JP2002191979A - Oxidation catalyst and method for producing carbonyl compound using the catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide oxidation catalysts which can efficiently oxidize an organic substrate and an oxidation method. SOLUTION: The oxidation catalysts comprising (A) palladium of a zero valence supported on active carbon, (B) a heteropolyacid, and (C) a strong acid are provided. These catalysts can be combined with a single substance or a compound which contains (D) at least one element selected from bismuth, tin, lead, and, antimony. The hetropolyacid (B) is preferably a complete proton type. The oxidation method for oxidizing the organic substrate by molecular oxygen is provided. An alkene or a cycloalkene can be used for the organic substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an oxidation catalyst useful for efficiently oxidizing an organic substrate, a method for oxidizing an organic substrate using the oxidation catalyst, and a method for producing a carbonyl compound.

[0002]

2. Description of the Related Art As a method for producing a carbonyl compound by directly oxidizing an olefin using molecular oxygen, PdC
Wacker method is known by the l ₂ -CuCl ₂ catalyst.
However, this method has disadvantages such as a decrease in the reaction rate when the number of carbon atoms of the raw olefin increases, and a low reactivity of the internal olefin. Further, since chloride is used, there is a problem that the corrosion of the apparatus is remarkable and a harmful chlorine-containing compound is produced as a by-product. Therefore, it is not industrially used except for the production of lower carbonyl compounds such as acetaldehyde and acetone. In order to overcome the problems of the conventional methods, studies such as devising a catalyst or a solvent have been made in recent years.

[0003] Japanese Patent Publication No. 63-500923 discloses a catalyst comprising a palladium compound and a polyoxoanion compound to which a redox metal such as copper, iron or cobalt and / or an organic substance (such as acetonitrile) is added. A method of oxidizing an olefin in the coexistence has been proposed. However, in this method, although the initial reaction is good, the catalyst component sediments as the reaction proceeds, and the reaction rate decreases.

JP-A-60-92234 reports that cyclopentanone can be obtained by directly oxidizing cyclopentene using a composite catalyst comprising a palladium compound and a bismuth compound. JP-A-5-5134
No. 4 proposes a method for obtaining a carbonyl compound from an olefin using a cyclic ether and water as a solvent and using a catalyst comprising a palladium compound and a polyoxoanion compound. JP-A-6-48974 discloses that a palladium compound, a polyoxoanion compound and an organic compound are used in a solvent composed of water and any one of an oxygen-containing organic compound, a sulfur-containing organic compound and a nitrogen-containing organic compound. A method of performing a reaction using a catalyst comprising a phosphorus compound has been proposed. A method using a catalyst containing an iron-containing compound in place of the organic phosphorus compound in the above method has been proposed in JP-A-7-14.
9685 publication. JP-A-7-1079
No. 7 discloses that a catalyst comprising a palladium compound and a polyoxoanion compound is used to oxidize an olefin in a solution containing water to produce a corresponding carbonyl compound. There has been proposed a method for producing a carbonyl compound, wherein at least a part thereof is at least one ion selected from nickel, copper, manganese, lanthanum, zinc and cerium. However, the above method is not always satisfactory from the industrial point of view in terms of the conversion of the raw material and the yield of the target oxidation product.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an oxidation catalyst and an oxidation method capable of efficiently oxidizing an organic substrate. Another object of the present invention is to provide a process for obtaining the corresponding carbonyl compounds from cycloalkenes or alkenes with high conversions and yields.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that using an oxidation catalyst composed of zero-valent palladium supported on activated carbon, a heteropolyacid and a strong acid. It has been found that the conversion rate and the yield of oxidation products are significantly improved, and the present invention has been completed.

That is, the present invention provides (A) a zero-valent palladium supported on activated carbon, (B) a heteropolyacid,
(C) An oxidation catalyst comprising a strong acid. In addition to the above oxidation catalyst, (D) a simple substance or a compound containing at least one element selected from bismuth, tin, lead and antimony may be combined. In this oxidation catalyst, the heteropolyacid is preferably of a completely proton type, for example, H _{x + 3} PA _{12 -x} V _x O ₄₀ (where A represents Mo or W, and x represents 1 to 4). (Which is an integer), such as molybdic acid molybdic acid or tungstic acid molybdenum.

