JP2002079108A - Catalyst for heterogeneous reaction and method for synthesizing organic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a catalyst for a heterogeneous reaction, with which high reaction efficiency is realized and which is easily recovered, regenerated and reused and to provide a method for synthesizing organic compounds. SOLUTION: The catalyst for the heterogeneous reaction (except polymerization reaction) is composed of a metal complex (A1) containing a zero-valent metal element selected from the group consisting of elements of groups 4 to 12 in the long-form periodic table, and/or a halogenated metal (A2) containing a metal element selected from the group consisting of the elements of groups 4 to 12 in the long-form periodic table and a halogen element selected from the group consisting of chlorine, brome and iodine and a carrier (B) loaded with a liquid capable of coordinating to the metal complex (A1) and/or the halogenated metal (A2). The method for synthesizing the organic compounds comprises using the catalyst mentioned above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a heterogeneous reaction catalyst containing a carrier carrying a specific ligand, and a carbon-carbon compound between organic compounds in the presence of the heterogeneous reaction catalyst. The present invention relates to a method for producing an organic compound for introducing a bond.

[0002]

2. Description of the Related Art In recent years, a method for producing a chemical substance called green chemistry, which has a small load on the environment and resources, has attracted attention. In particular, regenerating and reusing a metal catalyst of a substrate used in a chemical reaction using a metal catalyst as a substrate, which has been widely used so far, has been a major issue. As a technique for solving this problem, conventionally, in the synthesis of low molecular weight organic compounds, J. Org. Che
m. Vol. 48, P326-332 (1983), a heterogeneous solid catalyst in which a triphenylphosphine complex is supported on a polymer support has been reported as a catalyst used in a Wittig reaction or the like.

In recent years, in the field called combinatorial chemistry, organic polymer particles are provided with a functional group and a site having a pharmacological effect is reacted by a heterogeneous reaction in order to efficiently search for drug discovery. The technology to make it work is also attracting attention.

[0004] However, the products obtained by these organic small molecule reactions have excellent effects which cannot be obtained by other methods.
Although effective, in many cases, the yield is not very high, the concentration of the reaction system is low, and the substrate such as the catalyst used in the reaction is changed by the reaction, so it is difficult to reuse it. was there.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, an object of the present invention is to provide a heterogeneous reaction catalyst having high reaction efficiency and easy recovery, regeneration, and reuse, and a method for producing an organic compound using the heterogeneous reaction catalyst. And

[0006]

Means for solving the above problems are as follows. That is, <1> at least a metal complex (A1) containing a zero-valent metal element selected from the group consisting of elements of Groups 4 to 12 of the long-term periodic table and / or elements of Groups 4 to 12 of the long-term periodic table. A metal element selected from the group consisting of: a metal element (A2) containing a halogen element selected from the group consisting of chlorine, bromine and iodine; and the metal complex (A1) and / or the metal halide (A2). A carrier (B) supporting a ligand capable of coordination, and a catalyst for heterogeneous reaction (excluding a polymerization reaction).

A metal complex containing a zero-valent metal element selected from the group consisting of elements from Groups 4 to 12 of the long-term periodic table (A
1) and / or a metal element (A2) containing a metal element selected from the group consisting of elements of Groups 4 to 12 of the long-term periodic table and a halogen element selected from the group consisting of chlorine, bromine and iodine. In particular, the long-term periodic table 8th ~
It preferably contains a Group 12 transition metal.

As the carrier (B) carrying the ligand, insoluble organic polymer particles or inorganic fine particles such as silica gel, alumina, zeolite, and titanium oxide are particularly preferable. The molecular structure of the carrier (B) supporting the ligand preferably contains a crosslinked structure in the case of an organic polymer, and preferably has an active hydroxyl group on the surface in the case of an inorganic fine particle. Further, when the shape of the carrier (B) is a particle shape, the average particle size (D ₅₀ ) is 1 to 100 μm
Is preferred. The carrier (B) supporting a ligand preferably has, in its molecular structure, a unit having a ligand site and a unit capable of reacting with the unit. The proportion of the ligand in the carrier (B) supporting the ligand is 0.1 to
6.0 mmol / g is preferred.

