JP4473282B2 - Fluoroapatite surface-immobilized metal cation catalyst - Google Patents

Description

  The present invention relates to a catalyst useful for a reaction for obtaining a carbonyl compound by oxidation of an alcohol, and a method for producing a carbonyl compound using the catalyst.

  Conversion from alcohol to carbonyl compound is one of the most important reactions in organic synthesis, and various catalysts have been studied. For example, a synthetic hydrotalcite containing Ru, Mg and Al in the skeleton (Patent Document 1), or a synthetic hydrotalcite containing a metal selected from Ru, Al and Co, Mn, Fe and Zn in the basic skeleton ( A technique using Patent Document 2) as an oxidation catalyst for alcohols having a specific structure such as α, β-unsaturated alcohol is known. Further, as a more active catalyst, an oxidation catalyst in which a metal such as Ru is immobilized on the hydrotalcite surface (Patent Document 3), an oxidation catalyst in which palladium is immobilized on hydroxyapatite (Patent Document 4), and the like are disclosed. It is used for oxidation reactions of various alcohols. However, these catalysts do not have a sufficiently satisfactory activity, and in particular, a low-reactivity alcohol (for example, cyclohexanol) can be easily oxidized to give the corresponding carbonyl compound in a high yield. A catalyst was desired.

JP 2000-70723 A JP 2000-86245 A JP 2002-274852 A JP 2002-275116 A

  An object of the present invention is to easily and efficiently produce a carbonyl compound in a method for producing a corresponding carbonyl compound by oxidizing an alcohol, and in particular, conventionally, a carbonyl compound can be obtained in a sufficiently high yield by an oxidation reaction. Another object of the present invention is to provide a catalyst exhibiting high activity even for a low-reactivity alcohol which is difficult to obtain, and a method for producing a carbonyl compound using the catalyst.

  As a result of intensive studies to solve the above problems, the present inventors have found that a fluoroapatite surface-immobilized metal cation catalyst in which a Ru cation is immobilized on a fluoroapatite surface exhibits high catalytic activity, and the present invention has been completed. did.

That is, the present invention relates to a corresponding carbonyl compound obtained by oxidizing an alcohol and immobilizing at least one transition metal cation selected from the group consisting of Co cation, Ni cation, Mn cation and Fe cation together with Ru cation on the surface of fluoroapatite . A fluoroapatite surface-immobilized metal cation catalyst for use in the reaction to obtain the above is provided.

The present invention also provides a fluoroapatite surface-immobilized metal cation catalyst in which at least one transition metal cation selected from the group consisting of Co cation, Ni cation, Mn cation and Fe cation is immobilized on the fluoroapatite surface together with Ru cation. A method for producing a carbonyl compound is provided, wherein the corresponding carbonyl compound is produced by oxidizing an alcohol.

In the method for producing a carbonyl compound of the present invention , the reaction is preferably performed in the presence of a fluorinated solvent.

  The fluoroapatite surface-immobilized metal cation catalyst of the present invention can be easily produced and exhibits high activity for the reaction to obtain the corresponding carbonyl compound by oxidation of alcohol. In particular, it exhibits high activity against alicyclic alcohols such as cyclohexanol, which are low in reactivity and conventionally difficult to obtain the corresponding carbonyl compound in a sufficient yield. Furthermore, the fluoroapatite surface-immobilized metal cation catalyst of the present invention can be easily reused, and can be reused repeatedly while maintaining high activity without particularly requiring regeneration treatment.

  According to the method of the present invention, alcohol can be oxidized efficiently by a simple operation, and the corresponding carbonyl compound can be obtained in high yield.

[Fluoroapatite surface-immobilized metal cation catalyst]
The fluoroapatite surface-immobilized metal cation catalyst of the present invention is a solid catalyst in which a transition metal cation is immobilized, containing at least a Ru cation on the surface of the fluoroapatite. The fluoroapatite is, for example, the following formula (1)
Ca _10-n (HPO ₄ ) _n (PO ₄ ) _6-n (OH) _2-nm F _m · sH ₂ O (1)
(In formula (1), n is 0 or 1, m is 1 or 2, and satisfies n + m = 2. S is a number from 0 to 3)
In particular, the compound represented by the following formula (2)
Ca ₁₀ (PO ₄ ) ₆ F ₂ (2)
It is a compound represented by these.

