Catalytic reaction method, method for producing organic compound, 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

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

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

[0002] In organic synthesis, various reactions using transition metal complexes composed 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, there are high hopes for hydrogen energy 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 reacting carbon dioxide with hydrogen in the presence of a catalyst containing an element from Group 8, 9 or 10 of the periodic table, a tertiary amine (I) and a polar solvent.

[0005] Patent No. 5734286

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

[0007] Therefore, an object of the present invention is to provide a catalytic reaction method, a method for producing an organic compound, and a catalyst composition that are suitable for reducing catalyst deterioration.

[0008] The present invention provides a catalytic reaction method, which comprises reacting a starting compound using a catalyst in the presence of a solvent, wherein the solvent comprises 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.

[0009] The present invention further provides a method for producing an organic compound, comprising producing an organic compound from the starting compound by the catalytic reaction method.

[0010] The present invention further provides a catalyst composition comprising: a catalyst; a first antioxidant; a second antioxidant different from the first antioxidant; and a phase transfer catalyst.

[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 that are suitable for reducing catalyst deterioration.

[0012] Fig. 1 is a schematic diagram showing an example of a three-compartment electrodialysis apparatus. Fig. 2 is a schematic diagram showing an example of a formic acid production system.

[0013] A catalytic reaction method according to a first aspect of the present invention includes reacting a starting compound using a catalyst in the presence of a solvent, wherein 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.

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

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

[0016] In a fourth aspect of the present invention, for example, in the catalytic reaction method according to any one of the first to third aspects, the 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): (R 1 , R 2 , and R 3 each independently represents a hydrogen atom or an arbitrary 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): (R 4 , R 5 , and R 6 each independently represents an optional substituent.

[0019] In a seventh aspect of the present invention, for example, in the catalytic reaction method according to the sixth aspect, in the chemical formula (1C), R 4 , R 5 , and R 6 are each independently represented by the following chemical formula (1D). (* 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 an 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 a 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 a 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 an 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 a 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 the 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), a tautomer thereof, a stereoisomer thereof, and a salt thereof:

[0026] (In general formula (1A), X represents an atomic group containing a typical element of Groups 13 to 15 that can be coordinated to M; each Q independently represents a bridged structure that contains a typical element of Groups 14 to 16 and connects Y and X; each Y independently represents an atomic group containing a typical element of Groups 14 to 16 that can be coordinated to M; M represents a metal atom; Z represents an anionic ligand; n represents 0 to 3; and when a plurality of Ls are present, each independently represents a neutral or anionic ligand.)

[0027] In a 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 a metal complex represented by the following general formula (2A):

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

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

[0030] (In general formula (3A), R represents a hydrogen atom or an alkyl group; each A independently represents CH, CR, or N, and R represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxy group, or an alkoxy group; each Q independently represents CH, NH, or O, and CH and NH may further have a substituent; Y represents a phosphorus atom or a nitrogen atom; each R independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have a substituent; M represents a metal atom; Z represents an anionic ligand; n represents 0 to 3; and when a plurality of Ls are present, each independently represents a neutral or anionic ligand.)

[0031] In a sixteenth aspect of the present invention, for example, in the catalytic reaction method according to any one of the thirteenth to fifteenth aspects, the metal atom represented by M is ruthenium.

[0032] In a seventeenth aspect of the present invention, for example, in the catalytic reaction method according to any one of the first to sixteenth aspects, the organic solvent contains toluene.

[0033] A method for producing an organic compound according to an eighteenth aspect of the present invention includes producing an organic compound from the starting compound by the catalytic reaction method according to any one of the first to seventeenth aspects.

[0034] A catalyst composition according to a nineteenth aspect of the present invention includes a catalyst, a first antioxidant, a second antioxidant different from the first antioxidant, and a phase transfer catalyst.

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

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

[0037] In a 22nd aspect of the present invention, for example, in the 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), a tautomer thereof, a stereoisomer thereof, and a salt thereof: (In general formula (1A), X represents an atomic group containing a typical element of Groups 13 to 15 that can be coordinated to M; each Q independently represents a bridged structure that contains a typical element of Groups 14 to 16 and connects Y and X; each Y independently represents an atomic group containing a typical element of Groups 14 to 16 that can be coordinated to M; M represents a metal atom; Z represents an anionic ligand; n represents 0 to 3; and when a plurality of Ls are present, each independently represents a neutral or anionic ligand.)

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

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

[0040] In a 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 aspect of the present invention, for example, in the catalyst composition according to the 25th aspect, the solvent is at least one selected from the group consisting of organic solvents and aqueous solvents.

[0042] The present invention will be described in detail below, but the following description is not intended to limit the present invention to a specific embodiment.

[0043] [Catalytic Reaction Method] The catalytic reaction method according to a first embodiment of the present invention is a method of reacting starting compounds using 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 compounds is carried out in a two-phase system in which the organic solvent and the aqueous solvent are separated. In this specification, in the two-phase system, the phase containing the organic solvent is sometimes referred to as the organic phase, and the phase containing the aqueous solvent is sometimes referred to as the aqueous phase. The organic phase and the aqueous phase are sometimes collectively referred to as the reaction liquid.

[0044] By including the first antioxidant and the second antioxidant in the solvent, oxidation of the catalyst by oxygen contained in the system can be suppressed, and deterioration of the catalyst can be reduced. Therefore, the activity retention rate can be improved. This allows the catalyst to be reused, and production costs can be reduced.

[0045] The organic phase may contain a catalyst, and the aqueous phase may contain the starting compound. The product obtained by the catalytic reaction may be contained in the aqueous phase. This allows the catalyst to be easily separated, making it easy to reuse the catalyst and repeat the reaction. Another advantage of a two-phase reaction is that it is easy to prepare an aqueous phase with a high product concentration. 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.

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

[0047] Examples of methods to which the catalytic reaction method according to the first embodiment of the present invention can be applied include 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 a reduction reaction of an inorganic or organic compound. The 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 a hydrogenation reaction of the starting compound with hydrogen. The hydrogenation reaction of an inorganic compound is, for example, a reaction for producing a formate. 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, the starting compound being at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate. When the catalytic reaction method according to the first embodiment of the present invention is applied to a formate production reaction, there is an advantage that formate can be produced efficiently and at low cost.

[0048] (Antioxidant) The first antioxidant and the second antioxidant are antioxidants having different compositions. An antioxidant generally refers to a compound that, when added to a material such as plastic, can prevent polymer degradation caused by a chain reaction between radicals generated within the material and oxygen. Examples of antioxidants 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 an amine-based antioxidant, a phenol-based antioxidant, and a sulfur-based antioxidant, and more preferably an amine-based antioxidant or a phenol-based antioxidant.

[0051] It is preferable that the first antioxidant is a phosphorus-based antioxidant and the second antioxidant is an amine-based or phenol-based antioxidant. This configuration is particularly suitable for reducing catalyst deterioration and improving the activity retention rate.

[0052] The phosphorus-based antioxidant is preferably one that is resistant to decomposition such as hydrolysis and has high stability, and is preferably, for example, a compound having a relatively bulky structure. The phosphorus-based antioxidant is, for example, a phosphorus compound. The phosphorus compound may be an organic phosphorus compound, or may be a phosphorous ester (phosphite), a hypophosphite, or a phosphonite. Examples of phosphites include trialkyl phosphites, triaryl phosphites, alkylaryl phosphites, and thiophosphites.

[0053] The phosphorus-based antioxidant is, for example, a compound having an aryl group. The aryl group may be, for example, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a substituted or unsubstituted phenyl group, preferably a phenyl group having a t-butyl group.

