Catalyst, method for producing catalyst, and methods for producing aromatic compound and amine compound

Abstract

To provide a catalyst which can be prepared by an easy method comprising mixing an inorganic carrier and a homogeneous palladium complex in a solvent and drying the mixture, and in which the palladium complex is supported carried by an inorganic carrier at a high carrying rate, wherein the carrying rate of the complex does not decrease even when the catalyst is washed after preparation, it is possible to decrease the amount of residual palladium in the product by removing the unsupported complex by washing with a solvent, there is little leaching of supported palladium after a reaction, makes coupling reactions and reduction reactions proceed, and enables repeated use thereof.SOLUTION: Provided is a catalyst composed of an inorganic carrier having a palladium complex adsorbed, wherein the palladium complex has a ligand having a ferrocene skeleton.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a catalyst comprising an inorganic support having adsorbed thereon a palladium complex. [Background technology]

[0002] Metal complex-catalyzed organic synthesis reactions have been known for a long time, and Suzuki-Miyaura coupling The reaction of forming carbon-carbon bonds (CC bonds), such as It can be said to be a necessary reaction. The organoboron compounds required for the Suzuki-Miyaura coupling reaction are relatively non-toxic and are comparable to other organic Unlike metal compounds, it is stable in water. The reaction proceeds under mild conditions, making it highly valuable industrially.

[0003] The Suzuki-Miyaura coupling reaction is mainly carried out in homogeneous systems, as shown in Non-Patent Document 1. Radium catalysts are widely used, but homogeneous catalysts cannot be reused in principle, and In order to achieve this, an operation to remove the catalyst from the product is required, and if the removal of the catalyst is insufficient, , residual metals from the catalyst are mixed into the product, affecting the product's properties. It is known to have. To solve these problems, a palladium complex is supported on a solid support and used as a heterogeneous catalyst. Attempts have been made to make it function (see Non-Patent Document 2). Palladium complexes can be immobilized by covalent bonding between the functional groups of the ligand and the functional groups on the support surface. and the method of bonding functional groups of the ligand and the functional groups on the support surface by molecular bonding such as ionic bonding or hydrogen bonding. These methods involve supporting the catalyst on the support surface. Therefore, it is necessary to chemically modify the support and the catalyst complex in advance. This leads to an increase in the overall cost, limiting industrial use. Even if a complex for support is designed by imitating an efficient complex in the field, the complex will not have the ability to bond with the support. Therefore, it is necessary to introduce functional groups for the complex, and as a result, the electronic state of the complex is optimized for the reaction. This limits the scope of use. In palladium-catalyzed reactions, the support does not require chemical modification of the support or complex. For example, activated carbon is used as a support, and [Pd(acac)2] complex is used. Suzuki-Miyaura coupling reaction using [Pd(xantphos)Cl2] complex It has been reported to be useful in carbonylation reactions (see Non-Patent Documents 3 and 4). [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] Chem.Rev.95(1995)pp.2457-2483 [Non-patent document 2] Chem.Asian J.16(2021)p.3851-3853 [Non-patent document 3] Bull.Chem.Soc.J pn.84(2011)p.1136-1143 [Non-patent document 4] Ind.Eng.Chem.Res.58(2019)p.22951-22957 Summary of the Invention [Problem to be solved by the invention]

[0005] In the previous example, the complex solution was mixed with activated carbon, the solvent was dried, and the resulting mixture was used as it was. Attempts have been made to use it as a catalyst, but the present inventors have not found a method for using it as a catalyst. When a catalyst was prepared by supporting a homogeneous palladium complex on activated carbon, the catalyst yielded approximately half the amount of the homogeneous catalyst used. It was found that the component exists in a state where it is not supported on activated carbon. In this case, the product will inevitably be contaminated with components derived from the complex. When the amount is low and a coupling reaction is performed, a large amount of activated carbon must be used.

[0006] Therefore, the present inventors mixed an inorganic support and a homogeneous palladium complex in a solvent, dried it, and The palladium complex can be supported on the inorganic support at a high loading rate. The catalyst is a catalyst that has been prepared, and even if the catalyst is washed with a solvent after preparation, the loading rate of the complex does not decrease. It is possible to remove unsupported complexes by washing, thereby reducing the amount of residual palladium in the product. Even after the reaction, the elution of the supported palladium is small, and the coupling reaction and reduction reaction are highly efficient. The objective of the present invention is to provide a catalyst that can be used repeatedly and efficiently. do. [Means for solving the problem]

[0007] As a result of extensive investigation, the present inventors have found that a palladium complex having a specific ligand is adsorbed on the surface of the inorganic substance. The present inventors have found that a catalyst containing a metal carrier can solve the above problems, and have completed the present invention. That is, the present invention provides the following.

[0008] [1] A catalyst composed of an inorganic support on which a palladium complex is adsorbed, A catalyst in which the ruthenium complex has a ligand with a ferrocene skeleton. [2] The ligand having a ferrocene skeleton is represented by the following formula (1-1) or formula (1-2): The catalyst according to [1], comprising a structure:

[0009] [ka]

[0010] (In formula (1-1) and formula (1-2), A 1 and A 2 each independently represents a direct bond, a C 1 to 12 alkyl group which may have a substituent, represents an alkylene group or a phenylene group having 6 to 12 carbon atoms which may have a substituent, L is represented by the following formula (2-1) or the following formula (2-2): R 1 ~R 8 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. an alkyl group, a phenyl group having 6 to 10 carbon atoms which may have a substituent, It may have an alkoxycarbonyl group having 2 to 6 carbon atoms, a carboxy group, or a substituent. represents a phosphinyl group having 2 to 18 carbon atoms, R 11 ~R 12 are each independently a hydrogen atom or a C1 to C12 alkyl group which may have a substituent. an aliphatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or represents an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent.

[0011] [ka]

[0012] (In formula (2-1) and formula (2-2), R 13 ~R 16 are each independently a hydrogen atom or a C1 to C12 alkyl group which may have a substituent. an aliphatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or represents an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent, * indicates A in formula (1-1) or formula (1-2). 2 )

[0013] [3] The total mass of palladium atoms is 0.001 mass% or more relative to the total mass of the catalyst. The catalyst according to [1] or [2], wherein the content is 5% by mass or less. [4] The catalyst according to any one of [1] to [3], wherein the inorganic support is activated carbon. [5] The specific surface area of ​​the activated carbon is 800m 2 / g or more 2000m 2 / g or less, [4 The catalyst according to any one of the preceding claims. [6] Suzuki-Miyaura coupling reaction using the catalyst according to any one of [1] to [5] A method for producing an aromatic compound, comprising the step of synthesizing an aromatic compound by [7] Using the catalyst according to any one of [1] to [5], a compound having a nitro group is A method for producing an amine compound, comprising the step of synthesizing an amine compound. [8] A method for producing a catalyst, comprising a step of mixing a liquid containing a palladium complex with an inorganic support. There was, The method for producing a catalyst, wherein the palladium complex has a ligand having a ferrocene skeleton. [9] The method for producing the catalyst according to claim 8, further comprising a step of removing the solvent after the step. . [Effects of the Invention]