Fluoroapatite can be prepared, for example, by dropping ammonium fluoride and an aqueous phosphoric acid solution into a calcium hydroxide slurry, and collecting and firing the resulting slurry.
Alternatively, the powder of calcium fluoride, calcium carbonate and calcium phosphate or calcium hydrogen phosphate dihydrate can be prepared by mixing and stirring in pure water to form a slurry, and then drying and firing the slurry. . The mixing ratio of calcium fluoride: calcium carbonate: calcium phosphate or calcium hydrogen phosphate dihydrate can be about 1: 3: 6 in terms of molar ratio. The temperature at the time of stirring these in pure water is about 50-150 degreeC, and stirring time is about 5 to 30 hours. The obtained slurry is dried and fired at a temperature of about 800 ° C., and the firing time can be about 0.5 to 3 hours.

  Examples of commercially available fluoroapatite that can be suitably used in the present invention include trade names “Apatite FAP, hexagonal crystal” manufactured by Wako Pure Chemical Industries, Ltd.

By fixing at least one transition metal cation on the surface of fluoroapatite, a catalyst showing activity in the oxidation reaction of alcohols can be prepared. In order to ensure sufficient catalytic activity, at least a Ru cation is used as a transition metal cation. It is necessary to adopt. Examples of the Ru cation include Ru ⁺ , Ru ²⁺ , Ru ³⁺ , Ru ⁴⁺ , Ru ⁵⁺ , Ru ⁶⁺ , Ru ⁷⁺ , Ru ^{8+, and the} like. In the metal cation catalyst, the ruthenium cation is considered to exist mainly in the oxidation state of Ru ³⁺ or Ru ⁴⁺ .

In the fluoroapatite surface-immobilized metal cation catalyst of the present invention, in addition to the Ru cation, one or more transition metal cations are preferably immobilized on the fluoroapatite surface. Other transition metal cations include, for example, Cr ²⁺ , Cr ³⁺ , Mn ²⁺ , Mn ³⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Ni ⁺ , Ni ²⁺ , Ni ^{3+, Cu +, Cu 2+,} Cu 3+, Zn +, Zn 3+, Mo 3+, Mo 4+, Mo 5+, Mo 6+, Rh 3+, Pd 2+, Ag +, Ag 2 ⁺ Is mentioned, but not limited to these. Among these, Co cations such as Co ²⁺ and Co ³⁺ , Ni cations such as Ni ⁺ , Ni ²⁺ and Ni ³⁺ , Mn cations such as Mn ²⁺ and Mn ³⁺ , and Fe ²⁺ and Fe ³ Fe cations such as ⁺ can be preferably used.

  That is, as a particularly preferred form of the fluoroapatite surface-immobilized metal cation catalyst of the present invention, a fluoroapatite surface-immobilized metal cation catalyst (Ru / Co / FAP) in which a Ru cation and a Co cation are immobilized on the fluoroapatite surface, Fluoroapatite surface-immobilized metal cation catalyst (Ru / Ni / FAP) in which Ru and Ni cations are immobilized on the surface of fluoroapatite, Fluoroapatite surface-immobilized metal in which Ru and Mn cations are immobilized on the surface of fluoroapatite Examples thereof include a cation catalyst (Ru / Mn / FAP) and a fluoroapatite surface-immobilized metal cation catalyst (Ru / Fe / FAP) in which a Ru cation and an Fe cation are immobilized on the surface of the fluoroapatite. In particular, a fluoroapatite surface-immobilized metal cation catalyst (Ru / Co / FAP) in which a Ru cation and a Co cation are immobilized on a fluoroapatite surface exhibits a specific joint effect between the Ru cation and the Co cation. The catalytic activity of the compound is dramatically improved. For example, it exhibits extremely high activity even with a low-reactivity alcohol such as cyclohexanol, and the corresponding carbonyl compound is obtained in a high yield.

  In the fluoroapatite surface-immobilized metal cation catalyst of the present invention, three or more kinds of transition metal cations may be immobilized, for example, three kinds of metal cations of Ru cation, Co cation and Ni cation are immobilized. Examples include, but not limited to, forms and forms in which three types of Ru cation, Co cation and Fe cation are immobilized.