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

[0055]

[0056] In chemical formula (1B), R 1 , R 2 , and R 3 each independently represents a hydrogen atom or an arbitrary substituent. The substituent is, for example, a hydrocarbon group, a group containing an oxygen atom together with a hydrocarbon, or a group containing a sulfur atom together with a hydrocarbon. The number of carbon atoms in the hydrocarbon group is not particularly limited, and may be, for example, 1 to 50, 6 to 50, 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 include those mentioned above. The hydrocarbons of the group containing an oxygen atom together with a hydrocarbon and the group containing a sulfur atom together with a hydrocarbon are, for example, those mentioned above as hydrocarbon groups. R 1 , R 2 , and R3 At least two selected from the group consisting of may each independently have an aryl group, and R 1 , R 2 , and R 3 However, each of them may independently have an aryl group. Examples of the aryl group include those mentioned above.

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

[0058]

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

[0060]

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

[0062] Examples of phosphorus-based antioxidants include triphenyl phosphite, diisooctyl phosphite, heptakistriphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctylphenyl phosphite, diphenyltridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris(dipropylene glycol) phosphite, diisodecylpentaerythritol diphosphite, dioleylhydrogen phosphite, trilauryl phosphite, diisooctyl phenyl phosphite, tris(dipropylene glycol) phosphite, diisodecyl penta ...lauryl phosphite, diisooctyl phenyl phosphite, tris(dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleylhydrogen phosphite, trilauryl phosphite, trilauryl phosphite, tris(dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleylhydrogen phosphite, trilauryl phosphite, trilauryl phosphite, tris(dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleylhydrogen phosphite, trilauryl phosphite, trilauryl phosphite, tris(dipropylene glycol) Nuril 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, a 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)isopropylidenediphenol 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]dioxaphosphepin-6-yl)oxy]ethyl)amine, 3,9-bis(4-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5 ]undecane, 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly 4,4'-isopropylidenediphenol C12-15 alcohol phosphite, tetraalkyl(C12-15)-4,4'-isopropylidenediphenyl diphosphite, and the like.

[0063] The phosphorus-based antioxidant is preferably tris(2,4-di-tert-butylphenyl)phosphite, triphenyl phosphite, triisodecyl phosphite, tetraalkyl(C12-15)-4,4'-isopropylidene diphenyl diphosphite, or 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and particularly preferably tris(2,4-di-tert-butylphenyl)phosphite or triphenyl phosphite.

[0064] The amine-based antioxidant is an antioxidant having an amino group. Examples of the amine-based antioxidant include 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N-phenyl-1-naphthylamine, p,p'-dioctyldiphenylamine, phenothiazine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di-β-naphthyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, and N-phenyl-N'-isopropyl- Examples of suitable amines include p-phenylenediamine, aldol-α-naphthylamine, 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-tetramethylpiperidin-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-tetramethylpiperidin-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] The phenolic antioxidant is an antioxidant having a phenol group. Examples of the phenolic antioxidant include hindered phenolic antioxidants. Examples of the hindered phenolic antioxidant 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] The phenolic antioxidant is not limited to the above-mentioned hindered phenolic antioxidant. Examples of phenolic antioxidants other than the above-mentioned hindered phenolic antioxidants include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-thiobis-(6-tert-butyl-4-methylphenol), 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'-oxamido-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-ethyl hexyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate, 2,2'-ethylenebis(4,6-di-tert-butylphenol), 3,5-bis(1,1-dimethylethyl)-4-hydroxy-benzenepropanoic acid and C13-15 alkyl ester, 2,5-di-tert-amylhydroquinone, hindered phenol polymer (trade name AO.OH998 manufactured by Adeka Palmarol), 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol] ol], 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 6-[3-(3-tert-butyl-4-hydroxy-5-methyl)propoxy]-2,4,8,10-tetra-tert-butylbenz[d,f][1,3,2]-dioxaphosphepine, hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[monoethyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate] calcium salt, reaction products of 5,7-bis(1,1-dimethylethyl)-3-hydroxy-2(3H)-benzofuranone with o-xylene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, DL-α-tocopherol (vitamin E), 2,6-bis(α-methylbenzyl)-4-methylphenol , 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)butylic 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[ 5.5]undecane, triethylene glycol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 3-(3,5-dialkyl-4-hydroxyphenyl)propionic acid derivatives such as stearyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide, palmityl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide, myristyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide, and lauryl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide, and phenol.

[0067] The sulfur-based antioxidant is an antioxidant containing a sulfur atom (S). Examples of the sulfur-based antioxidant include didodecyl 3,3′-thiodipropionate, pentaerythritol tetrakis[3-laurylthiopropionate], dimyristyl 3,3′-thiodipropionate, and distearyl 3,3′-thiodipropionate.

[0068] From the viewpoint of fully exerting the function of the antioxidants, the total amount of the first antioxidant and the second antioxidant used is preferably 1 mmol or more per 1 L of solvent. From the viewpoint of reducing the cost of the antioxidants, the total amount of the first antioxidant and the second antioxidant used is preferably 100 mmol or less per 1 L of solvent. The first antioxidant and the second antioxidant may be added in their entirety when preparing the reaction solution, or 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 used 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 relative to 1 equivalent of the catalyst, more preferably 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 tertiary antioxidant that is different from the first antioxidant and the second antioxidant.

[0072] (Catalyst) In the catalytic reaction method according to the first embodiment of the present invention, it is preferable to use, as a catalyst, at least one compound selected from the group consisting of a metal complex represented by the following general formula (1A), a tautomer thereof, a stereoisomer thereof, and a salt thereof:

[0073]

[0074] (In general formula (1A), X represents an atomic group containing a typical element of Groups 13 to 15 that can be coordinated to M; each Q independently represents a bridged structure that contains a typical element of Groups 14 to 16 and connects Y and X; each Y independently represents an atomic group containing a typical element of Groups 14 to 16 that can be coordinated to M; M represents a metal atom; Z represents an anionic ligand; n represents 0 to 3; and when a plurality of Ls are present, each independently represents a neutral or anionic ligand.)

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

[0076] Examples of the typical elements of Groups 13 to 15 of the periodic table for X include a boron atom, a carbon atom, a silicon atom, a germanium atom, a tin atom, a nitrogen atom, a phosphorus atom, an arsenic atom, an oxygen atom, a sulfur atom, and a selenium atom, of which a boron atom, a carbon atom, a silicon atom, a germanium atom, a tin atom, a nitrogen atom, a phosphorus atom, an arsenic atom, and a sulfur atom are preferred, a carbon atom, a nitrogen atom, a phosphorus atom, and a sulfur atom are more preferred, and a carbon atom or a nitrogen atom is even more preferred.

[0077] X may be a zero- to monovalent atomic group. Examples of the atomic group represented by X include an alkyl group, an alkenyl group, an alkoxy group, an aromatic ring, and a heterocyclic ring, which may have a substituent or may be bonded to another substituent to form a ring.

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

[0079] The alkenyl group for X includes linear, branched, and cyclic substituted or unsubstituted alkenyl groups. The alkenyl group for X is preferably an alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an n-propenyl group, an i-propenyl group, a t-butenyl group, or an n-octenyl group, and is preferably an alkenyl group having 6 or less carbon atoms.

[0080] The alkoxy group for X includes a linear, branched, or cyclic substituted or unsubstituted alkoxy group. The alkoxy group for X is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, or a 2-methoxyethoxy group.

[0081] Examples of the aromatic ring in X include a phenyl ring and a naphthyl ring.

[0082] Examples of the heterocyclic ring for X include a pyrrolidine ring, a piperidine ring, a pyrroline ring, an imidazoline ring, an imidazolidine ring, a pyrrole ring, an imidazole ring, a pyridine ring, a pyrimidine ring, a triazine ring, a quinoline ring, and a quinazoline ring.

[0083] The zero- to monovalent atomic group represented by X preferably represents an atomic group containing a heteroaromatic ring formed together with two carbon atoms and a nitrogen atom, and this may have a substituent or may be bonded to another substituent to form a ring.

