POLYMER-SUPPORTED TRANSITION CATALYST

Abstract

A long life catalyst is provided that is conveniently and inexpensively capable of being produced and that is highly active and has inhibited metal leakage. According to aspects of the present invention, a catalyst is provided that includes: a polymer including a plurality of first structural units and a plurality of second structural units; and metal acting as a catalytic center, wherein at least part of the metal is covered with the polymer, each of the plurality of first structural units has a first atom constituting a main chain of the polymer and a first substituent group bonded to the first atom, a second atom included in each of the plurality of second structural units is bonded to the first atom, and the second atom is different from the first atom, or at least one of all substituent groups on the second atom is different from the first substituent group.

Claims

1. A catalyst, comprising: a polymer including a plurality of first structural units and a plurality of second structural units; and a metal acting as a catalytic center, wherein: at least part of the metal is covered with the polymer; each of the plurality of first structural units has a first atom constituting a main chain of the polymer and a first substituent group bonded to the first atom, a second atom included in each of the plurality of second structural units is bonded to the first atom; and the second atom is different from the first atom, or at least one of all substituent groups on the second atom is different from the first substituent group.

2. The catalyst of claim 1, wherein the main chain of the polymer does not include a carbon atom.

3. The catalyst of claim 1, wherein each of the first atom and the second atom is not a carbon atom.

4. The catalyst of claim 1, wherein the first atom is a silicon atom.

5. The catalyst of claim 1, wherein the second atom is an oxygen atom or a nitrogen atom.

6. The catalyst of claim 1, wherein the metal is any one of selected from the group consisting of palladium, platinum, ruthenium, rhodium, silver, gold, copper, nickel, cobalt, iron, chromium, manganese, technetium, osmium, molybdenum, tungsten, iridium, rhenium, titanium, zirconium, hafnium, tantalum, niobium, and vanadium.

7. The catalyst of claim 1, wherein: the first atom is a silicon atom; and the first substituent group is at least any one selected from the group consisting of a substituent group constituted only of a hydrogen atom, a substituent group including an oxygen atom, and a substituent group including a carbon atom.

8. The catalyst of claim 1, further comprising an inorganic member or an organic member.

9. The catalyst of claim 1, further comprising an alumina or a silicon oxide.

10. A method of producing a catalyst, the method comprising: preparing a first compound including a metal atom, and a polymer including a plurality of first structural units and a plurality of second structural units; and reacting the first compound and the polymer, wherein: at least one first structural unit of the plurality of first structural units has a first atom constituting a main chain of the polymer and a first substituent group bonded to the first atom; a second atom included in each of the plurality of second structural units is bonded to the first atom; the second atom is different from the first atom, or at least one of all substituent groups on the second atom is different from the first substituent group; and in the reacting the first compound and the polymer, the first substituent group reacts with the first compound.

11. The method of claim 10, wherein: the first atom is a silicon atom; and the first substituent group is a hydrogen atom.

12. The method of claim 10, wherein the second atom has an electronegativity higher than an electronegativity of the first atom.

13. The method of claim 11, wherein in the reacting the first compound and the polymer, insertion of the metal atom into the silicon atom and the hydrogen atom occurs.

14. A method of producing a compound, the method comprising progressing any one selected from the group consisting of reduction reaction, oxidation reaction, hydrometalation, carbon-carbon bond forming reaction and carbon-nitrogen bond forming reaction using the catalyst of any one of claims 1 to 10 to form the compound.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0133] FIG. 1 is a conceptual diagram of an equipment in a flow reaction system.

DESCRIPTION OF EMBODIMENTS

[0134] The following describes some embodiments of the present invention. Various characteristics described in the following embodiments may be combined with each other. Each characteristic establishes an independent invention.

1. Polymer-Supported Metal Catalyst

[0135] A polymer-supported metal catalyst according to some aspects of the present invention is composed of a metal acting as a catalytic center and a polymer supported by the metal. Preferably, the polymer supporting the metal is further supported by an organic member or an inorganic member.

<Polymer>

[0136] The polymer may be any polymer without particular limitation to the type as long as the polymer is excellent in supporting ability to strongly immobilize metal as a catalytic center and is stable in the reaction conditions.

[0137] The polymer may be a homopolymer configured with repeated identical structural units, or may be a copolymer having a plurality of structural units that are equal to or more than two and different. The copolymer includes a random copolymer having randomly bonded different structural units and a block copolymer having repeated same structural units. Preferably, the polymer includes a plurality of first structural units and a plurality of second structural units, [0138] wherein each of the plurality of first structural units has a first atom constituting a main chain of the polymer and a first substituent group bonded to the first atom, a second atom included in each of the plurality of second structural units is bonded to the first atom, and the second atom is different from the first atom, or at least one of all substituent groups on the second atom is different from the first substituent group.

[0139] More preferably, each atomic group in the structural units and a substituent group on a second atomic group satisfy any one of the following requisites (1) to (7). Even more preferably, they simultaneously satisfy another requisite. Most preferably, they satisfy all the requisites. [0140] (1) The main chain of the polymer does not include a carbon atom. [0141] (2) The first atom is an atom other than an oxygen atom and a nitrogen atom. [0142] (3) The first atom is a silicon atom. [0143] (4) The second atom is an oxygen atom or a nitrogen atom. [0144] (5) The first atom is a silicon atom, and the first substituent group is at least any one selected from the group consisting of a substituent group constituted only of a hydrogen atom, a substituent group including an oxygen atom, and a substituent group including a carbon atom. [0145] (6) The first atom is a silicon atom, and the first substituent group is a hydrogen atom. [0146] (7) The second atom has an electronegativity higher than an electronegativity of the first atom.

[0147] Representative examples of the polymer according to the present invention include: a polymer in which a 14th group element atom, such as a carbon atom and a silicon atom, and a 16th group element atom, such as an oxygen atom and a sulfur atom, are bonded; and a polymer in which a 14th element atom, such as a silicon atom, and a 15th group element atom, such as a nitrogen atom and a phosphorus atom, are bonded. The polymer may be a polymer, such as carbosilane, in which different 14th group element atoms are linked, or may be a polymer in which a -electron system is linked via a linking group, such as a methylene group. An even more preferred polymer preferably has an organic group, such as an alkyl group and an alkoxy group, or a hydrogen atom on group 14 element atom. Specific examples of the polymer include: a polymer having a main chain composed of a carbon atom and a heteroatom, such as polyethyleneimine, polyester, and polymethylene phenylene isocyanate; polysiloxanes, such as poly(oxymethylhydrosilylene), poly(oxydimethylsilylene) (oxymethylhydrosilylene), poly(oxydimethylsilylene) (oxydihydrosilylene), poly(oxydimethylsilylene) (oxydiphenylsilylene), and poly(oxymethylphenylsilylene); polysilazanes, such as perhydropolysilazane, polydimethylsilazane, poly(dimethyl-methyl)silazane, polymethylsilazane, poly(1,1-dimethyl-2-methylpolysilazane), poly(1,1-diphenyl-2-methylpolysilazane), poly(1,1-diphenyl-2-phenylpolysilazane), poly(1-methyl-1-phenyl-2-methylpolysilazane), and poly(poly(1-methyl-1-phenyl-2-phenylpolysilazane); and polysilanes, such as poly(methylene) (methylsilylene) and poly(methylene) (dimethylsilylene). The polymer may be synthesized in advance or may be generated in the reaction system during catalyst production. A preferably used polymer particularly includes a silicon atom and preferably has at least one hydrogen atom on the silicon atom. A silicon-hydrogen bond is capable of interacting with a transition metal, such as palladium ion, ruthenium ion, rhodium ion, and platinum ion, to reduce metal ions. Depending on the metal, the reduction sometimes generates a metal cluster exhibiting catalytic activity.