[0014] According to the present invention, an inorganic support and a homogeneous palladium complex are mixed in a solvent and then dried. It can be prepared by a simple method and does not require structural modification of the homogeneous palladium complex. The catalytic function of the complex can be maximized, and the palladium complex is highly effective on the inorganic support. The catalyst is supported at a low loading rate, and even if the catalyst is washed with a solvent after preparation, the loading rate of the complex is low. Since the unsupported complex is not easily degraded, solvent washing is used to remove the residual palladium in the product. The amount of palladium can be reduced, and the amount of supported palladium is small even after the reaction. It can be reused and is a homogeneous palladium catalyst in coupling reactions, reduction reactions, etc. It is possible to provide a catalyst that exhibits higher reactivity than when using DETAILED DESCRIPTION OF THE INVENTION

[0015] Hereinafter, an embodiment of the present invention (hereinafter sometimes referred to as the present embodiment) will be described in detail. It should be noted that the following description is merely an example of an embodiment, and the present invention is not limited to this in any way.

[0016] In the present application, when the number of carbon atoms of a substituent is specified, the number of carbon atoms may be any number that the substituent may have. Indicates the number of carbon atoms including any substituents.

[0017] [catalyst] The catalyst of the present invention is an inorganic catalyst having adsorbed thereon a palladium complex having a ligand with a ferrocene skeleton. The present invention is characterized in that it is composed of a support. Palladium complexes with ferrocene atoms will be described later. The catalyst according to the present invention has a monodentate or bidentate ligand having a basic structure of an amine skeleton. The inorganic support and the palladium complex are bonded by physical adsorption such as van der Waals force or chemical adsorption such as ionic bond. In particular, when the inorganic carrier is activated carbon, the graphite particles contained in the activated carbon are adsorbed. Both the phene structure and the cyclopentadienyl group of the palladium complex have aromaticity. It is thought that these ring structures interact with each other and are strongly adsorbed.

[0018] The catalyst of the present invention is composed of an inorganic support on which the palladium complex is adsorbed, and the total quality of the catalyst is The total mass of palladium atoms is 0.001 mass% or more and 25 mass% or less of the total mass of palladium atoms. If the content is 0.001 mass % or more, the desired function as a catalyst tends to be obtained. If the content is 25 mass% or less, the amount of palladium eluted from the catalyst is suppressed and reusability is improved. There is a tendency to be able to The lower limit is more preferably 0.01% by mass or more, and even more preferably 0.03% by mass or more. The upper limit is more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0019] The contents of the inorganic support and palladium atoms in the catalyst of the present invention may be determined, for example, by the method of preparing the catalyst. In the manufacturing process, the amount of unadsorbed complex is subtracted from the amount of complex used, or the amount of unadsorbed complex contained in the obtained catalyst is subtracted from the amount of complex used. It can be calculated by analyzing the ratio of palladium atoms and iron atoms contained in the material.

[0020] In the complex of the present invention, both the ligand of the palladium complex and the inorganic support as the carrier are Since no chemical modification is required to connect them, it is similar to the conventional solid state method using chemical modification. Compared to supported palladium catalysts, this catalyst has the advantage of being easier to synthesize. After use in the reaction, the palladium complex can be recovered in the state where it is adsorbed on the inorganic support. Therefore, it is highly reusable. Furthermore, the catalyst of the present invention, which comprises a palladium complex adsorbed on an inorganic support, The catalytic activity tends to be higher than that of a complex that does not have a catalyst. The reaction substrate is supported by an inorganic material through physical adsorption such as van der Waal forces or chemical adsorption such as ionic bonds. It can be taken up by the body and located in close proximity to the palladium complex that is also adsorbed on the support. In particular, when the inorganic carrier is activated carbon, the reaction proceeds easily. The substrate is located near the palladium complex through π-π interactions and CH-π interactions with activated carbon. Furthermore, when the reaction substrate contains an aromatic ring, the catalytic activity is increased. The interaction between the reaction substrate and activated carbon is strong, and it tends to act as a highly active catalyst. Suzuki-Miyaura coupling for the synthesis of aromatic compounds, and the conversion of aromatic nitro compounds to aromatic amines The catalyst of the present invention exhibits high activity in the reduction reaction of methyl methyl ether to methyl methyl ether.

[0021] [Inorganic support] Examples of inorganic supports in the present invention include activated carbon, silicon carbide, metal oxides, and metals. At least one selected from the group consisting of complex oxides and metal salts of oxoacids is included. It can be obtained. Examples of metal oxides include oxides of alkaline earth metals, alumina, silica, and titania. Iron oxide, cobalt oxide, yttrium oxide, zirconium oxide, niobium oxide, molybdenum oxide Examples include bismuth oxide, tungsten oxide, bismuth oxide, lanthanum oxide, and cerium oxide. can be done. Examples of metal composite oxides include silica-alumina, silica-titania, clay minerals, Zeolites can be mentioned. Examples of metal salts of oxoacids include alkaline earth metal phosphates, zirconium phosphate, and the like. Examples of suitable lanthanum phosphates include lanthanum phosphate and lanthanum phosphate. Palladium complexes with ferrocene skeletons undergo π-π and CH-π interactions, Activated carbon is preferred as the inorganic support because it can adsorb strongly.

[0022] The specific surface area of ​​activated carbon is 800m 2 / g or more 2000m 2 / g or less is preferable, and 1200m 2 / g or more 1800m 2 / g or less is more preferable. The specific surface area of ​​activated carbon is, for example, JIS Z8830:2013 (ISO 9277:2 010).

[0023] The average pore diameter of the activated carbon in the present invention affects the reaction activity of the catalyst, so it is set to 1.0 to 5. Preferably, the inorganic particles have a particle size of 0 nm, and more preferably, the inorganic particles have a particle size of 1.5 to 4.0 nm. The average pore diameter of the support can be calculated from the pore volume calculated from the nitrogen adsorption amount and the specific surface area. Cut.

[0024] The inorganic support in the present invention may be in the form of particles, powder or fibers. That is, when the inorganic support of the present invention is made of activated carbon, it can be in the form of granular activated carbon, powdered activated carbon, or fiber. Any of activated carbons can be used. Granular activated carbon is defined as carbon with a particle size of 0.150 mm or more as specified in JIS K1474. This refers to activated carbon, where the particle size specified in JIS K1474 is 0.150 mm or more. This means that the particle size measured according to the JIS K1474 standard is 0.150 mm or more. Specifically, the sample with a particle size range of 0.150 mm or more is 95 mass fraction or more. Above. On the other hand, powdered activated carbon is a material with a particle size of less than 0.150 mm as specified in JIS K1474. In addition, fibrous activated carbon refers to activated carbon that is in the form of fibers.

