JP2013031806A - Immobilized palladium catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly-active immobilized palladium catalyst which is prepared by utilizing an inexpensive polydimethylsilane and does not cause activity deterioration even in repeated use or long term use.SOLUTION: The immobilized palladium catalyst is obtained by making polymethylsilane and metal oxide carry palladium in such a state that the polymethylsilane and the metal oxide are dispersed in a solvent, and then separating insoluble matters from the solvent. In the immobilizing stage, the palladium becomes a palladium cluster having a diameter of several nm to be supported. The obtained immobilized palladium catalyst is highly active, and hardly causes activity deterioration even in repeated use or long term use.

Description

  The present invention relates to an immobilized palladium catalyst using polydimethylsilane.

Palladium has long been used as a catalyst for various chemical reactions, and heterogeneous palladium catalysts that are excellent in stability and easy to separate and reuse from products are widely used in chemical processes (Patent Document 1, etc.) ). In many of such heterogeneous palladium catalysts, palladium metal is fixed to an insoluble carrier such as a metal oxide such as alumina, barium sulfate, calcium carbonate, or activated carbon. In recent years, with the advancement of analytical techniques such as electron microscopes, it has become possible to observe several to thousands of palladium (palladium clusters). In heterogeneous palladium catalyzed reactions, the smaller the palladium cluster size, the more catalytic activity It has become clear that increases.
As a method for immobilizing a platinum-based catalyst, an example in which a platinum complex is encapsulated in a microcapsule of polysilane is known (eg, Patent Document 2), but the polysilane used here is easily softened or dissolved in a solvent. Therefore, it has been difficult to use as a catalyst for organic synthesis for industrial use, which has a high necessity for long-term use and reuse.
The present inventors have developed a microencapsulation (MC) method or a polymer incalcelland (PI) method as a method for producing a fine metal cluster, and a palladium cluster of several nanometers using poly (methylphenylsilane) as a carrier. It has been reported that these are isolated stably and are useful as catalysts for synthesis (Patent Documents 3 and 4, Non-Patent Document 1). Since poly (methylphenylsilane) used here is soluble, it has been necessary to heat and crosslink this polysilane in order to use it as an industrial organic synthesis catalyst.
On the other hand, unlike other polysilanes, polydimethylsilane is insoluble in most solvents (such as Non-Patent Document 2), and thus has not been used as a support for metal catalysts by the MC method or PI method.

Japanese Patent Publication No. 5-40739 Japanese Patent Laid-Open No. 2-9448 JP2007-260659A International Publication WO2007 / 102334

Org. Biomol. Chem., 6, 61-65 (2008). Supervised by Hideki Sakurai “Development of organosilicon polymers” CMC 1989 (p17)

Since polydimethylsilane is inexpensive, if it can be used as a polysilane for fixing a metal catalyst, the industrial merit is great.
However, since polydimethylsilane is the only polysilane that is not soluble in any solvent (Non-patent Document 1, etc.), it has not been known how to fix the metal catalyst with polydimethylsilane by any method.
Furthermore, the polysilane-immobilized metal catalyst used in the industry is required to have high activity and no decrease in activity even after repeated use or long-term use.
That is, an object of the present invention is to provide an immobilized palladium catalyst that uses an inexpensive polydimethylsilane and does not cause a decrease in activity even when used repeatedly or for a long time.

As a result of intensive studies on the above problems, the inventors have supported palladium in a state where polydimethylsilane and a metal oxide are dispersed in a solvent without trying to dissolve polydimethylsilane in the solvent, It has been found that an immobilized palladium catalyst can be obtained by separating from the solvent. Due to the presence of polydimethylsilane and metal oxide in the solvent, most palladium is immobilized as a zero-valent cluster having a diameter of several nm.
This immobilization step can be performed at room temperature, and as in the past (Patent Documents 3 and 4, Non-Patent Document 1), it is not necessary to heat and crosslink in order to stabilize polysilane.
It was confirmed that the immobilized palladium catalyst thus obtained has a high activity and has a remarkable characteristic that the activity is hardly lowered even after repeated use or long-term use (Examples 15 to 29). , See Examples 30-34).

