JP2001269577A - Catalyst for acyloxylation reaction and acyloxylation reaction method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrially and economically advantageous efficient acyloxylation reaction method. SOLUTION: Acyloxylation reaction is performed using a catalyst prepared by making a carrier carry particles with a particle size of 10 nm or less, which contain at least one element of groups VIII-XI of the periodic table, thereon.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for an acyloxylation reaction and a method for an acyloxylation reaction using the catalyst.

[0002] The acyloxylation reaction is a reaction for synthesizing various useful compounds used as a fragrance, a raw material for medicines and agrochemicals, as an organic synthesis intermediate, and as a polymerizable material.

[0003]

2. Description of the Related Art Conventionally, compounds having a hydrogen atom at the benzyl position, such as toluene and xylene, or propylene,
An acyloxylation reaction method using a compound having a hydrogen atom at the allyl position such as cyclohexene and a carboxylic acid such as acetic acid and oxygen is known.

As a catalyst for the acyloxylation reaction, a homogeneous catalyst such as palladium acetate and a heterogeneous catalyst in which palladium is supported on a carrier such as silica have been developed.

[0005]

However, the above-mentioned conventional acyloxylation catalyst has good activity and selectivity in the initial stage of the reaction, but its activity rapidly decreases in a short time, so that expensive palladium is eluted. However, there is a problem that a co-catalyst which cannot be sufficiently suppressed and a large amount of a reaction system requires a soluble co-catalyst, so that the separation / recycling process becomes complicated.

The present invention has been made in view of the above circumstances, and has as its object to provide a catalyst and a production method for efficiently performing an acyloxylation reaction and economically producing an acyloxylation product. Is what you do.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to provide a catalyst for efficiently performing an acyloxylation reaction and economically producing an acyloxylation product and an efficient reaction method. As a result, the catalyst for an acyloxylation reaction in which particles having a particle size of 10 nm or less comprising at least one element of Groups 8 to 11 of the periodic table are supported on a carrier, and an acyloxylation reaction method using the catalyst, provide economical advantages. The present inventors have found that an acyloxy product can be produced in a specific manner, and have completed the present invention.

That is, the present invention relates to a catalyst for an acyloxylation reaction in which a carrier is supported on a carrier, wherein the carrier comprises at least one element belonging to Groups 8 to 11 of the periodic table. The present invention relates to an acyloxylation catalyst containing particles having a diameter of 10 nm or less.

It is preferable that the catalyst further contains at least one element from Group 1 to Group 2 of the periodic table.

It is preferable that the catalyst further contains at least one element from the 12th to 16th groups of the periodic table or tellurium.

In another aspect of the present invention, a compound represented by the following general formula (1): CHR ¹ R ² -X (wherein R ¹ and R ² are each independently a hydrogen atom, in the presence of the acyloxylation catalyst) Or an organic residue, and X represents an aromatic hydrocarbon residue which may have a substituent or an olefin residue which may have a substituent), and a compound represented by the following general formula: (2): A carboxylic acid represented by R ³ —COOH (wherein R ³ represents a hydrogen atom or an organic residue) is reacted with oxygen to obtain the following general formula (3): R ³ —COO— CR ¹ R ² -X (wherein, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an organic residue, and X represents an aromatic hydrocarbon residue which may have a substituent or Which represents an olefin residue which may have a substituent). About carboxymethyl reaction process.

[0012] In the above reaction, it is preferable that the reaction is further performed in the presence of at least one substance selected from the group consisting of a basic compound, a nitrogen-containing compound and a phosphorus-containing compound.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described below in detail.

The catalyst for acylation reaction of the present invention is a catalyst for acylation reaction in which a carrier is carried on a carrier.

The carrier for the catalyst is not particularly limited, but specific examples thereof include metal oxides such as silica, alumina, zirconia, and titania, carbon, charcoal, activated carbon, asbestos, silica-alumina, and zeolite. , Organosol gel, ion exchange resin, clay, carbonate, carbonate and the like. Among them, metal oxides such as silica, alumina, zirconia and titania, activated carbon and zeolite are more preferred, silica, zirconia, titania, activated carbon and zeolite are more preferred, and activated carbon is particularly preferred.

The raw material of the activated carbon is not particularly limited, and examples thereof include wood, coconut shell, organic polymer, petroleum pitch, and rice hull. Among these, woody and coconut shells are preferred. The method of activating the raw material is not particularly limited, and examples thereof include a method by a chemical treatment with zinc chloride or the like and a method by steam. Among these, the method of activating with steam is preferred. The nature of the activated carbon used as the carrier is not particularly limited, but the ignition residue is 4% or less, preferably 3% or less, and the median diameter is 60 μm or less, preferably 40 μm or less.
m, the specific surface area is in the range of 800 to 2500 m ² / g, preferably in the range of 900 to 2000 m ² / g, more preferably in the range of 1000 to 1800 m ² / g, and the cumulative pore area is 0.3 -1.8 ml / g, preferably 0.4-1.7 ml / g, more preferably 0.5-1.6 ml / g, and the average pore diameter is 0.5-5 nm. Activated carbon having a range, preferably from 0.6 to 4 nm, more preferably from 0.8 to 3 nm is suitably used.

The activated carbon is treated with an aqueous solution of a basic compound such as sodium hydroxide and potassium hydroxide after activation to adjust the pH to 6 or more, preferably 7 or more, more preferably 8 or more. preferable. This treatment with a basic compound is more preferably performed after treating the activated carbon with an aqueous solution of an acidic compound such as nitric acid and sulfuric acid.