[0084] The zero- to monovalent atomic group represented by X is preferably a pyrroline ring, a pyridine ring, an imidazoline ring, a pyrimidine ring, or a triazine ring, more preferably a pyridine ring or a triazine ring, and even more preferably a pyridine ring.

[0085] When the zero- to monovalent atomic group represented by X has a substituent, examples of the substituent include those in Substituent Group A, and an alkyl group is preferred, and a methyl group is 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 bridged structure represented by Q, which connects Y and X and contains a typical element of Groups 14 to 16 of the periodic table, may have a double bond, a monocyclic structure or a fused ring structure, or may have a substituent.

[0088] Q can introduce various structures as described above. For example, the number of atoms in the portion between Y and X is preferably 1 to 5, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 1 or 2.

[0089] The atom contained between Y and X is not particularly limited, but is preferably a carbon atom, a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom, more preferably a carbon atom, a nitrogen atom, or an oxygen atom, still more preferably a carbon atom or an oxygen atom, and particularly preferably a carbon atom.

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

[0091] When 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 an alkylene group having 1 to 5 carbon atoms, an alkenylene group having 2 to 5 carbon atoms, a heteroatom such as an oxygen atom or a sulfur atom, or a combination of these bonded in series.

[0092] Each Q preferably independently represents CH2, NH, or O, and CH2 and NH may further have a substituent, and more preferably represents CH2 or NH.

[0093] Q may have a fused ring structure. In other words, the bridged structure represented by Q may contain a fused ring structure.

[0094] When 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 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 a substituent. When Q does not have either a monocyclic structure or a fused ring structure, the substituent is a substituent of the Q portion in the ring structure formed by including Q, Y, X, and M in general formula (1A).

[0096] When Q has a monocyclic structure or a fused ring structure, the substituent is a substituent of the monocyclic structure or the fused ring structure, or a substituent of Q in another ring structure formed by including Q, Y, X, and M in general formula (1A).

[0097] The substituent that Q may have may be, for example, one having a hetero atom, or another atom or atomic group.

[0098] Examples of the substituent having a hetero atom include an alkoxy group having 1 to 18 carbon atoms, an arylalkoxy group having 7 to 18 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, an acyl group having 2 to 18 carbon atoms, an aroyl group having 7 to 18 carbon atoms, a dialkylamino group having 2 to 18 carbon atoms, an oxygen atom, and a sulfur atom.

[0099] Examples of the other atoms or atomic groups include aromatic groups having 3 to 18 carbon atoms, alkyl groups having 1 to 18 carbon atoms, halogen atoms, etc. Examples of the 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 zero- to monovalent atomic group. Each Y independently represents a zero- to monovalent atomic group containing a typical element of Groups 14 to 16 of the periodic table that can be coordinated to M, and may further have a substituent. As the typical element of Groups 14 to 16 of the periodic table, a carbon atom, a nitrogen atom, a phosphorus atom, an arsenic atom, an oxygen atom, a sulfur atom, or a selenium atom is preferred, a carbon atom, a nitrogen atom, a phosphorus atom, or an arsenic atom is more preferred, a nitrogen atom or a phosphorus atom is still more preferred, and a phosphorus atom is particularly preferred.

[0102] In formula (1A), it is preferred that both Y's represent a nitrogen atom or a phosphorus atom, or that one Y represents a phosphorus atom and the other Y represents a nitrogen atom.

[0103] When the zero- to monovalent atomic group represented by Y has a substituent, examples of the substituent include those in Substituent Group A, and an alkyl group or an aryl group is preferred, and an ethyl group, a t-butyl group, or a phenyl group is more preferred.

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

[0105] Examples of the anionic ligand represented by Z include a halide ion (halogen atom), a hydride ion (hydrogen atom), a nitrate ion, and a cyanide ion. Z preferably represents a halogen atom or a hydrogen atom, and more preferably represents a halogen atom. Z is further preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.

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

[0107] When a plurality of Ls are present, each L independently represents a neutral or anionic ligand.

[0108] Examples of the neutral ligand 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, preferably triphenylphosphine or carbon monoxide, more preferably carbon monoxide.

[0109] Examples of the anionic ligand represented by L include a hydride ion (hydrogen atom), a nitrate ion, and a cyanide ion, and preferably a hydride ion (hydrogen atom).

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

[0111] It is also preferred that Z represents a chlorine atom, n represents 1 to 3, and each 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 an alkyl group is bonded to a nitrogen atom, Q represents CH, NH, or O, Y represents a phosphorus atom, M represents manganese, Z represents a bromine atom, n represents 2 or 3, and each 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, the metal complex represented by general formula (1A) is preferably a metal complex represented by the following general formula (2A).

[0114]

[0115] (In general formula (2A), X1 represents a heteroaromatic ring formed together with two carbon atoms and a nitrogen atom, which may have a substituent, or may be bonded to another substituent to form a ring; each Q1 independently represents CH2, NH, or O, and CH2 and NH may further have a substituent; each Y1 independently represents a phosphorus atom or a nitrogen atom; each R independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have a substituent; M represents a metal atom; Z represents an anionic ligand; n represents 0 to 3; and when a plurality of Ls are present, each independently represents a neutral or anionic ligand.)

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

[0117] The heteroaromatic ring formed together with the two carbon atoms and nitrogen atom represented by X is preferably a pyrroline ring, a pyridine ring, an imidazoline ring, a pyrimidine ring, or a triazine ring, more preferably a pyridine ring or a triazine ring, and even more preferably a pyridine ring.

[0118] Examples of the substituent that X1 may have include those in Substituent Group A, and an alkyl group is preferable, and a methyl group is more preferable.

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

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

[0121] Examples of the aryl group represented by R include substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group, a m-chlorophenyl group, and an o-hexadecanoylaminophenyl group. An aryl group having 12 or less carbon atoms is preferred, and a phenyl group is more preferred.

[0122] When R further has a substituent, examples of the substituent include those in Substituent Group A, and a methyl group, an ethyl group, an i-propyl group, a t-butyl group, and a phenyl group are preferred, and an ethyl group, an i-propyl group, or a t-butyl group is more preferred.

[0123] In 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] It is also preferred that Z represents a chlorine atom, n represents 1 to 3, and each L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

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

[0126]

[0127] (In general formula (3A), R represents a hydrogen atom or an alkyl group; each A independently represents CH, CR, or N, and R represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxy group, or an alkoxy group; each Q independently represents CH, NH, or O, and CH and NH may further have a substituent; Y represents a phosphorus atom or a nitrogen atom; each R independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have a substituent; M represents a metal atom; Z represents an anionic ligand; n represents 0 to 3; and when a plurality of Ls are present, each independently represents a neutral or anionic ligand.)

[0128] Y1, R, Q1, M, Z, n, and L in general formula (3A) have the same meanings as Y1, R, Q1, M, Z, n, and L in 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 the alkyl group represented by R0 include linear, branched, and cyclic substituted or unsubstituted alkyl groups. The alkyl group represented by R0 is preferably an alkyl group having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, an n-octyl group, an eicosyl group, and a 2-ethylhexyl group. From the viewpoint of ease of raw material procurement, an alkyl group having 6 or less carbon atoms is preferred, and a methyl group is preferred.

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

[0131] 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.

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

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

[0134] The aralkyl group represented by R5 includes a substituted or unsubstituted aralkyl group having 30 or less carbon atoms, such as a trityl group, a benzyl group, a phenethyl group, a tritylmethyl group, a diphenylmethyl group, and a naphthylmethyl group, and is preferably an aralkyl group having 12 or less 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, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, or a 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] It is also preferred that Z represents a chlorine atom, n represents 1 to 3, and each L independently represents a hydrogen atom, carbon monoxide, or triphenylphosphine.

