner as in Example 1.

[0279] Table 1 shows the reaction yields in Examples 1 to 9 and Comparative Examples 1 to 2. Table 2 shows the reaction yields in Examples 10 to 20. The activity retention rates shown in Tables 1 and 2 represent the ratio of the yield of the second reaction to the yield of the first reaction.

[0280] [Table 1]

[0281] [Table 2]

[0282] As can be seen from Tables 1 and 2, Examples 1 to 20, in which the reaction was carried out in a two-phase system containing the first and second antioxidants, showed a higher activity retention rate than Comparative Examples 1 to 2, which did not contain the second antioxidant. Therefore, catalyst degradation was reduced in Examples 1 to 20. Furthermore, the yields of Examples 1 to 20 were practically sufficient. [Industrial applicability]

[0283] According to the catalytic reaction method and organic compound production method of this embodiment, for example, the target organic compound can be produced efficiently at low cost.

Claims

1. This includes reacting a starting compound with a catalyst in the presence of a solvent, The solvent comprises an organic solvent, an aqueous solvent, a first antioxidant, and a second antioxidant different from the first antioxidant. The above reaction is carried out in a two-phase system in which the organic solvent and the aqueous solvent are separated. The starting compound is at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate. The above reaction is a hydrogenation reaction of the starting compound with hydrogen, The hydrogenation reaction produces a formate from the starting compound, The catalyst is at least one selected from the group consisting of a metal complex represented by the following general formula (4A), its tautomers, stereoisomers, and salts thereof. A method for producing formate, wherein the first antioxidant and the second antioxidant are two selected from the group consisting of phosphorus-based antioxidants, amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants. 【Chemistry 1】 (In general formula (4A), R0 represents a hydrogen atom or an alkyl group, Q1 independently represents CH2, NH, or O, and CH2 and NH may have further substituents. Each R1 independently represents an alkyl group or an aryl group (however, if Q1 represents NH or O, at least one of R1 represents an aryl group). A independently represents CH, CR5, or N, and R5 represents an alkyl group, aryl group, aralkyl group, amino group, hydroxyl group, or alkoxy group. Z represents a halogen atom, n represents 0 to 3, (If multiple Ls exist, each L independently represents a neutral or anionic ligand.)

2. The method for producing a formate salt according to claim 1, wherein the organic phase containing the organic solvent contains the catalyst, and the aqueous phase containing the aqueous solvent contains the starting compound.

3. The method for producing a formate salt according to claim 1, wherein the organic phase containing the organic solvent contains the first antioxidant and the second antioxidant.

4. The method for producing formate according to claim 1, wherein the first antioxidant is a phosphorus-based antioxidant.

5. The method for producing formate according to claim 4, wherein the phosphorus-based antioxidant is a compound represented by the following chemical formula (1B). 【Chemistry 2】 (In chemical formula (1B), R 1 , R 2 , and R 3 Each of these independently represents a hydrogen atom or any substituent.

6. The method for producing formate according to claim 4, wherein the phosphorus-based antioxidant is a compound represented by the following chemical formula (1C). 【Transformation 3】 (In chemical formula (1C), R 4 , R 5 , and R 6 Each of these independently represents an arbitrary substituent.

7. In Chemical Formula (1C), R 4 , R 5 , and R 6 are each independently the following Chemical Formula (1D). The method for producing a formate according to claim 6. 【Chemistry 4】 (In chemical formula (1D), * represents a bond. X) 1 , X 2 , X 3 , X 4 , and X 5 Each of these independently represents either a hydrogen atom or a hydrocarbon group.

8. The method for producing formate according to claim 4, wherein the second antioxidant is at least one selected from the group consisting of amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

9. The method for producing formate according to claim 8, wherein the second antioxidant is an amine-based antioxidant or a phenol-based antioxidant.

10. The method for producing formate according to claim 8, wherein the amine antioxidant is a hindered amine antioxidant.

11. The method for producing formate according to claim 1, wherein the organic solvent contains toluene.

12. A catalyst composition used in a hydrogenation reaction to produce a formate from a starting compound which is at least one selected from the group consisting of carbon dioxide, bicarbonates, and carbonates, Catalyst and First antioxidant, A second antioxidant different from the first antioxidant, Phase-transfer catalyst and Includes, The catalyst is at least one selected from the group consisting of a metal complex represented by the following general formula (4A), its tautomers, stereoisomers, and salts thereof. The first and second antioxidants are two selected from the group consisting of phosphorus-based antioxidants, amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants. Catalyst composition. 【Transformation 5】 (In general formula (4A), R0 represents a hydrogen atom or an alkyl group, Q1 independently represents CH2, NH, or O, and CH2 and NH may have further substituents. Each R1 independently represents an alkyl group or an aryl group (however, if Q1 represents NH or O, at least one of R1 represents an aryl group). A independently represents CH, CR5, or N, and R5 represents an alkyl group, aryl group, aralkyl group, amino group, hydroxyl group, or alkoxy group. Z represents a halogen atom, n represents 0 to 3, (If multiple Ls exist, each L independently represents a neutral or anionic ligand.)

13. The catalyst composition according to claim 12, wherein the first antioxidant is a phosphorus-based antioxidant.

14. The catalyst composition according to claim 13, wherein the second antioxidant is one selected from the group consisting of amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.

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