The present invention also provides an oxidation method for oxidizing an organic substrate with molecular oxygen in the presence of the above-mentioned oxidation catalyst. Alkenes or cycloalkenes are preferred as organic substrates. As the reaction solvent, it is preferable to use an aprotic polar solvent or a protic organic solvent.

The present invention further provides a method for producing a carbonyl compound which oxidizes an alkene or cycloalkene with molecular oxygen in the presence of the above-mentioned oxidation catalyst to produce a corresponding carbonyl compound. A process for producing a corresponding cycloalkanone and / or cycloalkenone by reacting, for example, a cycloalkene with molecular oxygen in the presence of the above oxidation catalyst is provided.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The oxidation catalyst of the present invention comprises (A) a zero-valent palladium supported on activated carbon as a catalyst component,
It contains (B) a heteropoly acid and (C) a strong acid.

[0-valent palladium supported on activated carbon (A)] As the 0-valent palladium supported on activated carbon, those generally available as supported palladium catalysts include those having 0-valent palladium. Should be fine. Further, zero-valent palladium may be added to the reaction system in a zero-valent state, or may be generated in the reaction system. Preferably,
Zero-valent palladium supported on activated carbon is added to the reaction system.

[Activated carbon] The activated carbon may be activated carbon obtained from any of plant, mineral and polymer raw materials. In the present invention, high catalytic activity can be obtained even when activated carbon having a large content of impurities such as sulfur is used.

Activated carbon is generally fired by activating a carbonized and sized raw material with steam, air (oxygen) and combustion gas (CO ₂ ) or by impregnating the raw material with an aqueous solution of zinc chloride or the like. It is manufactured by a chemical activation method or the like. The activated carbon in the present invention may be produced by any of the above methods. The shape of the activated carbon is not particularly limited, and may be any shape such as powder, granule, fiber, pellet, and honeycomb.

The average pore size of the activated carbon may be within a range that does not impair the catalytic activity, and is, for example, about 5 to 150 Å, preferably about 8 to 60 Å. When activated carbon having an average pore diameter of about 30 to 60 angstroms is used, excellent activity is often obtained. If the average pore diameter is too small, the catalyst activity tends to decrease, while if it is too large, the catalyst life tends to decrease.

The pore volume of the activated carbon (pore volume of pores having a pore diameter of less than 200 Å) is usually from 0.2 to 2.
Although it is about 5 ml / g, from the viewpoint of catalytic activity, it is preferably 0.7 to 2.5 ml / g, more preferably 0.8 to 2.5 ml / g.
It is about 2.0 ml / g (for example, 0.8 to 1.5 ml / g).

The specific surface area of the activated carbon is usually 500 to 400.
About 0 m ² / g, preferably 700 to 4000
m ² / g, and the specific surface area is particularly 800 to 4000.
m ² / g (e.g., 900~3000m ² / g) The use of about activated carbon, higher catalytic activity is obtained.

The loading amount of zero-valent palladium is usually about 0.5 to 80% by weight, preferably about 1 to 40% by weight, and more preferably about 2 to 20% by weight, based on activated carbon. 0
The support of a valence palladium can be performed by supporting a palladium compound such as palladium chloride on activated carbon, and then reducing it with hydrogen or the like. The loading of the palladium compound can be performed by a conventional method, for example, an impregnation method, a coating method, a spray method, an adsorption method, a precipitation method, or the like. The reduction can be performed by a conventional method such as using hydrogen. After supporting a catalyst component, for example, zero-valent palladium, the catalyst is formed into an appropriate shape, for example, a spherical shape, a cylindrical shape, a polygonal column shape, a honeycomb shape, etc., depending on the type of the reactor and the reaction type. Can also.

[Heteropolyacid (B)] The heteropolyacid is a condensate of an oxyacid containing two or more different types of central ions, and is also called a heteronuclear condensed acid. Heteropoly acids are
For example, oxygen acid ions (for example, phosphoric acid, silicic acid, etc.) of elements such as P, As, Sn, Si, Ti, and Zr;
It is composed of oxyacid ions of elements such as V, Mo, W and the like (for example, vanadic acid, molybdic acid, tungstic acid, etc.), and various heteropoly acids can be obtained by combining them.