[0025] The average particle size of the inorganic support in the present invention is not particularly limited, and inorganic supports of various particle sizes can be used. However, from the viewpoint of operability before and after the reaction and reaction efficiency, it is preferable to use a 0.1 μm The thickness can be set to 10,000 μm, and more preferably 1 μm to 3,000 μm.

[0026] Activated carbon includes plant-based activated carbon made from charcoal, coconut shell charcoal, palm kernel charcoal, and ash, Coal-based activated carbon made from peat, lignite, brown coal, bituminous coal, anthracite, etc., petroleum residue, oil carbon Petroleum-based activated carbon made from carbon or polyvinylidene chloride The activated carbon that can be used in the present invention is a commercially available activated carbon. For example, Shirasagi C, Shirasagi M, Shirasagi P, Granular Shirasagi GX. , SX, CX, XRC, KL (Osaka Gas Chemicals Co., Ltd.), PCB (Toyo Calgon Co., Ltd.), Yasicol (manufactured by Taihei Chemical Industry Co., Ltd.), Kuraray Coal GG, GC (manufactured by Kuraray Co., Ltd.), activated carbon ( Powder) (manufactured by Kanto Chemical Co., Ltd.) and the like.

[0027] [Palladium complexes] The catalyst of the present invention is an inorganic catalyst having adsorbed thereon a palladium complex having a ligand with a ferrocene skeleton. The palladium complex has a ligand having a ferrocene skeleton. The inorganic support and the cyclopentadienyl group of the ferrocene skeleton are In particular, when the inorganic carrier is activated carbon, the graphite particles contained in the activated carbon are adsorbed. Both the phene structure and the cyclopentadienyl group of the palladium complex have aromaticity. It is thought that these ring structures interact with each other and are strongly adsorbed. Therefore, the palladium complex exhibits a high loading rate when prepared as a catalyst, and Even after use, the inorganic support remains attached and maintains a high loading rate, so the reaction This process proceeds efficiently, preventing palladium atoms from being mixed into the product after use. .

[0028] The palladium complex of the present invention has a ligand having a ferrocene skeleton. The ligand of the ferrocene complex may be directly bonded to the coordination atom and the ferrocene skeleton, or the coordination atom and the ferrocene skeleton may be bonded to the ferrocene skeleton. A linking group may be present between the ferrocene skeletons. As a coordination atom of the palladium complex, palladium becomes electron-rich, and thus the catalyst Nitrogen atoms, oxygen atoms, sulfur atoms, and phosphorus atoms are preferred because they accelerate the reaction. The nitrogen atom, which can take the electronic state on palladium where the reaction proceeds efficiently, A phosphorus atom is preferred.

[0029] The ligand having a ferrocene skeleton has a structure represented by the following formula (1-1) or (1-2): It is preferred that the structure include:

[0030] [ka]

[0031] (In formula (1-1) and formula (1-2), A 1 and A 2 each independently represents a direct bond, a C 1 to 12 alkyl group which may have a substituent, represents an alkylene group or a phenylene group having 6 to 12 carbon atoms which may have a substituent, L is represented by the following formula (2-1) or the following formula (2-2): R 1 ~R 8 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. an alkyl group, a phenyl group having 6 to 10 carbon atoms which may have a substituent, It may have an alkoxycarbonyl group having 2 to 6 carbon atoms, a carboxy group, or a substituent. represents a phosphinyl group having 2 to 18 carbon atoms, R11 ~R 12 are each independently a hydrogen atom or a C1 to C12 group which may have a substituent. an aliphatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or represents an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent.

[0032] [ka]

[0033] (In formula (2-1) and formula (2-2), R 13 ~R 16 are each independently a hydrogen atom or a C1 to C12 alkyl group which may have a substituent. an aliphatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or represents an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent, * represents A in the above formula (1-1) or (1-2). 2 )

[0034] A 1 and A 2 each independently represents a direct bond, a C 1 to 12 alkyl group which may have a substituent, It represents an alkylene group or a phenylene group having 6 to 12 carbon atoms which may have a substituent. Examples of the alkylene group having 1 to 12 carbon atoms include a methylene group, an ethylene group, and a 1,3-propylene group. Examples of the alkylene group include a 1,4-butylene group and a 1,4-butylene group. The substituents that the alkylene group having 1 to 12 carbon atoms may have include a methyl group, an ethyl group, and the like. Examples of the aryl group include a cyclohexyl group, a phenyl group, and a 4-methylphenyl group. Examples of the phenylene group having 6 to 12 carbon atoms include a 1,2-phenylene group and a 1,3-phenylene group. group, a 1,4-phenylene group, and the like. The substituents that the phenylene group having 6 to 12 carbon atoms may have include a methyl group, an ethyl group, and the like. group, a cyclohexyl group, a phenyl group, and the like. A 1 and A 2 are directly related to the ferrocene skeleton because of the reduced steric congestion. Preferably, it is a bond, a methylene group, an ethylidene group, or a 1,2-phenylene group.

[0035] R 1 ~R 8 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. an alkyl group, a phenyl group having 6 to 10 carbon atoms which may have a substituent, It may have an alkoxycarbonyl group having 2 to 6 carbon atoms, a carboxy group, or a substituent. It represents a phosphinyl group having 2 to 18 carbon atoms.

[0036] Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an isopropyl group, a tert -butyl group, cyclohexyl group, etc. Examples of the substituent that the alkyl group having 1 to 6 carbon atoms may have include a hydroxyl group, a methoxy group, Examples include a dimethylamino group. Specific examples of the alkyl group having 1 to 6 carbon atoms which may have a substituent include a methyl group, an ethylene group, ethyl group, isopropyl group, tert-butyl group, cyclohexyl group, methoxymethyl group, Examples include a hydroxymethyl group and a 1-dimethylaminomethyl group.

[0037] The substituents that the phenyl group having 6 to 10 carbon atoms may have include a methyl group, a methoxy group, group, a trifluoromethyl group, a halogen atom, and the like. Specific examples of the phenyl group having 6 to 10 carbon atoms which may have a substituent include phenyl groups such as , 4-methylphenyl group, 4-methoxyphenyl group, 2,4,6-trimethylphenyl group , 4-methoxy-2,6-dimethylphenyl group, and the like.

[0038] Examples of the alkoxycarbonyl group having 2 to 6 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, and a methyl group. Examples include a carbonyl group and an isopropyloxycarbonyl group. The substituent that the alkoxycarbonyl group having 2 to 6 carbon atoms may have is, for example, methoxy. groups, ethoxy groups, and the like. Specific examples of the alkoxycarbonyl group having 2 to 6 carbon atoms which may have a substituent include: Methoxycarbonyl group, ethoxycarbonyl group, isopropyloxycarbonyl group, 2- Examples include a methoxyethoxycarbonyl group.