  Examples of the method for immobilizing the transition metal cation on the surface of fluoroapatite include a method of immobilizing the metal cation on the surface of fluoroapatite by mixing and stirring a solution of the compound containing the metal and fluoroapatite. It is done. As a compound containing a metal, a metal complex or the like can be used in addition to a metal salt such as chloride, bromide, iodide, carbonate, nitrate, sulfate, phosphate, and the like. The solvent is not particularly limited as long as it can dissolve the metal compound to be used, and examples thereof include water, acetone, alcohols and the like. The density | concentration of the solution of the compound containing a metal at the time of performing a metal fixing process is not restrict | limited, For example, it can select from the range of 0.1-1000 mM. Although the temperature at the time of stirring can be selected from the range of 20-150 degreeC, for example, it can carry out normally at room temperature. The metal content of the fluoroapatite surface-immobilized metal particle catalyst is not particularly limited, and can be selected, for example, from the range of 0.01 to 10 mmol, preferably 2.5 to 10 mmol, with respect to 1 g of fluoroapatite. Although stirring time changes also with the temperature at the time of stirring, it can be selected from the range of 1-240 minutes, for example, Preferably it is 5-90 minutes. After completion of the stirring, the fluoroapatite surface-immobilized metal cation catalyst of the present invention can be prepared by washing with water or an organic solvent, if necessary, and drying.

  If a halide such as chloride, bromide or iodide is used as a compound containing a metal, after fixing the halide on the fluoroapatite surface, treatment with an aqueous sodium carbonate solution or the like can be performed. And hydroxide ions may be exchanged.

If a halide such as chloride, bromide or iodide is used as the compound containing the above metal, it is immobilized on the fluoroapatite surface in the halide state, and then reacted with a dehalogenating agent to react with the fluoride. An apatite surface-immobilized metal cation catalyst can be prepared. The case where Ru cation is immobilized using RuCl ₃ will be described as an example. Fluoroapatite is treated with a ruthenium (III) trichloride RuCl ₃ solution so that ruthenium monochloride is immobilized on the fluoroapatite surface. An apatite slurry is obtained. Subsequently, the slurry is treated with a dehalogenating agent to obtain the fluoroapatite surface-immobilized metal cation of the present invention. Examples of the dehalogenating agent include alkali metals such as lithium, sodium, potassium, rubidium and cesium. In addition, when performing a dehalogenation agent process, it is preferable to carry out in inert gas atmosphere, such as argon and nitrogen.

When immobilizing two or more kinds of transition metal cations on the surface of fluoroapatite, that is, when immobilizing Ru cations and other transition metal cations, for example, fluoroapatite was treated with a solution of a compound containing other transition metals. However, immobilization may be performed by adding a solution of a Ru compound (RuCl ₃ or the like), and further performing a treatment such as stirring, and after treating with a solution of the Ru compound, a solution of a compound containing another transition metal. May be processed. Alternatively, a solution containing both a Ru compound and a compound containing another transition metal may be prepared, and two or more kinds of metals may be immobilized simultaneously.

[Production of carbonyl compounds]
The corresponding carbonyl compound can be produced by oxidizing various alcohols using the above-described fluoroapatite surface-immobilized metal cation catalyst of the present invention. By the method of the present invention, both the alicyclic alcohol and the acyclic alcohol (chain aliphatic alcohol) can be efficiently oxidized to produce the corresponding carbonyl compound in a high yield.

  An alicyclic alcohol is a compound in which a hydroxyl group is bonded to a carbon atom constituting an alicyclic hydrocarbon ring. Specifically, for example, cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol. Alicyclic saturated alcohols such as cyclododecanol; alicyclic unsaturated alcohols such as cyclopentenol and cyclohexenol; polycyclic alicyclic saturated or unsaturated alcohols such as 1-adamantanol and 2-adamantanol Etc.