The heteroatom of the oxyacid constituting the heteropolyacid is not particularly limited. For example, Cu, Be, B, Al,
C, Si, Ge, Sn, Ti, Zr, Ce, Th, N,
P, As, Sb, V, Nb, Ta, Cr, Mo, W,
U, Se, Te, Mn, I, Fe, Co, Ni, Rh,
Os, Ir, Pt and the like can be exemplified. Preferred heteropoly acids contain at least one element of P, Si, V, Mo, W, and more preferably contain P and at least one element selected from V, Mo and W. . Particularly preferred heteropoly acids contain at least P and V as constituent elements.

As the heteropolyacid anion constituting the heteropolyacid, an anion represented by the following composition formula can be exemplified. XM ₁₂ O ₄₀ , XM ₁₀ O ₃₄ , XM ₁₂ O ₄₂ , XM
₁₁ O ₃₉ , XM ₁₀ O _m , XM ₉ O ₃₂ , XM ₆ O ₂₄ , X ₂ M ₁₈ O
_{62, X 2 M 18 O 56} , X 2 M 12 O 42, X 2 M 17 O m, XM 6 O m
In the formula, X represents an element such as B, Si, P, C, Al, and N. M represents an element such as Mo, W, V, Nb, Ta, Cr, and U. m shows the integer of 15-80. Preferred X is an element such as B, Si, or P, and preferred M is
Elements such as Mo, W, and V. Note that M is not limited to one kind of element, and may be two or more kinds of elements.

M is from 15 to 80, depending on the valences of M and X.
Can be selected from the range of the degree, usually the composition formula “XM ₁₀ O _m ”
In the heteropolyacid anion represented by about 25 to 35,
Formula "X ₂ M ₁₇ O _m" 60 to 80 in the heteropoly acid anion represented by, in the heteropoly acid anion represented by the formula "XM ₆ O _m" it is about 15-25.

The preferred composition of the heteropolyacid anion is
It can be represented by XM ₁₂ O ₄₀ . In this composition formula,
X is an element such as Si or P, and M is Mo, W, V
And other elements. Examples of heteropolyacid anions having such a composition include anions of phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, and phosphovanadomolybdic acid. Particularly preferred heteropolyacid anions are the anions of phosphomolybdate, phosphovanadomolybdate, and phosphovanadotungstate, and among them, the phosphoanadomolybdate anion and the phosphovanadotungstate anion are preferred.

The heteropolyacid is obtained by substituting a part of the hydrogen atom corresponding to the cation of the heteropolyacid with another cation,
It can also be used as a partial proton type. The replaceable cation is not particularly limited, and examples thereof include ammonium (NH ₄ or the like) and alkali metal (Cs, R
b, K, Na, Li, etc.), alkaline earth metals (Ba,
Sr, Ca, Mg, etc.). As the heteropoly acid, a completely proton type is preferred. When a completely proton type heteropoly acid is used, the conversion and the yield are remarkably improved as compared with the ammonium type or partial proton type.

Preferred heteropolyacids are H _{x + 3} PA _12-x V _x
O ₄₀ (where A represents Mo or W, and x is an integer of 1 to 4), such as phosphorus vanado molybdic acid or phosphorus vanado tungstic acid. A may be a combination of Mo and W. Specifically, H ₄ PMo ₁₁ VO
_{40, H 5 PMo 10 V 2} O 40, H 6 PMo 9 V 3 O 40, H 7 PM
o ₈ V ₄ O ₄₀ , H ₄ PW ₁₁ VO ₄₀ , H ₅ PW ₁₀ V ₂ O ₄₀ , H ₆
PW ₉ V ₃ O ₄₀ , H ₇ PW ₈ V ₄ O _{40 and the} like.

The heteropolyacid or a salt thereof may be an anhydride or a substance containing water of crystallization, and may be used in a form supported on a carrier such as activated carbon. Further, the activated carbon supporting the heteropolyacid may be activated carbon supporting the zero-valent palladium, or may be another activated carbon. The heteropoly acids and salts thereof may be used alone or in combination of two or more. The heteropoly acid or a salt thereof can be prepared by a conventional method.

[Strong acid (C)] It is presumed that the strong acid (excluding the heteropoly acid) (C) functions to enhance the action of the heteropoly acid and activate the alkene and the like.