[0039] Examples of the phosphinyl group having 2 to 18 carbon atoms include a diphenylphosphinyl group, a dimethylphosphinyl group, and a methylphosphinyl group. phosphinyl group, di(tert-butyl)phosphinyl group, dicyclohexylphosphinyl group etc. The substituent that the phosphinyl group having 2 to 18 carbon atoms may have is a methyl group, ... Examples thereof include an oxy group. Specific examples of the optionally substituted phosphinyl group having 2 to 18 carbon atoms include dimethyl diphenylphosphinyl group, diphenylphosphinyl group, di(tert-butyl)phosphinyl group , dicyclohexylphosphinyl group, dimesitylphosphinyl group, dixylylphosphinyl group di(4-methoxy-2,6-dimethylphenyl)phosphinyl group, ditolylphosphinyl group, ... Examples of such groups include vinyl groups.

[0040] R 1 ~R 8 The steric crowding around the ferrocene skeleton is small, and the interaction with the inorganic support is strong. In view of the above, each independently represents a hydrogen atom, a methyl group, a phenyl group, or a diphenylphosphine It is preferably a yl group, and more preferably a hydrogen atom.

[0041] L is represented by the above formula (2-1) or (2-2). The nitrogen atom, phosphorus atom, or phosphorus atom in the molecule of L coordinates with palladium, thereby forming the above The ligands represented by formula (1-1) and the above formula (1-2) act as bidentate ligands, and palladium A fluorine complex can be formed. L is preferably represented by formula (2-1) because it allows for stronger coordination.

[0042] R 11 ~R 16 are each independently a hydrogen atom or a C1 to C12 alkyl group which may have a substituent. an aliphatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or represents an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent. Examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, Chain fatty acids such as isopropyl, n-butyl, sec-butyl, and tert-butyl groups Aliphatic hydrocarbon groups, cycloaliphatic groups such as cyclopentyl groups, cyclohexyl groups, and adamantyl groups Examples include hydrocarbon groups. The substituent that the aliphatic hydrocarbon group having 1 to 12 carbon atoms may have is, for example, a substituent that is substituted with palladium. The substituents are preferably those having 1 to 10 carbon atoms, such as methoxy and ethoxy groups. 6 alkoxy groups, halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms, trifluoromethyl groups, Examples include a methyl group. The aromatic hydrocarbon group having 6 to 12 carbon atoms is preferably a monocyclic or cyclic group such as a phenyl group or a naphthyl group. Examples include bicyclic aromatic hydrocarbon groups. The aromatic hydrocarbon group having 6 to 12 carbon atoms may have a substituent, which may be a substituent that reacts with palladium. The substituents are preferably those having a low coordinating property, such as methyl groups and ethyl groups having 1 to 6 carbon atoms. Alkyl groups, alkoxy groups with 1 to 6 carbon atoms such as methoxy groups and ethoxy groups, fluorine atoms, salts halogen atoms such as fluorine atom, bromine atom, and iodine atom, and trifluoromethyl group. . Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms include a furyl group, a benzofuryl group, an isobenzofuryl group, and aryl group, thiophene group, benzothiophenyl group, pyrrolyl group, indolyl group, isoindo Examples thereof include an aryl group and a pyridyl group. The substituent that the aromatic heterocyclic group having 3 to 12 carbon atoms may have is, for example, a substituent that can be attached to palladium. Substituents consisting of elements with low coordinating properties are preferred, and alkyl groups having 1 to 6 carbon atoms such as methyl groups and ethyl groups are preferred. Alkoxy groups having 1 to 6 carbon atoms, such as alkyl groups, methoxy groups, and ethoxy groups; fluorine atoms; chlorine atoms; atoms, halogen atoms such as bromine atoms and iodine atoms, and trifluoromethyl groups.

[0043] R 11 ~R 16 is obtained by being composed of elements with low coordination ability to palladium. In the complex, the coordination structure with the palladium ligand is uniquely determined, and the ferrocene skeleton is inorganic. Methyl groups, ethyl groups, tert-butyl groups, and silyl groups are preferred because they facilitate interaction with the support. Cyclohexyl group, adamantyl group, phenyl group, 3,5-dimethylphenyl group, 3,5- A di(trifluoromethyl)phenyl group or a furyl group is preferred, and particularly a group substituted with a phosphorus atom is preferred. In the case of a group like this, the three-dimensional structure around the phosphorus atom becomes crowded, preventing deterioration such as oxidation. From this viewpoint, tert-butyl group, cyclohexyl group, adamantyl group, phenyl group, 3, 5-dimethylphenyl group, 3,5-di(trifluoromethyl)phenyl group, or furyl group is more preferred.

[0044] The palladium complex contains a ligand having a structure represented by the formula (1-1) or (1-2). The reason why it is preferable is that one phosphorus atom and another phosphorus atom or nitrogen atom and palladium The palladium atom forms a coordinate bond with the ligand, and the palladium atom and the ligand are strongly bonded in a bidentate manner. As a result, the steric hindrance around the cyclopentadienyl ring in the ferrocene skeleton is relatively low. Since the size of the inorganic support is relatively small, the cyclopentadienyl ring has a strong interaction with the inorganic support. This is because it is possible. In particular, when the inorganic support is activated carbon, it is bound by π-π interactions.

[0045] Specific examples of the ligand having a ferrocene skeleton include the following.

[0046] [ka]

[0047] Furthermore, examples of the ligand containing a structure represented by formula (1-1) or (1-2) include: The following are specific examples:

[0048] [ka]

[0049] [ka]

[0050] [ka]

[0051] [ka]

[0052] [ka]

[0053] In the above specific examples, Ph represents a phenyl group, Me represents a methyl group, Cy represents a cyclohexyl group, and t- Bu is a tert-butyl group, i-Pr is an isopropyl group, Ad is a 1-adamantyl group, O Me represents a methoxy group.

[0054] The palladium complex in the present invention can be prepared by, for example, using the above-mentioned ligands as described in the non-patent document J. The method described in Am. Chem. Soc. 106 (1984) pp. 158-163 Those skilled in the art can synthesize the palladium complex by the method described above. Commercially available products may also be used. Palladium complexes with ferrocene-based ligands are The ligand other than the ligand having a ferrocene skeleton may be: Halogen atom, trifluoromethylsulfonyloxy group, tosyloxy group, mesyloxy group anionic ligands such as a group, an acetyloxy group, or a trifluoromethylacyloxy group; 1,5-Cyclooctadiene, trans,trans-Dibenzylideneacetone, Tri Among these, neutral ligands such as phenylphosphine are preferred. From the viewpoint of the presence of chlorine atom, bromine atom and mesyloxy group are preferred. The valence of palladium in the palladium complex is 0, 1 or 2, and preferably 2. is preferable from the viewpoint of catalyst stability. Specific examples of the palladium complex include the following.

[0055] [ka]

[0056] In the above specific examples, Ph represents a phenyl group, Me represents a methyl group, and t-Bu represents a tert-butyl group. Represents.