The state of the carrier is not particularly limited, and may be powdery, crushed, particulate, columnar, etc., depending on the reaction mode to be carried out, such as a fixed bed system, a fluidized bed system and a suspension catalyst system. You can choose.

The catalyst for the acyloxylation reaction of the present invention comprises:
The support material essentially contains particles having a particle size of 10 nm or less and containing at least one element (I) of Groups 8 to 11 of the periodic table.

The particle size referred to here is JEM-2000.
Based on a photograph taken by an FX transmission electron microscope (manufactured by JEOL Ltd .; hereinafter, referred to as “electron microscope”), 200 particles of the element (I) on the carrier were arbitrarily selected, and the measured particle diameter was measured. Is the average value.

The element (I) having an average particle size of 10 nm or less.
Are active against the acyloxylation reaction. Further, the particle diameter of the element (I) is more preferably 8 nm or less, further preferably 6 nm or less, particularly preferably 5 nm or less, and most preferably 3 nm or less.

The maximum value of the particle size distribution of the element (I) is preferably 12 nm or less, more preferably 10 nm or less, further preferably 8 nm or less, and more preferably 6 nm or less. Particularly preferred 5
Most preferably, it is not more than nm.

As the element (I), Group 8 of the periodic table
At least one element (I) of group 11;
Iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, and silver, of which, cobalt, ruthenium, rhodium, palladium, silver, platinum and gold are more preferred,
Palladium is more preferred. One kind of the metal atom may be used, or two or more kinds may be used in appropriate combination.

The amount of the element (I) supported on the carrier in the catalyst is not particularly limited, but is 0.01 to 20% by weight, preferably 0.1 to 20% by weight based on the carrier. 15% by weight, more preferably 0.5 to 10
%, Particularly preferably 1 to 8% by weight. The range of the supported amount is preferable in terms of yield, suppression of elution of the element (I), and economic efficiency.

It is preferable that the catalyst for the acyloxylation reaction of the present invention further support a carrier of a Group 1 or 2 element (II) of the periodic table as a supporting substance. An acyloxylation reaction is carried out by supporting the element (II) of the Periodic Table Group 1 or 2 on a carrier together with particles having a particle size of 10 nm or less comprising at least one element (I) of the Group 8 to 11 of the Periodic Table. The conversion and selectivity in the above are improved, and an acyloxy product can be produced economically.

The element (II) includes lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium and barium, of which lithium, sodium, potassium and cesium are more preferred. Preferably, lithium, sodium and potassium are more preferred, with lithium being particularly preferred. The metal atom is 1
The types may be used, or two or more types may be used in appropriate combination. Further, the metal atoms may be supported independently of the Group 8-11 metals, or may be supported in a state where a part and / or all of the metal forms an alloy.

The amount of the element (II) supported on the carrier in the catalyst is not particularly limited, but is 0.001 to 10% by weight, preferably 0.01 to 10% by weight, based on the carrier. 8% by weight, more preferably 0.05
-6% by weight, particularly preferably 0.05-5% by weight. The above range of the supported amount is preferable in terms of the conversion and the selectivity and the economic efficiency.

The catalyst for the acyloxylation reaction of the present invention may further comprise, as a supporting substance, an element (III) of Groups 12 to 16 of the periodic table.
Preferably, and / or tellurium is supported on a carrier. Along with a particle having a particle size of 10 nm or less comprising at least one element (I) belonging to groups 8 to 11 of the periodic table, and an element (II) belonging to group 1 or 2 of the periodic table, the periodic table 12 to 1
By supporting the Group 6 element (III) and / or tellurium on a carrier, the conversion rate in the acetoxylation reaction can be reduced.
The selectivity is improved, and the elution of the element (I) into the reaction system can be suppressed, so that an acyloxy product can be produced economically.

The element (III) includes, for example, zinc, cadmium, mercury, aluminum, gallium, indium, thallium, germanium, tin, lead, antimony, bismuth and polonium. Of these, zinc, mercury, Tin, lead, antimony and bismuth are more preferred, and zinc, tin, lead, antimony and bismuth are even more preferred. One kind of the metal atom may be used, or two or more kinds may be used in appropriate combination.
Further, the metal atoms may be supported independently of the Group 8-11 metals, or may be supported in a state where a part and / or all of the metal forms an alloy.

In the above catalyst, 12 supported on a carrier
As the supported amount of the metal of group 16 and / or tellurium,
Although not particularly limited, 0.00 to the carrier.
1 to 10% by weight, preferably 0.01 to 8% by weight, more preferably 0.05 to 6% by weight, particularly preferably 0.1 to 8% by weight.
0.5 to 5% by weight. The range of the supported amount is preferable from the viewpoint of suppressing the elution of the element (I) and the economical efficiency.

In preparing the acyloxylation reaction catalyst of the present invention, the raw material of the element (I) is not particularly limited. Specifically, when palladium is mentioned as an example of the element (I), palladium metal, ammonium hexachloropalladate, potassium hexachloropalladate, sodium hexachloropalladate, ammonium tetrachloropalladate, potassium tetrachloropalladate, tetrachloropalladium Sodium palladium, potassium tetrabromopalladate, palladium oxide, palladium chloride, palladium bromide, palladium iodide, palladium nitrate, palladium sulfate, palladium acetate, potassium dinitrosulfite palladium, chlorocarbonyl palladium, dinitrodiammine palladium, tetraammine palladium Chloride, tetraamminepalladium nitrate, tetraamminepalladium hydroxide, cis-dichlorodiamminepara Umm, tran
Examples thereof include s-dichlorodiammine palladium, dichloro (ethylenediamine) palladium, and potassium tetracyanopalladate.