[0148] As an example, a polysiloxane analog is described in detail. The polymer has a main chain composed of a silicon atom and an oxygen atom. Further in detail, the main chain may be composed of repeated units derived from a single monomer having the same substituent group on silicon or may be composed of repeated units derived from equal to or more than two monomers having different substituent groups on silicon. In the latter case, the polymer may be particularly either a random copolymer or a block copolymer.

[0149] The polysiloxane analog preferably has a hydrogen atom at a certain ratio as a substituent group on silicon. The ratio of the hydrogen atom to all substituent groups on the silicon atoms is preferably determined in accordance with reduction efficiency required to reduce a target metal atom. When a hydrogen atom is included as a substituent group on the silicon atoms, the polysiloxane analog may also act as a reducing agent. In addition, when a hydrogen atom is included as a substituent group on the silicon atoms, the polysiloxane analog reduce the target metal atom and change to a silanol group by a trace amount of moisture and the like. The silanol group is further subjected to a dehydration condensation, and then capable of forming a crosslinked structure. The silanol group is thus considered to immobilize and coat the target metal atom more effectively.

[0150] Typically, the polysiloxane analog preferably has the average molecular weight of equal to or more than 500. The average molecular weight is even more preferably equal to or more than 1000. The hydrogen content is preferably equal to or more than 60 g/mol. A too-high hydrogen content sometimes causes hydrogen gas generation when the polysiloxane analog reacts with the metal atom. The hydrogen content is thus preferably equal to or less than 200 g/mol.

[0151] The polysiloxane analog, such as poly(oxymethylhydrosilylene), poly(oxydimethylsilylene) (oxymethylhydrosilylene), and poly(oxydimethylsilylene) (oxydihydrosilylene), are readily synthesized or inexpensively available. The polysiloxane analog are also very stable and readily handled. Accordingly, mass production of a catalyst using the polysiloxane analog as a carrier for the metal is excellent in that the raw materials are readily available and no special facilities in consideration of deterioration of the raw materials and the like are required.

<Metal>

[0152] The metal acting as a catalytic center may be any metal compound as long as being applicable to the target reaction. The metal is preferably a transition metal compound including a transition metal element of the 3rd group to the 13th group. The metal more preferably includes palladium, platinum, ruthenium, rhodium, silver, gold, copper, nickel, cobalt, iron, chromium, manganese, technetium, osmium, molybdenum, tungsten, iridium, rhenium, titanium, zirconium, hafnium, tantalum, niobium, vanadium, and any other transition metal element.

[0153] Although the type of ligands of the transition metal and the valence of the transition metal are not particularly limited, palladium, platinum, gold, and any other transition metals are considered to be supported by a polymer as a 0-valent metal cluster when, for example, the step of using a reducing agent is included in the production of a catalyst.

[0154] In some aspects of the present invention, a transition metal compound that may be used for the production of a catalyst is considered not to have a ligand or to have an anionic ligand or a neutral ligand. Such anion may be halide ion, such as chloro-, bromo-, and iodo-ions, acetate, triflate, mesylate, alkoxide, acetylacetonate, trifluoroacetate, propionate, cyano, hexafluoroacetylacetonate, hydroxide ions, nitrate, sulfonate, and composite salts and hydrate thereof.

[0155] More specific examples include bis(2,4-pentanedionate) titanium (IV) oxide, dichlorotitanium diisopropoxide, tetra-n-butylorthotitanate, tetraethylorthotitanate, tetraisopropylorthotitanate, titanium (III) chloride, titanium (IV) chloride, bis(2,4-pentanedionate) vanadium (IV) oxide, vanadium (III) chloride, vanadium (IV) chloride, chromium (III) acetate, chromium (II) chloride, chromium (III) chloride, chromium (III) nitrate, pyridinium chlorochromate, pyridinium dichromate, tris(2,4-pentanedionate) chromium (III), manganese (II) acetate, manganese (III) acetate, manganese (II) chloride, manganese (II) nitrate, manganese (II), bis(hexafluoroacetylacetonato) manganese (II), bis(2,4-pentanedionate) manganese (II), tris(2,4-pentanedionate) manganese (III), iron (II) acetate, iron (III) oxalate, iron (II) chloride, iron (III) chloride, iron (III) nitrate, iron (II) sulfate, iron (III) sulfate, ferrocene (II), n-butylferrocene (II), tris(2,4-pentanedionate) iron (III), cobalt (II) acetate, bis(2,4-pentanedionate) cobalt (II), tris(2,4-pentanedionate) cobalt (III), cobalt (II) chloride, cobalt (II) nitrate, nickel (II) acetate, bis(2,4-pentanedionate) nickel (II), nickel (II) chloride, nickel (II) nitrate, nickel (II) oxalate, tetrakis(triphenylphosphine) nickel (0), potassium tetracyanonickelate (II), copper (I) acetate, copper (II) acetate, copper (I) bromide, copper (II) bromide, copper (I) chloride, copper (II) chloride, copper (I) iodide, copper (II) iodide, copper (II) nitrate, copper (II) sulfate, bis(2,4-pentanedionate) copper (II), potassium tetrachlorocupurate (II), zinc (II) acetate, bis(2,4-pentadionate) zinc (II), zinc (II) nitrate, zinc (II) sulfate, tetrakis(2,4-pentanedionate) zirconium (IV), zirconocene dichloride (IV), zirconium (IV) chloride, zirconium (IV) ethoxide, zirconium (IV) propoxide, zirconium (IV) nitrate, niobium (V) chloride, niobium (V) ethoxide, molybdenum (II) acetate, molybdenum (III) chloride, molybdenum (IV) chloride, molybdenum (V) chloride, bis(2,4-pentanedionate) molybdenum (IV) dioxide, ruthenium (III) chloride, rhodium (II) acetate, rhodium (III) chloride, rhodium (III) nitrate, bis(1,5-cyclooctadiene)-p,p′-dichlororhodium, tris(triphenylphosphine) rhodium (I) chloride, palladium (II) acetate, palladium (II) chloride, palladium (II) nitrate, bis(2,4-pentanedionate) palladium (II), tetrakis(triphenylphosphine) palladium (0), potassium tetrachloropalladate (II), silver (I) acetate, silver (I) trifluoromethanesulfonate, silver (I) chloride, silver (I) nitrate, silver (I) sulfate, silver (I) p-toluenesulfonate, cadmium (II) acetate, cadmium (II) chloride, cadmium (II) nitrate, cadmium (II) sulfate, acetylacetonato hafnium (IV), hafnium (IV) chloride, hafnium (IV) ethoxide, hafnium (IV) isopropoxide, hafnocene dichloride, hafnium (IV) trifluoromethanesulfonate, tantalum (V) chloride, tantalum (V) ethoxide, tungsten (IV) chloride, tungsten (IV) ethoxide, hexacarbonyl tungsten, tungstic acid, rhenium (III) chloride, rhenium (IV) chloride, rhenium (V) chloride, rhenium pentacarbonyl chloride, osmium (III) chloride, iridium (III) chloride, iridium (IV) chloride, platinum (II) chloride, platinum (IV) chloride, potassium hexachloroplatinate (IV), hexahydrate hexachloroplatinate (IV), tetrakis(triphenylphosphine) platinum (0), potassium tetrachloroplatinate (II), gold (I) chloride, gold (III) chloride, gold (III) bromide, potassium tetracyanoaurate (III), tetrachloroauric (III) acid, tetrachloroaurate (III) tetrahydrate, (triphenylphosphine) gold (I) chloride, mercury (I) acetate, mercury (II) acetate, mercury (I) chloride, mercury (II) chloride, mercury (I) nitrate, mercury (II) nitrate, mercury (I) sulfate, and mercury (II) sulfate.