[0057] <Catalyst manufacturing method: complex state and preparation solvent> The catalyst of the present invention is a mixture of a liquid containing a palladium complex having a ligand with a ferrocene skeleton and an inorganic It is produced by mixing the carrier in a solvent. During the preparation of the catalyst, the state of the palladium complex with a ferrocene-based ligand was Although not particularly limited, it is preferable to dissolve the compound in a preparation solvent. Although there is no particular limitation on the compound, it is preferable that the compound has the solubility of the complex and does not strongly coordinate to the central metal. non-aromatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; Aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene, methanol, ethanol, etc. Aliphatic alcohol solvents such as toluene and ethanol are preferred, as they have a high solubility of the complex. Ethanol and methanol are preferred. If the complex is difficult to dissolve in the preparation solvent, Two or more solvents may be mixed and used depending on the circumstances. In addition, in the catalyst of the present invention, although not particularly limited, as described above, the total amount of the inorganic support The total mass of palladium atoms is usually in the range of 0.001 mass% to 25 mass%. It is preferable to prepare the amount so that the amount falls within this range.

[0058] <Supporting conditions: heating and stirring conditions> The catalyst may be prepared by stirring or by leaving it to stand. The temperature during the preparation is not particularly limited, but The preparation may be carried out at room temperature or with heating. The complex is dissolved in the solution immediately after the start of preparation, and the solution is generally concentrated. While the solution appears brown, discoloration of the solution is observed over time as the impregnation progresses. Although it depends on the type and amount of inorganic support and complex, when activated carbon is used, it is practically 1 The conditions should be set so that the impregnation is completed within 2 hours to 7 days. The solvent may be removed by evaporation at the preparation temperature or by distillation under atmospheric or reduced pressure. The inorganic support may be removed by distillation or by filtration such as pressure filtration or vacuum filtration. The catalyst prepared below can be easily handled by washing and drying it. From this viewpoint, it is preferable to include a step of removing the solvent.

[0059] <Loading conditions: washing and drying conditions> The inorganic support containing the palladium complex obtained after removing the preparation solvent is then subjected to the addition of an organic solvent. Washing may or may not be necessary, but in the reaction using the catalyst, if the reaction solution contains para To prevent the inclusion of sodium, it is advisable to carry out cleaning. When washing is performed, the washing solvent is not particularly limited, but it is preferable to use the same solvent as that used in the preparation. It is preferred to use The resulting inorganic support having the palladium complex adsorbed thereon may or may not contain a washing solvent. Although it is not necessary to remove the solvent by drying under reduced pressure, it is preferable in terms of storing the catalyst. The degree of vacuum during drying is not particularly limited, but it is preferably about 20 torr or less. The heating temperature is preferably 40°C or lower.

[0060] <Catalytic reaction> The catalyst of the present invention can be applied to various organic synthesis reactions using palladium complexes as catalysts. For example, aromatic compounds can be synthesized by Suzuki-Miyaura coupling reaction using the catalyst of the present invention. The present invention can be applied to the synthesis of aromatic compounds. The Suzuki-Miyaura coupling reaction is a reaction described in, for example, the aforementioned Non-Patent Document 1. It is also applicable to examples not listed here.

[0061] The solvent used in the Suzuki-Miyaura coupling reaction should be one that does not interfere with the desired reaction. It is preferable that the solvent has a high solubility for the compounds used in the reaction. Lower alcohols such as methanol and ethanol, trifluoroacetic acid, acetone, 1,2- Dimethoxyethane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide amide, N,N-dimethylacetamide, dimethyl sulfoxide, benzene, toluene, xylene toluene, mesitylene, ethyl acetate, 1,4-dioxane, dichloromethane, chloroform and and 1,2-dichloroethane are preferred.

[0062] The reaction temperature in the Suzuki-Miyaura coupling reaction is selected appropriately depending on the raw material compounds used. However, it is preferably 10°C or higher and 200°C or lower, more preferably 20°C or higher and 100°C or lower. The temperature is preferably 40°C or higher and 90°C or lower. The reaction time for the Suzuki-Miyaura coupling reaction can be appropriately selected depending on the raw material compounds used. However, it is preferably 1 minute or more and 20 hours or less, more preferably 3 minutes or more and 15 hours or less. The time is preferably from 5 minutes to 12 hours.

[0063] In the Suzuki-Miyaura coupling reaction, the reaction is preferably carried out in the presence of a base.

[0064] The base may be an organic base or an alkali metal salt or alkali metal salt having a pKa of 1 or more for the conjugate acid. It is preferable that the conjugate acid contains an alkaline earth metal salt. The boron ring partner can be activated effectively, allowing the reaction to proceed smoothly. This becomes:

[0065] Specific examples of organic bases include triethylamine, tri-n-butylamine, N-ethyldiisopropyl propylamine, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1 ,5-diazabicyclo[4.3.0]-5-nonene (DBN), 1,5,7-triazabicyclo[4.3.0]-5-nonene Cyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), Cyclo[4.4.0]dec-5-ene (MTBD), 1,4-diazabicyclo[2.2. 2]octane (DABCO), 1,1,3,3-tetramethylguanidine (TMG), 2 -tert-butyl-1,1,3,3-tetramethylguanidine (BTMG), tert -butylimino-tri(pyrrolidino)phosphorane (BTPP), tert-butylimino -Tris(dimethylamino)phosphorane, N'-tert-butyl-N,N,N',N' ,N”,N”-Hexamethylphosphorimidic triamide (phosphazene base P1-t- Bu), 1-ethyl-2,2,4,4,4-pentakis(dimethylamino)-2λ5,4 λ5-catenadi(phosphazene), tetramethyl(tris(dimethylamino)phosphoranidium) Lithium)phosphoric acid triamide-Et-imine (phosphazene base P2-Et), 1-ter t-Butyl-2,2,4,4,4,-pentakis(dimethylamino)-2λ5,4λ5- Catenadi(phosphazene) (Phosphazene base P2-t-Bu), 1-tert-butyl -4,4,4-tris(dimethylamino)-2-bis[tris(dimethylamino)phospho Ranylideneamino]-2λ5,4λ5-catenadi(phosphazene) (phosphazene base P At least one selected from the group consisting of 4-t-butyl-2-propanol (4-t-butyl-2-propanol), ...

[0066] Specific examples of alkali metal salts or alkaline earth metal salts include potassium carbonate, sodium carbonate, Potassium hydroxide, sodium hydroxide, trisodium phosphate, tripotassium phosphate, phosphoric acid water At least one selected from the group consisting of sodium phosphate and potassium hydrogen phosphate is used. It is possible. As the base, preferably potassium carbonate, tripotassium phosphate, triethylamine, DBU can be used.

[0067] When an alkali metal salt or an alkaline earth metal salt is used as a base, the base is dissolved in water. 0.01 mol / m 3 More than 12mol / m 3 Add as an aqueous base containing: If the molar concentration of the aqueous base solution is within the above range, the overall reaction yield is improved. When the base is added as an aqueous base solution, the molar concentration is preferably 0.1 mol / m 3 More than 10mol / m 3 or less, more preferably 0.2 mol / m 3 Over 8m ol / m 3 or less, even more preferably 0.5 mol / m 3 More than 6mol / m 3 Below is do.

