JP4925050B2 - Preparation of carbonyl compounds - Google Patents

Description

  The present invention relates to a method for producing a carbonyl compound by oxidizing an alcohol in the presence of a ruthenium catalyst.

Carbonyl compounds such as aldehydes and ketones are positioned as one of the most useful compounds in organic synthetic chemistry, and many synthetic methods have been developed so far. Especially in the synthesis of aldehydes, the oxidation state of the product aldehyde is located between alcohol and carboxylic acid, so it is difficult to control over-oxidation and over-reduction in the reaction. Controlling these is also an important issue. It becomes.
On the other hand, the present inventors have fixed ruthenium on an aromatic polymer and developed a “polymer-immobilized ruthenium catalyst” that is insoluble in ordinary solvents. Using this catalyst, the oxidation reaction of alcohol is effective. It was found that this can be done (Patent Document 1). This polymer-immobilized ruthenium catalyst is highly active due to the small size of the ruthenium cluster, and since it is cross-linked, it has excellent solvent resistance, no metal leakage, and is easy to recover and reuse.
JP2006-205124

  However, even when the above polymer-immobilized ruthenium catalyst is used, it is required to improve the efficiency of the oxidation reaction and reduce the amount of reoxidant used to perform the oxidation reaction in a more economical manner. It was done.

In the above oxidation reaction (Patent Document 1), the present inventors have found that when the oxidation reaction is performed in an oxygen atmosphere, the amount of reoxidant used can be reduced, and the efficiency of the oxidation reaction is improved. The invention has been completed.
That is, the present invention relates to a method for producing a carbonyl compound comprising oxidizing an alcohol in an oxygen atmosphere and in the presence of a polymer-immobilized ruthenium catalyst and a reoxidant, wherein the reoxidant is an amine oxide. , Iodosylbenzene diacetate, iodosylbenzene oxide, sodium periodate, or tert-butyl hydroperoxide (TBHP), using 0.01 to 1.0 equivalent of the reoxidizer to the alcohol, A molecular-immobilized ruthenium catalyst is formed by supporting ruthenium on a cross-linked polymer, and the cross-linked polymer is formed by subjecting a cross-linkable polymer having an aromatic side chain, a hydrophilic side chain and a cross-linking group to a cross-linking reaction. It is a manufacturing method of the made carbonyl compound.

  The production method of the present invention can be incorporated into a production process for pharmaceutical intermediates and the like, and the search and narrowing down of target compounds is a problem. It seems that demand development can be promoted by selling the catalyst as a reagent. In addition, demand is expected due to environmentally conscious reactions.

The polymer-immobilized ruthenium catalyst of the present invention has a form in which ruthenium is supported on the polymer as ultrafine particles by interaction with the polymer.
The method for supporting ruthenium on a polymer is not particularly limited as long as it can be supported in this manner. For example, a polymer having a structure as described above and a ruthenium precursor are a) a suitable solvent having a suitable polarity. B) Aggregate with an appropriate polar poor solvent and b) Add an appropriate non-polar solvent after dissolving in a polar good solvent to form a ruthenium-supported micelle-like aggregate, and further aggregate with a polar poor solvent C) dissolved in a suitable non-polar good solvent and then aggregated with a suitable non-polar poor solvent; d) dissolved in a non-polar good solvent and then added with a suitable polar solvent to form a ruthenium-supported micelle-like aggregate. And agglomerating with a nonpolar poor solvent. In this case, in the methods a) and b), the hydrophobic side chains are located in the inner direction and the hydrophilic side chains are located in the outer direction of the formed micelle-like aggregates, and the methods c) and d) Then, the hydrophobic side chain is located in the outward direction of the formed micelle-like aggregate, and the hydrophilic side chain is located in the inward direction.

  Examples of polar good solvents include THF, dioxane, acetone, DMF, NMP, and nonpolar good solvents include toluene, cyclohexane, dichloromethane, chloroform, and the like. Examples of the polar poor solvent include methanol, ethanol, butanol, and amyl alcohol, and examples of the nonpolar poor solvent include hexane, heptane, and octane. The concentration of the crosslinkable polymer dissolved in the good solvent varies depending on the solvent used, but is preferably about 0.1 to 100 mg / mL in the polar solvent.