The strong acid (C) has a pKa (at 25 ° C.) of, for example, 4 or less, preferably -15 to 2, and more preferably -1.
It is in the range of about 0 to 0, and such a strong acid (C) includes:
Includes inorganic and organic acids. Examples of the inorganic acid include sulfuric acid, nitric acid, hydrogen halide (hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, and the corresponding hydrohalic acid), phosphoric acid, superacid (ClSO ₃ H, H ₂ SO ₄ -S
O ₃ , HF-SbF _5, etc.). Organic acids include haloalkanoic acids (eg, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, etc.); alkylsulfonic acids (eg, methanesulfonic acid, ethanesulfonic acid, etc.), haloalkylsulfonic acids (eg, trifluorofluoric acid) And sulfonic acids such as arylsulfonic acids (eg, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, etc.). A cation exchange resin (for example, a strongly acidic ion exchange resin such as a sulfonic acid type ion exchange resin) can be used as the strong acid (C).

Preferred strong acids (C) include, for example, sulfuric acid,
Inorganic acids such as nitric acid, hydrogen halide (including hydrohalic acid) and phosphoric acid; sulfonic acids such as alkylsulfonic acid, haloalkylsulfonic acid and arylsulfonic acid; and haloalkanoic acids such as trichloroacetic acid.
The strong acid (C) may be used alone or in combination of two or more.

[Other Catalyst Components] The oxidation catalyst of the present invention contains other catalyst components in addition to the zero-valent palladium (A) supported on the activated carbon, the heteropolyacid (B), and the strong acid (C). You may go out. As such a catalyst component, for example, a simple substance of Bi, Sn, Pb, and Sb, or a compound (D) and the like can be mentioned. When these catalyst components are used in combination, the yield and selectivity of the target compound may be improved depending on the type of the organic substrate and the reaction. For example, when a cycloalkene such as cyclopentene is oxidized, the addition and addition of these components (D) greatly increase the yield and selectivity of cycloalkanone such as cyclopentanone as compared with the case without addition. improves.

The simple substance or compound (D) of Bi, Sn, Pb, Sb is not particularly limited as long as it is a simple substance of Bi, Sn, Pb, Sb or a compound containing Bi, Sn, Pb, Sb as a metal component. Instead, various compounds known per se can be used. For example, Bi, Sn, Pb, Sb
Oxides, hydroxides, salts (inorganic salts such as nitrates, sulfates, halides and the like, and organic acid salts such as acetates), complex salts and complexes.

The aforementioned Bi, Sn, Pb, and Sb alone or the compound (D) may be used alone or in combination of two or more as a mixture, a composite compound, a composition, or the like. The simple substance or compound (D) of Bi, Sn, Pb, or Sb is used in various forms such as various solutions such as an aqueous solution or an organic solvent solution, a suspension, or a state of being supported on a carrier such as activated carbon. can do. As a preferred embodiment, it can be used in a state in which zero-valent palladium is supported on the same activated carbon, and in this case, the supported amount is about 1 to 20% by weight based on the activated carbon.

[Oxidation Method] In the oxidation method of the present invention, an organic substrate is oxidized with molecular oxygen in the presence of the oxidation catalyst.
Organic substrates include non-aromatic unsaturated compounds, for example,
Alkenes, cycloalkenes and the like can be mentioned.

Examples of the alkene include ethene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene, 3-methyl-1-butene, 1-hexene, 2-hexene, 3-hexene and 1-hexene. Heptene, 2-heptene,
1-octene, 2-octene, 1-decene, 1-undecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-icosene, 1-triaconten, etc. About 30 (preferably 2
Alkenes). Alkenes also include alkapolyenes (eg, alkadienes such as butadiene).

Further, as the cycloalkene, for example,
Examples thereof include cycloalkenes having about 3 to 30 carbon atoms, such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, and cyclooctadecene. Cycloalkenes also include cycloalkapolyenes such as cycloalkadiene.

These compounds may have various substituents in the molecule. Examples of such a substituent include a halogen atom, a hydroxyl group, a substituted oxy group (eg, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an acyloxy group, a silyloxy group, etc.),
Mercapto group, substituted thio group (for example, alkylthio group,
A cycloalkylthio group, an arylthio group, etc.), a carboxyl group, a substituted oxycarbonyl group (eg, an alkyloxycarbonyl group, an aryloxycarbonyl group, etc.), a substituted or unsubstituted carbamoyl group, a cyano group, an acyl group, a formyl group, a nitro group, Examples thereof include a substituted or unsubstituted amino group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and a heterocyclic group.