<2> A method for producing an organic compound, comprising introducing a carbon-carbon bond between organic compounds using the catalyst for heterogeneous reaction according to <1>. <3> The method for producing an organic compound according to <2>, wherein a carbon-carbon bond is introduced between the low-molecular organic compounds. <4> The method for producing an organic compound according to <2>, wherein a carbon-carbon bond is introduced between the organic polymer compounds. <5> The method for producing an organic compound according to <2>, wherein a carbon-carbon bond is introduced between the organic polymer compound and the organic low-molecular compound.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Heterogeneous reaction catalyst] The heterogeneous reaction catalyst of the present invention contains a zero-valent metal element selected from the group consisting of elements from Groups 4 to 12 of the long-term periodic table. Metal complex (A1) and / or long-term periodic table 4th to 12th
A metal element selected from the group consisting of group III elements, and a metal halide (A2) containing a halogen element selected from the group consisting of chlorine, bromine and iodine, and the metal complex (A
1) and / or a ligand capable of coordinating to the metal halide (A2) (hereinafter sometimes referred to as “ligand X”).
And a carrier (B) carrying the compound, and other components as necessary. The heterogeneous reaction catalyst of the present invention is used for reactions other than the polymerization reaction,
Further, the metal complex (A1) and / or the metal halide (A2) containing a zero-valent metal element may be coordinated in advance to the carrier (B) supporting the ligand. Also,
The heterogeneous reaction catalyst of the present invention refers to a catalyst of a system different from the solution in which the reactant and the target substance are dissolved, that is, a catalyst having an insoluble component of a solvent.

(Zerovalent Metal Complex (A1)) -Metal Element- The metal element in the metal complex (A1) is a metal element selected from the group consisting of elements of Groups 4 to 12 of the long-term periodic table. A transition metal element belonging to Groups 8 to 12 is more preferable in that bonding with a ligand is easy. These may be used alone or in combination of two or more. In particular,
Iron, cobalt, nickel, copper, ruthenium, rhodium,
Palladium, osmium, iridium, platinum and the like can be mentioned.

-Ligand- A ligand which binds to the metal element to form a metal complex (A1) (hereinafter sometimes referred to as "ligand Y") can be coordinated to the metal element. Is not particularly limited as long as it is a phosphine compound having a diphenylphosphino group, a triphenylphosphino group, an alkylphosphino group, a compound having a cyclopentadienyl group, 2,2 ′
Dipyridyl compounds such as dipyridyl; and nitrile compounds such as benzonitrile. Phosphine compounds are particularly preferable from the viewpoint of ligand exchange rate and the like.

-Metal Complex- As the metal complex (A1) to which the ligand Y is bonded, a metal complex in which tetrakis (triphenylphosphine) is coordinated as a ligand Y to a zero-valent metal element, or a metal halide And a metal complex in which acetate is coordinated as a ligand Y to a zero-valent metal element.
Specific examples include a tetrakis (triphenylphosphine) complex and a dichlorobis (triphenylphosphine) complex of palladium, platinum, and nickel, and a complex in which acetic acid is coordinated.

(Metal halide (A2)) The metal halide (A2) is a metal element selected from the group consisting of elements of Groups 4 to 12 of the long-term periodic table, and selected from the group consisting of chlorine, bromine and iodine. Having a halogen element. —Metal Element— Examples of the metal element in the metal halide (A2) include iron, cobalt, nickel, copper, ruthenium, rhodium, palladium, osmium, iridium, platinum, titanium, zinc, and the like.

-Halogen element- The halogen element is a halogen element selected from the group consisting of chlorine, bromine and iodine, and these may be used alone or in combination of two or more. . Among them, chlorine is preferable in that the metal compound is inexpensive and easily available.

(Support (B) Supporting Ligand) The support (B) supporting the ligand is a ligand capable of coordinating with the metal complex (A1) and / or the metal halide (A2). X and a carrier substrate.