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

[0139] The ruthenium complex represented by general formula (4A) is soluble in organic solvents and insoluble in water, making it suitable as a catalyst for the production of organic compounds. The ruthenium complex represented by general formula (4A) is suitable as a catalyst for, for example, the production of formate. Since the formate produced by the reaction is easily soluble in water, the reaction in a two-phase system makes it easy to separate the catalyst and the formate, making it easy to separate and recover the catalyst and the formate from the reaction system, making it possible to produce formate with a high yield and facilitating the reuse of expensive catalysts.

[0140]

[0141] (In general formula (4A), R represents a hydrogen atom or an alkyl group; each Q independently represents CH, NH, or O, and CH and NH may further have a substituent; each R independently represents an alkyl group or an aryl group (provided that when Q represents NH or O, at least one R represents an aryl group); each A independently represents CH, CR, or N, and R represents an alkyl group, aryl group, aralkyl group, amino group, hydroxy group, or alkoxy group; X represents a halogen atom; n represents 0 to 3; and when a plurality of Ls are present, each L independently represents a neutral or anionic ligand.)

[0142] R0, A, Q1, Z, L, and n in general formula (4A) have the same meanings as 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 have the same meanings as the alkyl group and aryl group represented by R in general formula (3A), respectively, and the preferred ranges are also the same.

[0144] The metal complexes represented by the general formulae (1A) to (4A) may produce stereoisomers depending on the coordination mode or conformation of the ligand, and may be a mixture of these stereoisomers or a pure isomer.

[0145] The metal complexes represented by general formulas (1A) to (4A) may be produced by known methods, such as those described in E. Pidko et al., ChemCatChem 2014, 6, 1526-1530.

[0146] Specific examples of the ruthenium complex represented by general formula (4A) include the compounds shown below: In the compounds shown below, Et represents an ethyl group, tBu represents a tertiary butyl group, and Ph represents a phenyl group.

[0147]

[0148]

[0149]

[0150] The amount of catalyst (preferably ruthenium complex) used is not particularly limited. From the viewpoint of fully exhibiting the function of the catalyst, the amount of catalyst used is preferably 0.1 μmol or more per 1 L of solvent, more preferably 0.5 μmol or more, and even more preferably 1 μmol or more. Furthermore, from the viewpoint of cost, it is preferably 1 mol or less per 1 L 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 per 1 L of solvent, or may be 10 μmol or less. When two or more catalysts are used, the total amount used may be within the above range.

[0151] (Phase Transfer Catalyst) The catalytic reaction method according to the first embodiment of the present invention requires a reaction to be carried out in a two-phase system, and therefore a phase transfer catalyst that facilitates the transfer of substances between the two phases may be used. 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 glycols and alkyl ethers thereof, etc. Among these, quaternary ammonium salts are preferred from the viewpoint of facilitating the transfer of substances between an aqueous solvent and an organic solvent even under mild reaction conditions.

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

[0153] The amount of the phase transfer catalyst used is not particularly limited. The amount of the 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 1 L of the organic and aqueous solvents. From the viewpoint of cost, the amount is preferably 1 mol or less, more preferably 500 mmol or less, and even more preferably 100 mmol or less, per 1 L of the organic and aqueous solvents. When two or more phase transfer catalysts are used, the total amount used may be within 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 a separated state, and preferably includes a solvent that dissolves the catalyst to form a homogeneous system.

[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 the organic solvent include toluene, benzene, xylene, propylene carbonate, dioxane, dimethyl sulfoxide, tetrahydrofuran, ethyl acetate, methylcyclohexane, cyclopentyl methyl ether, and mixed solvents thereof, and from the viewpoint of separability from the aqueous solvent, the organic solvent preferably contains toluene or dioxane, and more preferably contains toluene. An example of 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. In addition, the reaction conditions can be appropriately changed during the reaction process. The shape of the reaction vessel used for the reaction is not particularly limited.

[0158] The reaction temperature in the catalytic reaction method is not particularly limited, but in order 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. 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, and is preferably increased by heating. For example, in the reaction of hydrogen and carbon dioxide, hydrogen and carbon dioxide may be introduced into a reaction vessel and then heated to increase the temperature, or carbon dioxide may be introduced into the reaction vessel, the temperature may be increased, and then hydrogen may be introduced.

[0160] The reaction time in the catalytic reaction method is not particularly limited, and may be, for example, 0.5 hours or more, 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, 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] It should be noted that the catalytic reaction method of the present invention is not limited to the above-described embodiment. 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 using a catalyst in the presence of a solvent, the solvent including an antioxidant. The solvent may include, for example, an organic solvent.

[0162] [Method for Producing Organic Compound] 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 the catalytic reaction method according to the first embodiment. That is, the method for producing an organic compound according to the second embodiment of the present invention includes reacting a starting compound using a catalyst in the presence of a solvent to produce an organic compound from the starting compound, the solvent including 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 the first antioxidant and the second antioxidant in the solvent, oxidation of the catalyst by oxygen contained in the system can be suppressed, and catalyst deterioration can be reduced. Therefore, the activity retention rate can be improved. This allows the catalyst to be reused, 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 produced organic compound. This allows the catalyst to be easily separated, making it easy to reuse the catalyst and repeat the reaction. Another advantage of a two-phase reaction is that it is easy to produce an aqueous phase with a high concentration of the produced organic compound. 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 reaction may be a hydrogenation reaction of the starting compound with hydrogen, and the organic compound may be a hydride of the starting compound.

[0166] The starting compound may be at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate, and the organic compound may be formate, i.e., the reaction is a hydrogenation reaction of at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate with hydrogen, and the organic compound may be formate.

[0167] The first antioxidant and the second antioxidant may be the same as those described above as antioxidants used in the catalytic reaction method according to the first embodiment. It is preferable that 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 fully exerting the function of the antioxidants, the total amount of the first antioxidant and the second antioxidant used is preferably 1 mmol or more per 1 L of solvent. From the viewpoint of reducing the cost of the antioxidants, the total amount of the first antioxidant and the second antioxidant used is preferably 100 mmol or less per 1 L of solvent. The first antioxidant and the second antioxidant may be added in their entirety when preparing the reaction solution, or 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 relative to 1 equivalent of the catalyst, more preferably 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 as the catalyst used 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 general formulas (1A) to (4A) above, their tautomers, stereoisomers, and salts thereof. The preferred ranges are also the same as those in the first embodiment. In the general formulas (1A) to (4A), it is preferable that M is ruthenium.

[0171] The amount of catalyst (preferably ruthenium complex) used is not particularly limited. From the viewpoint of fully exhibiting the function of the catalyst, the amount of catalyst used is preferably 0.1 μmol or more per 1 L of solvent, more preferably 0.5 μmol or more, and even more preferably 1 μmol or more. Furthermore, from the viewpoint of cost, it is preferably 1 mol or less per 1 L 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 per 1 L of solvent, or may be 10 μmol or less. When two or more catalysts are used, the total amount used may be within the above range.

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

[0173] The amount of the phase transfer catalyst used is not particularly limited as long as an organic compound (e.g., formate) can be produced. The amount of the 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 1 L of the organic and aqueous solvents, in order to efficiently assist the transfer of, for example, carbonate or bicarbonate. From the viewpoint of cost, the amount is preferably 1 mol or less, more preferably 500 mmol or less, and even more preferably 100 mmol or less, per 1 L of the organic and aqueous solvents. When two or more phase transfer catalysts are used, the total amount used may be within 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 a separated state, and preferably includes a solvent that dissolves the catalyst to form a homogeneous system.

[0175] As the aqueous solvent, for example, the solvents described above in the first embodiment are used. From the viewpoint of low environmental impact, the aqueous solvent is preferably water.

[0176] As the organic solvent, for example, the organic solvent described above in the first embodiment can be used. From the viewpoint of separability from the aqueous solvent, it is preferable that the organic solvent contains toluene or dioxane, and more preferably 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 shape of the reaction vessel used for the reaction is not particularly limited.