As specific examples of the alkene having a substituent,
For example, styrene derivatives such as styrene and methylstyrene; α, β-unsaturated esters such as ethyl acrylate;
Α, β-unsaturated nitriles such as acrylonitrile; α, β-unsaturated aldehydes such as acrolein; α, β-unsaturated acetals such as acrolein diethyl acetal; and α, β-unsaturated ketones such as vinyl methyl ketone. Can be Preferred organic substrates include cycloalkenes such as cyclopentene.

The molecular oxygen used for the oxidation of the organic substrate is not particularly limited, and pure oxygen may be used, or oxygen or air diluted with an inert gas such as nitrogen, helium, or argon may be used. . The amount of molecular oxygen used can be selected according to the type of the organic substrate and the like, and is usually 0.5 mol or more (eg, 1 mol or more), preferably 1 to 100 mol, and Preferably it is about 1 to 50 mol. Often an excess of molecular oxygen is used relative to the organic substrate.

The amount of the zero-valent palladium (A) used is, for example, 0.001 to 1 mol, preferably 0.01 to 0.5 mol, more preferably 0.1 to 1 mol, per 1 mol of the organic substrate.
It is about 02 to 0.2 mol. The amount of the heteropolyacid (B) used is, for example, 0.000 to 1 mol of the organic substrate.
It is about 1 to 1 mol, preferably about 0.001 to 0.1 mol, and more preferably about 0.002 to 0.05 mol. The amount of the strong acid (C) used is, for example, 0.001-1 mol, preferably 0.01-0.5 mol, per 1 mol of the organic substrate.
Mole, more preferably about 0.05 to 0.3 mole. When Bi, Sn, Pb, or Sb alone or the compound (D) is used, the amount thereof is, for example, 0.0001 to 0.5 mol, preferably 0.1 to 0.5 mol, per 1 mol of the organic substrate.
0005-0.05 mol, more preferably 0.001
About 0.02 mol.

The reaction may be carried out in the presence or absence of a solvent. The solvent can be appropriately selected depending on the type of the organic substrate and the target product, and the like. As the solvent, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as hexane, heptane and octane; cycloaliphatic hydrocarbons such as cyclopentane and cyclohexane; carbon tetrachloride, chloroform, dichloromethane, Halogenated hydrocarbons such as 1,2-dichloroethane; carboxylic acids such as acetic acid, propionic acid and butyric acid; ketones such as acetone, methyl ethyl ketone, cyclopentanone and cyclohexanone; esters such as methyl acetate, ethyl acetate, isopropyl acetate and butyl acetate N, N-
Amides such as dimethylformamide and N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile and benzonitrile; linear or cyclic ethers such as diethyl ether, dibutyl ether, dimethoxyethane, dioxane, tetrahydrofuran and ethylene glycol monobutyl ether; Examples include alcohols such as methanol, ethanol, isopropanol, and 2-ethylhexyl alcohol. These solvents are used singly or as a mixture of two or more.

When the reaction is carried out using an aprotic polar solvent such as acetonitrile, the corresponding cycloalkanone can be obtained with high selectivity and yield by oxidation of the cycloalkene. Also, a protic organic solvent, for example,
When the reaction is performed using an alcohol such as methanol, ethanol, or isopropanol; or a carboxylic acid such as acetic acid, propionic acid, or butyric acid, the selectivity for cycloalkenones is significantly improved.

The reaction temperature can be appropriately selected in consideration of the reaction rate and the reaction selectivity according to the organic substrate and the type of the reaction, and is, for example, 0 to 200 ° C., preferably 10 to 100 ° C.
It is about ° C. The reaction may be performed at normal pressure or under pressure. The reaction may be performed by any method such as a batch system, a semi-batch system, and a continuous system.

The oxidation method of the present invention can be applied to, for example, a Wacker-type reaction for producing a corresponding ketone from an alkene or a cycloalkene.

The Wacker-type reaction does not necessarily require water, but is usually carried out in the presence of water. In this reaction, when an alkene is used as an organic substrate, a corresponding oxoalkane (aliphatic ketone) is generated. In addition, when a terminal olefin is used among the alkenes, a corresponding methyl ketone is obtained. More specifically, methyl octyl ketone and acetophenone are produced from 1-decene and styrene, respectively. When a cycloalkene is used as an organic substrate, a corresponding cycloalkanone and a cycloalkene are produced depending on reaction conditions. For example, from cyclopentene, cyclopentanone and, depending on conditions, cyclopentenone can be obtained.