-Carrier Substrate- The carrier substrate preferably carries the ligand by chemical bonding or ionic bonding, and its shape is not particularly limited. From the viewpoint, a spherical shape or a particle shape close to the spherical shape is preferable, and a porous shape may be used if the surface area needs to be further increased. When the carrier substrate is in the form of particles, the size of the particles is preferably from 0.1 to ₅₀₀ μm, more preferably from 1 to 100 μm, in terms of average particle diameter (D ₅₀ ). When the average particle diameter (D ₅₀ ) is smaller than 0.1 μm, separation from the reaction solution becomes difficult, and the ligand X easily enters and is taken into the obtained product. While the obtained product may be colored, if it exceeds 500 μm, the yield of the obtained product may be poor.

In the present invention, it is considered that the reason why the ligand X needs to be supported on the carrier substrate is as follows. When the ligand X is not supported on the carrier substrate, the ligand X is dissolved in the reaction system because it is usually a low-molecular substance having high lipophilicity. For this reason, during the reaction, it is mixed in the product and the reaction efficiency is lowered, or the product is easily taken into the product. As a result, the ligand X incorporated between the products reacts with the metal ions to form a complex, which results in secondary problems such as strong coloring of the products and troublesome purification. There is.

On the other hand, when the ligand X is supported on the carrier substrate, the ligand X is immobilized on the carrier substrate.
It is considered that the surface can always be kept active without being mixed with the product. Therefore, by supporting the ligand X on the carrier substrate, it is possible to obtain the desired product in a simple purification step in a high yield, as described later.

As the carrier substrate, the ligand X is used so that the ligand X does not enter between the obtained reaction products.
Needs to be able to be carried. For this reason, the carrier base material is preferably insoluble in other components such as a reaction solvent and an organic compound as a raw material.

The material of the carrier substrate is not particularly limited as long as the above conditions are satisfied.
Suitable examples include organic compounds such as polyacrylic resin, polymethacrylic resin, and polyester resin, and inorganic compounds such as silica gel, alumina, zeolite, and titanium oxide. These may be used alone or in combination of two or more. Among these, an organic compound is preferable from the viewpoint of easily supporting the ligand X, and particularly, in terms of appropriate affinity for an organic solvent and ease of forming a crosslinked structure,
Organic polymer particles such as polystyrene resin and polymethacrylic resin are preferred. As the inorganic compound, inorganic fine particles such as silica gel, alumina, zeolite, and titanium oxide are preferable.

When the carrier substrate is the above-mentioned organic compound, it is particularly preferred that the molecular structure thereof contains a crosslinked structure. In such a case, if the cross-linking structure is not included in the molecular structure of the carrier base material, the catalyst dissolves in other components such as a reaction solvent or a raw material of an organic low-molecular material, or enters into a reaction product and reacts. The product may be colored.

In order to obtain the crosslinked structure, it is preferable to use a crosslinking agent. The crosslinking agent is not particularly limited, but, for example, when the carrier substrate is a polystyrene resin, divinylbenzene, ethylene glycol dimethacrylate, and the like are preferable in terms of easy control of the degree of crosslinking. .

-Ligand X-The ligand X to be supported on the carrier substrate is a ligand capable of coordinating with the metal complex (A1) and / or the metal halide (A2). There are no particular restrictions,
This is the same as the ligand Y of the metal complex (A1).

The ratio of the ligand X in the carrier (B) supporting the ligand is preferably from 0.1 to 6.0 mmol / g, more preferably from 0.5 to 4 mmol / g. When the ratio is less than 0.1 mmol / g, the yield of the obtained reaction product may decrease. On the other hand, 6.0
When the amount exceeds mmol / g, the carrier (B) may not be easily supported.

The carrier (B) supporting the ligand X can be prepared, for example, by the following method. 1) A method of copolymerizing a monomer having a ligand X, another monomer such as styrene, and, if necessary, a monomer such as divinylbenzene as a crosslinking agent. 2) A carrier substrate having a functional group such as a chloromethyl group is
A method in which a ligand X is introduced by a polymer reaction after preparation in advance. 3) When the support is an inorganic compound, a method in which a hydroxyl group of the inorganic oxide fine particles obtained by the sol-gel method is reacted with a silane coupling agent containing a ligand X, a halide, or the like.