<Inorganic Member, Organic Member>

[0156] The polymer-supported metal catalyst according to some aspects of the present invention may further include, in addition to a metal acting as a catalytic center and the polymer to support the metal, an inorganic member to support the polymer with the metal catalyst immobilized thereon or an organic member, such as a polystyrene resin and a polyacrylic resin.

[0157] As the inorganic member, a metal compound, activated carbon, and the like may be used. As metal oxide, a compound, such as silicon oxide (SiO.sub.2) and oxide including, titanium, zirconium, magnesium, and aluminum, and any other metals, may be used. More specific examples include titanium oxide (TiO.sub.2), zirconium oxide (ZrO.sub.2), magnesium oxide (MgO), alumina (Al.sub.2O.sub.3), zeolite,and hydrotalcite.

2. Method of Producing Metal Catalyst Supported by Polymer

[0158] A method of producing a metal catalyst supported by a polymer includes the step of mixing the metal atom compound and the polymer for support of the metal on the polymer. The method may further include the step of mixing the compound and the polymer with an inorganic member or an organic member for further support of the polymer including the transition metal on the inorganic member or the organic member.

<Mixing>

[0159] In the step of mixing the metal compound with the polymer for support, a considered method is that the metal compound and the polymer compound are directly kneaded or are mixed together with a solvent. When the metal compound is reacted with a reducing agent to reduce the valence of the metal to be supported by the polymer, the method using a solvent for mixed is preferred.

<Solvent>

[0160] The type of solvent may be freely selected as long as it can dissolve or disperse the reactant to some extent. An organic solvent is preferably used that is capable of effectively mixing the polymer. To use a reducing agent, an aprotic organic solvent is preferred considering the reactivity. The aprotic organic solvent includes ether solvent, such as diethyl ether and tetrahydrofuran (THF), aromatic hydrocarbons, such as benzene and toluene, and halide hydrocarbons, such as dichloromethane and chloroform, and the like. Tetrahydrofuran (THF), toluene, and the like are preferably used.

<Reducing Agent>

[0161] To reduce a metal compound in the step of producing a catalyst, the type of reducing agent to be used may be selected appropriately. Examples of the reducing agent include metallic hydrogen complex compounds and metal hydrides, such as lithium aluminum hydride, diisobutylaluminum hydride, sodium borohydride, triphenyltin hydride, and tri-n-butyltin hydride, [0162] hydrosilanes, such as trichlorosilane, trimethylsilane, triethylsilane, trimethoxysilane, and triethoxysilane, [0163] borane derivatives, such as diborane, amine borane complex, and alkylborane, [0164] alcohols, such as methanol, ethanol, and isopropyl alcohol, [0165] formic acid, hydrogen gas, and any other reducing agents. In particular, sodium borohydride, triethylsilane, and hydrogen gas are preferred considering costs, safety, influence on the environment, and the like. When poly(oxydimethylsilylene) (oxymethylhydrosilylene) (PMHS) is used as the polymer, the polymer itself as a carrier acts as a reducing agent. Accordingly, a separate reducing agent does not have to be added, and the catalyst is prepared by a more convenient method.

<Conditions for Mixing and Reduction>

[0166] To mix the metal compound and the polymer in a solvent, a reaction temperature may be set any temperature that is equal to or less than the boiling point and equal to or more than the freezing point. However, when the metal compound has to be reduced, the reaction temperature is in a range to allow reduction reaction for the metal compound to proceed with no problems. At this point, a reducing agent is separately added if necessary, and if a polymer is prepared in the system, instead of the polymer, equal to or more than one type of corresponding monomer is appropriately added. In some aspects of the present invention, reduction reaction to a transition metal compound does not require a high temperature, and such reduction reaction is preferably carried out in a temperature range approximately from 0° C. to room temperature from the perspective of costs for facilities and utilities.

[0167] Further, to have the polymer supported by an inorganic member or an organic member, the inorganic member or the organic member is added to the reaction solution including a transition metal compound, a polymer, and a reducing agent if necessary for support. The metal compound, the reducing agent, and the inorganic member or the organic member may be simultaneously added for mixing, and the order of mixing is considered not to particularly influence the production greatly.

3. Method of Producing Compound using Polymer-Supported Metal Catalyst

[0168] For reduction reaction, oxidation reaction, hydrometalation, carbon-carbon bond forming reaction, or carbon-nitrogen bond forming reaction using the polymer-supported metal catalyst, some aspects of the present invention enable smooth proceeding of the reaction and production of a compound in high yield. Further, after the reaction, the catalyst according to some aspects of the present invention is capable of being readily recovered and is confirmed not to cause metal leakage. That is, the catalyst according to some aspects of the present invention is highly active and has a long life to allow repeated use.

<Reduction Reaction>

[0169] According to some aspects of the present invention, various types of reduction reaction may be provided using the polymer-supported metal catalyst according to the aspects. Metallic hydrogen complex compounds, metal hydrides, hydrosilanes, borane derivatives, and the like may be used as a reducing agent. The reducing agent, such as alcohols, formic acid, and hydrogen gas, and the like is preferably used, which is readily handled and inexpensive. Hydrogen gas is more preferably used as the reducing agent, which allows easy scaling up and large-scale synthesis. FIG. 1 is a conceptual diagram of an equipment in a flow reaction system. A equipment configured to pass a reactant and hydrogen gas supplied without interruption through the polymer-supported metal catalyst according to some aspects of the present invention fixed to a flow path enables continuous reduction reaction.

[0170] According to some aspects of the present invention, hydrogenation reaction to various unsaturated bonds proceeds in relatively mild conditions. Although the reaction proceeds at a reaction temperature approximately at room temperature, the temperature is not particularly limited to around room temperature and may be at lower or higher temperatures. In addition, although the reaction proceeds in a hydrogen gas atmosphere approximately at atmospheric pressure, it may be in a mixed gas atmosphere with an inert gas, such as a nitrogen gas and an argon gas, and the pressure may be appropriately prepared.

<Oxidation Reaction>

[0171] Some aspects of the present invention enable various types of oxidation reaction using the polymer-supported metal catalyst according to the aspects. Oxygen gas, peroxide, hypervalence iodic acid, and the like may be used as an oxidant.