The amount of water may be a catalytic amount or may be present in an excess molar amount with respect to the organic substrate. For example,
The amount of water used is 0.001 to 1 with respect to 1 mol of the organic substrate.
000 mol, preferably about 1 to 100 mol.

The oxidation product produced by the reaction can be easily separated by conventional separation means, for example, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography and the like, or a combination thereof. It can be separated and purified.

Since the oxidation catalyst of the present invention is composed of zero-valent palladium supported on activated carbon, a heteropolyacid, and a strong acid, it exhibits extremely high catalytic activity, for example, an organic catalyst such as an alkene or a cycloalkene. The corresponding carbonyl compound can be efficiently produced from the substrate in a high yield under a mild condition. Bi, S is added to the oxidation catalyst.
By adding a simple substance or a compound of n, Pb and Sb, a carbonyl compound can be obtained in a higher yield. Furthermore, when the reaction is carried out using an aprotic polar solvent as a solvent, cycloalkanone can be obtained in a high selectivity and a high yield by oxidation of cycloalkene, and when a protic organic solvent is used, Oxidation of the cycloalkene can greatly improve the selectivity of the cycloalkenones. Therefore, it is extremely useful as an industrial oxidation catalyst.

[0047]

According to the oxidation catalyst and the oxidation method of the present invention, an organic substrate can be efficiently oxidized. Further, according to the production method of the present invention, a corresponding carbonyl compound can be obtained from cycloalkene or alkene at a high conversion and a high yield.

[0048]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 cyclopentene 273mg (4.01mmol), H _{5
PMo 10 V 2 O 40 · 31H} 2 O46.3mg (0.020
2 mmol), 55.25% by weight water-containing 10% by weight Pd /
C (trade name "PE-Type", NE CHEMCA
446.4 mg (manufactured by T Company) (Pd; 0.188 mmol)
l), 41.7 mg of methanesulfonic acid (0.434 mm
ol) and acetonitrile / water (9 ml / 1 ml) were placed in a glass flask and placed in an oxygen atmosphere (0.1MP
a), The mixture was stirred at a temperature of 50 ° C. for 8 hours. As a result of analysis by gas chromatography, the conversion of cyclopentene was 9
3%, cyclopentanone (CPon) yield 82%, 2
The yield of -cyclopenten-1-one (CPenon) was 5%. The results are shown in Table 1.

[0049] In Example 2 Example _{1, H 5 PMo 10 V 2} O 40 · 31H 2 O4
Instead of 6.3 mg (0.0202 mmol), H ₆
44.9 mg of PMo ₉ V ₃ O ₄₀ .30H ₂ O (0.020
The reaction was performed in the same manner as in Example 1 except that 1 mmol) was used. As a result of analysis by gas chromatography, the conversion of cyclopentene was 98%, the yield of cyclopentanone was 71%, and the yield of 2-cyclopenten-1-one was 5%. The results are shown in Table 1.

[0050] In Example 3 Example _{1, H 5 PMo 10 V 2} O 40 · 31H 2 O4
Instead of 6.3 mg (0.0202 mmol), H ₇
PMo ₈ V ₄ O ₄₀ .28H ₂ O 43.5 mg (0.020
The reaction was performed in the same manner as in Example 1 except that 2 mmol) was used. As a result of analysis by gas chromatography, the conversion of cyclopentene was 98%, the yield of cyclopentanone was 68%, and the yield of 2-cyclopenten-1-one was 2%. The results are shown in Table 1.

Example 4 280 mg (4.11 mmol) of cyclopentene, H _{5
PMo 10 V 2 O 40 · 31H} 2 O46.1mg (0.020
1 mmol), 10 wt% Pd-3 wt% Bi / C (trade name “NX-Type”, manufactured by NE CHEMCAT) 200 mg (Pd; 0.188 mmol), 47.4 mg (0.483 mmol) concentrated sulfuric acid And acetonitrile / water (9 ml / 1 ml) were placed in a glass flask and stirred at 50 ° C. for 8 hours under an oxygen atmosphere (0.1 MPa). As a result of analysis by gas chromatography, the conversion of cyclopentene was 99%, the yield of cyclopentanone was 88%, and the yield of 2-cyclopenten-1-one was 3%. The results are shown in Table 1.