As the carrier (B) carrying the ligand X, commercially available products can also be suitably used. For example, as the polymer particles carrying the phosphines, Wit
A commercially available catalyst for the tig reaction, specifically, TriphenylPhosphine Resi
n, Diphenylmethyl Phosphin
e Resin (manufactured by Kokusan Chemical Co., Ltd.) or the like can be suitably used.

The compounding ratio of the components in the heterogeneous reaction catalyst of the present invention ((sum of the number of moles of the metal complex (A1) and the metal halide (A2)) / (coordination supported on a carrier substrate) (Sum of the number of moles of the child X))
0.1-10 / 0.1-40 is preferred, and 0.5-8 /
0.5-20 is more preferable. If the mixing ratio is less than the above range, the reaction yield and the like may be reduced. On the other hand, when the value exceeds the above range, the reaction to the carrier substrate may be insufficient or the metal salt may be adsorbed to the product.

When the heterogeneous reaction catalyst of the present invention is used,
Conventionally, since the problem of "incorporation of a ligand between products", which has been a problem with substrates such as reaction catalysts, does not occur, the reaction occurs at a high yield, and coloring of the products is prevented. Therefore, in the production of a product, it is not necessary to provide a decolorization / purification step, or decolorization can be performed by a simple decolorization / purification step. Further, the catalyst can be recovered by filtration after the completion of the reaction, and the recovered catalyst can be reused by simple washing.

[Organic Compound Formation Method] In the organic compound formation method of the present invention, a carbon-carbon bond is introduced between organic compounds using the heterogeneous reaction catalyst of the present invention.

Suitable examples of the organic compound include an organic low molecular weight compound and an organic high molecular weight compound. Further, in the method for producing an organic compound of the present invention, the carbon-containing compound between an organic low-molecular compound and an organic low-molecular compound, an organic high-molecular compound and an organic high-molecular compound, or an organic high-molecular compound and an organic low-molecular compound. Preferably, a carbon bond is introduced.
In the present invention, the organic high molecular compound refers to an organic compound having a weight average molecular weight (Mw) of 1000 or more, and the organic low molecular compound has a weight average molecular weight (Mw) of
Refers to organic compounds that are less than 1000.

As the organic low molecular weight compound, an aryl halide, an aromatic derivative using alkyl, allyl, arylmagnesium halide or the like usually called a Grignard reagent, or a raw material for synthesizing an aryl borate is preferable. It is listed. For example, examples of the aryl halide derivative include bromobenzene, chlorobenzene, iodobenzene, bromo, chloro, iodo-substituted toluene, xylene, and methylene. Examples of the alkyl, allyl, and arylmagnesium halides called Grignard reagents include methylmagnesium bromide, vinylmagnesium bromide, and phenylmagnesium bromide. Examples of the aryl borate include phenyl boric acid and the like.

As the organic polymer compound, poly 4-
Halogenated polystyrene such as bromostyrene,
Chloromethylstyrene and Gri made from them
gnard type polymer, further substituted polyester,
Examples include polyether, polycarbonate, and polyacrylic acid substituted ester.

In the method for producing an organic compound according to the present invention, a carbon-carbon bond is introduced between the organic compounds by a cross-coupling reaction in the presence of the heterogeneous reaction catalyst to produce an organic compound. .

In the method for producing an organic compound according to the present invention, the compounding ratio of the organic compound (organic low molecular weight compound, organic high molecular weight compound) to the heterogeneous reaction catalyst ((ligand X supported on a carrier substrate) The number of moles) / (the number of moles of the organic compound (in the case of an organic polymer compound, the number of moles calculated with the constituting monomers))) varies depending on the desired product, but cannot be specified unconditionally. In general, 0.0001 to 0.5 is preferable, and 0.0
01-0.2 is more preferable. The compounding ratio is 0.00
If it is less than 01, a decrease in yield may be observed. On the other hand, if it exceeds 0.5, the product may be adsorbed and lost.

The method for producing an organic compound according to the present invention may be performed without a solvent or may be performed using an organic solvent. The organic solvent is not particularly limited, but may be cyclohexane, benzene, toluene, xylene, dimethylformamide (DMF), dimethylsulfoxide (DMS).
Known organic solvents such as O), chloroform, tetrahydrofuran and the like are listed, and among these, tetrahydrofuran, toluene, xylene and the like are preferable in view of the type of reaction used. These organic solvents may be used alone or in combination of two or more.