  Specific examples of the acyclic alcohol (chain aliphatic alcohol) include, for example, methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1 -Primary linear aliphatic saturated alcohols such as nonanol, 1-decanol; 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 2-heptanol, Secondary linear aliphatic saturated alcohols such as 3-heptanol, 2-octanol, 3-octanol, 4-octanol, 2-nonanol, 2-decanol; allyl alcohol, 3-buten-1-ol, 2- Primary linear unsaturated alkyl such as hexen-1-ol and 2,4-hexadien-1-ol Secondary linear unsaturated alcohols such as 4-penten-2-ol; primary branched aliphatic saturated alcohols such as 3-methyl-1-butanol; 3-methyl-2- Secondary branched aliphatic saturated alcohols such as butanol; primary branched aliphatic unsaturated alcohols such as 3-methyl-2-buten-1-ol and 4-methyl-2-propen-1-ol Saturated alcohols; secondary branched aliphatic unsaturated alcohols such as 5-methyl-3-hexen-2-ol; 1-hydroxymethyladamantane, 1-cyclohexyl-2-propanol, myrtenol, perillyl alcohol, etc. And a chain aliphatic alcohol having a saturated or unsaturated alicyclic group as a substituent.

  The alicyclic alcohol and acyclic alcohol (chain aliphatic alcohol) may have an aromatic hydrocarbon group or a heterocyclic group as a substituent. The aromatic hydrocarbon group may contain a monocycle such as a phenyl group, or may contain a condensed polycycle such as a naphthyl group or an azulenyl group. The aromatic hydrocarbon group may have a substituent such as a nitro group, a sulfo group, a chloro group, a fluoro group, an alkyl group, an alkenyl group, or an alkynyl group. Specific examples of the alcohol having an aromatic hydrocarbon group as a substituent include benzyl alcohol, p-methylbenzyl alcohol, p-isopropylbenzyl alcohol, p-nitrobenzyl alcohol, p-chlorobenzyl alcohol, 1-phenyl. Examples include ethanol, benzhydrol, cinnamyl alcohol, and phenylcyclopropylmethanol.

  Examples of the heterocyclic group include O-containing heterocyclic groups such as furanyl group and benzodioxole group, N-containing heterocyclic groups such as pyrrolyl group, and S-containing heterocyclic groups such as thionyl group. It is done.

  Alcohols that can be oxidized by the method of the present invention include hydroxy ketones, hydroxy aldehydes and the like. Examples of the hydroxy ketone include α-hydroxy ketones such as 6-hydroxydecan-5-one, acetoin, and benzoin, and the corresponding α-diketone can be obtained by dehydrogenation thereof.

  The corresponding carbonyl compound can be produced by oxidizing the alcohol in the presence of a fluoroapatite surface-immobilized metal cation catalyst. When a primary alcohol is used as a raw material, a corresponding aldehyde is obtained, and when a secondary alcohol is used, a corresponding ketone is obtained.

  The reaction can be performed, for example, by mixing and stirring the raw material alcohol and the fluoroapatite surface-immobilized metal cation catalyst. Although the usage-amount of a catalyst is not restrict | limited in particular, For example, a metal cation will be 0.001-1 mol with respect to 1 mol of raw material alcohol, Preferably it will be 0.05-0.1 mol, Most preferably, it will be 0.01-0.05 mol. A range can be selected. The reaction may be performed in the liquid phase or in the gas phase. In consideration of workability and the like, in the present invention, the reaction is preferably performed in a liquid phase.

  The reaction can be carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it can dissolve alcohols used as a raw material and does not inhibit the reaction, and can be appropriately selected from known and commonly used solvents. For example, fluorinated solvents such as trifluorotoluene, fluorobenzene and fluorohexane; aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene and nitrobenzene; aliphatic carbonization such as pentane, hexane, heptane, octane, cyclohexane and methylcyclohexane Hydrogen; Ethers such as diethyl ether, tetrahydrofuran and tetrahydropyran; Nitriles such as acetonitrile and benzonitrile; Amides such as acetamide, dimethylacetamide, dimethylformamide, diethylformamide and N-methylpyrrolidone; Ethyl acetate, propyl acetate and butyl acetate Esters; water; and mixtures thereof. Among these, a fluorinated solvent can be preferably used, and trifluorotoluene can be particularly preferably used.