Example 5 In Example 4, 10% by weight of Pd-3% by weight of Bi / C
Instead of 200 mg (Pd; 0.188 mmol),
50.39% by weight water-containing 10% by weight Pd / C (trade name "N
X-Type ", N.M. E. FIG. CHEMCAT) 40
The reaction was carried out in the same manner as in Example 4, except that 3.7 mg (0.188 mmol) was used. As a result of analysis by gas chromatography, the conversion of cyclopentene was 1
00%, the yield of cyclopentanone was 74%, and the yield of 2-cyclopenten-1-one was 4%. The results are shown in Table 1.

Example 6 277 mg (4.06 mmol) of cyclopentene, H _{5
PMo 10 V 2 O 40 · 31H} 2 O46.4mg (0.020
2 mmol), 55.25% by weight water-containing 10% by weight Pd /
C (trade name "PE-Type", NE CHEMCA
447 mg (Pd; 0.188 mmol), 43.2 mg (0.440 mmol) of concentrated sulfuric acid, and ethanol / water (9 ml / 1 ml) were placed in a glass flask and placed in an oxygen atmosphere (0.1 MPa). Stirred at 50 ° C. for 8 hours. As a result of analysis by gas chromatography, the conversion of cyclopentene was 92%, the yield of cyclopentanone was 49%, and the yield of 2-cyclopenten-1-one was 25%. The results are shown in Table 1.

Example 7 A reaction was carried out in the same manner as in Example 6, except that 9 ml of acetonitrile was used instead of 9 ml of ethanol. As a result of analysis by gas chromatography, the conversion of cyclopentene was 97%, the yield of cyclopentanone was 67%,
The yield of 2-cyclopenten-1-one was 6%.
The results are shown in Table 1.

[0055] In Comparative Example 1 Example _{1, H 5 PMo 10 V 2} O 40 · 31H 2 O4
Instead of 6.3 mg (0.0202 mmol), (N
H ₄ ) ₅ PMo ₁₀ V ₂ O ₄₀ 36 mg (0.0219 mmo
The reaction was carried out in the same manner as in Example 1, except that l) was used. As a result of analysis by gas chromatography, the conversion of cyclopentene was 86%, the yield of cyclopentanone was 33%, and the yield of 2-cyclopenten-1-one was 0.8.
%Met. The results are shown in Table 1.

[Table 1]

Continued on front page F-term (reference) 4G069 AA02 AA03 AA08 BA08A BA08B BA43A BB07A BB07B BC21A BC22A BC25A BC25B BC26A BC54A BC54B BC59A BC59B BC60A BD07A BD07B CB07 CB72 DA03 FA01 4H006 AA02 BA42 BA14 BA14 BA26 CA62 CC30

Claims (9)

[Claims] An oxidation catalyst comprising (A) zero-valent palladium supported on activated carbon, (B) a heteropolyacid, and (C) a strong acid. 2. The oxidation catalyst according to claim 1, further comprising (D) a simple substance or a compound containing at least one element selected from bismuth, tin, lead and antimony. 3. The oxidation catalyst according to claim 1, wherein the heteropolyacid (B) is of a complete proton type. 4. The heteropolyacid (B) is represented by the following formula: H _{x + 3} PA _12-x V _x O ₄₀ (where A represents Mo or W, and x is an integer of 1 to 4). The oxidation catalyst according to any one of claims 1 to 3, wherein the oxidation catalyst is phosphorus vanado molybdic acid or phosphorus vanado tungstic acid. 5. An oxidation method for oxidizing an organic substrate with molecular oxygen in the presence of the oxidation catalyst according to claim 1. 6. The oxidation method according to claim 5, wherein an aprotic polar solvent or a protic organic solvent is used as the reaction solvent. 7. The method according to claim 5, wherein the organic substrate is an alkene or a cycloalkene. 8. An alkene or cycloalkene is reacted with molecular oxygen in the presence of the oxidation catalyst according to claim 1,
A method for producing a carbonyl compound, which comprises obtaining a corresponding carbonyl compound. 9. The process for producing a carbonyl compound according to claim 8, wherein the cycloalkene is reacted with molecular oxygen to obtain the corresponding cycloalkanone and / or cycloalkenone.