After completion of the above-mentioned organic compound formation reaction, the heterogeneous reaction catalyst is appropriately separated from the obtained reaction solution by a known method such as filtration and centrifugation. The separated heterogeneous reaction catalyst can be reused in the reaction.

According to the organic compound producing method of the present invention described above, the reaction efficiency is high. In addition, since the recovery, regeneration, and reuse of the heterogeneous reaction catalyst are easy, little waste is generated. Further, since the coloring of the product is prevented, it is not necessary to provide a decolorizing and refining step.

[0039]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 Preparation of Heterogeneous Reaction Catalyst 0.05 g of nickel chloride (II) hexahydrate (metal halide (A2)) (0.2 mmol) was placed in a 50 ml reaction vessel.
l) and triphenylphosphine resin (Loading)
capa. 0.94 mmol / g, manufactured by Kokusan Chemical Co., Ltd. (Carrier (B) supporting ligand) (Carrier (B): Resin obtained by crosslinking styrene with divinylbenzene (crosslinking agent), average particle size (D ₅₀ ) = 45 μm) 0.16 g (mol number of ligand:
0.15 mmol) and tetrahydrofuran (solvent) 1
And 0.0g was added to prepare a heterogeneous reaction catalyst of the present invention.

-Production of organic compound (4-methylbiphenyl)-Here, 5.13 g (0.03 mol) of 4-bromotoluene
l Tokyo Chemical Industry Co., Ltd.) and cooled to 0 ° C. with ice water. 18.7 g of a phenylmagnesium bromide 32% by mass tetrahydrofuran solution (phenylmagnesium bromide: 5.98 g (0.033 mol, manufactured by Tokyo Chemical Industry)) was added dropwise thereto. After the completion of the dropwise addition, the mixture was stirred at room temperature for about 4.0 hours.
It was confirmed that phenylmagnesium bromide (a low-molecular organic compound) as a reaction raw material disappeared. After the reaction,
Methanol was added to stop the reaction, and the catalyst (particles) for heterogeneous reaction was removed by suction filtration. Then, tetrahydrofuran (solvent) was recovered under reduced pressure to obtain a reaction product. The obtained reaction product had no coloring, and almost no impurities were detected by gas chromatography. The recovered reaction product was distilled under reduced pressure to obtain 4.79 g (yield 95%) of a product (4-methylbiphenyl) whose structure could be supported by H ¹ NMR.

(Example 2) -Preparation of catalyst for heterogeneous reaction- 0.05 g (0.2 mmol) of nickel chloride (II) hexahydrate (metal halide (A2)) was placed in a 50 ml reaction vessel.
l), triphenylphosphine-coordinated silicon oxide fine particles prepared from chlorodiphenylphosphine and carrier (B) (carrier (B) carrying ligand) (carrier (B): silicon oxide having hydroxyl group, average particle Diameter (D ₅₀ ) = 20 μm)
0.16 g (mol number of ligand: 0.15 mmol);
And 10.0 g of tetrahydrofuran (solvent),
The catalyst for heterogeneous reaction of the present invention was prepared.

-Formation of organic compound (3-ethyl-m-xylene)-In the "Formation of organic compound (4-methylbiphenyl)" of Example 1, 32% by mass of phenylmagnesium bromide in 18.7% by mass of a tetrahydrofuran solution was used. Instead, ethyl magnesium bromide 39 mass% ethyl ether solution 11.2 g (ethyl magnesium bromide: 4.4 g (0.033 mol, Tokyo Chemical Industry))
And instead of 5.13 g of 4-bromotoluene,
5.5 g (0.03 mol) of 4-bromo-m-xylene
A reaction product was obtained in the same manner as in Example 1 except that was used.
The obtained reaction product had no coloring, and almost no impurities were detected by gas chromatography. The recovered reaction product was distilled under reduced pressure to obtain a product (3-ethyl-m-xylene) whose structure can be supported by H ¹ NMR (3.2).
2 g (80% yield) was obtained.