[0172] According to some aspects of the present invention, Wacker oxidation reaction to various unsaturated bonds proceeds in relatively mild conditions. Although the reaction proceeds at a reaction temperature approximately at room temperature, the temperature is not particularly limited to around room temperature and may be at lower or higher temperatures. In addition, although the reaction proceeds in an oxygen gas atmosphere approximately at atmospheric pressure, it may be in a mixed gas atmosphere with an inert gas, such as a nitrogen gas and an argon gas, and the pressure may be appropriately prepared.

<Carbon-Carbon Bond forming Reaction>

[0173] Some aspects of the present invention enable various types of carbon-carbon bond forming reaction using the polymer-supported metal catalyst according to the aspects and are applicable to various types of reaction, such as cyclopropanation reaction, en reaction, pericyclic reaction, aldol reaction, Michael addition reaction, Sakurai reaction, cross-coupling reaction, and metathesis reaction. Examples of the cross-coupling reaction include Heck reaction, Sonogashira coupling reaction, Suzuki-Miyaura coupling reaction, Kumada coupling reaction, Negishi coupling reaction, Tsuji-Trost reaction, and Stille coupling reaction.

<Carbon-Nitrogen Bond forming Reaction>

[0174] Some aspects of the present invention enable various types of carbon-nitrogen bond forming reaction using the polymer-supported metal catalyst according to the aspects and are applicable to reaction, such as Buchwald-Hartwig cross-coupling reaction and allylation reaction of amine.

<Hydrometalation>

[0175] Some aspects of the present invention enable various types of hydrometalation reaction using the polymer-supported metal catalyst according to the aspects and are applicable to reaction, such as hydroboration, hydroalumination, hydrozirconation, hydrostannylation, and hydrosilylation.

EXAMPLES

[0176] Specific Examples of the present invention are described below while the present invention is not limited to them.

<Production of Polymer-Supported Metal Catalyst>

[0177] A polymer (may be a monomer constituting a polymer) and a reducing agent, as needed, are mixed with a solvent. A transition metal compound is added to the mixed solution and stirred at an appropriate temperature for a certain period of time. An inorganic member (suspension thereof) is then added and further stirred. Methanol is added and further stirred for a while for reprecipitation. Suction filtration and twice of methanol washing are carried out to produce a polymer-supported metal catalyst in powder. Specific examples of a catalyst according to some aspects of the present invention are described with respective details in Examples 1 to 35 below.

TABLE-US-00001 TABLE 1 Reducing Agent Metal Type Polymer or Monomer Carrier Name of Catalyst Example 1 Hydrogen Gas Palladium (II) Acetate PDMS Silicon Oxide PSiO—Pd/SiO.sub.2 Example 2 Hydrogen Gas Palladium (II) Nitrate PDMS Titanium Oxide PSiO—Pd/TiO.sub.2 Example 3 Hydrogen Gas Palladium (II) Chloride PEI Zirconium Oxide PEI—Pd/ZrO.sub.2 Example 4 Hydrogen Gas Palladium (II) Chloride PDMS Activated Carbon PSiO—Pd/C Example 5 Hydrogen Gas Palladium (II) Acetate PMPP Magnesium PNCO—Pd/MgO Oxide Example 6 Sodium Borohydride Palladium (II) Acetate PDMS Silicon Oxide PSiO—Pd/SiO.sub.2 Example 7 Sodium Borohydride Palladium (II) Nitrate PDMS Titanium Oxide PSiO—Pd/TiO.sub.2 Example 8 Sodium Borohydride Palladium (II) Chloride PEI Zirconium Oxide PEI—Pd/ZrO.sub.2 Example 9 Sodium Borohydride Palladium (II) Chloride PDMS Activated Carbon PSiO—Pd/C Example 10 Sodium Borohydride Palladium (II) Acetate PMPP Magnesium PNCO—Pd/MgO Oxide Example 11 Triethylsilane Palladium (II) Acetate PDMS Silicon Oxide PSiO—Pd/SiO.sub.2 Example 12 Triethylsilane Palladium (II) Nitrate PDMS Titanium Oxide PSiO—Pd/TiO.sub.2 Example 13 Triethylsilane Palladium (II) Chloride PEI Zirconium Oxide PEI—Pd/ZrO.sub.2 Example 14 Triethylsilane Palladium (II) Chloride PDMS Activated Carbon PSiO—Pd/C Example 15 Triethylsilane Palladium (II) Acetate PMPP Magnesium PNCO—Pd/MgO Oxide Example 16 PMHS Palladium (II) Acetate PMHS Silicon Oxide PSiOH—Pd/SiO.sub.2 Example 17 PMHS Palladium (II) Nitrate PMHS Titanium Oxide PSiOH—Pd/TiO.sub.2 Example 18 PMHS Palladium (II) Chloride PMHS Zirconium Oxide PSiOH—Pd/ZrO.sub.2 Example 19 PMHS Palladium (II) Chloride PMHS Activated Carbon PSiOH—Pd/C Example 20 PMHS Palladium (II) Acetate PMHS Alumina PSiOH—Pd/Al.sub.2O.sub.3 Example 21 PMHS Hexahydrate PMHS Alumina PSiOH—Pt/Al.sub.2O.sub.3 Hexachloroplatinate (IV) Example 22 Triethylsilane Hexahydrate PDMS Silicon Oxide PSiO—Pt/SiO.sub.2 Hexachloroplatinate (IV) Example 23 PMHS Nickel (II) Chloride PMHS Alumina PSiOH—Ni/Al.sub.2O.sub.3 Example 24 Triethylsilane Nickel (II) Chloride PDMS Silicon Oxide PSiO—Ni/SiO.sub.2 Example 25 PMHS Ruthenium (III) Chloride PMHS Alumina PSiOH—Ru/Al.sub.2O.sub.3 Example 26 Triethylsilane Ruthenium (III) Chloride PDMS Silicon Oxide PSiO—Ru/SiO.sub.2 Example 27 PMHS Rhodium (III) Chloride PMHS Alumina PSiOH—Rh/Al.sub.2O.sub.3 Example 28 Triethylsilane Rhodium (III) Chloride PDMS Silicon Oxide PSiO—Rh/SiO.sub.2 Example 29 PMHS Tetrachloroaurate (III) Tetrahydrate PMHS Alumina PSiOH—Au/Al.sub.2O.sub.3 Example 30 Triethylsilane Tetrachloroaurate (III) Tetrahydrate PDMS Silicon Oxide PSiO—Au/SiO.sub.2 Example 31 Diphenyl Silane Palladium (II) Acetate Diphenyl Silane + Alumina PSiNPh—Pd/Al.sub.2O.sub.3 (R)-(+)-1-Phenylethylamine Example 32 1,1,3,3- Palladium (II) Acetate 1,1,3,3-Tetramethyldisiloxane + Alumina PSiON—Pd/Al.sub.2O.sub.3 Tetramethyldisiloxane (R)-(+)-1-Phenylethylamine Example 33 1,1,3,3- Palladium (II) Acetate 1,1,3,3-Tetramethyldisiloxane + Alumina PSiOQ—Pd/Al.sub.2O.sub.3 Tetramethyldisiloxane Hydroquinone Example 34 1,1,3,3- Palladium (II) Acetate 1,1,3,3-Tetramethyldisiloxane + Alumina PSiOD—Pd/Al.sub.2O.sub.3 Tetramethyldisiloxane 1,6-Hexanediol Example 35 Polysilazane Palladium (II) Acetate Polysilazane — PSiN—Pd

Example 1

[0178] A THF solution containing 250 mg of poly(oxydimethylsilylene) (PDMS) (by Shin-Etsu Chemical Co., Ltd., catalog number: KF-96) is prepared, and 6 mg of palladium (II) acetate (Pd(OAc).sub.2) is added to be stirred in a hydrogen gas (H.sub.2) atmosphere at 0° C. for 55 minutes. Subsequently, 1.25 g of silicon oxide (SiO.sub.2) is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain poly(oxydimethylsilylene) and a palladium catalyst (PSiO-Pd/SiO.sub.2) in powder supported by silicon oxide.