  The reaction is usually performed in the presence of an oxidizing agent (hydrogen scavenger) such as molecular oxygen. The reaction can be carried out at normal pressure or under pressure. The reaction temperature can be selected according to the type of alcohol and the type of solvent used as a raw material, and is not particularly limited, but is, for example, 0 to 250 ° C, preferably 60 to 200 ° C, particularly preferably 150 to 190 ° C. You can choose from a range.

  The reaction time can be appropriately selected according to the type of alcohol used as a raw material, the type of solvent, the reaction temperature, and the like, and is not particularly limited. For example, the reaction time is from 0.5 to 200 hours, preferably from 1 to 150 hours. You can choose. The reaction can be carried out in a conventional manner such as batch, semi-batch, or continuous. After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, etc., or a separation means combining these.

  After completion of the reaction, the fluoroapatite surface-immobilized metal cation catalyst is recovered by an operation such as filtration or centrifugation, and is used as it is or after being washed with water or an organic solvent as necessary, and repeatedly used as an oxidation catalyst for alcohol. Can do. Even when the reaction is carried out by repeatedly using a fluoroapatite surface-immobilized metal cation catalyst, the catalytic activity does not decrease, and the corresponding carbonyl compound can be produced in a high yield.

  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

( Reference Example 1-0)
To a solution obtained by dissolving RuCl ₃ .2H ₂ O (0.0364 g (Ru: 0.15 mmol)) in water (10 mL), fluoroapatite (manufactured by Wako Pure Chemical Industries, Ltd .: trade name “Apatite FAP, hexagonal crystal” ] 1.5 g was added, stirred at room temperature for 15 minutes, washed with deionized water, and further dried at 110 ° C. for 12 hours to obtain fluoroapatite surface-immobilized metal cation catalyst A (Ru / FAP). It was.

( Reference Example 1-1)
Cyclohexanol 1 mmol, trifluorotoluene 2.4 ml, 0.2 g of the fluoroapatite surface-immobilized metal cation catalyst A (Ru / FAP) obtained in Reference Example 1-0 was placed in a glass pressure-resistant reaction tube. The mixture was stirred at 1 atm (0.1 MPa) and 180 ° C. for 3 hours. The corresponding carbonyl compound (cyclohexanone) corresponding to a GC (gas chromatography) yield of 22% was obtained.

(Example 2-0)
To a solution obtained by dissolving CoCl ₂ · 6H ₂ O (0.1330 g) in water (30 mL), 1.5 g of fluoroapatite (manufactured by Wako Pure Chemical Industries, Ltd .: trade name “Apatite FAP, hexagonal crystal”) is added. Further, a solution obtained by dissolving Na ₂ CO ₃ (0.8 g) in water (5 mL) was added. After stirring at room temperature for 1 hour, a solution obtained by dissolving RuCl ₃ .2H ₂ O (0.0364 g (Ru: 0.15 mmol)) in water (10 mL) was added, and the mixture was further stirred at room temperature for 15 minutes. It was washed with ionized water and dried at 110 ° C. for 12 hours to obtain a fluoroapatite surface-immobilized metal cation catalyst B (Ru / Co / FAP).

(Example 2-1)
Cyclohexanol 1 mmol, trifluorotoluene 2.4 ml, 0.2 g (Ru / Co / FAP) fluoroapatite surface immobilized metal cation catalyst B (Ru / Co / FAP) obtained in Example 2-0 made of glass It put in the pressure | voltage resistant reaction tube, and stirred at 1 atm (0.1 MPa) and 180 degreeC for 3 hours by oxygen atmosphere. The corresponding carbonyl compound (cyclohexanone) corresponding to a GC (gas chromatography) yield of 96% was obtained.

(Example 2-2)
Cyclopentanol (1 mmol), trifluorotoluene (2.4 ml), fluoroapatite surface-immobilized metal cation catalyst B (Ru / Co / FAP) 0.2 g (Ru content: 0.02 mmol) obtained in Example 2-0 It put into the pressure-resistant reaction tube made, and stirred at 1 atm (0.1 MPa) and 180 degreeC for 3 hours by oxygen atmosphere. The corresponding carbonyl compound (cyclopentanone) corresponding to a GC (gas chromatography) yield of 99% was obtained.