[0068] The catalyst of the present invention is useful for hydrogenation reactions such as Suzuki-Miyaura coupling reactions and nitro group reduction reactions. It can also be used as a catalyst for reactions, such as the synthesis of amine compounds from compounds with nitro groups. It can also be applied to the synthesis of amine compounds, This is the method described in ances 5(2015)pp.83391-83407, It is also applicable to examples not listed here.

[0069] Examples of hydrogen donors in hydrogenation reactions include hydrogen molecules and hydrazine monohydrate. can be. The solvents used in the hydrogenation reaction include water, lower alcohols such as methanol and ethanol, trimethylsilyl alcohol, and the like. Fluoroacetic acid, acetone, 1,2-dimethoxyethane, tetrahydrofuran, acetonite N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfonamide oxide, benzene, toluene, ethyl acetate, 1,4-dioxane, dichloromethane, chloro At least one selected from the group consisting of chloroform and 1,2-dichloroethane is preferred. stomach. The reaction temperature in the hydrogenation reaction can be appropriately selected depending on the raw material compound used. Alternatively, the temperature is -20°C or higher and 200°C or lower, more preferably 20°C or higher and 150°C or lower, and even more preferably The temperature is preferably 40°C or higher and 120°C or lower. In this embodiment, when the catalytic reaction is carried out, an inorganic additive may be present in the reaction system. The inorganic additive may include celite or neutral silica. Addition of the catalyst may facilitate separation of the reaction mixture from the catalyst after the reaction.

[0070] As the commercially available inorganic additive, there is a non-aqueous solution containing 80 to 95 mass % of SiO2 as the main component. Crystalline silicates include Radiolite #100, Radiolite #200, and Radiolite Ito #500, Radio Light #600, Radio Light #900, Zemulite Super M, Zemulite Super 1, Zemulite Super 56, Zemulite Super 2, Celite 50 1. Celite 503, Celite 535, Celite 545, Hyflo Supercell, Stan Examples include Dad Super Cell and Filter Cell. Also, the main component, SiO2, is about 7 Examples of aluminum silicate containing 0% by mass include Topco #31 and Topco #34. These may be used alone or in combination of two or more. However, standard supercells with large surface areas can be preferably used.

[0071] The inorganic additives mentioned above are used in an amount of 1 to 200 times by mass of the catalyst used in the catalytic reaction. If the amount of inorganic additive added is within the above range, it is possible to prevent the reaction solution from being catalytically reacted with the inorganic additive. This facilitates separation of the catalyst and improves overall product recovery. The amount of the catalyst to be added is more preferably 2 times or more and 180 times or less, and even more preferably 5 times or less. It is preferably from 10 to 150 times greater than the original amount, and more preferably from 10 to 160 times greater than the original amount.

[0072] <Post-treatment and reuse after reaction> After the reaction is complete, the catalyst of the present invention and the target substance can be separated by simple methods such as decantation or filtration. The reaction mixture can be separated from the target. The catalyst of the present invention separated by decantation or filtration can be used directly in the next reaction. In this case, the extracted catalyst can be reused by removing the solvent through a drying process, etc. The catalyst may be removed, or the solvent may remain. The removed catalyst may be washed with a solvent. The solvent used to wash the catalyst interacts with the inorganic support to form the catalyst. To extract the remaining product, the product is highly soluble and interacts with the inorganic support. A strong solvent is preferable. When activated carbon is used as the inorganic carrier, the It is preferable that the solvent contains an aromatic ring, which has a strong π-π interaction with the laphene structure. It is particularly preferable to use an aromatic hydrocarbon solvent. Silene, mesitylene, ethylbenzene, cumene, 1,2,3,4-tetrahydronaphthalene Examples of solvents include cyclohexane, indane, and phenylcyclohexane. When the solubility of is low, it is preferable to use it by mixing with a solvent in which the product is soluble.

[0073] <About flow reactions> The catalyst of the present invention can be used in a continuous flow reaction. After the inorganic support is packed into a column, the column is maintained at the reaction temperature. By using a metering pump to pump the substrate and base mixed with the catalyst, there is no need to separate the catalyst. The target product can be produced. [Example]

[0074] The present invention will be explained in more detail below with reference to examples, but the present invention does not exceed the gist of the present invention. However, the present invention is not limited to the following examples. In the examples, "parts" and "%" are by mass unless otherwise specified. . The yield was calculated by sampling the filtrate or the supernatant of the recovered reaction mixture and analyzing it by high performance liquid chromatography. HPLC (High Performance Liquid Chromatography) measurement was performed, and commercially available 4-methylbiphenyl or aniline was used. By comparing the peak areas with those measured by HPLC as a standard, carried out.

[0075] (Comparative Example 1) [Synthesis Example 1] Add tetrakis(triphenylphosphine)palladium (72.1 mL) to a 300 mL beaker. mg, 0.062 mmol), toluene (39 mL), ethanol (2 mL), activated carbon ( Powder) (Kanto Chemical Co., Ltd.) (5.02 g) was added and the resulting suspension was stirred until the solvent evaporated. The mixture was left to stand for 4 days. The resulting solid was mixed with toluene (30 mL) and ethanol (1.5 mL). After stirring for 1 minute, the mixture was filtered under suction. The solid was transferred to a 300 mL beaker. Add toluene (30 mL) and ethanol (1.5 mL) again, stir for 1 minute, and then filter with suction. The solid component recovered by filtration was dried under reduced pressure at 40°C for 11 hours. The recovered filtrate was concentrated under reduced pressure to recover the solid. The amount of palladium complex adsorbed was 37.8 mg, which indicates that the adsorption rate of the palladium complex onto activated carbon was The total mass of palladium atoms relative to the total mass of the catalyst was calculated to be 47.6% by elemental analysis. Therefore, the calculated value was 0.097%.

[0076] (Comparative Example 2) [Synthesis Example 2] In a 300 mL beaker, add bis(acetylacetonato)palladium (19.3 mg, 0. 063mmol), toluene (39mL), ethanol (2mL), activated carbon (powder) ( Toka Chemical Co., Ltd. (5.03 g) was added, and the resulting suspension was allowed to stand for 4 days until the solvent evaporated. Toluene (30 mL) and ethanol (1.5 mL) were added to the obtained solid component, and the mixture was stirred for 1 hour. After stirring for 1 minute, the solid was filtered by suction. The solid was transferred to a 300 mL beaker and then added with toluene. (30 mL) and ethanol (1.5 mL) were added again, and the mixture was stirred for 1 minute, followed by suction filtration. The solid component recovered by filtration was dried under reduced pressure at 40°C for 5 hours to obtain supported catalyst B. The collected filtrate was concentrated under reduced pressure to collect the solid. The amount of the complex was 8.4 mg, so the adsorption rate of the palladium complex to activated carbon was 56.5%. The total mass of palladium atoms relative to the total mass of the catalyst was calculated to be 0.05 by elemental analysis. It was calculated to be 9%.