The method for preparing the catalyst of the present invention is not particularly limited, and the catalyst can be prepared by using the raw material of the element (I) and supporting it by a known method. Specifically, it can be adjusted by, for example, an impregnation method, an ion exchange method, a coprecipitation method, a deposition method, or a kneading method. Of these, the impregnation method and the ion exchange method are more preferable.

In preparing a catalyst containing the element (II), the raw materials used are not particularly limited. Specific examples include metals, oxides, hydroxides, halides, oxyhalides, alkoxides, aliphatic carboxylate such as acetate, nitrate, carbonate, phosphate, borate and the like. Take sodium for example.
Sodium metal, sodium hydroxide, sodium chloride,
Sodium bromide, sodium iodide, sodium oxychloride, sodium methoxide, sodium ethoxide,
Examples thereof include sodium butoxide, sodium acetate, sodium propionate, sodium acrylate, sodium methacrylate, sodium nitrate, sodium carbonate, sodium phosphate, and sodium borate.

The method of supporting the element (II) is not particularly limited, and the element (II) can be supported by a known method. Specifically, it can be adjusted by, for example, an impregnation method, an ion exchange method, a coprecipitation method, a deposition method, or a kneading method. Of these, the impregnation method and the ion exchange method are more preferable. Said 1
The Group 2 to Group 2 metals may be carried simultaneously with the Group 8 to 11 metals, or one of them may be carried followed by the other.

When preparing a catalyst containing the element (III) and / or tellurium, the raw materials used are not particularly limited.
I) and / or tellurium metals, oxides, hydroxides, halides, oxyhalides, alkoxides, aliphatic carboxylates such as acetates, nitrates, carbonates,
Phosphates and borates. Examples of bismuth include bismuth metal, bismuth hydroxide, bismuth chloride, bismuth bromide, bismuth iodide, bismuth oxychloride, bismuth methoxide, bismuth ethoxide, bismuth butoxide, bismuth acetate, bismuth propionate, and bismuth acrylate , Bismuth methacrylate, bismuth nitrate, bismuth carbonate, bismuth phosphate and bismuth borate.

The method of carrying the group 12-16 element and / or tellurium is not particularly limited, and can be carried by a known method. Specifically, for example, the impregnation method,
It can be adjusted by an ion exchange method, a coprecipitation method, a deposition method, or a kneading method. Of these, the impregnation method and the ion exchange method are more preferable. The Group 12 to 16 metal and / or tellurium may be supported simultaneously with the Group 8 to 11 metal, or one of them may be supported and then the other.

The supported catalyst can be prepared by reducing if necessary. The reduction method is not particularly limited, and can be reduced by a known method. Specifically, for example, the reduction in the gas phase can be performed by performing the treatment in a gas flow of a reducing gas such as hydrogen and / or carbon monoxide. Further, the reduction in the liquid phase can be carried out by contacting with a known reducing agent such as hydrazine, formic acid, sodium formate or formaldehyde.

The acyloxylation reaction in the present invention is represented by the general formula (1): CHR ¹ R ² -X (wherein R ¹ and R ² each independently represent a hydrogen atom or an organic residue, and X represents a substituent. A compound represented by an aromatic hydrocarbon residue which may have a group or an olefin residue which may have a substituent), and R ³ —COOH (wherein , R ³ represents a hydrogen atom or an organic residue) and reacting oxygen with a carboxylic acid represented by the following general formula (3): R ³ —COO—CR ¹ R ² —X (wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an organic residue, and X represents an aromatic hydrocarbon residue which may have a substituent or an olefin residue which may have a substituent. Which represents a compound represented by the following formula:

The compound represented by the general formula (1) used as a raw material has a structure in which the substituents represented by R ¹ and R ² in the formula are hydrogen atoms or organic residues, and the substituent represented by X is The compound is not particularly limited as long as it is a compound composed of an aromatic hydrocarbon residue which may have a substituent or an olefin residue which may have a substituent.

The organic residue represented by R ¹ or R ² is, for example, a linear, branched or cyclic saturated and / or unsaturated alkyl group having 1 to 18 carbon atoms, It is a hydroxyalkyl group, an alkoxyalkyl group having 2 to 20 carbon atoms, a halogenated (for example, chlorinated, brominated or fluorinated) alkyl group having 1 to 8 carbon atoms, or an aryl group. Among them, a saturated and / or unsaturated alkyl group having 1 to 10 carbon atoms is preferably used.

The optionally substituted aromatic residue represented by X is, for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms; a hydroxy group having 1 to 8 carbon atoms. An alkyl group; an alkoxy group having 2 to 20 carbon atoms; a phenoxy group which may have a substituent; a halogenated (eg, chlorinated, brominated or fluorinated) alkyl group having 1 to 8 carbon atoms; a hydroxyl group; It is a phenyl group which may have a substituent such as a halogen atom such as chlorine, bromine and iodine.