That is, the present invention is an immobilized palladium catalyst comprising polydimethylsilane, a metal oxide and a palladium cluster, wherein the palladium cluster is supported on the polydimethylsilane and the metal oxide. It is a palladium catalyst.
Moreover, this invention is a manufacturing method of the fixed palladium catalyst which consists of the following processes.
(1) a step of preparing a solution or dispersion in which a palladium salt or a palladium complex is dissolved or dispersed at −20 to 60 ° C. and polydimethylsilane and a metal oxide are dispersed; and (2) from the solution or the dispersion. Step of separating insoluble matter Further, the present invention is a method of using the above catalyst or the catalyst produced by the above production method in a hydrogenation reaction or a Suzuki-Miyaura coupling reaction.

  In the conventional method for producing a (polysilane-metal oxide) -supported palladium catalyst using a polysilane other than polydimethylsilane (ie, soluble polysilane), a step of precipitating polysilane by adding a poor solvent for polysilane after reducing palladium, Although a process for insolubilizing polysilane by heating was necessary (Patent Documents 3 and 4, Non-Patent Document 1), such a process is unnecessary in the production method using insoluble polydimethylsilane of the present invention. As a result, the manufacturing cost can be greatly reduced.

It is a schematic diagram of the hydrogenation reaction apparatus of the flow system used in the Example. It is an electron micrograph (STEM) of the catalyst of this invention obtained in the Example. Black spots indicate palladium clusters (about 3-7 nm), and it is polydimethylsilane that looks like a cloud.

  The (polydimethylsilane-metal oxide) -supported palladium catalyst of the present invention is obtained by fixing a palladium cluster to polydimethylsilane and a metal oxide.

  Polydimethylsilane (hereinafter also referred to as “PMPSi”) used in the present invention is a polymer composed of a main chain having a silicon-silicon bond and a substituent of only a methyl group. Does not dissolve. Its molecular weight is preferably from about 1,000 to about 10,000. Such polydimethylsilane can usually be produced from dichlorodimethylsilane and metallic sodium by the Kipping method.

The metal oxide (hereinafter also referred to as “MO”) used in the present invention is an oxide of aluminum, silicon, zirconium, magnesium, or a combination thereof. As such a metal oxide, γ-alumina, α-alumina, and silica-alumina are preferable.
α-Alumina is usually obtained by precipitating, filtering and heating aluminum hydroxide from an aqueous solution of a soluble aluminum salt (Bayer method), has a corundum type crystal form, is chemically stable, and has a high melting point. (1999-2032 ° C). γ-alumina is obtained by heating and dehydrating trihydrate or α-hydrated alumina, and keeping it at 900 ° C., and has a spinel crystal form. Silica-alumina is produced by firing a crude silica-alumina hydrogel obtained by kneading silica and alumina hydrogel, has a solid acidity, and is mostly amorphous.
When the catalyst is packed in a column and used in a flow system, the metal oxide is preferably one having a uniform particle size for column chromatography (for example, a particle size of 10 to 200 μm). If the particle size of the metal oxide is too large, the catalytic activity is lowered, but if it is too small, the filtration rate is lowered, and the pressure loss is increased when used in the flow method.

Palladium in the catalyst of the present invention is fixed to polydimethylsilane and metal oxide as a zero-valent palladium cluster, but divalent palladium may be mixed. The size of this cluster is about 2 to 10 nm and can be observed with an electron microscope.
The palladium / PMPSi / MO ratio in the catalyst of the present invention is 0.01 to 0.5 mmol / 0.02 to 0.5 g / 1 g, preferably 0.02 to 0.2 mmol / 0.05 to 0.25 g / 1 g.