[0077] (Comparative Example 3) [Synthesis Example 3] Add [4,5-bis(diphenylphosphino)-9,9-dimethyl xanthene]dichloropalladium (47.3 mg, 0.063 mmol), toluene (3 9 mL), ethanol (2 mL), activated carbon (powder) (Kanto Chemical Co., Ltd.) (5.00 g) were added. The resulting suspension was left to stand for 6 days until the solvent evaporated. After adding ethanol (1.5 mL) and stirring for 1 minute, the mixture was filtered under suction. The solid was transferred to a 300 mL beaker and then re-added with toluene (30 mL) and ethanol ( After stirring for 1 minute, the mixture was filtered under suction. The mixture was dried under reduced pressure at 40°C for 5 hours to obtain 6.03 g of supported catalyst C. The mixture was concentrated under reduced pressure, and the solid was recovered. The amount of the recovered palladium complex was 21.1 mg. From this, the adsorption rate of the palladium complex onto the activated carbon was calculated to be 55.4%. The total mass of palladium atoms was calculated by elemental analysis to be 0.064%.

[0078] Example 1 [Synthesis Example 4] Add [1,1'-bis(diphenylphosphino)ferrocene]dichloride to a 300 mL beaker. Choletropalladium dichloromethane adduct (51.4 mg, 0.063 mmol), toluene (39 mL), ethanol (2 mL), activated carbon (powder) (Kanto Chemical Co., Ltd.) (5.04 g) The resulting suspension was allowed to stand for 4 days until the solvent evaporated. Add toluene (30 mL) and ethanol (1.5 mL), stir for 1 minute, and then suction filter. The obtained solid was transferred to a 300 mL beaker and then reconstituted with toluene (30 mL) and ethanol. After stirring for 1 minute, the mixture was filtered under suction. The recovered catalyst was dried under reduced pressure at 40°C for 11 hours to obtain 6.02 g of supported catalyst D. The filtrate was concentrated under reduced pressure, and the solid was recovered. The recovered palladium complex was 0.1 mg. From this, the adsorption rate of the palladium complex onto the activated carbon was calculated to be 99.8%. The total mass of palladium atoms relative to the total mass of palladium was calculated to be 0.099% by elemental analysis.

[0079] Example 2 [Synthesis Example 5] In a 60 mL test tube, 4-bromotoluene (0.086 g, 0.5 mmol), phenyl Boronic acid (0.098 g, 0.8 mmol), supported complex D (0.48 g, 0.005 mmol) was added, and then ethanol (5 mL) and potassium carbonate (0. Aqueous solution of potassium carbonate (346 g, 2.5 mmol) dissolved in water (1.25 mL) The test tube was purged with nitrogen, heated to 80°C and stirred. The reaction was monitored by HPLC. The reaction was continued until the area percentage of the target substance reached its maximum, which took 1 hour. The target 4-methylbiphenyl was obtained in a yield of 93%. The filtered solid was dried under reduced pressure at 40°C for 2 hours to obtain supported catalyst D (0.45 g ) was recovered.

[0080] Comparative Example 4 [Synthesis Example 6] In a 60 mL test tube, 4-bromotoluene (0.086 g, 0.5 mmol), phenyl Boronic acid (0.098 g, 0.8 mmol), [1,1'-bis(diphenylphosphino )Ferrocene]dichloropalladium dichloromethane adduct (0.00040g, 0.00 5mmol), and then ethanol (5mL) and potassium carbonate (0.346g, 2 An aqueous solution of potassium carbonate (0.5 mmol) dissolved in water (1.25 mL) was added. The test tube was purged with nitrogen, heated to 80°C, and stirred. The reaction was monitored by HPLC. The reaction was continued until the area percentage of the material reached its maximum, which took 2 hours. After filtration, the target 4-methylbiphenyl was obtained in a yield of 90%.

[0081] Example 3 [Synthesis Example 7] In a 60 mL test tube, 4-bromotoluene (0.086 g, 0.5 mmol), phenyl Boronic acid (0.098 g, 0.8 mmol), the supported catalyst D (0.45 g, 0.005 mmol) was added, and then ethanol (5 mL) and potassium carbonate (0. Aqueous solution of potassium carbonate (346 g, 2.5 mmol) dissolved in water (1.25 mL) The test tube was purged with nitrogen, heated to 80°C, and stirred for 12 hours, after which suction filtration was performed. The target 4-methylbiphenyl was obtained in a yield of 47%. The catalyst was recovered as Supported Catalyst D (0.44 g) by drying at 40° C. for 2 hours.

[0082] Example 4 [Synthesis Example 8] In a 60 mL test tube, 4-bromotoluene (0.086 g, 0.5 mmol), phenyl Boronic acid (0.098 g, 0.8 mmol), supported catalyst D (0.48 mmol) obtained in Synthesis Example 4 g, 0.005 mmol) was added, and then ethanol (5 mL) and potassium carbonate (0. Aqueous solution of potassium carbonate (346 g, 2.5 mmol) dissolved in water (1.25 mL) The test tube was purged with nitrogen, heated to 80°C, and stirred for 1 hour, then left to stand at room temperature for 2 hours. The supernatant was collected and the remaining solid was added to ethanol (8 mL) and water (2 mL). After stirring at room temperature for 1 minute, the mixture was left to stand at room temperature for 1 hour, and the supernatant was collected and combined with the previous supernatant. As a result, the target 4-methylbiphenyl was obtained in a yield of 74%. To the solid remaining in the test tube, add 4-bromotoluene (0.086 g, 0.5 mmol) Phenylboronic acid (0.098 g, 0.8 mmol) was added, and ethanol (5 ml) L) and potassium carbonate (0.346 g, 2.5 mmol) in water (1.25 mL) The test tube was purged with nitrogen and heated to 80°C. After stirring for 1 hour, the mixture was suction filtered and then diluted with water (7.5 mL), ethanol (4 mL), and toluene. (35 mL) to give the desired 4-methylbiphenyl in 121% yield. The average yield of the reaction was calculated to be 98%.