The olefin residue optionally having a substituent represented by X is represented by the general formula (4): -CR ⁴ ＝ CHR ⁵ (wherein R ⁴ and R ⁵ are hydrogen atoms or (Represented by an organic residue). Here, the organic residue represented by R ⁴ or R ⁵ means, for example, a linear, branched or cyclic saturated and / or unsaturated alkyl group having 1 to 18 carbon atoms,
A hydroxyalkyl group having 1 to 8 carbon atoms, 2 to 20 carbon atoms
An alkoxyalkyl group, a halogenated (eg, chlorinated, brominated or fluorinated) alkyl group having 1 to 8 carbon atoms,
Aldehyde groups, aliphatic and / or aromatic ketone groups,
Carboxylic acid groups, aliphatic and / or aromatic carboxylic acid ester groups. Among these, a linear, branched or cyclic saturated and / or unsaturated alkyl group having 1 to 10 carbon atoms, a carboxylic acid group, an aliphatic and / or aromatic carboxylic acid ester group is preferably used. Also, R ¹ or R ² and R ⁴ or R ⁵ may form a ring.

Representative examples of the compound represented by the general formula (1) are not particularly limited, but specific examples include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and methacrylic acid. Butyl acid,
2-hydroxyethyl methacrylate and 2-ethylhexyl methacrylate, propylene, butene, pentene,
Hexene, heptene, nonene, decene, butadiene, cyclopentene, cyclopentadiene, cyclohexene,
Cyclohexadiene, cycloheptene, cyclooctene, cyclononene, cyclodecene, toluene, ethylbenzene, propylbenzene, butylbenzene, styrene, xylene, trimethylbenzene, tetramethylbenzene, pentamethylbenzene, hexamethylbenzene,
Examples include methylbiphenyl, dimethylbiphenyl, diphenylmethane, triphenylmethane, methylphenol, methoxytoluene, ethoxytoluene, and phenokititoluene. Among these, those containing isomers may be each isomer alone and / or each isomer mixture. Of these, methyl methacrylate, butyl methacrylate, propylene, butene, pentene, hexene, butadiene,
Cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, toluene, xylene, trimethylbenzene, methoxytoluene, and phenoxytoluene are preferably used.

The carboxylic acid represented by the general formula (2) used as a raw material in the method of the present invention is represented by R ^{3 in} the formula
Is not particularly limited as long as the group represented by is a compound composed of a hydrogen atom or an organic residue.

The organic residue represented by R ³ includes, for example, a linear, branched or cyclic saturated and / or unsaturated alkyl group having 1 to 18 carbon atoms, and a hydroxyalkyl group having 1 to 8 carbon atoms. An alkoxyalkyl group having 2 to 20 carbon atoms, an acetoxyalkyl group having 2 to 20 carbon atoms, and 1 carbon atom
To 8 halogenated (for example, chlorinated, brominated or fluorinated) alkyl groups, and optionally substituted aromatic groups. Among them, a saturated and / or unsaturated alkyl group having 1 to 5 carbon atoms is preferably used.

Representative examples of the carboxylic acids represented by the general formula (2) are not particularly limited, but specific examples include formic acid, acetic acid, propionic acid, butyric acid, valeric acid,
Caproic acid, caprylic acid, lauric acid, myristic acid,
Examples include palmitic acid, stearic acid, acetoacetic acid, hydroxypropionic acid, isobutanoic acid, hydroxyisobutanoic acid, t-butylacetic acid, benzoic acid, acrylic acid, methacrylic acid, and the like. Of these, acetic acid, propionic acid, butyric acid, benzoic acid, acrylic acid and methacrylic acid are more preferred, and acetic acid, propionic acid, acrylic acid and methacrylic acid are particularly preferred.

The molar ratio of the compound represented by the general formula (1) and the carboxylic acid represented by the general formula (2) in the initial stage of the reaction is not particularly limited, but is 10/10.
What is necessary is just to be in the range of 1/10. 8 within the above range
The range is preferably from 1/1 to 1/8, more preferably from 6/1 to 1/6, and particularly preferably from 5/1 to 1/5. Even if either the compound represented by the general formula (1) or the carboxylic acid represented by the general formula (2) is added in excess of the above range, the yield and the reaction time can be improved. No effect is expected, and the process of recovering excess raw materials becomes longer, which is economically disadvantageous.

The oxygen used in the reaction according to the present invention is
Atomic and / or molecular oxygen, preferably molecular oxygen. The molecular oxygen is nitrogen, argon,
It is preferably used as a mixed gas with an inert gas such as helium and carbon dioxide. In this case, it is more preferable that the oxygen concentration is adjusted to a range where the gas does not have an explosive composition in the reaction system before use.

As a method for supplying molecular oxygen and a mixed gas containing molecular oxygen to the reaction system, it may be supplied to one or both of a liquid phase portion and a gas phase portion in the reaction system. When supplying molecular oxygen and a mixed gas containing molecular oxygen into the reaction system, the oxygen partial pressure is 0.01 to 20 MPa, preferably 0.1 to 10 MPa, more preferably 0.1 to 10 MPa.
What is necessary is just to supply so that it may be in the range of 2-8 MPa, especially preferably 0.2-5 MPa.

In the reaction method of the present invention, the acylation reaction is carried out in the presence of the acylation catalyst of the present invention.

The amount of the catalyst depends on the type and combination of the compound represented by the general formula (1) and the carboxylic acid represented by the general formula (2). 0.01 mmol to 1 mol, preferably 0.0 mol, per 1 mol of the compound represented by the general formula (1)
5 mmol to 0.1 mol, more preferably 0.1 mmol to 0.05 mol, particularly preferably 0.5 mmol to
What is necessary is just to use it so that it may be in the range of 0.01 mol. The range of the amount of the catalyst used is preferable in terms of yield and economy.