[0178] The reaction temperature is not particularly limited, but in order 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. 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, and is preferably increased by heating. For example, in the reaction of hydrogen and carbon dioxide, hydrogen and carbon dioxide may be introduced into a reaction vessel and then heated to increase the temperature, or carbon dioxide may be introduced into the reaction vessel, the temperature may be increased, and then hydrogen may be introduced.

[0180] The reaction time is not particularly limited, but may be, for example, 0.5 hours or more, 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, from the viewpoint of ensuring a sufficient amount of organic compound produced and suppressing a decrease in catalytic efficiency. The upper limit of the reaction time is not particularly limited, and 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.

[0181] The production method according to the second embodiment is suitable for reducing catalyst deterioration. The reduction in catalyst deterioration 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 product yield in the second or subsequent reaction to the product yield in the first reaction.

[0182] In the production method according to the second embodiment, it is preferable that the reaction of the starting compounds has 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 compounds is repeatedly carried out 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] It should be noted that the method for producing an organic compound of the present invention is not limited to the above-described embodiment. In some cases, the reaction in the method for producing an organic compound of the present invention is not limited to a two-phase system. That is, the present invention provides a method for producing an organic compound, which includes reacting starting compounds using a catalyst in the presence of a solvent to produce an organic compound from the starting compounds, and the solvent includes a first antioxidant and a second antioxidant. The solvent may include, for example, an organic solvent.

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

[0185] Hereinafter, in the method for producing an organic compound according to the second embodiment of the present invention, the case where the organic compound is a formate, that is, the case where a method for producing a formate is performed will be described in detail.

[0186] (Method for Producing Formate) The 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 containing a first antioxidant and a second antioxidant, thereby producing 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 prevents the catalyst from being oxidized by oxygen contained in the system. By preventing catalyst oxidation, catalyst deterioration is reduced, and the activity retention rate can be improved even 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 an organic solvent and an 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 production reaction from terminating due to equilibrium, allowing formate production in high yield. Furthermore, since the aqueous phase and the organic phase 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 formates (e.g., alkali metal formates). Formates have the advantages of high hydrogen storage density, safety, and chemical stability, allowing for easy handling and enabling long-term storage of hydrogen and carbon dioxide. Formates have high solubility in aqueous solvents and can be separated off as a highly concentrated aqueous solution of formate. The aqueous solution of formate can be subjected to the formic acid production process described below after adjusting the formate concentration as necessary.

[0188] The first step can be performed, for example, as follows. First, a reaction vessel equipped with a stirrer is prepared, and a solvent is introduced into the reaction vessel. If necessary, a phase transfer catalyst may also be added. A catalyst is added to the reaction vessel and dissolved in a solvent to prepare a catalyst solution. A first antioxidant and a second antioxidant are added to the catalyst solution in the reaction vessel. Then, hydrogen and at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate are introduced into the reaction vessel to carry out a reaction. The order in which the catalyst, first antioxidant, and second antioxidant are added to the reaction vessel is not particularly limited. The first antioxidant and second antioxidant may be added in their entirety when the reaction solution is prepared, or may be added to the reaction solution in multiple portions during the reaction.

[0189] The reaction conditions in the method for producing a formate salt (the reaction conditions in the first step) are not particularly limited, and although the reaction conditions may be appropriately changed during the reaction process in some cases, it is preferable not to change them. The shape of the reaction vessel used in the reaction is not particularly limited.

[0190] In the first step, the reaction solution is stirred, for example. The stirring conditions for the reaction solution are not particularly limited, but a stirring power of 0.2 kW / m 3 It is preferable that the power consumption is 0.5 kW / m or more. 3 More preferably, the above value is satisfied. The greater the stirring power, the more likely it is that the gas disperses better in the aqueous phase and the organic phase. When the reaction liquid is stirred, the gas (e.g., gaseous hydrogen) is drawn into the reaction liquid from above the liquid surface of the reaction liquid, thereby filling the aqueous phase and the organic phase with the gas. However, the method for filling the aqueous phase and the organic phase with the gas is not limited to the above, and a sparger may also be used.

[0191] The shape of the stirring blade used to stir the reaction solution is not particularly limited. Examples of the stirring blade include anchor blades, turbine blades, paddle blades, and also large blades such as Fullzone (registered trademark) blades (Kobe Eco-Solutions Co., Ltd.) and Maxblend (registered trademark) blades (Sumitomo Heavy Industries Process Equipment Co., Ltd.).

[0192] Methods for producing formate include the reaction between hydrogen and carbon dioxide, the reaction between hydrogen and bicarbonate, and the reaction between hydrogen and carbonate. In the reaction between hydrogen and carbon dioxide, for example, the reaction of carbon dioxide to form carbonate and the reaction of carbonate and hydrogen to produce formate proceed simultaneously.

[0193] There are no particular limitations on the method and order of introducing 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, with regard to the introduction of hydrogen and carbon dioxide, one or both of them may be introduced continuously or intermittently. With regard to the reaction of hydrogen with bicarbonate and the reaction of hydrogen with carbonate, it is preferable to introduce hydrogen after introducing bicarbonate or carbonate into the reaction vessel. With regard to the introduction of hydrogen and bicarbonate or carbonate, one or both of them may be introduced continuously or intermittently.

[0194] The reaction temperature in the reaction between hydrogen and carbon dioxide, bicarbonate, or carbonate is not particularly limited, but is preferably 30°C or higher, more preferably 40°C or higher, and even more preferably 50°C or higher, in order to efficiently proceed with the reaction. From the viewpoint of energy efficiency, the reaction temperature 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, hydrogen and carbon dioxide may be introduced into a reaction vessel and then the temperature may be raised by heating, 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 preferred to introduce (produce) bicarbonate or carbonate into a reaction vessel, then introduce hydrogen, and then raise the temperature.

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

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

[0197] (Carbon dioxide and hydrogen) The hydrogen used in the second embodiment can be either gaseous hydrogen from a gas cylinder or liquid hydrogen. Examples of hydrogen sources that can be used include hydrogen generated during the iron smelting process and hydrogen generated during the soda production process. Hydrogen generated by the electrolysis of water can also be used.

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

[0199] Hydrogen gas and carbon dioxide gas may be introduced into the reaction system either singly or as a mixed gas. The ratio of hydrogen to carbon dioxide used may be equal on a molar basis, but an excess of hydrogen is preferred.

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

[0201] From the viewpoint of ensuring sufficient reactivity, the pressure of carbon dioxide is preferably 0.1 MPa or more, more preferably 0.2 MPa or more, and even more preferably 0.5 MPa or more. In addition, since the equipment tends to become large, the pressure is preferably 50 MPa or less, more preferably 20 MPa or less, and even more preferably 10 MPa or less.

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

[0203] The method for introducing carbon dioxide, hydrogen, a catalyst, a solvent, and the like used in the reaction into a reaction vessel is not particularly limited, and all of the raw materials may be introduced at once, some or all of the raw materials may be introduced stepwise, some or all of the raw materials may be introduced continuously, or a combination of these introduction methods may be used.

[0204] (Bicarbonate and Carbonate) Examples of the bicarbonate and carbonate used in this embodiment include carbonates or bicarbonates of alkali metals or alkaline earth metals. Examples of the bicarbonate include sodium bicarbonate and potassium bicarbonate, with potassium bicarbonate being preferred from the viewpoint of high solubility in water. That is, in this embodiment, it is preferable that the starting compound contains potassium bicarbonate as the bicarbonate. Examples of the carbonate include sodium carbonate, potassium carbonate, potassium sodium 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] The solvent for the basic solution used in producing the bicarbonate or carbonate is not particularly limited, and examples thereof include water, methanol, ethanol, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, benzene, toluene, and mixed solvents thereof. It is preferable for the solvent to contain water, and water is more preferable. The base used in the basic solution is not particularly limited as long as it can react with carbon dioxide to produce the bicarbonate or carbonate, and a hydroxide is preferable. Examples include lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, potassium hydroxide, sodium hydroxide, diazabicycloundecene, and triethylamine. Of the above, a hydroxide is preferable, with potassium hydroxide and sodium hydroxide being more preferable, and potassium hydroxide being even more preferable.