(Example 2-3)
Cyclooctanol 1 mmol, trifluorotoluene 2.4 ml, 0.2 g (Ru / Co / FAP) fluoroapatite surface-immobilized metal cation catalyst B (Ru / Co / FAP) obtained in Example 2-0 made of glass It put in the pressure | voltage resistant reaction tube, and stirred at 1 atm (0.1 MPa) and 180 degreeC for 3 hours by oxygen atmosphere. A corresponding carbonyl compound (cyclooctanone) corresponding to a GC (gas chromatography) yield of 99% or more was obtained.

(Example 2-4)
2-Adamantanol 1 mmol, trifluorotoluene 2.4 ml, 0.2 g (Ru content: 0.02 mmol) of the fluoroapatite surface-immobilized metal cation catalyst B (Ru / Co / FAP) obtained in Example 2-0 The mixture was placed in a glass pressure-resistant reaction tube and stirred at 180 ° C. for 2 hours in an oxygen atmosphere at 1 atm (0.1 MPa). The corresponding carbonyl compound (2-adamantanone) corresponding to a GC (gas chromatography) yield of 99% was obtained.

(Example 2-5)
2-octanol 1 mmol, trifluorotoluene 2.4 ml, fluoroapatite surface-immobilized metal cation catalyst B (Ru / Co / FAP) 0.2 g (Ru content: 0.02 mmol) obtained in Example 2-0 was added to glass. It put into the pressure-resistant reaction tube made, and stirred at 1 atm (0.1 MPa) and 180 degreeC for 3 hours by oxygen atmosphere. The corresponding carbonyl compound (2-octanone) corresponding to a GC (gas chromatography) yield of 99% was obtained.

(Example 3-0)
To a solution obtained by dissolving NiCl ₂ .6H ₂ O (0.03562 g) in water (30 mL), 1.5 g of fluoroapatite (manufactured by Wako Pure Chemical Industries, Ltd .: trade name “Apatite FAP, hexagonal crystal”) is added. Further, a solution obtained by dissolving Na ₂ CO ₃ (0.8 g) in water (5 mL) was added. After stirring at room temperature for 1 hour, RuCl ₃ .2H ₂ O (0.0364 g (Ru: 0.15 mmol)) was dissolved in water (10 mL) and added to the resulting solution, followed by further stirring at room temperature for 15 minutes. The product was washed with deionized water and dried at 110 ° C. for 12 hours to obtain a fluoroapatite surface-immobilized metal cation catalyst C (Ru / Ni / FAP).

(Example 3-1)
1 mmol of cyclohexanol, 2.4 ml of trifluorotoluene, 0.2 g (Ru content: 0.02 mmol) of the fluoroapatite surface-immobilized metal cation catalyst C (Ru / Ni / FAP) obtained in Example 3-0 made of glass It put in the pressure | voltage resistant reaction tube, and stirred at 1 atm (0.1 MPa) and 180 degreeC for 3 hours by oxygen atmosphere. The corresponding carbonyl compound (cyclohexanone) corresponding to a GC (gas chromatography) yield of 78% was obtained.

(Example 4-0)
To a solution obtained by dissolving MnCl ₂ .4H ₂ O (0.0345 g) in water (30 mL), 1.5 g of fluoroapatite (manufactured by Wako Pure Chemical Industries, Ltd .: trade name “Apatite FAP, hexagonal crystal”) is added. Further, a solution obtained by dissolving Na ₂ CO ₃ (0.8 g) in water (5 mL) was added. After stirring at room temperature for 1 hour, a solution obtained by dissolving RuCl ₃ .2H ₂ O (0.0364 g (Ru: 0.15 mmol)) in water (10 mL) was added, and the mixture was further stirred at room temperature for 15 minutes. The fluoroapatite surface-immobilized metal cation catalyst D (Ru / Mn / FAP) was obtained by washing with ion water and drying at 110 ° C. for 12 hours.

(Example 4-1)
Cyclohexanol 1 mmol, trifluorotoluene 2.4 ml, 0.2 g (Ru / Mn / FAP) fluoroapatite surface-immobilized metal cation catalyst D (Ru / Mn / FAP) obtained in Example 4-0 made of glass It put in the pressure | voltage resistant reaction tube, and stirred at 1 atm (0.1 MPa) and 180 degreeC for 3 hours by oxygen atmosphere. The corresponding carbonyl compound (cyclohexanone) corresponding to a GC (gas chromatography) yield of 66% was obtained.