  Here, the ruthenium precursor is a suitable compound containing ruthenium (for example, an oxide, a halide, a complex with a ligand, etc.), and a halide is preferable. When a halide is used, Cl, Br, I or a hydrate thereof can be used. When using a ruthenium complexed with an appropriate ligand, ruthenium in the precursor is supported on the polymer by ligand exchange with the aromatic ring of the polymer having the structure described above. .

Examples of such a ligand include dimethylphenylphosphine (P (CH ₃ ) ₂ Ph), diphenylphosphinoferrocene (dPPf), trimethylphosphine (P (CH ₃ ) ₃ ), triethylphosphine (P (Et) ₃ ), Tri-tert-butylphosphine (P ( ^t Bu) ₃ ), tricyclohexylphosphine (PCy ₃ ), trimethoxyphosphine (P (OCH ₃ ) ₃ ), triethoxyphosphine (P (OEt) ₃ ), tri-tert- Butoxyphosphine (P (O ^t Bu) ₃ ), triphenylphosphine (PPh ₃ ), 1,2-bis (diphenylphosphino) ethane (DPPE), triphenoxyphosphine (P (OPh) ₃ ), tri-o- Organic phosphine ligands such as tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, 1,5-cyclooctadiene (COD), dibenzylideneacetone (DBA), bipyridine (BPY) , Phenanthroline (PHE), benzonitrile (PhCN), isocyanide (RNC), triethylarsine (As (Et) ₃ ), halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, acetylacetonato, cyclooctadiene , Cyclopentadiene, pentamethylcyclopentadiene, ethylene, carbonyl, acetate, trifluoroacetate, biphenylphosphine, ethylenediamine, 1,2-diphenylethylenediamine, 1,2-diaminocyclohexane, acetonitrile, hexafluoroacetylacetonate, sulfonate, carbonate, Hydroxide, nitrate, perchlorate, sulfate and the like can be mentioned. Among these, organic phosphine ligands, 1,5-cyclooctadiene (COD), dibenzylideneacetone (DBA), bipyridine (BPY), phenanthroline (PHE), benzonitrile (PhCN), isocyanide (RNC), And triethylarsine (As (Et) ₃ ) are preferable, triphenylphosphine, tritert-butylphosphine, and tri-o-tolylphosphine are more preferable, and triphenylphosphine is particularly preferable.
The number of ligands is usually 1 to 4, although it depends on the type of polymer used in the preparation and the crosslinking reaction conditions.

  The polymer of the present invention needs to have an aromatic side chain and a hydrophilic side chain (amphiphilic polymer), and further needs to have a crosslinking group. The polymer may further have a hydrophobic side chain other than the aromatic side chain. These side chains are directly bonded to the main chain of the polymer. You may have multiple types of these side chains. The bridging group may be bonded to any of these side chains, and may be directly bonded to the polymer main chain, but preferably a hydrophobic side chain or a hydrophilic side chain containing an aromatic side chain or Both are more preferably bonded to aromatic side chains.

Aromatic side chains include aryl groups and aralkyl groups.
Examples of the aryl group include those having 6 to 10 carbon atoms, preferably 6 carbon atoms, and specific examples include a phenyl group and a naphthyl group.
In addition, the carbon number defined in this specification shall not include the carbon number of the substituent which the group has.
Examples of the aralkyl group include those having 7 to 12 carbon atoms, preferably 7 to 9 carbon atoms, and specific examples include a benzyl group, a phenylethyl group, and a phenylpropyl group.
The aromatic ring in the aryl group and aralkyl group may have a hydrophobic substituent such as an alkyl group, an aryl group, or an aralkyl group.

  The alkyl group which the aromatic ring may have may be linear, branched or cyclic, and in the case of cyclic, it may be monocyclic or polycyclic and usually has 1 to 20 carbon atoms, preferably 1 ˜12, specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group , Isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, n-heptyl group, isoheptyl group, sec-heptyl group, tert- Examples include heptyl group, n-octyl group, sec-octyl group, tert-octyl group, nonyl group, decyl group, cyclopentyl group, cyclohexyl group and the like.

Examples of the aryl group and aralkyl group that the aromatic ring may have include those similar to the aryl group and aralkyl group as the aromatic group as described above.
These aromatic rings optionally have 1 to 5 substituents, preferably 1 to 2 substituents on the aromatic ring in the aryl group and aralkyl group.
Examples of the alkyl group as the hydrophobic side chain include the same alkyl groups that the aromatic ring as described above may have.