The (polydimethylsilane-metal oxide) -supported palladium catalyst of the present invention can be obtained by fixing Pd from a palladium source to polydimethylsilane and a metal oxide in a solvent.
In general, a palladium salt or a palladium complex is used as the palladium source. Examples of such a palladium source include palladium acetate, palladium chloride, palladium bromide, palladium iodide, palladium oxide, palladium nitrate, palladium sulfate, palladium (II) acetylacetonate, tetrakis (triphenylphosphine) palladium (0 And preferably palladium acetate or palladium chloride.

Palladium is reduced by mixing the palladium salt in a solvent containing polydimethylsilane and a metal oxide. Depending on the palladium salt, a reducing agent may coexist in this solvent in order to promote the reduction reaction. As the reducing agent, sodium borohydride, hydrosilane compound, hydrogen gas and the like are suitable. When palladium is supported only on polydimethylsilane without using a metal oxide, the supported amount per weight cannot be increased (for example, see Catalyst O, Tables 1 and 2).
The solvent used at this time is preferably a solvent that dissolves the palladium source. However, a solvent in which the palladium source is simply dispersed may be used. Moreover, since polydimethylsilane and a metal oxide do not melt | dissolve in a solvent, they are dispersed in a solvent. Furthermore, when an organic solvent miscible with water such as tetrahydrofuran or dioxane is used, a palladium salt may be added as an aqueous solution.
As such a solvent, aliphatic hydrocarbons, aromatic hydrocarbons, ethers, alcohols and the like can be used, and among these, toluene, tetrahydrofuran and the like are preferable. Moreover, the reduction reaction of palladium can be promoted and completed by allowing a low molecular weight alcohol to coexist in a solvent. As the low molecular weight alcohol, an alcohol having 3 or less carbon atoms is preferable, and methanol is particularly preferable. The timing of adding the alcohol may be previously added to the solvent or may be added during the mixing. The amount of alcohol to be added is 1 to 100% (V / V) with respect to the main solvent.

As for the palladium salt, the color of the reaction system changes to black as the reduction proceeds. This reduction reaction is usually performed at -20 ° C to 60 ° C, preferably 0 to 40 ° C, more preferably 0 ° C to room temperature, and a reaction time of 1 minute to 24 hours. If the temperature is too high, the cluster size increases, so a lower one is preferable. Even when heating is performed for the purpose of speeding up the reduction reaction, the heating is performed at 60 ° C. or lower.
After completion of the reduction reaction, insoluble matters are separated from the solution or dispersion. As this separation method, filtration or centrifugation is performed. Usually, the insoluble matter separated from the solvent is then thoroughly washed and dried. By this filtration or washing step, the impurities that are not fixed and impurities derived from the reducing agent are removed. The washing solvent is preferably the solvent used in the reaction, methanol, water or the like. Although there is no restriction | limiting in the drying method, it is easy to heat-dry under reduced pressure.

  When a palladium (0) complex is used as a palladium source, ligand exchange is performed by mixing the palladium complex with polydimethylsilane and a metal oxide in a solvent, and palladium is converted into a polymethylphenylsilane and a metal as a palladium cluster. Fixed to oxide. This ligand exchange is usually performed at 0 to 40 ° C. and a reaction time of 0.5 to 24 hours. When a non-valent complex is used, a reduction operation is necessary, and the above-described reduction operation may be performed as this reduction operation. As the solvent, the same solvent as described above is used.

The concentration of the palladium source in the solvent is 0.01 to 0.2 M as Pd, the amount of polymethylsilane is 20 to 200 g / liter, and the amount of metal oxide is 100 to 500 g / liter.
When the reducing agent is used, the amount of the reducing agent used is about 10 to 10 equivalents with respect to the palladium source.
The (polydimethylsilane-metal oxide) -supported palladium catalyst thus obtained can be used for hydrogenation reactions such as hydrogenation reactions and hydrocracking reactions, and Suzuki-Miyaura coupling reactions.