##STR00001##

Example 2

[0179] A THF solution containing 250 mg of poly(oxydimethylsilylene) is prepared, and 6 mg of palladium (II) nitrate (Pd(NO.sub.3).sub.2) is added to be stirred in a hydrogen gas atmosphere at 0° C. for 55 minutes. Subsequently, 1.25 g of titanium oxide (TiO.sub.2) is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain poly(oxydimethylsilylene) and a palladium catalyst (PSiO-Pd/TiO.sub.2) in powder supported by titanium oxide.

##STR00002##

Example 3

[0180] A THF solution containing 250 mg of polyethyleneimine (PEI) (by Wako Pure Chemical Industries, Ltd., catalog number: 167-1195) is prepared, and 6 mg of palladium (II) chloride (PdCl.sub.2) is added to be stirred in a hydrogen gas atmosphere at 0° C. for 55 minutes. Subsequently, 1.25 g of zirconium oxide (ZrO.sub.2) is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain polyethyleneimine and a palladium catalyst (PEI-Pd/ZrO.sub.2) in powder supported by zirconium oxide.

##STR00003##

Example 4

[0181] A THF solution containing 250 mg of poly(oxydimethylsilylene) is prepared, and 6 mg of palladium (II) chloride is added to be stirred in a hydrogen gas atmosphere at 0° C. for 55 minutes. Subsequently, 1.25 g of activated carbon is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain poly(oxydimethylsilylene) and a palladium catalyst (PSiO-Pd/C) in powder supported by activated carbon.

##STR00004##

Example 5

[0182] A THF solution containing 250 mg of polymethylene phenylene isocyanate (PMPP) (by Sigma-Aldrich Co. LLC., catalog number 406597) is prepared, and 6 mg of palladium (II) acetate is added to be stirred in a hydrogen gas atmosphere at 0° C. for 55 minutes. Subsequently, 1.25 g of magnesium oxide (MgO) is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain polymethylene phenylene isocyanate and a palladium catalyst (PNCO-Pd/MgO) in powder supported by magnesium oxide.

##STR00005##

Example 6

[0183] A THF suspension containing 250 mg of poly(oxydimethylsilylene) and 5 mg of sodium borohydride (NaBH.sub.4) is prepared, and 6 mg of palladium (II) acetate is added to be stirred at 0° C. for 55 minutes. Subsequently, 1.25 g of silicon oxide is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain poly(oxydimethylsilylene) and a palladium catalyst (PSiO-Pd/SiO.sub.2) in powder supported by silicon oxide.

##STR00006##

Example 7

[0184] A THF suspension containing 250 mg of poly(oxydimethylsilylene) and 5 mg of sodium borohydride is prepared, and 6 mg of palladium (II) nitrate is added to be stirred at 0° C. for 55 minutes. Subsequently, 1.25 g of titanium oxide is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain poly(oxydimethylsilylene) and a palladium catalyst (PSiO-Pd/TiO.sub.2) in powder supported by titanium oxide.

##STR00007##

Example 8

[0185] A THF suspension containing 250 mg of polyethyleneimine and 5 mg of sodium borohydride is prepared, and 6 mg of palladium (II) chloride is added to be stirred at 0° C. for 55 minutes. Subsequently, 1.25 g of zirconium oxide is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain polyethyleneimine and a palladium catalyst (PEI-Pd/ZrO.sub.2) in powder supported by zirconium oxide.

##STR00008##

Example 9

[0186] A THF suspension containing 250 mg of poly(oxydimethylsilylene) and 5 mg of sodium borohydride is prepared, and 6 mg of palladium (II) chloride is added to be stirred at 0° C. for 55 minutes. Subsequently, 1.25 g of activated carbon is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain poly(oxydimethylsilylene) and a palladium catalyst (PSiO-Pd/C) in powder supported by activated carbon.

##STR00009##

Example 10

[0187] A THF suspension containing 250 mg of polymethylene phenylene isocyanate and 5 mg of sodium borohydride is prepared, and 6 mg of palladium (II) acetate is added to be stirred at 0° C. for 55 minutes. Subsequently, 1.25 g of magnesium oxide is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain polymethylene phenylene isocyanate and a palladium catalyst (PNCO-Pd/MgO) in powder supported by magnesium oxide.

##STR00010##

Example 11

[0188] A THF solution containing 250 mg of poly(oxydimethylsilylene) and 16 mg of triethylsilane (Et.sub.3SiH) is prepared, and 6 mg of palladium (II) acetate is added to be stirred at 0° C. for 55 minutes. Subsequently, 1.25 g of silicon oxide is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain poly(oxydimethylsilylene) and a palladium catalyst (PSiO-Pd/SiO.sub.2) in powder supported by silicon oxide.

##STR00011##

Example 12

[0189] A THF solution containing 250 mg of poly(oxydimethylsilylene) and 16 mg of triethylsilane is prepared, and 6 mg of palladium (II) nitrate is added to be stirred at 0° C. for 55 minutes. Subsequently, 1.25 g of titanium oxide is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain poly(oxydimethylsilylene) and a palladium catalyst (PSiO-Pd/TiO.sub.2) in powder supported by titanium oxide.

##STR00012##

Example 13

[0190] A THF solution containing 250 mg of polyethyleneimine and 16 mg of triethylsilane is prepared, and 6 mg of palladium (II) chloride is added to be stirred at 0° C. for 55 minutes. Subsequently, 1.25 g of zirconium oxide is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain polyethyleneimine and a palladium catalyst (PEI-Pd/ZrO.sub.2) in powder supported by zirconium oxide.

##STR00013##

Example 14

[0191] A THF solution containing 250 mg of poly(oxydimethylsilylene) (PDMS) and 16 mg of triethylsilane is prepared, and 6 mg of palladium (II) chloride is added to be stirred at 0° C. for 55 minutes. Subsequently, 1.25 g of activated carbon is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain poly(oxydimethylsilylene) and a palladium catalyst (PSiO-Pd/C) in powder supported by activated carbon.

##STR00014##

Example 15

[0192] A THF solution containing 250 mg of polymethylene phenylene isocyanate and 16 mg of triethylsilane is prepared, and 6 mg of palladium (II) acetate is added to be stirred at 0° C. for 55 minutes. Subsequently, 1.25 g of magnesium oxide is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain polymethylene phenylene isocyanate and a palladium catalyst (PNCO-Pd/MgO) in powder supported by magnesium oxide.

##STR00015##

Example 16

[0193] A THF solution containing 250 mg of poly(oxydimethylsilylene) (oxymethylhydrosilylene (PMHS)) (by Shin-Etsu Chemical Co., Ltd., catalog number KF-99) is prepared, and 6 mg of palladium (II) acetate is added to be stirred at 0° C. for 55 minutes. Subsequently, 1.25 g of silicon oxide is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a palladium catalyst (PSiOH-Pd/SiO.sub.2) in powder supported by silicon oxide.