In the reaction method of the present invention, the presence of a compound selected from a basic compound, a nitrogen-containing compound and a phosphorus-containing compound in the reaction system is preferred in terms of conversion and selectivity. The basic compound is not particularly limited, but specifically, lithium formate, sodium formate, potassium formate, magnesium formate, calcium formate, barium formate, lithium acetate, sodium acetate, potassium acetate, magnesium acetate , Calcium acetate, barium acetate, lithium propionate, sodium propionate, potassium propionate, magnesium propionate, calcium propionate, barium propionate, lithium acrylate, sodium acrylate, potassium acrylate, magnesium acrylate, calcium acrylate , Barium acrylate, lithium methacrylate, sodium methacrylate, potassium methacrylate, magnesium methacrylate, calcium methacrylate, barium methacrylate, benzoic Alkali metal and / or alkaline earth metal carboxylate such as lithium, sodium benzoate, potassium benzoate, magnesium benzoate, calcium benzoate, barium benzoate; lithium hydroxide, sodium hydroxide, potassium hydroxide, hydroxide Alkali metal and / or alkaline earth metal hydroxides such as magnesium, calcium hydroxide and barium hydroxide; alkali metals and / or alkaline earths such as lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate and barium carbonate Lithium carbonate, sodium phosphate, potassium phosphate, magnesium phosphate, calcium phosphate,
Alkali metal and / or alkaline earth metal carbonates such as barium phosphate; and alkali metal and / or alkaline earth metal borates such as lithium borate, sodium borate, potassium borate, magnesium borate, calcium borate and barium borate. Can be

Examples of the nitrogen-containing compound include, but are not particularly limited to, ammonia such as gas or aqueous solution; methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, and the like. Aliphatic amines such as triethanolamine, ethylenediamine, N, N-dimethylethylenediamine, N, N, N ', N'-tetramethylethylenediamine; heterocyclic amines such as pyridine, methylpyridine, bipyridine, hydropyridine, phenanthroline; aniline And aromatic amines such as diphenylamine and triphenylamine.

The phosphorus-containing compound is not particularly limited, but specific examples thereof include trialkylphosphines such as trimethylphosphine and triethylphosphine; triphenylphosphine and tris (2-methoxyphenyl) phosphine. A triarylphosphine;
Monodentate phosphines such as diarylalkylphosphines such as diphenylmethylphosphine and diphenylethylphosphine; 1,2-diphenylphosphinoethane, 1,4-
Bidentate phosphines such as bisdiphenylphosphinobutan;
Trialkyl phosphites such as trimethyl phosphite triethyl phosphite and tributyl phosphite; and triaryl phosphites such as triphenyl phosphite. These can be used alone or in an appropriate combination of two or more.

Among these, lithium acetate, sodium acetate, potassium acetate, lithium propionate, sodium propionate, potassium propionate, lithium acrylate, sodium acrylate, potassium acrylate, lithium methacrylate, sodium methacrylate,
Potassium methacrylate, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, pyridine, phenanthroline, trimethylphosphine, triethylphosphine, triphenylphosphine, tris (2-methoxyphenyl) phosphine are preferred. Used. In particular, lithium acetate, sodium acetate, potassium acetate, lithium carbonate, sodium carbonate, potassium carbonate, trimethylphosphine, and triphenylphosphine are more preferably used.

The total amount of at least one compound selected from the group consisting of the basic compound, the nitrogen-containing compound and the phosphorus-containing compound depends on the type of the raw material used.
With respect to 1 mol of the compound represented by the general formula (1),
0.001 to 3 mol, preferably 0.01 to 2 mol, more preferably 0.05 to 1.8 mol, and particularly preferably 0.1 to 1.5 mol. . The range of the total amount of the compound selected from the basic compound, the nitrogen-containing compound and the phosphorus-containing compound is preferable in terms of yield and economy.

In the present invention, it is not necessary to use a solvent, but an organic solvent can be used. Examples of the organic solvent include, but not limited to, aromatic hydrocarbons such as benzene; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; ethers such as diethyl ether and diisopropyl ether; chloroform. , Methylene chloride, dichloroethane, chlorobenzene and other halogenated hydrocarbons; methyl acetate, ethyl acetate,
Examples include carboxylic acid esters such as methyl propionate, ethyl propionate, methyl (meth) acrylate and ethyl (meth) acrylate.

The amount of the organic solvent used depends on the raw materials, but it is 0 to 200% by weight, preferably 0 to 1% by weight of the total amount of the raw materials.
It may be used in an amount of 00% by weight, more preferably 0 to 80% by weight, particularly preferably 0 to 70% by weight. The range of the amount of the organic solvent used is preferable in terms of yield and economy.

In the present invention, when the compound represented by the above general formula (1) and the acyloxylation product, which are the raw materials, are polymerizable compounds, the reaction may be carried out in the presence of a polymerization inhibitor. Is preferred from the viewpoint of suppressing the polymerization of the polymer. Examples of the polymerization inhibitor include, but are not particularly limited to, quinone-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; 2,6-di-tert-butylphenol, and 2,4. Alkyl phenols such as -di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol Polymerization inhibitors; amine-based polymerization inhibitors such as alkylated diphenylamine, N, N'-diphenyl-p-phenylenediamine, phenothiazine; copper-based dithiocarbamate such as copper dimethyldithiocarbamate, copper diethyldithiocarbamate, and copper dibutyldithiocarbamate; Inhibitors, etc. You. These can be used alone or in an appropriate combination of two or more. Among these, quinone polymerization inhibitors,
In particular, hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol and phenothiazine are preferably used.