The following examples illustrate the invention but are not intended to limit the invention.
The amount of palladium supported was measured with an ICP emission spectrometer (ICPS-7510, manufactured by Shimadzu Corporation). ¹ H-NMR was measured with a nuclear magnetic resonance apparatus (JNM-LA500, manufactured by JEOL Ltd.) using deuterated chloroform as a solvent.

Example 1
In a separable flask (300 ml) containing polydimethylsilane (Nippon Soda Co., Ltd. permethylpolysilane, number average molecular weight 2,500, 5.0 g) and activated alumina (Wako Pure Chemical Industries, Ltd., 300 mesh, 45.0 g) Toluene (100 ml) was added under an argon stream. Palladium acetate (Aldrich, 5.0 mmol) was added while stirring under ice cooling, and the ice bath was replaced with a water bath (25 ° C.) after 5 minutes. After 15 minutes, methanol (100 ml) was added dropwise over 10 minutes and stirring was continued for another 15 minutes. The product was filtered and the solid was washed sequentially with toluene (3 times), methanol (3 times) and water (4 times). The obtained powder was dried at 80 ° C. under reduced pressure to obtain a grayish brown powder ((polydimethylsilane-γ-alumina) -supported palladium, hereinafter referred to as “catalyst A”) (50.1 g).

Example 2
In a separable flask (300 ml) containing polydimethylsilane (5.0 g), activated alumina (300 mesh, 45.0 g) and sodium borohydride (Wako Pure Chemical Industries, Ltd., 25 mmol), toluene was added under an argon stream. (100 ml) was added. A methanol (25 ml) suspension of palladium chloride (Aldrich, 5.0 mmol) was added with stirring under ice cooling, and then the ice bath was replaced with a water bath (25 ° C.). After 5 minutes, methanol (75 ml) was added dropwise over 5 minutes and stirring was continued for another 30 minutes. The product was filtered and the solid was washed sequentially with methanol (3 times) and water (4 times). The obtained powder was dried at 80 ° C. under reduced pressure to obtain white gray powder ((polydimethylsilane-γ-alumina) -supported palladium, hereinafter referred to as “catalyst B”) (51.4 g).

Example 3
A toluene / methanol mixed solvent (100 ml / 1 ml) was added to a separable flask (300 ml) containing polydimethylsilane (5.0 g) and activated alumina (300 mesh, 45.0 g) under an argon stream. Palladium acetate (Aldrich, 5.0 mmol) was added while stirring under ice cooling, and the ice bath was replaced with a water bath (25 ° C.) after 5 minutes. After 5 minutes, methanol (4 ml) was added dropwise over 30 minutes and stirring was continued for another 20 minutes. The product was filtered and the solid was washed sequentially with toluene (3 times), methanol (3 times) and water (4 times). The obtained powder was dried at 80 ° C. under reduced pressure to obtain a grayish brown powder ((polydimethylsilane-γ-alumina) -supported palladium, hereinafter referred to as “catalyst C”) (52.0 g).

Examples 4-8
As shown in Table 1, (polydimethylsilane-γ-alumina) -supported palladium was synthesized in the same manner as in Example 1 except that the ratios of palladium acetate, polydimethylsilane, and alumina were changed. The obtained catalysts are called “catalysts D to H”, respectively.
Examples 9-14
As shown in Table 1, (polydimethylsilane-metal oxide) -supported palladium was synthesized in the same manner as in Example 1 except that the type of metal oxide was changed. For γ-alumina, silica-alumina and magnesia, Aldrich was used, for zirconia, Kanto Chemical Co., and for zeolite, Tosoh Corp. The obtained (polydimethylsilane-metal oxide) -supported palladium is referred to as “catalysts I to N”, respectively.