##STR00016##

Example 17

[0194] A THF solution containing 250 mg of poly(oxydimethylsilylene) (oxymethylhydrosilylene) is prepared, and 6 mg of palladium (II) nitrate is added to be stirred at 0° C. for 55 minutes. Subsequently, 1.25 g of titanium oxide is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a palladium catalyst (PSiOH-Pd/TiO.sub.2) in powder supported by titanium oxide.

##STR00017##

Example 18

[0195] A THF solution containing 250 mg of poly(oxydimethylsilylene) (oxymethylhydrosilylene) is prepared, and 6 mg of palladium (II) chloride is added to be stirred at 0° C. for 55 minutes. Subsequently, 1.25 g of zirconium oxide is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a palladium catalyst (PSiOH-Pd/ZrO.sub.2) in powder supported by zirconium oxide.

##STR00018##

Example 19

[0196] A THF solution containing 250 mg of poly(oxydimethylsilylene) (oxymethylhydrosilylene) is prepared, and 6 mg of palladium (II) chloride is added to be stirred at 0° C. for 55 minutes. Subsequently, 1.25 g of activated carbon is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a palladium catalyst (PSiOH-Pd/C) in powder supported by activated carbon.

##STR00019##

Example 20

[0197] A THF solution containing 250 mg of poly(oxydimethylsilylene) (oxymethylhydrosilylene) is prepared, and 6 mg of palladium (II) acetate is added to be stirred at 0° C. for 55 minutes. Subsequently, 1.25 g of alumina (Al.sub.2O.sub.3) is added to be stirred at room temperature for 25 minutes. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a palladium catalyst (PSiOH-Pd/Al.sub.2O.sub.3) in powder supported by alumina.

##STR00020##

Example 21

[0198] A toluene suspension containing 250 mg of poly(oxydimethylsilylene) (oxymethylhydrosilylene) and 1.25 g of alumina is prepared, and 6 mg of hexahydrate hexachloroplatinate (IV) (H.sub.2PtCl.sub.6.6(H.sub.2O)) is added to be stirred at room temperature for 14 hours. Methanol is added to be further stirred for 5 hours for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a platinum catalyst (PSiOH-Pt/Al.sub.2O.sub.3) in powder supported by alumina.

##STR00021##

Example 22

[0199] A toluene suspension containing 250 mg of poly(oxydimethylsilylene), 16 mg of triethylsilane, and 1.25 g of silicon oxide is prepared, and 6 mg of hexahydrate hexachloroplatinate (IV) is added to be stirred at room temperature for 14 hours. Methanol is added to be further stirred for 5 hours for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a platinum catalyst (PSiO-Pt/SiO.sub.2) in powder supported by silicon oxide.

##STR00022##

Example 23

[0200] A THF suspension containing 250 mg of poly(oxydimethylsilylene) (oxymethylhydrosilylene) and 1.25 g of alumina is prepared, and 6 mg of nickel (II) chloride (NiCl.sub.2) is added to be stirred at room temperature for 14 hours. Methanol is added to be further stirred for 5 hours for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a nickel catalyst (PSiOH-Ni/Al.sub.2O.sub.3) in powder supported by alumina.

##STR00023##

Example 24

[0201] A THF suspension containing 250 mg of poly(oxydimethylsilylene), 16mg of triethylsilane, and 1.25 g of silicon oxide is prepared, and 6 mg of nickel (II) chloride is added to be stirred at room temperature for 14 hours. Methanol is added to be further stirred for 5 hours for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a nickel catalyst (PSiO-Ni/SiO.sub.2) in powder supported by silicon oxide.

##STR00024##

Example 25

[0202] A THF suspension containing 250 mg of poly(oxydimethylsilylene) (oxymethylhydrosilylene) and 1.25 g of alumina is prepared, and 6 mg of ruthenium (III) chloride (RuCl.sub.3) is added to be stirred at room temperature for 14 hours. Methanol is added to be further stirred for 5 hours for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a ruthenium catalyst (PSiOH-Ru/Al.sub.2O.sub.3) in powder supported by alumina.

##STR00025##

Example 26

[0203] A THF suspension containing 250 mg of poly(oxydimethylsilylene), 16mg of triethylsilane, and 1.25 g of silicon oxide is prepared, and 6 mg of ruthenium (III) chloride is added to be stirred at room temperature for 14 hours. Methanol is added to be further stirred for 5 hours for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a ruthenium catalyst (PSiO-Ru/SiO.sub.2) in powder supported by silicon oxide.

##STR00026##

Example 27

[0204] A THF suspension containing 250 mg of poly(oxydimethylsilylene) (oxymethylhydrosilylene) and 1.25 g of alumina is prepared, and 6 mg of rhodium (III) chloride (RhCl.sub.3) is added to be stirred at room temperature for 14 hours. Methanol is added to be further stirred for 5 hours for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain poly(oxydimethylsilylene) (oxymethylhydrosilylene) and a rhodium catalyst (PSiOH-Rh/Al.sub.2O.sub.3) in powder supported by alumina.

##STR00027##

Example 28

[0205] A THF suspension containing 250 mg of poly(oxydimethylsilylene), 16mg of triethylsilane, and 1.25 g of silicon oxide is prepared, and 6 mg of rhodium (III) chloride is added to be stirred at room temperature for 14 hours. Methanol is added to be further stirred for 5 hours for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a rhodium catalyst (PSiO-Rh/SiO.sub.2) in powder supported by silicon oxide.

##STR00028##

Example 29

[0206] A THF suspension containing 250 mg of poly(oxydimethylsilylene) (oxymethylhydrosilylene) and 1.25 g of alumina is prepared, and 6 mg of tetrachloroaurate (III) tetrahydrate (HAuCl.sub.4.4(H.sub.2O)) is added to be stirred at room temperature for 14 hours. Methanol is added to be further stirred for 5 hours for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a gold catalyst (PSiOH-Au/Al.sub.2O.sub.3) in powder supported by alumina.

##STR00029##

Example 30

[0207] A THF suspension containing 250 mg of poly(oxydimethylsilylene), 16mg of triethylsilane, and 1.25 g of silicon oxide is prepared, and 6 mg of tetrachloroaurate (III) tetrahydrate is added to be stirred at room temperature for 14 hours. Methanol is added to be further stirred for 5 hours for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a gold catalyst (PSiO-Au/SiO.sub.2) in powder supported by silicon oxide.

##STR00030##

Example 31

[0208] A chloroform solution containing 20.0 mg of diphenylsilane and 13.0 mg of (R)-(+)-1-phenylethylamine, which is a chiral compound, is prepared, and 10 mg of palladium (II) acetate is added to be stirred at room temperature for 30 minutes. Subsequently, 165 mg of alumina is added to be stirred at room temperature for 10 minutes. Methanol is added to be further stirred for 10 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a palladium catalyst (PSiN-Pd/Al.sub.2O.sub.3) in gray powder supported by alumina.