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

[0208] The ratio of the amounts of carbon dioxide to base used in the reaction of carbon dioxide and base is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more, in terms of producing carbonate from carbon dioxide. Furthermore, from the viewpoint of carbon dioxide utilization efficiency, it is preferably 8.0 or less, more preferably 5.0 or less, and even more preferably 3.0 or less. The ratio of the amounts of carbon dioxide to base used may be the ratio of the molar amounts of carbon dioxide to base introduced into the reaction vessel, and is expressed as the molar amount (mol) of CO2 / the molar amount (mol) of base. By setting the ratio of the amounts of carbon dioxide to base used within the above range, excessive introduction of carbon dioxide into the reaction vessel can be suppressed, unreacted carbon dioxide can be minimized, and the final conversion efficiency of formic acid can be easily improved. Furthermore, carbon dioxide can be hydrogenated from the reaction of carbon dioxide and base to produce bicarbonate or carbonate in the same vessel, thereby producing formate. The unreacted carbon dioxide can be recovered from the reaction vessel and reused.

[0209] Although there are no particular limitations on the method and order of introducing carbon dioxide and a base into a reaction vessel, it is preferable to introduce carbon dioxide into the reaction vessel after introducing the base. Furthermore, the introduction of carbon dioxide and the base may be carried out continuously or intermittently, with respect to either or both of them.

[0210] The reaction temperature in the reaction of carbon dioxide with a base to produce a bicarbonate or a carbonate is not particularly limited, but in order to dissolve carbon dioxide in the aqueous phase, the reaction temperature is preferably 0° C. or higher, more preferably 10° C. or higher, and even more preferably 20° C. or higher. The reaction temperature 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 for producing a bicarbonate or carbonate by the reaction of carbon dioxide with a base is not particularly limited, but is, for example, preferably 0.5 hours or more, more preferably 1 hour or more, and even more preferably 2 hours or more from the viewpoint of ensuring a sufficient amount of produced bicarbonate or carbonate, and is preferably 24 hours or less, more preferably 12 hours or less, and even more preferably 6 hours or less from the viewpoint of cost.

[0212] The bicarbonate or carbonate 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 organic compound production method according to the second embodiment of the present invention. Alternatively, the bicarbonate or carbonate may be produced by reacting carbon dioxide with a base in a reaction vessel, and then introduced into the reaction vessel.

[0213] [Method for Producing Formic Acid] The method for producing formic acid of this embodiment includes a step of producing a formate by the method for producing a formate described above, and a step of protonating at least a portion of the formate to generate formic acid. In this specification, the step of protonating at least a portion of the formate to generate formic acid may be referred to as the second step. The method for producing formic acid of this embodiment includes, for example, the first step and the second step described above.

[0214] In the first step, the formate salt produced is eluted into the aqueous phase, and an aqueous solution of the formate salt can be obtained by separating the aqueous phase. It is preferable to separate the aqueous phase in the first step and treat the resulting aqueous solution with, for example, an electrodialysis device in the second step to produce formic acid. The aqueous phase to be separated is the aqueous phase after the first step.

[0215] In the second step, the aqueous solution of formate obtained in the first step may be used as is, or, if necessary, the concentration of the formate in the aqueous solution may be adjusted by concentration or dilution. Examples of methods for diluting the aqueous solution of formate include adding pure water for dilution. Examples of methods for concentrating the aqueous solution of formate include distilling water from the aqueous solution and concentrating the aqueous solution using a separation membrane unit equipped with a reverse osmosis membrane. When performing treatment using an electrodialysis device, a high-concentration aqueous solution of formate may suffer from a loss of formate due to concentration diffusion. To prevent this, it is preferable to separate the aqueous phase in the first step, adjust the formate concentration by dilution, and then use the resulting aqueous solution 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 a higher yield and with better productivity.

[0216] The degree of concentration adjustment (preferably dilution) of the aqueous solution of formate obtained in the first step is not particularly limited. The concentration of formate in the aqueous solution after the concentration adjustment is preferably a concentration suitable for electrodialysis, preferably 2.5 mol / L or more, more preferably 3 mol / L or more, more preferably 4.75 mol / L or more, and even more preferably 5 mol / L or more. Furthermore, when performing treatment using an electrodialysis device, from the viewpoint of suppressing 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. Alternatively, the water produced in the second step may be used for dilution. Reusing the water produced in the second step for dilution is preferable because it has the advantage of reducing the cost of wastewater treatment and the environmental load.

[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 decarbonation, and then the resulting 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, and the resulting solution may be decarbonated before being used in the second step. The aqueous solution of formate obtained in the first step may contain unreacted carbonate or bicarbonate produced by a side reaction. Electrodialysis of a solution containing carbonate or bicarbonate may result in the generation of carbon dioxide, which may reduce the dialysis efficiency. Therefore, by adding an acid to the aqueous solution of formate obtained in the first step, followed by decarbonation, and then electrodialysis, formic acid can be produced in a higher yield and with better productivity.

[0219] Examples of acids used in the 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, and it is preferable to use formic acid.

[0220] From the viewpoint of suppressing the amount of carbon dioxide generated during electrodialysis, the amount of acid used relative to the amount of carbon dioxide present in the solution is preferably 50% or more, more preferably 80% or more. Furthermore, by maintaining the pH of the formate solution near neutral during electrodialysis, deterioration of the electrodialysis apparatus can be suppressed, so the amount of acid used relative to the amount of carbon dioxide present in the solution is preferably 150% or less, more preferably 120% or less.

[0221] In the present embodiment, the proportion of the formate salt protonated in the second step is preferably 10% or more, more preferably 20% or more, and even more preferably 30% or more, relative to the initial molar amount of formate salt in the aqueous solution of formate salt, from the viewpoint of increasing the purity of the recovered aqueous solution of formic acid.

[0222] Examples of the electrodialysis apparatus used in the second step include a two-compartment electrodialysis apparatus using a bipolar membrane and an anion exchange membrane or a cation exchange membrane, and a three-compartment electrodialysis apparatus using 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-compartment electrodialysis apparatus. The electrodialysis apparatus shown in FIG. 1 includes a plurality of bipolar membranes, anion exchange membranes, and cation exchange membranes. These bipolar membranes, anion exchange membranes, and cation exchange membranes are arranged between an anode and a cathode to form a base tank, a sample tank (salt tank), and an acid tank. By circulating an aqueous solution of formate salt to the sample tank while energizing the electrodialysis apparatus, the formate salt is converted to formic acid, and formic acid can be recovered from the acid tank, water from the sample tank, and hydroxide from the base tank.

[0224] The two-compartment electrodialysis device includes, for example, a plurality of bipolar membranes and cation exchange membranes. These bipolar membranes and cation exchange membranes are alternately arranged between an anode and a cathode, so that a salt chamber is formed between each bipolar membrane and the cation exchange membrane located on the cathode side thereof, and a base chamber is formed between each bipolar membrane and the cation exchange membrane located on the anode side thereof. By circulating an aqueous solution of formate salt through the salt chamber while energizing the electrodialysis device, hydroxide is produced in the base chamber, and the formate salt circulating through the salt chamber is converted to formic acid.

[0225] In the second step, the formate salt can be protonated in a simple manner using an electrodialysis device to obtain a solution of formic acid.

[0226] 2, a formic acid production system 100 of this embodiment includes, for example, a formate 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, 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 pipes L1 and L2.

[0227] The formate produced in the production apparatus 10 is separated into an aqueous phase, and then supplied as an aqueous solution of formate to the electrodialysis apparatus 30. At this time, as shown in Fig. 2 , the aqueous solution of formate may be previously sent to the dilution apparatus 20 via a 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 in which the formate concentration has been adjusted by the dilution device 20 is sent to the electrodialysis device 30 via the flow path L4, where at least a portion of the formate is protonated. As a result, formic acid and water are produced from the formate. The produced formic acid can be extracted via the flow path L5. The produced water may also be sent to the storage unit 40 via the flow path L7.