Example 3 Preparation of Heterogeneous Reaction Catalyst A heterogeneous reaction catalyst of the present invention was prepared in the same manner as in Example 1 "Preparation of Heterogeneous Reaction Catalyst".

Formation of Organic Compound (Poly-4-phenylstyrene) 0.16 g of the obtained heterogeneous reaction catalyst (moles of ligand: 0.15 mmol) was placed in a 100 ml reaction vessel.
5.46 g of poly 4-bromostyrene (Mw = 100,000)
(0.03 mol as 4-bromostyrene) and 30 ml of tetrahydrofuran were added and dissolved. Here, 18.7 g of a 32% by mass phenylmagnesium bromide solution in tetrahydrofuran (5.98 g (0.033 mol, manufactured by Tokyo Chemical Industry Co., Ltd., as phenylmagnesium bromide)) was added dropwise. After completion of the dropwise addition, heat reflux for 8 hours.
After completion of the reaction, after completion of the reaction, the catalyst for heterogeneous reaction is removed by filtration, the filtrate is gradually added to 300 ml of methanol, and the precipitated crystals are filtered and dried to obtain a product whose structure can be supported by H ¹ NMR. 4.30 g (yield: 80.0%) of (poly 4-phenylstyrene) was obtained.

Example 4 Preparation of Heterogeneous Reaction Catalyst A heterogeneous reaction catalyst of the present invention was prepared in the same manner as in "Preparation of Heterogeneous Reaction Catalyst" in Example 2.

Formation of Organic Compound (p- (Poly (phenyl methacrylate) polystyrene)) In a 100 ml reaction vessel, poly 4-bromostyrene (M
5.46 g (w = 100,000) (0.03 mol as 4-bromostyrene) and 30 ml of tetrahydrofuran were added and dissolved. Here, 0.8 g of metal magnesium
(0.033 mol) and 0.1 g of iodine were added at room temperature, and the mixture was gradually heated and reacted under reflux for 5 hours. Here, 0.16 g of the obtained heterogeneous reaction catalyst and 7.20 g of polymethacrylic acid P-phenyl ester (Mw = 50,000) were obtained.
(0.03 mol) and further heated under reflux for 8 hours to obtain a reaction solution. After the completion of the reaction, the obtained reaction solution was gradually poured into 500 ml of methanol, and the precipitated crystals were filtered and dried to obtain 6.3 g of a thread-like white substance (yield: 80.0%).
%)Obtained. The obtained white matter was confirmed by C ¹³ NMR to be a compound in which organic polymer compounds were bonded to each other.

Example 5 Preparation of Catalyst for Heterogeneous Reaction Tetrakis (triphenylphosphine) palladium (metal complex (A1)) was placed in a 50 ml reaction vessel under nitrogen.
23 g (0.2 mmol); chem. Voi.
48, P326-332 (1983).
capa. (1.9 mmol / g) (Carrier (B) supporting ligand) (Carrier (B): resin obtained by crosslinking styrene with divinylbenzene (crosslinking agent), average particle size (D50) = 5
0.08 g (mol number of ligand: 0.15 mmol)
l) and 10.0 g of toluene (solvent) were added to prepare a heterogeneous reaction catalyst of the present invention.

-Formation of Organic Compound (4-phenylpyridine)-Here, 4.02 g (0.033 mol) of phenylboric acid was added.
l), 5.84 g (0.03 g) of 4-bromopyridine hydrochloride
mol), 6.4 g (0.06 mol) of sodium carbonate
Of toluene / ethanol / pure water (5: 1: 1) mixture 1
The solution dissolved in 4 g was added and refluxed for 24 hours. After completion of the reaction, the catalyst for heterogeneous reaction was removed by suction filtration, and the filtrate was distilled off. Toluene was added again, followed by washing with water. Further, the oil phase was dissolved in toluene / ethanol (1:
1) After recrystallization from the mixture, drying and 4.5 g of a product (4-phenylpyridine) whose structure can be supported by H ¹ NMR.
(97%).