##STR00031##

Example 32

[0209] A THF solution containing 100 mg of 1,1,3,3-tetramethyldisiloxane and 90 mg of (R)-(+)-1-phenylethylamine as chiral amine is prepared, and 7 mg of palladium (II) acetate is added to be stirred at 0° C. for 30 minutes. Subsequently, 1.5 g of alumina is added to be stirred at room temperature for 1 hour. Methanol is added to be further stirred for 10 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a palladium catalyst (PSiON-Pd/Al.sub.2O.sub.3) in gray powder supported by alumina. The catalyst includes at least two elements, such as an oxygen atom and a nitrogen atom, for example, having an electronegativity higher than an electronegativity of a hydrogen atom. According to EDX measurement results, the respective composition ratios of aluminum atoms, silicon atoms, and palladium atoms are 97.446, 2.030, and 0.134.

##STR00032##

Example 33

[0210] A THF solution containing 20 mg of 1,1,3,3-tetramethyldisiloxane and 20 mg of hydroquinone is prepared, and 2 mg of palladium (II) acetate is added to be stirred at 0° C. for 30 minutes. Subsequently, 380 mg of alumina is added to be stirred at room temperature for 35 minutes. Methanol is added to be further stirred for 10 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a palladium catalyst (PSiOQ-Pd/Al.sub.2O.sub.3) in gray powder supported by alumina. According to EDX measurement results, the respective composition ratios of aluminum atoms, silicon atoms, and palladium atoms are 97.864, 1.634, and 0.163.

##STR00033##

Example 34

[0211] A THF solution containing 50 mg of 1,1,3,3-tetramethyldisiloxane and 44 mg of 1,6-hexanediol is prepared, and 3 mg of palladium (II) acetate is added to be stirred at 0° C. for 55 minutes. Subsequently, 380 mg of alumina is added to be stirred at room temperature for 1 hour. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a palladium catalyst (PSiOD-Pd/Al.sub.2O.sub.3) in gray powder supported by alumina.

##STR00034##

Example 35

[0212] A THF solution containing 100 mg of polysilazane is prepared, and 34 mg of palladium (II) acetate is added to be stirred in reflux conditions for 2 hours. Methanol is added to be further stirred for 5 minutes for reprecipitation and is subjected to suction filtration and twice of methanol washing to obtain a palladium catalyst (PSiN-Pd) in black powder.

##STR00035##

<Production of Compound using Polymer-Supported Metal Catalyst>

[0213] Using some of the synthesized metal catalysts, high catalytic activity is exhibited in some chemical reactions. The catalyst is recovered after termination of reaction, and metal leakage is checked to be found that any catalyst had almost no leakage and the polymer had high retentivity. In some of the catalysts, no metal leakage at all is confirmed by the employed method, resulting in obtaining the catalysts with extremely high durability.

[Method of Confirming Metal Leakage]

[0214] The solution after reaction is filtered by a syringe filter, followed by measuring the filtrate by EDX to detect leakage of the catalyst.

[Reduction Reaction using Polymer-Supported Palladium Catalyst]

[0215] A hexane solution containing a substrate of 1.0 mmol is prepared, and 10 mg of a palladium catalyst is added to make a suspension and to be stirred in a hydrogen gas atmosphere at 1 atmospheric pressure at room temperature for several hours. The palladium catalyst is then removed from the suspension by filtration. Subsequently, the filtrate is concentrated for purification by column chromatography to obtain a corresponding reductant. Results of Examples 36 to 50 and Comparative Examples 1 to 3 are shown in Table 2. (In Examples 46 to 50 and Comparative Example 3, THF is used for the solvent instead of hexane.)

TABLE-US-00002 TABLE 2 Pd Yield Leak- Substrate Catalyst (%) age* Example 36 Ethyl Cinnamate PSiOH—Pd/Al.sub.2O.sub.3 100 ⊙ Example 37 PSiO—Pd/TiO.sub.2 97 ◯ Example 38 PNCO—Pd/MgO 95 ◯ Example 39 PEI—Pd/ZrO.sub.2 92 ◯ Example 40 PSiON—Pd/Al.sub.2O.sub.3 100 ◯ Comparative Pd/C 99 X Example 1 Example 41 Diphenylacetylene PSiOH—Pd/Al.sub.2O.sub.3 92 ⊙ Example 42 PSiO—Pd/TiO.sub.2 85 ⊙ Example 43 PNCO—Pd/MgO 82 ◯ Example 44 PEI—Pd/ZrO.sub.2 80 ◯ Example 45 PSiON—Pd/Al.sub.2O.sub.3 93 ◯ Comparative Pd/C 93 X Example 2 Example 46 Nitrobenzene PSiOH—Pd/Al.sub.2O.sub.3 88 ⊙ Example 47 PSiO—Pd/TiO.sub.2 84 ◯ Example 48 PNCO—Pd/MgO 82 ◯ Example 49 PEI—Pd/ZrO.sub.2 84 ◯ Example 50 PSiON—Pd/Al.sub.2O.sub.3 84 ◯ Comparative Pd/C 89 X Example 3 *Pd Leakage Not Found at All-> ⊙ Found Very Trace Amount-> ◯ Found Trace Amount-> Δ Found Substantial Amount-> X

[0216] As shown in Examples 36 to 40, in reduction reaction to ethyl cinnamate, the reaction smoothly proceeded and the corresponding reductant is obtained in high yield. Using a palladium catalyst supported by a polymer according to some aspects of the present invention, almost no palladium is detected from the filtrate obtained by removing the palladium catalyst from the suspension after reaction. Particularly using PSiOH-Pd/Al.sub.2O.sub.3, it is not at all detected, resulting in high supporting power. In contrast, in Comparative Example 1 using Pd/C not supported by the polymer, a substantial amount of palladium leakage is confirmed.

[0217] As shown in Examples 41 to 45, in reduction reaction to diphenylacetylene, the reaction smoothly proceeded and the corresponding reductant is obtained in high yield. At this point, one hydrogen molecule is added to one acetylene molecule, and cis-stilbene is chemoselectively and stereoselectively obtained as a product. Using a palladium catalyst supported by a polymer according to some aspects of the present invention, almost no palladium is detected from the filtrate obtained by removing the palladium catalyst from the suspension after reaction. Particularly, using PSiOH-Pd/Al.sub.2O.sub.3, it is not at all detected, resulting in high supporting power. In contrast, in Comparative Example 2 using Pd/C not supported by the polymer, a substantial amount of palladium leakage is confirmed.

[0218] As shown in Examples 46 to 50, reduction reaction proceeded even to nitrobenzene having a nitro group, and amine as the corresponding reductant is obtained in high yield. Using a palladium catalyst supported by a polymer according to some aspects of the present invention, almost no palladium is detected from the filtrate obtained by removing the palladium catalyst from the suspension after reaction. Particularly, using PSiOH-Pd/Al.sub.2O.sub.3, it is not at all detected, resulting in high supporting power. In contrast, in Comparative Example 3 using Pd/C not supported by the polymer, a substantial amount of palladium leakage is confirmed.

[Hydrogenation Reaction using Polymer-Supported Platinum Catalyst]

[0219] A hexane solution containing 1.0 mmol of diphenylacetylene is prepared and 0.05 mmol of a platinum catalyst is added to make a suspension and to be stirred in a hydrogen gas atmosphere at 1 atmospheric pressure at room temperature for several hours. The platinum catalyst is then removed from the suspension by filtration. Subsequently, the filtrate is concentrated for purification by column chromatography to obtain bibenzyl as a product in which two hydrogen molecules are added to diphenylacetylene.