Comparative Example 1
Polydimethylsilane (5.0 g) was weighed into a flask (100 ml), and toluene (20 ml) was added under an argon stream. Palladium acetate (manufactured by Aldrich, 0.2 mmol) was added with stirring under ice-cooling, and methanol (50 ml) was added dropwise after 90 minutes, and stirring was further continued for 15 minutes. The product was filtered and the solid was washed with methanol (3 times). The obtained powder was dried at 80 ° C. under reduced pressure to obtain a gray powder (polydimethylsilane-supported palladium, hereinafter referred to as “catalyst O”) (5.0 g).

Table 1 shows the amount of palladium supported on the catalyst and the palladium recovery rate.

Examples 15-28
In this example, the squalene hydrogenation reaction of the following formula was performed by a flow method.

A flow-type hydrogenation reactor used in this example is shown in FIG. This equipment consists of a liquid feed pump (LC-6AD manufactured by Shimadzu Corporation), a mass flow controller (MC-3000E and RP-300 manufactured by Lintec Corporation), and a glass column for medium / low pressure liquid chromatography (Tokyo Rika as a reaction vessel). Instrument Co., Ltd., 10φ × 100 mm or 5φ × 50 mm, glass filter pore size: 10 μm) was used, and these were connected by 1/16 inch (1.6 mm) SUS tube or PEEK tube. The raw material sent from the server by the liquid feed pump and the hydrogen gas sent through the mass flow controller are mixed at the upper end of the column filled with the catalyst, and sent to the column filled with the catalyst in the thermostatic bath. The product flows out from the lower end of the column together with excess hydrogen gas.
The amount of catalyst A to N shown in Table 2 was packed in the glass column (inner diameter 10φ × 100 mm) of the hydrogenation reactor, and the hydrogenation reaction of squalene (Wako Pure Chemical Industries, Ltd.) was performed under the following conditions. . Squalene: 200 μl / min, hydrogen gas: 120 ml / min, column temperature: 40 ° C. or 60 ° C.

Comparative Example 2
The catalyst O was packed in a glass column (inner diameter 5φ × 50 mm), and the squalene hydrogenation reaction was carried out under the following conditions in the same manner as in Example 15. Squalene (neat): 50 μl / min, hydrogen gas: 30 ml / min, column temperature: 80 ° C.
Since the catalyst not containing alumina has a low bulk specific gravity, the amount of palladium that can be packed in the same volume column is small (Table 2).
Example 29
Using catalyst G instead of catalyst O, a hydrogenation reaction of squalene was carried out in the same manner as in Comparative Example 2.
Comparative Example 3
Instead of the catalyst A, a commercially available 1% palladium / alumina (manufactured by Aldrich, hereinafter referred to as “catalyst P”) was used to carry out a hydrogenation reaction of squalene in the same manner as in Example 15.

The results are shown in Table 2. The reduction rate of the product was calculated from the integral ratio of vinyl protons and methyl and methylene protons measured by ¹ H-NMR.

When the metal oxide was γ-alumina, α-alumina, or silica-alumina (Examples 15 to 25, catalysts A to K), the squalene hydrogenation reaction proceeded efficiently even under mild conditions. It is considered that the reduction rate decreases with the passage of time due to impurities in the raw material squalene, and the initial activity is recovered by washing the catalyst after completion of the reaction (see Examples 30 to 34).
On the other hand, when the same reaction was carried out using a catalyst (catalyst O) in which palladium was supported only on polydimethylsilane (Comparative Example 2), the catalyst of the present invention in which a high reduction rate (quant) was maintained for 3 hours or more ( Compared with Example 29), the reduction rate was low, and it was deactivated early.
Moreover, when the same reaction was performed using the catalyst (catalyst P) which supported palladium only on the metal oxide (comparative example 3), the reduction rate was low compared with the catalyst (Example 15 etc.) of this invention. (Comparative Example 3, 56-58% at 40 ° C).