  Examples of the hydrophobic side chain other than the aromatic side chain include an alkyl group, an alkenyl group, and an alkynyl group.

As the hydrophilic side chain, —R ⁵ (R ⁵ represents —OH or an alkoxy group, preferably —OH) is bonded to a relatively short alkyl group, for example, an alkylene group having about 1 to 6 carbon atoms. -R ⁶ (OR ⁷ ) _m R ⁵ , -R ⁶ (COOR ⁷ ) _n R ⁵ or -R ⁶ (COOR ⁷ ) _o (OR ⁸ ) _p R ⁵ (wherein R ⁵ is the same as above, R ⁶ represents a covalent bond or an alkylene group having 1 to 6 carbon atoms, preferably 1 to 2 carbon atoms, preferably R ⁷ and R ⁸ are each independently 2 to 4 carbon atoms, Preferably, it represents an alkylene group of 2, m, n and p are integers of 1 to 10, and o represents 1 or 2. More preferred hydrophilic side chains include —CH ₂ (OC ₂ H ₄ ) ₄ OH and —CO (OC ₂ H ₄ ) ₄ OH.

  Examples of the crosslinking group include an epoxy group, a carboxyl group, an isocyanate group, a thioisocyanate group, a hydroxyl group, a primary or secondary amino group, and a thiol group, preferably an epoxy group, a carboxyl group, an isocyanate group, and a thioisocyanate group. These crosslinking groups may be used alone or in combination as required.

Preferred combinations of crosslinking groups contained in the polymer include only epoxy groups, epoxy groups and hydroxyl groups, epoxy groups and amino groups, epoxy groups and carboxyl groups, only isocyanate groups or thioisocyanate groups, isocyanate groups and hydroxyl groups, and isocyanate groups. An amino group, an isocyanate group, a carboxyl group, etc. are mentioned. Among these, only an epoxy group and a combination of an epoxy group and a hydroxyl group are preferable.
When the polymer has a plurality of types of crosslinking groups, the bonding position of the crosslinking groups is not limited, but is preferably contained in side chains at different positions.

  On the other hand, the crosslinkable polymer may be any polymer having these side chains, but is preferably a polymer obtained by polymerizing monomers having these side chains. Further, as such a monomer, those having a vinyl group such as a double bond or a triple bond for addition polymerization, such as a vinyl group or an acetylene group, are preferable.

Examples of the crosslinkable polymer of the present invention include the following crosslinkable polymers.
(A) 1) a monomer having an aromatic side chain, a hydrophilic side chain and a polymerizable double bond, 2) a monomer having an aromatic side chain and a polymerizable double bond, and 3) an aromatic side having a crosslinking group A crosslinkable polymer obtained by copolymerizing a monomer having a chain and a polymerizable double bond,
(B) 1) Crosslinkable polymer obtained by polymerizing or copolymerizing at least one monomer having a hydrophobic side chain, a hydrophilic side chain having a crosslinking group, or a hydrophobic side chain and a polymerizable double bond. Or (C) 1) a hydrophobic side chain, a hydrophilic side chain having a crosslinking group or a monomer having a hydrophobic side chain and a polymerizable double bond, 2) a monomer having a hydrophobic side chain and a polymerizable double bond And 3) a crosslinkable polymer obtained by copolymerizing at least two monomers selected from the group consisting of a hydrophilic side chain having a crosslinkable group or a hydrophobic side chain and a monomer having a polymerizable double bond Preferably, it is the crosslinkable polymer (A).
Here, the same type of monomer may include two or more different monomers.

  Styrenic monomers are preferred as the monomer having an aromatic side chain and a polymerizable double bond. Examples of the styrenic monomer include styrene, α-methylstyrene, β-methylstyrene, α-ethylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and the like. Among them, styrene and α-methylstyrene Is preferable, and styrene is particularly preferable.

Ruthenium can be incorporated into the polymer aggregate or micelle-like aggregate by dissolving such a polymer and the above ruthenium precursor in a good solvent and then adding a suitable poor solvent to cause phase separation. When ruthenium is complexed with an appropriate ligand, a phenomenon in which a part or all of the ruthenium precursor ligand is eliminated is observed.
Here, the concentration of the polymer in the good solvent is about 1 to 100 mg / ml, the amount of the ruthenium precursor is 0.01 to 0.5 (w / w) with respect to the polymer, and the amount of the poor solvent is 0.2 to 0.2 with respect to the good solvent. 10 (v / v) is used, and the addition time of the poor solvent is usually 10 minutes to 2 hours. The temperature at the time of phase separation is not particularly limited, but is usually performed at room temperature.