The amount of the polymerization inhibitor to be added depends on the kind of the compound represented by the general formula (1) used, but is 0.001 to 5% by weight, preferably 0.005% by weight of the polymerizable compound.
5 to 1% by weight, particularly preferably 0.01 to 0.1% by weight
May be added so as to fall within the range. The above-mentioned range of the amount of the polymerization inhibitor is preferable from the viewpoint of suppression of polymerization and economy.

The reaction temperature is not particularly limited, but is preferably in the range of 0 ° C to 500 ° C, and is preferably in the range of 20 ° C to 40 ° C.
The temperature is more preferably in the range of 0 ° C, particularly preferably in the range of 30 ° C to 300 ° C. The reaction time, the type and combination of the raw materials, the catalyst and the organic solvent so that the above reaction is completed,
What is necessary is just to set suitably according to a usage amount etc.

The reaction pressure depends on the combination of the raw material and the reaction temperature, but is not particularly limited, and may be normal pressure (atmospheric pressure) or pressurization.

The reaction system is not particularly limited, and specific examples include a batch system, a semi-batch system, and a continuous system.

The acyloxylation product produced according to the present invention can be obtained by purifying the reaction solution after separating the catalyst when the catalyst is used. The purification means is not particularly limited,
It can be separated and purified by a distillation method, an extraction method, a column chromatography method and the like. These methods may be implemented in combination. Of these, distillation and extraction are particularly preferred.

The raw material and the organic solvent separated in the above purification step can be used again for the reaction. Further, the separated catalyst can be used again for the reaction.

[0066]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 (Preparation of Catalyst A for Acyloxylation Reaction) Activated carbon (1.5% residue on ignition, median diameter: 500%) was placed in a 500 ml four-necked flask equipped with a thermometer, a stirrer, a condenser and a gas inlet tube. 22.1 μm, specific surface area 125
0 m ² / g, cumulative pore volume 0.66 ml / g, wood-based steam activated carbon (average pore diameter 2.3 nm) 50 g,
Under a nitrogen stream, 200 ml of concentrated nitric acid was added dropwise at room temperature over 1 hour, and after completion of the addition, the temperature was raised to the reflux temperature. 5 at reflux
After stirring for an hour, the activated carbon is filtered off and deionized water 30
Washed 4 times with 0 ml. The thus obtained acid-washed activated carbon was added to a 500 ml four-necked flask equipped with a thermometer, a stirrer, a condenser and a gas inlet tube,
After adding 250 ml of a 5N aqueous potassium hydroxide solution under a nitrogen stream, the temperature was raised to the reflux temperature. After stirring for 5 hours under reflux, the activated carbon was filtered off and washed with 300 ml of deionized water four times to prepare alkali-treated activated carbon. (PH at this time was 8.3.) 150 ml of deionized water adjusted to pH 9 with ammonia water was added to a 500 ml beaker, and 9.5 g of the alkali-treated activated carbon obtained above was suspended in the aqueous solution. Turbid, palladium 0.
Aqueous solution of tetraammine palladium chloride containing 5 g 5
0 ml was added with stirring. While maintaining the pH at 9 with aqueous ammonia, the mixture was stirred at 40 ° C for 24 hours to adsorb palladium on activated carbon. Next, 37% formalin aqueous solution 1
0 ml was added, and the mixture was reduced by stirring at 80 ° C. for 2 hours, and then washed with deionized water. The obtained palladium-supported activated carbon was dried to prepare an acyloxylation reaction catalyst A.

A PW2404 type fluorescent X-ray analyzer (PHI
The amount of supported palladium was determined to be 5% by weight by measuring the amount supported by LIPS; hereinafter, referred to as “fluorescent X-ray”. Also, based on the electron micrograph, the particles 20
0 grains are arbitrarily selected, and the average value of the measured grain system is 1.8 n.
m and the maximum grain size was 2.2 nm.

Example 2 (Preparation of Catalyst B for Acyloxylation Reaction) In a 500 ml beaker, 150 ml of deionized water adjusted to pH 9 with aqueous ammonia was added, and Example 1 was added to the aqueous solution.
9.3 alkali-treated activated carbon prepared by the same method as described above.
g was suspended, and 50 ml of an aqueous solution of lithium acetate containing 0.5 g of tetraammine palladium chloride and 0.2 g of potassium was added thereto with stirring. While maintaining the pH at 9 with aqueous ammonia, the mixture was stirred at 40 ° C. for 24 hours to adsorb palladium and lithium on activated carbon. Next, 20 ml of hydrazine was added and the mixture was reduced by stirring at 80 ° C. for 2 hours, and then washed with deionized water. The obtained palladium + lithium-supported activated carbon was dried to prepare an acyloxylation reaction catalyst B.

The amount of supported palladium was determined to be 5% by weight and the amount of supported lithium was determined to be 2% by weight by measuring the amount of the carried X-ray fluorescence. Further, based on the electron micrograph, 200 particles on the carrier were arbitrarily selected, and the average value of the measured grain system was 2.0 nm, and the maximum grain system was 2.2 nm.