Example 30
In this example, the catalyst A was packed in a glass column (inner diameter 5φ × 50 mm), and using the same apparatus as in Example 15, α-methylstyrene (Tokyo Chemical Industry Co., Ltd.) was hydrogenated under the following conditions. Went. α-methylstyrene (neat): 132 μl (1.0 mmol) / min, hydrogen gas: 44.8 ml (2.0 mmol) / min, column temperature: 25 ° C. When ^{1 H-NMR} of the product was measured every 1 hour, starting material completely disappeared until 3 hours, 2-phenylpropane was obtained quantitatively. The analytical data of the product is shown below:
¹ H-NMR (CDCl ₃ ) δ 1.27 (d, 6H), 2.88-2.93 (m, 1H), 7.16-7.19 (m, 1H), 7.22-7.24 (m, 2H), 7.26-7.31 (m, 2H ).
Example 31
In this example, the column containing catalyst A used in Example 30 was reused by washing with isopropyl alcohol (50 ml), and the same apparatus was used and 2-cyclohexen-1-one ( The hydrogenation reaction of Tokyo Chemical Industry Co., Ltd. was conducted. 2-cyclohexen-1-one (neat): 97 μl (1.0 mmol) / min, hydrogen gas: 31.4 ml (1.4 mmol) / min, column temperature: 25 ° C. When ^{1 H-NMR} of the product was measured every 1 hour, starting material completely disappeared until 3 hours, cyclohexanone was obtained quantitatively. The analytical data of the product is shown below:
¹ H-NMR (CDCl ₃ ) δ 1.67-1.72 (m, 2H), 1.82-1.87 (m, 4H), 2.30-2.33 (m, 4H).

Example 32
In this example, the column containing catalyst A used in Example 31 was reused by washing with hexane (50 ml), and the same apparatus was used and phenylacetylene (Tokyo Chemical Industry Co., Ltd.) was used under the following conditions. The hydrogenation reaction was performed. Phenylacetylene (neat): 110 μl (1.0 mmol) / min, hydrogen gas: 62.7 ml (2.8 mmol) / min, column temperature: 25 ° C. When ^{1 H-NMR} of the product was measured every 1 hour, starting material completely disappeared until 3 hours, ethylbenzene was obtained quantitatively. The analytical data of the product is shown below:
¹ H-NMR (CDCl ₃ ) δ 1.28 (t, 3H), 2.67 (q, 2H), 7.18-7.33 (m, 5H).
Example 33
In this example, the column containing catalyst A used in Example 32 was reused by washing with isopropyl alcohol (50 ml), and using the same apparatus, maleic acid (Wako Pure Chemical Industries, Ltd.) was used under the following conditions. Company) hydrogenation reaction. Maleic acid aqueous solution (1 M): 200 μl / min, hydrogen gas: 9.0 ml / min, column temperature: 80 ° C. When the product was concentrated every 1 hour and ¹ H-NMR was measured, the raw material completely disappeared until 3 hours, and succinic acid was quantitatively obtained. The analytical data of the product is shown below:
¹ H-NMR (CD ₃ OD) δ 2.56 (s, 4H).

Example 34
In this example, the column containing catalyst A used in Example 33 was reused by washing with water (50 ml) followed by washing with methanol (50 ml), using the same apparatus and under the following conditions: The reduction reaction of the nitro group of 4-nitrotoluene (Tokyo Chemical Industry Co., Ltd.) was performed. 4-nitrotoluene (0.5 M, methanol solution): 500 μl / min, hydrogen gas: 22.4 ml / min, column temperature: 50 ° C. When the product was concentrated every 1 hour and ¹ H-NMR was measured, the raw material completely disappeared until 3 hours, and p-toluidine was quantitatively obtained. The analytical data of the product is shown below:
¹ H-NMR (CDCl ₃ ) δ 2.25 (s, 3H), 6.61 (d, 2H), 6.97 (d, 2H).
In Examples 30 to 34, the catalyst A was reused to carry out several different hydrogenation reactions, but the catalyst A maintained high catalytic activity as described above. That is, it can be seen that the catalyst of the present invention has a remarkable characteristic that the activity does not decrease even after repeated use or long-term use.