The crosslinking reaction can be caused to react by heating or ultraviolet irradiation depending on the type of the crosslinkable functional group. In addition to these methods, the crosslinking reaction is a conventionally known method for crosslinking a linear organic polymer compound to be used. For example, a method using a crosslinking agent, a method using a condensing agent, a peroxide or an azo compound. A method using a radical polymerization catalyst such as a compound, a method in which an acid or a base is added and heated, for example, a method in which a dehydrating condensing agent such as carbodiimides is combined with an appropriate crosslinking agent, a reaction method, or the like can be performed. .
The temperature at which the crosslinking group is crosslinked by heating is usually 50 to 200 ° C, preferably 70 to 180 ° C, more preferably 100 to 160 ° C.
The reaction time for the heat crosslinking reaction is usually 0.1 to 100 hours, preferably 1 to 50 hours, more preferably 2 to 10 hours.
The ruthenium in the polymer-immobilized ruthenium catalyst obtained in this way is considered to be bound by weak interaction with this polymer as ultrafine particles, and has high catalytic activity for the oxidation reaction of alcohol. Indicates.

There is no particular limitation on the alcohol that is the substrate. There is no particular limitation on the number of hydroxyl groups of the alcohol, and they may be any alcohol of the first and second class. When the alcohol is represented by R ¹ R ² CHOH, R ¹ may be a hydrogen atom, an aliphatic group, an alicyclic aliphatic group, or an aromatic group, and may contain a hetero atom. R ² may be an aliphatic group, an alicyclic aliphatic group, or an aromatic group, and may contain a hetero atom.

The oxidation reaction is performed in a liquid phase, and the polymer-immobilized ruthenium catalyst is used in an amount of 0.1% to 10% (mol / mol) as ruthenium with respect to the substrate (alcohol).
In addition, this oxidation reaction is performed in the presence of a reoxidant, and as the reoxidant, 2,2,6,6- tetramethylpiperidine N- oxyl (TEMPO), N-methylmorpholine N-oxide (NMO) , Amine oxides such as trimethylamine-N-oxide (TMAO) and pyridine-N-oxide, iodosylbenzene diacetate, iodosylbenzene oxide, sodium periodate, tert-butyl hydroperoxide (TBHP), etc., preferably 2, 2,6,6- tetramethylpiperidine N- oxyl (TEMPO). This reoxidant is used in an amount of 0.01 to 1.0 equivalent based on the substrate (alcohol) .
The solvent is not particularly limited, and the reaction proceeds even without a solvent, but preferably a solvent capable of swelling the catalyst, more preferably a halogenated solvent such as dichloromethane.
The reaction is carried out under an oxygen atmosphere, in the presence of a polymer-immobilized ruthenium catalyst and a reoxidant, at room temperature to reflux for 1 to 48 hours.
As a result of the oxidation reaction of the alcohol, an aldehyde or a ketone corresponding to the alcohol is generated.
After the reaction, the catalyst can be easily recovered by filtration, and the recovered solvent can be reused simply by washing and drying. In some cases, metal leakage from the catalyst may be observed during the reaction and at the time of recovery, but the leakage is slight, and no decrease in chemical yield is observed even after repeated use.

The following examples illustrate the invention but are not intended to limit the invention. ¹ H NMR and ¹³ C NMR were measured with a JNM-ECX400 or 600 MHz apparatus manufactured by JEOL Ltd. using tetramethylsilane as a solvent and CDCl ₃ as an internal standard.

Production Example 1
Styrene (12.44 g, 119.58 mmol), 4-vinylbenzyl glycidyl ether (2.83 g, 14.9 mmol), tetraethyleneglycol mono-2-phenyl-2-propenyl ether (4.6 g, 14.9 mmol), AIBN (175 mg, 1.06 mmol) This was dissolved in chloroform (18 mL) and stirred under heating under reflux for 48 hours under an argon atmosphere. After cooling, the reaction mixture was poured into methanol (600 mL) to solidify the polymer. After decanting and removing the supernatant, the residue was dissolved in a small amount of tetrahydrofuran and poured again into methanol. The precipitated polymer was filtered and dried at room temperature under reduced pressure. 10.18 g of polymer was obtained (51% yield).