##STR00036##

[Carbon-Carbon Bond forming Reaction using Polymer-Supported Metal Catalyst]

(Heck Reaction)

[0220] A toluene (PhMe) solution containing 1.0 mmol of iodobenzene (A), 1.1 mmol of acrylic acid (B) and 1.5 mmol of triethylamine (NEt.sub.3) is prepared and 0.05 mmol of a palladium catalyst is added to be stirred in heating reflux conditions for several hours. Dichloromethane is then added, and the palladium catalyst is removed from the suspension by filtration. Subsequently, the filtrate is concentrated for purification by column chromatography to obtain trans-cinnamic acid (C), which is a corresponding coupling body, in a white solid. Results are shown in Examples 51 to 54 Table 3.

[0221] As shown in Example 55, instead of iodobenzene and acrylic acid, 1.5 mmol of 3,5-dimethoxy iodobenzene (D) and 3.0 mmol of 4-acetoxystyrene (E) are used respectively to obtain trans-4-acetoxy-3′-5′-dimethoxy stilbene (F) in a white solid.

[0222] As shown in Examples 51 to 55, in Heck reaction using aryl halide and olefin as raw materials, the reaction smoothly proceeded and corresponding aryl olefin is obtained. Using a palladium catalyst supported by a polymer according to some aspects of the present invention, almost no palladium is detected from the filtrate obtained by removing the palladium catalyst from the suspension after reaction. Particularly, using PSiOH-Pd/Al.sub.2O.sub.3, no palladium at all is detected from the filtrate by measurement using EDX (energy dispersive x-ray spectrosopy). This shows that PSiOH-Pd/Al.sub.2O.sub.3 had high palladium supporting power. In contrast, in Comparative Example 4 using Pd/C not supported by the polymer, a substantial amount of palladium leakage is confirmed.

##STR00037## ##STR00038##

(Sonogashira Coupling Reaction)

[0223] A dimethylformamide (DMF) solution containing 1.0 mmol of iodobenzene (A), 1.5 mmol of phenyl acetylene (G), and 1.5 mmol of triethylamine (NEt.sub.3) is prepared, and 0.05 mmol of a palladium catalyst and 0.05 mmol of copper iodide (CuI) are added to be stirred at 90° C. for several hours. The palladium catalyst is then removed from the suspension by filtration. Subsequently, the filtrate is concentrated for purification by column chromatography to obtain diphenylacetylene (H), which is a corresponding coupling body, in a white solid. Results of Examples 56 to 59 and Comparative Example 5 are shown in Table 3.

[0224] As shown in Examples 56 to 59, in coupling reaction using iodobenzene (A) and phenyl acetylene (G) as raw materials, the reaction smoothly proceeded and diphenylacetylene (H) is obtained in high yield. Using a palladium catalyst supported by a polymer according to some aspects of the present invention, almost no palladium is detected from the filtrate obtained by removing the palladium catalyst from the suspension after reaction. Particularly using PSiOH-Pd/Al.sub.2O.sub.3, no palladium at all is detected from the filtrate by measurement using EDX (energy dispersive x-ray spectrosopy). This indicates that PSiOH-Pd/Al.sub.2O.sub.3 had high palladium supporting power. In contrast, in Comparative Example 5 using Pd/C not supported by the polymer, a substantial amount of palladium leakage is confirmed.

##STR00039##

(Suzuki-Miyaura Coupling Reaction)

[0225] An aqueous 40% ethanol solution (EtOH-H.sub.2O) containing 1.0 mmol of iodobenzene (A), 1.5 mmol of phenylboronic acid (I), and 3.0 mmol of sodium phosphate (Na.sub.3PO.sub.4) is prepared, and 0.05 mmol of a palladium catalyst is added to be stirred in heating reflux conditions for several hours. The palladium catalyst is then removed from the suspension by filtration. Subsequently, the filtrate is concentrated for purification by column chromatography to obtain biphenyl (J), which is a corresponding coupling body, in a white solid. Results of Examples 60 to 63 and Comparative Example 6 are shown in Table 3.

[0226] As shown in Examples 60 to 63, in Suzuki-Miyaura coupling reaction using iodobenzene (A) and phenylboronic acid (I) as raw materials, the reaction smoothly proceeded and biphenyl (J) is obtained in high yield. Using a palladium catalyst supported by a polymer according to some aspects of the present invention, almost no palladium is detected from the filtrate obtained by removing the palladium catalyst from the suspension after reaction. Particularly, using PSiOH-Pd/Al.sub.2O.sub.3, no palladium at all is detected from the filtrate by measurement using EDX (energy dispersive x-ray spectrosopy). This indicates that PSiOH-Pd/Al.sub.2O.sub.3 had high palladium supporting power.

##STR00040##

TABLE-US-00003 TABLE 3 Pd Yield Leak- Reaction Catalyst (%) age* Example 51 Heck PSiOH—Pd/Al.sub.2O.sub.3 96 ⊙ Example 52 PSiO—Pd/TiO.sub.2 97 ◯ Example 53 PNCO—Pd/MgO 95 ◯ Example 54 PEI—Pd/ZrO.sub.2 92 Δ Example 55 PSiOH—Pd/Al.sub.2O.sub.3 82 ⊙ Comparative Pd/C 75 X Example 4 Example 56 Sonogashira PSiOH—Pd/Al.sub.2O.sub.3 85 ⊙ Example 57 PSiO—Pd/TiO.sub.2 80 ◯ Example 58 PNCO—Pd/MgO 82 ◯ Example 59 PEI—Pd/ZrO.sub.2 83 ◯ Comparative Pd/C 79 X Example 5 Example 60 Suzuki-Miyaura PSiOH—Pd/Al.sub.2O.sub.3 82 ⊙ Example 61 PSiO—Pd/TiO.sub.2 79 ◯ Example 62 PNCO—Pd/MgO 80 Δ Example 63 PEI—Pd/ZrO.sub.2 76 Δ Comparative Pd/C 78 Δ Example 6 *Pd Leakage Not Found at All-> ⊙ Found Very Trace Amount-> ◯ Found Trace Amount-> Δ Found Substantial Amount-> X
[Oxidation Reaction using Polymer-Supported Pd Catalyst]

[0227] A DMA solution containing 1.0 mmol of 1-decene is prepared, and 0.05 mmol of a Pd catalyst, (0.15 mm of) copper (II) chloride dihydrate, and a small amount of H.sub.2 are added thereto to make a suspension and to be stirred in an oxygen gas atmosphere at 1 atmospheric pressure for several hours. The catalyst is then removed from the suspension by filtration. Subsequently, the filtrate is concentrated for purification by column chromatography to obtain 2-decanone as an oxidation product.

##STR00041##

[Hydrosilylation Reaction using Polymer-Supported Platinum Catalyst]

[0228] A hexane solution containing 1.0 mmol of diphenylacetylene and 1.5 mmol of triethoxysilane is prepared, and 0.05 mmol of a platinum catalyst is added to be stirred at 60° C. for several hours. The platinum catalyst is then removed from the suspension by filtration. Subsequently, the filtrate is concentrated for purification by column chromatography to obtain a hydrosilylation product.

##STR00042##