Example 3 (Preparation of catalyst C for acyloxylation reaction) In a 500 ml beaker, 150 ml of deionized water adjusted to pH 9 with aqueous ammonia was added, and the aqueous solution of Example 1 was added to the aqueous solution.
9.3 alkali-treated activated carbon prepared by the same method as described above.
g was suspended, and 50 ml of an aqueous solution of tetraammine palladium chloride containing 0.5 g of palladium and sodium acetate containing 0.2 g of sodium were added with stirring. While maintaining the pH at 9 with aqueous ammonia, the mixture was stirred at 40 ° C. for 24 hours to adsorb palladium and sodium on activated carbon. Next, 20 ml of hydrazine was added and the mixture was reduced by stirring at 80 ° C. for 2 hours, and then washed with deionized water. The obtained palladium + sodium-supported activated carbon was dried to prepare an acyloxylation reaction catalyst C.

The amount of palladium supported was 5% by weight, and the amount of sodium supported was 2% by weight.
It was decided. Further, based on the electron micrograph, 200 particles on the carrier were arbitrarily selected, and the average value of the measured grain system was 2.1 nm, and the maximum grain system was 2.3 nm.

Example 4 (Preparation of catalyst D for acyloxylation reaction) In a 500 ml beaker, 150 ml of deionized water was added.
9.3 g of alkali-treated activated carbon prepared in the same manner as in Example 1 was suspended in the aqueous solution, and 0.5 g of palladium was suspended.
50 ml of a 1N hydrochloric acid aqueous solution of tellurium dioxide containing tetraamine palladium chloride containing 0.2 g of tellurium and 0.2 g of tellurium
Was added with stirring. After stirring at 40 ° C. for 24 hours, palladium and tellurium were adsorbed on activated carbon. Next, 37%
After reducing by adding 20 ml of formalin aqueous solution and stirring at 80 ° C. for 2 hours, it was washed with aqueous sodium hydroxide solution and deionized water. The resulting palladium + tellurium-supported activated carbon was dried to prepare an acyloxylation reaction catalyst C.

The amount of palladium carried was determined to be 5% by weight and the amount of tellurium carried was determined to be 2% by weight by measuring the amount of the carried X-ray fluorescence. Further, based on the electron micrograph, 200 particles on the carrier were arbitrarily selected, and the average value of the measured grain system was 2.
0 nm, and the maximum grain size was 2.3 nm.

Example 5 (Preparation of Catalyst E for Acyloxylation Reaction) In a 500 ml beaker, 150 ml of deionized water adjusted to pH 9 with aqueous ammonia was added, and Example 1 was added to the aqueous solution.
9.3 alkali-treated activated carbon prepared by the same method as described above.
The suspension was stirred, and 50 ml of an aqueous solution of bismuth acetate containing tetraammine palladium chloride containing 0.5 g of palladium and bismuth acetate containing 0.2 g of bismuth was added. While maintaining the pH at 9 with aqueous ammonia, the mixture was stirred at 40 ° C. for 24 hours to adsorb palladium and bismuth on activated carbon. Next, 10 ml of a 37% formalin aqueous solution was added,
After reduction by stirring at 80 ° C. for 2 hours, the mixture was washed with deionized water. The obtained palladium + bismuth-supported activated carbon was dried to prepare an acyloxylation reaction catalyst E.

The amount of supported palladium was determined to be 5% by weight, and the amount of supported bismuth was determined to be 2% by weight, by measuring the amount of the carried X-ray fluorescence. Further, based on the electron micrograph, 200 particles on the carrier were arbitrarily selected, and the average value of the measured grain system was 2.2 nm, and the maximum grain system was 2.6 nm.

Example 6 (Preparation of catalyst F for acyloxylation reaction) In a 500 ml beaker, 150 ml of deionized water was added.
9.3 g of alkali-treated activated carbon prepared in the same manner as in Example 1 was suspended in the aqueous solution, and 0.5 g of palladium was suspended.
, 50 ml of a 1N aqueous solution of tellurium dioxide containing 0.1 g of sodium and tellurium dioxide containing 0.1 g of tellurium were added under stirring. After stirring at 40 ° C. for 24 hours, palladium, sodium and tellurium were adsorbed on activated carbon. Next, 37
A 20% aqueous solution of formalin was added, and the mixture was reduced by stirring at 80 ° C. for 2 hours, and then washed with an aqueous sodium hydroxide solution and deionized water. The obtained palladium + tellurium-supported activated carbon was dried to prepare an acyloxylation reaction catalyst F.

The amount of palladium supported was 5% by weight, and the amount of sodium supported was 1% by weight.
And the tellurium loading was determined to be 1% by weight. Further, based on the electron micrograph, 200 particles on the carrier were arbitrarily selected, and the average value of the measured grain system was 2.8 nm, and the maximum grain system was 3.1 nm.

Example 7 (Preparation of catalyst G for acyloxylation reaction) In a 500 ml beaker, 150 ml of deionized water adjusted to pH 9 with aqueous ammonia was added, and the aqueous solution of Example 1 was added to the aqueous solution.
9.3 alkali-treated activated carbon prepared by the same method as described above.
The suspension was added with stirring, and 50 ml of an aqueous solution of tetraammine palladium chloride containing 0.5 g of palladium, potassium acetate containing 0.1 g of potassium, and bismuth chloride containing 0.1 g of bismuth were added. PH 9 with ammonia water
, And the mixture was stirred at 40 ° C for 24 hours to adsorb palladium, potassium and bismuth on activated carbon.
Next, 15 ml of 37% formalin aqueous solution was added,
After reduction by stirring at 2 ° C. for 2 hours, the mixture was washed with deionized water. The obtained palladium + potassium +
By drying the bismuth-supported activated carbon, an acyloxylation reaction catalyst G was prepared.