(Example 6: Reuse of catalyst for heterogeneous reaction)
The heterogeneous reaction catalyst recovered in Example 1 was stirred and washed with about 50 ml of acetone, and then dried with a vacuum drier. A product was obtained in the same manner as in Example 1 except that it was reused as a heterogeneous reaction catalyst, and impurities were detected by gas chromatography. The purity was the same as that of Example 1. And the yield was 75%. Therefore, it was confirmed that the heterogeneous reaction catalyst of the present invention can be reused.

Comparative Example 1 In Example 1, a triphenylphosphine resin (Loadingcapa. 0.9) was used.
A catalyst for a homogeneous reaction was prepared in the same manner as in Example 1 except that 0.14 g of 4 mmol / g (manufactured by Kokusan Chemical Co., Ltd.) was replaced with 0.04 g (0.15 mmol) of triphenylphosphine. A product (4-methylbiphenyl) was obtained in the same manner as in Example 1. The obtained product had a strong green coloration of nickel ions, and when impurities were detected by gas chromatography, many impurity peaks were formed. Although the target product was obtained by performing isolation and purification, the yield was significantly reduced to 45%.

Comparative Example 2 In Example 1, a triphenylphosphine resin (Loadingcapa. 0.9) was used.
A catalyst for a homogeneous reaction was prepared in the same manner as in Example 1 except that 0.14 g of 4 mmol / g, manufactured by Kokusan Chemical Co., Ltd. was replaced with 0.04 g (0.15 mmol) of triphenylphosphine. The product (3-ethyl-m-xylene) was obtained in the same manner as in Example 2 (yield: 60).
%). The product obtained was strongly colored green, was reprecipitated and washed, but did not remove the coloration. Analysis by fluorescent X-ray showed that nickel was strongly observed and strongly adhered inside. Was estimated.

Comparative Example 3 A reaction was carried out in the same manner as in Example 1, except that only triphenylphosphine resin was used without using nickel (II) chloride hexahydrate. 4-methylbiphenyl) was not found.

[0054]

According to the present invention, there is provided a heterogeneous reaction catalyst having high reaction efficiency and easy to recover, regenerate and reuse, and a method for producing an organic compound using the heterogeneous reaction catalyst. Can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08G 81/00 C08G 81/00 4J100 85/00 85/00 // C07B 61/00 300 C07B 61/00 300 C07D 213/127 C07D 213/127 (72) Inventor Katsuhiro Sato 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Fuji Xerox Co., Ltd. F-term (reference) 4C055 AA01 BA01 CA01 DA08 FA09 FA31 FA34 FA37 4G069 AA03 AA08 BA02B BA21B BA22B BA27A BA27A BB08A BB08B BC30A BC34A BC49A BC53A BC57A BC61A BC65A BC68B BC69A BC72B BD12A BD12B BD13A BD14A BE26B BE37B CB41 DA05 EA02Y EB18Y FA01 FA02 4H006 AA02 AC29 BA21 BA48 BA62 BA81 AA12 CA13 A01 AB12 A12 CA12 A13 ACA4 CD08 4J100 AB04Q AB07Q AB08P AB09P AB15Q BC43H BC43Q CA01 CA04 CA31 HA33 HA62 HC 04 HC83 HE14 HE41

Claims (5)

[Claims] 1. A metal complex (A1) containing at least a zero-valent metal element selected from the group consisting of elements from Groups 4 to 12 of the long-term periodic table, and / or a long-term periodic table of the fourth to twelfth elements.
A metal element selected from the group consisting of group 12 elements, chlorine,
A metal halide (A2) containing a halogen element selected from the group consisting of bromine and iodine, and a carrier carrying a ligand capable of coordinating with the metal complex (A1) and / or the metal halide (A2) ( B) and a catalyst for heterogeneous reaction (excluding polymerization reaction). 2. A method for producing an organic compound, comprising using the catalyst for heterogeneous reaction according to claim 1 and introducing a carbon-carbon bond between the organic compounds. 3. The method for producing an organic compound according to claim 2, wherein a carbon-carbon bond is introduced between the low-molecular organic compounds. 4. The method according to claim 2, wherein a carbon-carbon bond is introduced between the organic polymer compound. 5. The method for producing an organic compound according to claim 2, wherein a carbon-carbon bond is introduced between the organic polymer compound and the organic low molecular compound.