^From the measurement of ¹ H-NMR, the ratio of the obtained polymer was (styrene / 4-vinylbenzylglycidyl ether / tetraethylene glycol mono-2-phenyl-2-propenyl ether) ratio of each monomer unit (x / y / z) = 84/12/4. The weight average molecular weight (Mw) was 41,000. The structure of the obtained polymer is represented by the following formula.

Production Example 2
Dissolve the copolymer (3.00 g) obtained in Production Example 1 in THF (60 mL), and then add ruthenium chloride.n hydrate (RuCl ₃ .nH ₂ O) (Strem Chemicals, Inc.) and stir for about 30 minutes. did. To this solution, cyclohexane (60 mL) was slowly added dropwise in an air atmosphere and left for 24 hours. Further, hexane (420 mL) was slowly added dropwise to the solution under an air atmosphere and left for 7 hours. After evaporating the solvent, the precipitated solid was collected by filtration, thoroughly washed with hexane, and then dried under reduced pressure at room temperature. Thereafter, an aqueous sodium hydroxide solution (0.5 N, 300 mL) was added to the solid, and the suspension was stirred at room temperature for 19 hours. Thereafter, the solid was collected by filtration, washed with water and hexane, and then heated at 120 ° C. for 4 hours in the absence of a solvent. The obtained solid was sufficiently washed with THF, methanol, water, acetone and dichloromethane, and then dried under reduced pressure to obtain polymer-immobilized ruthenium (hereinafter referred to as “PI Ru”) (3.26 g).
The ruthenium content of PI Ru was determined as follows. Concentrated sulfuric acid (1.0 ml) was added to PI Ru (11.4 mg) and heated at 180 ° C. for 2 hours. Nitric acid (0.5 ml) was added thereto at room temperature, and the polymer was decomposed by heating again at 180 ° C. for 1 hour. Using this solution, a ruthenium content (0.427 mmol / g) was obtained by high-frequency inductively coupled plasma atomic emission spectrometry (hereinafter referred to as “ICP analysis”).

Example 1
In this example, 4-methoxybenzyl alcohol was oxidized.
4-methoxybenzyl alcohol (28 mg, 0.20 mmol) (Tokyo Chemical Industry Co., Ltd.), PI Ru (0.427 mmol / g, 23 mg, 0.01 mmol), 2,2,6,6-tetramethylpiperidine N-oxyl ( 5 mg, 0.03 mmol), 1,2-dichloroethane (0.8 mL) was placed in a 20 mL eggplant flask, and the flask was purged with oxygen, followed by stirring at 80 ° C. for 3 hours. After cooling to room temperature, about 5 mL of hexane was added to stop the reaction, and the catalyst was filtered and washed with dichloromethane. The identity of the product 4-methoxybenzaldehyde was confirmed by comparison with a commercially available reagent, and the chemical yield was determined to be 96% from gas chromatography by using naphthalene as a standard substance in the solution after filtration.
The leakage of ruthenium from PI Ru into the reaction solution was determined by the following procedure. After the chemical yield was determined, the filtered solution was concentrated under reduced pressure. Further, after heating to 180 ° C. under normal pressure, 0.5 mL of concentrated sulfuric acid was added, and the mixture was allowed to stand at the same temperature for 2 hours. Thereafter, nitric acid was slowly added dropwise until the remaining solid became a uniform liquid, and left at the same temperature for 1 hour. Using this solution, the amount of leaked ruthenium was measured by ICP analysis and determined to be below the limit of quantification of the analyzer.

（注、a: 他に注釈がなければ、反応は基質となるアルコール0.2 mmolスケールで一気圧の酸素雰囲気下実施した。括弧内の数値は炭酸カリウムを基質に対して等モル量添加して行った実験結果である。b: ガスクロマトグラフィにより決定した。c: ICP分析により決定した。d: 10 mol%のPI Ru及び30 mol%のTEMPO存在下反応を実施した。e: 反応溶媒にクロロベンゼンを用いて100℃で実施した。） Examples 2-11
In this example, various alcohols were oxidized to aldehydes or ketones.
The oxygen oxidation reaction of various alcohols was performed by the same procedure as in Example 1. The results are shown in Table 1. The identity of the product was confirmed by comparison with commercially available reagents, and the chemical yield was determined by gas chromatography using naphthalene or anisole as a standard substance. Ruthenium leakage was determined in the same manner as in Example 1.