[0229] A portion of the formic acid produced by the electrodialysis device 30 may be delivered to the storage unit 40 through 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 flow path L9, thereby subjecting the aqueous solution of formate to decarbonation treatment. Each flow path of the production system 100 may include a valve (e.g., valves 3 and 5 in FIG. 2 ) for adjusting the pressure or supply amount.

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

[0231] The formate salts and formic acid thus obtained have a wide range of applications in various fields, such as use as a silage additive, a feed preservative, a leather tanning agent, a textile dyeing agent, a rubber coagulant, an antifreeze agent, a cleaning agent for precision machinery, a neutralizing agent, a precipitant for heavy metals, a deicing agent, a cutting fluid, a heat transfer fluid, a lubricant, a hydride ion source, and a hydrogen supply source.

[0232] [Catalyst Composition] The 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 requirement selected from the group consisting of the following (A) to (D): (A) The catalyst further comprises a phase transfer catalyst; (B) The catalyst is a compound represented by general formula (1A), in which Y is an atomic group having a phosphorus atom and a substituent, and the substituent is an alkyl group; (C) The total content of the first antioxidant and the second antioxidant is 10 equivalents or more relative to 1 equivalent of the catalyst; (D) The first antioxidant comprises a phosphorus-based antioxidant. (In general formula (1A), X represents an atomic group containing a typical element of Groups 13 to 15 that can be coordinated to M; each Q independently represents a bridged structure that contains a typical element of Groups 14 to 16 and connects Y and X; each Y independently represents an atomic group containing a typical element of Groups 14 to 16 that can be coordinated to M; M represents a metal atom; Z represents an anionic ligand; n represents 0 to 3; and when a plurality of Ls are present, each independently represents a neutral or anionic ligand.)

[0233] When the catalyst composition contains the first antioxidant and the second antioxidant, deterioration of the catalyst can be reduced and the activity retention rate in the catalytic reaction can be improved.

[0234] The catalyst composition of this embodiment may satisfy the above-mentioned condition (A). That is, the present invention provides a catalyst composition comprising 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 preferred range is also the same as that of the first embodiment. Such a catalyst composition is useful, for example, for two-phase reactions, and may be able to further suppress a decrease in catalytic efficiency in catalytic reactions.

[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 preferred range is also the same as in the first embodiment.

[0236] The catalyst composition of this embodiment may satisfy the above-mentioned condition (B). That is, in another aspect, the present invention provides a catalyst composition comprising a catalyst, a first antioxidant, and a second antioxidant, and the catalyst is a compound represented by general formula (1A), in which Y is an atomic group having a phosphorus atom and a substituent, and the substituent is an alkyl group. The catalyst may be a compound represented by general formulas (2A) and (3A) described above for the first embodiment, in which Y is a phosphorus atom and R is an alkyl group, or a compound represented by general formula (4A), in which R is an alkyl group.

[0237] The catalyst composition of this embodiment may satisfy the above-mentioned condition (C). That is, in another aspect, the present invention provides a catalyst composition comprising a catalyst, a first antioxidant, and a second antioxidant, wherein the content of the antioxidants is 10 equivalents or more relative to 1 equivalent of the catalyst. The content of the antioxidants is, for example, 10 equivalents or more and 10,000 equivalents or less, preferably 100 equivalents or more and 10,000 equivalents or less, and more preferably 100 equivalents or more and 1,000 equivalents or less relative to 1 equivalent of the catalyst.

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

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

[0240] The first antioxidant and the second antioxidant are the compounds described above as the first antioxidant and the second antioxidant used in the catalytic reaction method according to the first embodiment, and the preferred ranges are also the same as those 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 an amine-based antioxidant, a phenol-based antioxidant, and a sulfur-based antioxidant, 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 producing an organic compound, preferably a catalyst composition for producing a formate salt. The catalyst composition of this embodiment is, for example, a catalyst composition for a hydrogenation reaction. The starting compound is, for example, at least one selected from the group consisting of carbon dioxide, hydrogen carbonate, and carbonate.

[0242] The catalyst composition of this embodiment may be contacted with a starting compound to produce an organic compound. The contact between the catalyst composition and the starting compound may be performed, for example, by mixing the catalyst composition with a solution containing the starting compound, mixing the catalyst composition and the starting compound in a solvent, or mixing a solution containing the starting compound with a solution containing the catalyst composition.

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

[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 an organic solvent and an aqueous solvent. In a preferred embodiment of the present invention, the catalyst composition contains only an organic solvent as the solvent. In another preferred embodiment of the present invention, the catalyst composition contains an organic solvent and an aqueous solvent. As the organic solvent, for example, the one described above in the first embodiment is used. The organic solvent is preferably toluene or dioxane, more preferably toluene. As the aqueous solvent, for example, the one described above in the first embodiment is used.

[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 of the starting compounds with hydrogen 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 (see below) was added to a suspension of 95.3 mg (0.1 mmol) of [RuHCl(PPh)(CO)] in 5 mL of tetrahydrofuran (THF). The mixture was stirred and heated at 65°C for 3 hours to carry out the reaction. The mixture was then 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 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 the following catalyst 1 (55 mg, 97% yield) as yellow crystals. In the catalyst 1 and ligand A shown below, tBu represents a tertiary butyl group.

[0247]

[0248] 31 P{ 1 H}(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 = 9.5 Hz), 37.7 (t, J = 6.0 Hz), 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 of the aqueous phase obtained after the reaction was taken out, and 100 μL of dimethyl sulfoxide was added as a reference substance, and the mixture was dissolved in 500 μL of heavy water. In this way, a measurement sample was prepared. 1 H NMR measurement was performed. From the obtained NMR spectrum, the integral value Ia of the peak derived from potassium formate and the integral value Ib of the peak derived from dimethyl sulfoxide were identified. The amount of potassium formate, X (mol), 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 in the quantification of potassium formate, M is the molecular weight of dimethyl sulfoxide, R is the ratio of the number of protons in dimethyl sulfoxide per molecule to the number of protons in potassium formate per molecule, Ia is the integral value of the NMR peak derived 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, and B is the mass (g) of the aqueous solution used in the quantification of potassium formate.)

[0251] Then, based on the amount of substance X (mol) of the produced formate and the total amount of substances Z (mol) of carbon dioxide, hydrogen carbonate, and carbonate used in the reaction (the amount of substance Z is potassium hydrogen carbonate in the following Examples and Comparative Examples), the yield (%) of the formate was calculated according to the following formula (2): Yield of formate = 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 first antioxidant, and 2,6-di-tert-butyl-p-cresol as a second antioxidant were placed in a pressure-resistant glass vial equipped with a stirrer and then introduced into a reactor. In the aqueous phase, the concentration of potassium bicarbonate was 2 mol / 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 first antioxidant and second antioxidant were each 6 mmol / L. Subsequently, for the first reaction, hydrogen gas was introduced 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 inside of the reactor was purged with nitrogen gas.

[0253] The reaction mixture was removed from the reactor under a nitrogen gas atmosphere, and the organic and aqueous phases were separated. The yield of formate in the first reaction was calculated using the aqueous phase according to 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 stirrer, and the mixture was then placed in a reactor. The potassium bicarbonate concentration in the aqueous phase was adjusted to 2 mol / L. Then, for 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. The atmosphere inside the reactor was replaced with nitrogen gas.

[0255] The reaction mixture was removed from the reactor under a nitrogen gas atmosphere, and the organic and aqueous phases were separated. The yield of formate in the second reaction was calculated by the method described above, in the same manner as in the first reaction.

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

[0257] Example 3 A 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 salt in each of 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 yield of formate in each of the first and second reactions was 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 salt in each of the first and second reactions were calculated in the same manner as in Example 1.