(Example 5-0)
To a solution obtained by dissolving FeCl ₃ .6H ₂ O (0.0269 g) in water (30 mL), 1.5 g of fluoroapatite (manufactured by Wako Pure Chemical Industries, Ltd .: trade name “Apatite FAP, hexagonal crystal”) is added. Further, a solution obtained by dissolving Na ₂ CO ₃ (0.8 g) in water (5 mL) was added. After stirring at room temperature for 1 hour, RuCl ₃ .2H ₂ O (0.0364 g (Ru: 0.15 mmol)) was dissolved in water (10 mL) and added to the resulting solution, followed by further stirring at room temperature for 15 minutes. By washing with deionized water and drying at 110 ° C. for 12 hours, a fluoroapatite surface-immobilized metal cation catalyst E (Ru / Fe / FAP) was obtained.

(Example 5-1)
Cyclohexanol 1 mmol, trifluorotoluene 2.4 ml, 0.2 g (Ru content: 0.02 mmol) of the fluoroapatite surface-immobilized metal cation catalyst E (Ru / Fe / FAP) obtained in Example 5-0 made of glass It put in the pressure | voltage resistant reaction tube, and stirred at 1 atm (0.1 MPa) and 180 degreeC for 3 hours by oxygen atmosphere. The corresponding carbonyl compound (cyclohexanone) corresponding to a GC (gas chromatography) yield of 61% was obtained.

(Comparative Example 1)
To a solution obtained by dissolving CoCl ₂ · 6H ₂ O (0.1330 g) in water (30 mL), 1.5 g of fluoroapatite (manufactured by Wako Pure Chemical Industries, Ltd .: trade name “Apatite FAP, hexagonal crystal”) is added. Further, a solution obtained by dissolving Na ₂ CO ₃ (0.8 g) in water (5 mL) was added. After stirring at room temperature for 1 hour, it was washed with deionized water and dried at 110 ° C. for 12 hours to obtain a fluoroapatite surface-immobilized Co cation catalyst (Co / FAP).
1 mmol of cyclohexanol, 2.4 ml of trifluorotoluene, and 0.2 g of the above-described fluoroapatite surface-immobilized Co cation catalyst (Co / FAP) were put in a pressure-resistant reaction tube made of glass, and 1 atm (0.1 MPa), 180 in an oxygen atmosphere. Stir at 0 ° C. for 3 hours. The corresponding carbonyl compound (cyclohexanone) corresponding to a GC (gas chromatography) yield of 7% was obtained.

(Example 6)
[Reuse of metal cation catalyst immobilized on fluoroapatite surface]
The fluoroapatite surface-immobilized metal cation catalyst was reused up to 11 times according to the following procedure. In Example 2-1, after the reaction was completed, the reaction liquid was recovered, and the reaction tube containing the used fluoroapatite surface-immobilized metal cation catalyst B (Ru / Co / FAP) was placed in a cyclohexanol ( About 1.1 to 1.4 mmol) was added for each reuse, and the reaction was carried out under the same conditions as in Example 2-1. The fluoroapatite surface-immobilized metal cation catalyst B was reused up to 11 times, and the GC (gas chromatography) yield of each obtained cyclooctanone was determined. Table 1 shows the yield of cyclooctanone and the TON (turnover number) per Ru. The activity of the fluoroapatite surface-immobilized metal cation catalyst hardly decreased even after 11 reuses.

Claims (3)

It is used for the reaction to obtain the corresponding carbonyl compound by oxidizing alcohol , in which at least one transition metal cation selected from the group consisting of Co cation, Ni cation, Mn cation and Fe cation is immobilized together with Ru cation on the fluoroapatite surface. Fluoroapatite surface-immobilized metal cation catalyst. Alcohol is oxidized in the presence of a fluoroapatite surface-immobilized metal cation catalyst in which at least one transition metal cation selected from the group consisting of Co cation, Ni cation, Mn cation and Fe cation is immobilized on the fluoroapatite surface together with Ru cation. To produce a corresponding carbonyl compound. The method for producing a carbonyl compound according to claim 2, wherein the reaction is carried out in the presence of a fluorinated solvent.