(Note, a: Unless otherwise noted, the reaction was carried out in a 0.2 mmol scale of the alcohol used as the substrate in an oxygen atmosphere of 1 atm. The figures in parentheses were carried out by adding equimolar amounts of potassium carbonate to the substrate. B: determined by gas chromatography, c: determined by ICP analysis, d: reaction was carried out in the presence of 10 mol% PI Ru and 30 mol% TEMPO, e: chlorobenzene was used as the reaction solvent. And carried out at 100 ° C.)

Example 12
In this example, 4-methoxybenzaldehyde was isolated.
4-methoxybenzyl alcohol (137 mg, 1.0 mmol), PI Ru (0.376 mmol / g, 133 mg, 0.05 mmol), 2,2,6,6-tetramethylpiperidine N-oxyl (24 mg, 0.15 mmol), 1,2-Dichloroethane (4.0 mL) was placed in a 30 mL eggplant flask, and the atmosphere in the flask was replaced with oxygen, followed by stirring at 80 ° C. for 4 hours. After cooling to room temperature, about 15 mL of hexane was added to stop the reaction, and the catalyst was filtered and washed with dichloromethane. The solution after filtration was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (hexane-ethyl acetate) to obtain 4-methoxybenzaldehyde (129 mg, 95%).

（注、a: ガスクロマトグラフィにより決定した。b: ICP分析により決定した。） Example 13
In this example, the catalyst was recovered and reused.
4-methoxybenzyl alcohol (111 mg, 0.8 mmol), PI Ru (0.376 mmol / g, 106 mg, 0.04 mmol), 2,2,6,6-tetramethylpiperidine N-oxyl (19 mg, 0.12 mmol), 1,2-Dichloroethane (3.2 mL) was placed in a 20 mL eggplant flask, the inside of the flask was replaced with oxygen, and the mixture was stirred at 80 ° C. for 4 hours. After cooling to room temperature, about 15 mL of hexane was added to stop the reaction, and the catalyst was filtered and washed with dichloromethane. The identity of the product 4-methoxybenzaldehyde was confirmed by comparison with a commercially available reagent, and the chemical yield was determined to be 98% from gas chromatography using naphthalene as a standard substance in the solution after filtration. The filtered catalyst (PI Ru) was dried at room temperature under reduced pressure and used for the second and subsequent experiments. Ruthenium leakage was determined in the same manner as in Example 1. Table 2 shows the results of 10 repeated experiments.

(Note, a: determined by gas chromatography. B: determined by ICP analysis.)

Claims (6)

A method for producing a carbonyl compound comprising oxidizing an alcohol in an oxygen atmosphere and in the presence of a polymer-immobilized ruthenium catalyst and a reoxidant, wherein the polymer-immobilized ruthenium catalyst is converted to ruthenium with respect to the alcohol. 0.1% to 10% (mol / mol) is used, and the reoxidant is amine oxides, iodosylbenzene diacetate, iodosylbenzene oxide, sodium periodate, or tert-butyl hydroperoxide (TBHP); The reoxidant is used in an amount of 0.01 to 1.0 equivalent with respect to the alcohol, the polymer-immobilized ruthenium catalyst has ruthenium supported on a crosslinked polymer, and the crosslinked polymer has an aromatic side chain. A method for producing a carbonyl compound formed by subjecting a crosslinking polymer having a hydrophilic side chain and a crosslinking group to a crosslinking reaction. The amine oxides are 2,2,6,6-tetramethylpiperidine N-oxyl (TEMPO), N-methylmorpholine N-oxide (NMO), trimethylamine-N-oxide (TMAO) or pyridine-N-oxide. The production method according to claim 1. The process according to claim 1 or 2 , wherein the crosslinkable polymer further has a hydrophobic side chain other than the aromatic side chain. The crosslinkable polymer in which the polymer-immobilized ruthenium catalyst causes phase separation by adding a poor solvent having different polarity to the solution containing the crosslinkable polymer and the ruthenium, and the ruthenium is supported by the phase separation. The manufacturing method as described in any one of Claims 1-3 formed by attaching | subjecting to a crosslinking reaction. The process according to claim 4 , wherein the crosslinkable polymer has both an epoxy group and a hydroxyl group, and is formed by subjecting the polymer to a crosslinking reaction by heating. The crosslinkable polymer A process according to claim 1 to 5 which is a copolymer of a polymerizable monomer comprising styrene.