[0083] Example 5 [Synthesis Example 9] In a 60 mL test tube, 4-bromotoluene (0.086 g, 0.5 mmol), phenyl Boronic acid (0.098 g, 0.8 mmol), supported catalyst D (0.48 mmol) obtained in Synthesis Example 4 g, 0.005 mmol), Celite (0.10 g), and ethanol (5 mL ) and potassium carbonate (0.346 g, 2.5 mmol) were added to water (1.25 mL) and dissolved. The test tube was purged with nitrogen, heated to 80°C, and stirred for 1 hour. After stirring, the mixture was left to stand at room temperature for 30 minutes, and the supernatant was collected. After adding the solution to 8 mL of ethanol and water (2 mL), the mixture was stirred for 1 minute, and then left to stand at room temperature for 2.5 hours. The remaining solid was added again to ethanol (8 mL) and water (2 mL) and stirred for 1 minute. After stirring, the mixture was left to stand at room temperature for 1 hour, and the supernatant was collected and combined with the previously collected supernatant. The resulting 4-methylbiphenyl was obtained in a yield of 77%. To the solid remaining in the test tube, add 4-bromotoluene (0.086 g, 0.5 mmol) Phenylboronic acid (0.098 g, 0.8 mmol) was added, and ethanol (5 ml) L) and potassium carbonate (0.346 g, 2.5 mmol) in water (1.25 mL) The test tube was purged with nitrogen and heated to 80°C for 1 hour. After stirring, the mixture was left to stand at room temperature for 18 hours, and the supernatant was collected. (8 mL) and water (2 mL), stirred for 1 minute, then left to stand at room temperature for 1.5 hours. The supernatant was collected and combined with the supernatant collected earlier, and the target 4-methylbiphenyl was obtained in a yield of 90%. I got it. To the solid remaining in the test tube, add 4-bromotoluene (0.086 g, 0.5 mmol) Phenylboronic acid (0.098 g, 0.8 mmol) was added, and ethanol (5 ml) L) and potassium carbonate (0.346 g, 2.5 mmol) in water (1.25 mL) The test tube was purged with nitrogen and heated to 80°C for 4 hours. After stirring, the mixture was left to stand at room temperature for 18.5 hours, and the supernatant was collected. Add the mixture to alcohol (8 mL) and water (2 mL), stir for 1 minute, then let it stand at room temperature for 1.5 hours. The supernatant was collected and combined with the previously collected supernatant to obtain the target 4-methylbiphenyl in a yield of 9%. Got it at 0%. To the solid remaining in the test tube, add 4-bromotoluene (0.086 g, 0.5 mmol) Phenylboronic acid (0.098 g, 0.8 mmol) was added, and ethanol (5 ml) L) and potassium carbonate (0.346 g, 2.5 mmol) in water (1.25 mL) The test tube was purged with nitrogen and heated to 80°C for 5 hours. After stirring, the mixture was filtered under suction, and the resulting solid was dissolved in water (7.5 mL), ethanol (4 mL), and The desired 4-methylbiphenyl was obtained in 116% yield by washing with toluene (35 mL) and then with toluene (35 mL). The average yield of the four reactions was calculated to be 93%.

[0084] Example 6 [Synthesis Example 10] In a 60 mL test tube, add nitrobenzene (0.12 g, 1.0 mmol) and hydrazine monohydrate. solvate (0.50 g, 10.0 mmol), supported catalyst D obtained in Synthesis Example 4 (0.98 g, To this was added ethanol (5 mL). The test tube was purged with nitrogen. The mixture was heated to 80°C and stirred for 6 hours, then suction filtered and washed with toluene (30 mL). The target aniline was obtained in a yield of 73%.

[0085] From the results of Comparative Examples 1 to 3 and Example 1, it is clear that palladium having a ligand with a ferrocene skeleton It was confirmed that the complex was highly supported on the inorganic support. From the results of Comparative Example 4 and Example 2, it is clear that the palladium complex having a ligand with a ferrocene skeleton When comparing the case where the catalyst was used as is and the case where the catalyst was supported on activated carbon, Example 2 where the catalyst was supported on activated carbon It was confirmed that the reaction time can be shortened by using the palladium complex supported on activated carbon. This indicates that the activity of the catalyst is improved by using the catalyst. Example 3 shows that the catalyst of the present invention can be recovered and reused. Furthermore, according to Example 4, the catalyst can be repeatedly used without drying it, and the It was confirmed that high catalytic activity could be maintained even after increasing the number of cycles. Furthermore, according to Example 5, celite was used to improve the separation of the reaction mixture from the catalyst after the reaction. The results showed that the addition of ethanol improved the operability without reducing the activity of the catalyst. . On the other hand, according to Examples 4 and 5, when the catalyst was used repeatedly, toluene was mixed after the reaction was completed. When the catalyst was washed with the combined solvent, the yield of the target product exceeded 100%. The target substance that strongly interacts with the catalyst can be efficiently extracted by using a solvent containing toluene. This shows that it is possible. According to Example 6, the catalyst of the present invention catalyzes the reaction of reducing a nitro group and converting it into an amino group. It was confirmed that it can be used as a catalyst with high activity. [Industrial Applicability]

[0086] As described above, the catalyst of the present invention allows various coupling reactions and reduction reactions to proceed with high efficiency. This makes it possible to anticipate its use as a catalyst for various reactions.

Claims

1. A catalyst comprising an inorganic support on which a palladium complex is adsorbed, A catalyst having a ligand having a ferrocene skeleton.

2. The ligand having a ferrocene skeleton is represented by the following formula (1-1) or (1-2):

2. The catalyst of claim 1, comprising: 【Chemical Formula 1】 (In formula (1-1) and formula (1-2), A １ and A ２ each independently represents a direct bond, a C 1 to 12 alkyl group which may have a substituent, represents an alkylene group or a phenylene group having 6 to 12 carbon atoms which may have a substituent, L is represented by the following formula (2-1) or the following formula (2-2): R １ ~R ８ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. an alkyl group, a phenyl group having 6 to 10 carbon atoms which may have a substituent, It may have an alkoxycarbonyl group having 2 to 6 carbon atoms, a carboxy group, or a substituent. represents a phosphinyl group having 2 to 18 carbon atoms, R １１ ~R １２ each independently represents a hydrogen atom or a C1 to C12 group which may have a substituent an aliphatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or represents an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent. 【Chemistry 2】 (In formula (2-1) and formula (2-2), R １３ ~R １６ each independently represents a hydrogen atom or a C1 to C12 group which may have a substituent an aliphatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, or represents an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent, * represents A in formula (1-1) or formula (1-2). ２ represents the bonding position with

3. The total mass of palladium atoms is 0.001 mass% or more and 25 mass% or less relative to the total mass of the catalyst. % or less of the catalyst of claim 1 .

4. 2. The catalyst of claim 1, wherein the inorganic support is activated carbon.

5. The specific surface area of ​​the activated carbon is 800 m ２ / g or more 2000m ２ / g or less according to claim 4. The catalyst described.

6. A method for producing a compound by Suzuki-Miyaura coupling reaction using the catalyst according to any one of claims 1 to 5. A method for producing an aromatic compound, comprising the step of synthesizing an aromatic compound using a methyl group.

7. A method for producing amino acids from compounds having a nitro group by using the catalyst according to any one of claims 1 to 5. A method for producing an amine compound, comprising the step of synthesizing an amine compound.

8. A method for producing a catalyst, comprising a step of mixing a liquid containing a palladium complex with an inorganic support. 、 The method for producing a catalyst, wherein the palladium complex has a ligand having a ferrocene skeleton.

9. The method for producing a catalyst according to claim 8, further comprising the step of removing the solvent after the step.

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