[0260] Example 6 A 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 salt in each of 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 secondary antioxidant was changed to N1,N3-bis(2,2,6,6-tetramethylpiperidin-4-yl)isophthalamide. The yields of formate salt in each of the first and second reactions were calculated in the same manner as in Example 1.

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

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

[0264] Example 10 A 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 in the first reaction was calculated in the same manner as in Example 1.

[0265] After the first reaction, a 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 in the second reaction was calculated as follows.

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

[0267] Example 11 A 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 in the first reaction was calculated in the same manner as in Example 1. In addition, a second reaction was carried out in the same manner as in Example 10, and the yield of formate in the second reaction was calculated.

[0268] Example 12 A 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 in the first reaction was calculated in the same manner as in Example 1. In addition, a second reaction was carried out in the same manner as in Example 10, and the yield of formate in the second reaction was calculated.

[0269] Example 13 A 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 in the first reaction was calculated in the same manner as in Example 1. In addition, a second reaction was carried out in the same manner as in Example 10, and the yield of formate in the second reaction was calculated.

[0270] Example 14 A 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 in the first reaction was calculated in the same manner as in Example 1. In addition, a second reaction was carried out in the same manner as in Example 10, and the yield of formate in the second reaction was calculated.

[0271] Example 15 A 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 in the first reaction was calculated in the same manner as in Example 1. In addition, a second reaction was carried out in the same manner as in Example 10, and the yield of formate in the second reaction was calculated.

[0272] Example 16 A 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 in the first reaction was calculated in the same manner as in Example 1. In addition, a second reaction was carried out in the same manner as in Example 10, and the yield of formate in the second reaction was calculated.

[0273] [Example 17] Reactions were 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 12 mmol / L. The yields of formate in each of the first and second reactions were 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 each changed to 24 mmol / L. The yields of formate in each of the first and second reactions were calculated in the same manner as in Example 1.

[0275] [Example 19] A reaction was carried out in the same manner as in Example 1, except that the first antioxidant was changed to triphenyl phosphite. In the same manner as in Example 1, the yield of formate in each of the first and second reactions was calculated.

[0276] Example 20 A 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 salt in each of the first and second reactions were calculated in the same manner as in Example 1.

[0277] Comparative Example 1 A 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 12 mmol / L and no second antioxidant was added. The yields of formate in each of the first and second reactions were calculated in the same manner as in Example 1.

[0278] Comparative Example 2 A reaction was carried out in the same manner as in Example 1, except that the second antioxidant was not added. The yield of formate in each of 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 and 2. Table 2 shows the reaction yields in Examples 10 to 20. The activity retention rates shown in Tables 1 and 2 refer to the ratio of the yield in the second reaction to the yield in the first reaction.

[0280]

[0281]

[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 a first antioxidant and a second antioxidant, showed a higher activity retention rate than Comparative Examples 1 and 2, in which the reaction did not contain a second antioxidant. Therefore, catalyst deterioration was reduced in Examples 1 to 20. Furthermore, the yields in Examples 1 to 20 were sufficient for practical use.

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

Claims

1. A catalytic reaction method comprising reacting a starting compound using a catalyst in the presence of a solvent, wherein the solvent comprises 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.

2. The catalytic reaction method 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 catalytic reaction method according to claim 1, wherein the organic phase containing the organic solvent contains the first antioxidant and the second antioxidant.

4. The catalytic reaction method according to claim 1, wherein the first antioxidant is a phosphorus-based antioxidant.

5. The catalytic reaction method according to claim 4, wherein the phosphorus-based antioxidant is a compound represented by the following chemical formula (1B): (In the chemical formula (1B), R 1 , R 2 , and R 3 each independently represents a hydrogen atom or an arbitrary substituent.

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

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

8. The catalytic reaction method according to claim 4, wherein 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.

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

10. The catalytic reaction method according to claim 8, wherein the amine-based antioxidant is a hindered amine-based antioxidant.

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

12. The catalytic reaction method according to claim 11, wherein the starting compound is at least one selected from the group consisting of carbon dioxide, bicarbonate, and carbonate, and the reaction produces a formate from the starting compound.

13. The catalytic reaction method according to claim 1, wherein the catalyst is at least one selected from the group consisting of a metal complex represented by the following general formula (1A), its tautomer, stereoisomer, and salt thereof: (In general formula (1A), X represents an atomic group containing a typical element of Groups 13 to 15 that can be coordinated to M; each Q independently represents a bridged structure that contains a typical element of Groups 14 to 16 and connects Y and X; each Y independently represents an atomic group containing a typical element of Groups 14 to 16 that can be coordinated to M; M represents a metal atom; Z represents an anionic ligand; n represents 0 to 3; and when a plurality of Ls are present, each independently represents a neutral or anionic ligand.) 14. The catalytic reaction method according to claim 13, wherein the metal complex represented by the general formula (1A) is a metal complex represented by the following general formula (2A): (In general formula (2A), X1 represents a heteroaromatic ring formed together with two carbon atoms and a nitrogen atom, which may have a substituent, or may be bonded to another substituent to form a ring; each Q1 independently represents CH2, NH, or O, and CH2 and NH may further have a substituent; each Y1 independently represents a phosphorus atom or a nitrogen atom; each R independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have a substituent; M represents a metal atom; Z represents an anionic ligand; n represents 0 to 3; and when a plurality of Ls are present, each independently represents a neutral or anionic ligand.) 15. The catalytic reaction method according to claim 14, wherein the metal complex represented by the general formula (2A) is a metal complex represented by the following general formula (3A): (In general formula (3A), R represents a hydrogen atom or an alkyl group; each A independently represents CH, CR, or N, and R represents an alkyl group, an aryl group, an aralkyl group, an amino group, a hydroxy group, or an alkoxy group; each Q independently represents CH, NH, or O, and CH and NH may further have a substituent; Y represents a phosphorus atom or a nitrogen atom; each R independently represents an alkyl group, an aryl group, or an aralkyl group, which may further have a substituent; M represents a metal atom; Z represents an anionic ligand; n represents 0 to 3; and when a plurality of Ls are present, each independently represents a neutral or anionic ligand.) 16. The catalytic reaction method according to claim 13, wherein the metal atom represented by M is ruthenium.

17. The catalytic reaction method of claim 1, wherein the organic solvent comprises toluene.

18. A method for producing an organic compound, comprising producing the organic compound from the starting compound by the catalytic reaction method according to any one of claims 1 to 17.

19. A catalyst composition comprising: a catalyst; a first antioxidant; a second antioxidant different from the first antioxidant; and a phase transfer catalyst.

20. The catalyst composition of claim 19, wherein the first antioxidant is a phosphorus-based antioxidant.

21. The catalyst composition of claim 20, wherein the second antioxidant is one selected from the group consisting of an amine-based antioxidant, a phenol-based antioxidant, and a sulfur-based antioxidant.

22. The catalyst composition according to claim 19, wherein the catalyst is at least one selected from the group consisting of a metal complex represented by general formula (1A), its tautomer, stereoisomer, and salt thereof: (In general formula (1A), X represents an atomic group containing a typical element of Groups 13 to 15 that can be coordinated to M; each Q independently represents a bridged structure that contains a typical element of Groups 14 to 16 and connects Y and X; each Y independently represents an atomic group containing a typical element of Groups 14 to 16 that can be coordinated to M; M represents a metal atom; Z represents an anionic ligand; n represents 0 to 3; and when a plurality of Ls are present, each independently represents a neutral or anionic ligand.) 23. The catalyst composition of claim 19 for the production of formate.

24. The catalyst composition of claim 19 for use in hydrogenation reactions.

25. The catalyst composition of claim 19, further comprising a solvent.

26. The catalyst composition according to claim 25, wherein the solvent is at least one selected from the group consisting of organic solvents and aqueous solvents.

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