Example 35
In this example, the hydrogenation reaction of ethyl cinnamate was performed in a batch mode.
Hydrogen gas (10 ml / min) was blown into ethyl cinnamate (Tokyo Chemical Industry Co., Ltd., 20 mmol) and catalyst A (1.09 g, Pd = 100 μmol) in an eggplant-shaped flask (10 ml). ^When the progress of the reaction was followed by ¹ H-NMR, the signal of ethyl cinnamate completely disappeared after 7 hours, and only the signal of ethyl 3-phenylpropionate was obtained. The analytical data of the product is shown below:
¹ H-NMR (CDCl ₃ ) δ 1.23 (t, 3H), 2.62 (t, 2H), 2.95 (t, 2H), 4.13 (q, 2H), 7.19-7.21 (m, 3H), 7.26-7.30 ( m, 2H).

Example 36
(Polydimethylsilane-γ-alumina) -supported palladium was prepared in the same manner as in Example 1 (Pd: 59 μmol / g, recovery rate 77%). An electron micrograph (STEM) of the obtained catalyst is shown in FIG.
The following Suzuki-Miyaura coupling reaction was performed using this catalyst.
Catalyst (Pd = 0.5μmol), 2-bromoanisole (0.50 mmol), phenylboronic acid (0.60 mmol), P (o-MeOC ₆ H ₄ ) ₃ (0.5 μmol) and potassium carbonate (0.75 mmol) in an argon atmosphere Suspended in ethanol (1 ml) and stirred at 70 ° C. for 16 hours. Ethyl acetate was added to the reaction solution, the catalyst was removed by filtration, and the organic layer was washed with water. The organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure, and the resulting residue was purified by thin layer chromatography to obtain 2-methoxybiphenyl (yield> 99%). The analytical data of the product is shown below:
¹ H NMR (CDC1 ₃ ) δ 3.59 (s, 3H), 6.79 (d 1H, J = 5.3 Hz), 6.87 (t, 1H, J = 6.2 Hz), 7.15-7.18 (m, 3H), 7.25 (t , 2H, J = 7.6 Hz) , 7.39 (d, 2H, J = 7.6 Hz). 13 C NMR (CDC1 3) δ 55.3, 111.1, 120.7, 126.8, 127.0, 128.6, 129.4, 130.6, 130.8, 138.4, 156.3 .

Claims (8)

An immobilized palladium catalyst comprising a polydimethylsilane, a metal oxide and a palladium cluster, wherein the palladium cluster is supported on the polydimethylsilane and the metal oxide. The catalyst according to claim 1, wherein the metal oxide is γ-alumina, α-alumina or silica-alumina. The catalyst according to claim 1, wherein a palladium / PMPSi / MO ratio in the catalyst is 0.01 to 0.5 mmol / 0.02 to 0.5 g / 1 g. A process for producing an immobilized palladium catalyst comprising the following steps.
(1) a step of preparing a solution or dispersion in which a palladium salt or a palladium complex is dissolved or dispersed at −20 to 60 ° C. and polydimethylsilane and a metal oxide are dispersed; and (2) from the solution or the dispersion. Process for separating insoluble materials The manufacturing method of Claim 4 using the solvent which dissolves a palladium salt or a palladium complex in the said process (1). The manufacturing method of Claim 4 or 5 which mixes a reducing agent with the said process (1). The solvent used for the said solution or dispersion liquid is a solvent containing a C3-C3 or less alcohol, The manufacturing method as described in any one of Claims 4-6. The method of using the catalyst as described in any one of Claims 1-3 or the catalyst manufactured by the manufacturing method as described in any one of Claims 4-7 for hydrogenation reaction or Suzuki-Miyaura coupling reaction.