The amount of palladium carried was determined to be 5% by weight, the amount of potassium carried was 1% by weight, and the amount of bismuth carried was 1% by weight. Further, based on the electron micrograph, 200 particles on the carrier were arbitrarily selected, and the average value of the measured grain system was 2.7 nm, and the maximum grain system was 3.0 nm.

Example 8 (Preparation of catalyst H for acyloxylation reaction) In a 500 ml beaker, 150 ml of deionized water adjusted to pH 9 with aqueous ammonia was added, and Example 1 was added to the aqueous solution.
9.3 alkali-treated activated carbon prepared by the same method as described above.
g of ammonium chloride containing 0.5 g of palladium, lithium acetate containing 0.1 g of lithium, and antimony chloride containing 0.1 g of antimony (I
50 ml of the aqueous solution of II) was added with stirring. While maintaining the pH at 9 with aqueous ammonia, the mixture was stirred at 40 ° C. for 24 hours,
Palladium, lithium and antimony were adsorbed on activated carbon. Next, 30 ml of formic acid was added, the mixture was reduced by stirring at 60 ° C. for 2 hours, and then washed with deionized water. The obtained palladium + lithium + antimony-supporting activated carbon was dried to prepare an acyloxylation reaction catalyst H.

The amount of the carried palladium was determined to be 5% by weight, the amount of the supported lithium was 1% by weight, and the amount of the supported antimony was 1% by weight. Also, based on the electron micrograph, 200 particles on the carrier were arbitrarily selected, and the average value of the measured grain system was 3.1 nm, and the maximum grain system was 3.5 nm.

Example 9 (Reaction Example 1 of Toluene and Methacrylic Acid) In a 100 ml Hastelloy C autoclave equipped with a thermometer, a stirrer, a pressure gauge, and a gas introduction tube, 36.9 g of toluene and 17.9 g of methacrylic acid were added. 2 g, phenothiazine 17 mg, and catalyst A2.
After adding 0 g, the inside of the autoclave was completely replaced with a mixed gas of 10 mol% oxygen and 90 mol% nitrogen. 10
After adding 50 atm of a mixed gas of mol% oxygen-90 mol% nitrogen, the mixture was gradually heated while mixing and stirring, and the internal temperature was set to 125 ° C.
And

Next, the reaction was completed by stirring for 8 hours while adding oxygen so that the pressure at 125 ° C. was maintained at 60 atm.

After completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was subjected to GC-1700 type gas chromatography (manufactured by Shimadzu Corporation; hereinafter referred to as "GC").
As a result, the yield of the target benzyl methacrylate was 65 mol%. At this time, SPS400
The elution of Pd into the reaction system measured by ICP emission spectroscopy using a 0-type plasma emission spectrometer (manufactured by Seiko Denshi Kogyo KK; hereinafter referred to as “emission spectroscopy”) was 2 ppm.

Example 10 (Reaction Example 2 of Toluene and Methacrylic Acid) The same operation as in Example 9 was carried out except that the catalyst was changed to 2.0 g of an acyloxylation catalyst B.

After completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was measured by GC. As a result, the yield of the target benzyl methacrylate was 81 mol%. At this time, the elution of Pd into the reaction system measured by ICP emission spectroscopy was 3 ppm.

Example 11 (Example 3 of reaction between toluene and methacrylic acid) The same operation as in Example 9 was carried out except that the catalyst was changed to 2.0 g of an acyloxylation reaction catalyst D.

After completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was measured by GC. As a result, the yield of the target benzyl methacrylate was 73 mol%. At this time, elution of Pd into the reaction system measured by ICP emission spectroscopy was not detected.

Example 12 (Reaction Example 4 of Toluene and Methacrylic Acid) The same operation as in Example 9 was performed except that the catalyst was changed to 2.0 g of an acyloxylation reaction catalyst F.

After completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was measured by GC. As a result, the target yield of benzyl methacrylate was 75 mol%. At this time, elution of Pd into the reaction system measured by ICP emission spectroscopy was not detected.

Example 13 (Example of reaction between toluene and acrylic acid) The same operation as in Example 9 was performed except that 14.4 g of acrylic acid was used instead of methacrylic acid.

After completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was measured by GC. As a result, the yield of the target benzyl acrylate was 64 mol%.
At this time, Pd was added to the reaction system measured by ICP emission spectroscopy.
Was eluted at 4 ppm.

Example 14 (Reaction Example 1 of Methyl Methacrylate and Acetic Acid) In a 100 ml Hastelloy C autoclave equipped with a thermometer, a stirrer, a pressure gauge, and a gas inlet tube, 20.0 g of methyl methacrylate, acetic acid 12.0 g, hydroquinone 10 mg, and catalyst A2.
After adding 0 g, the inside of the autoclave was completely replaced with a mixed gas of 10 mol% oxygen and 90 mol% nitrogen. 10
After adding 50 atm of a mixed gas of mol% oxygen-90 mol% nitrogen, the mixture was gradually heated while mixing and stirring, and the internal temperature was set to 120 ° C.
And

Next, the reaction was completed by stirring for 8 hours while adding oxygen so as to maintain the pressure at 120 ° C. at 60 atm.

After completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was measured by GC. As a result, the yield of the intended α-acetoxymethyl acrylate was 6%.
It was 6 mol%. At this time, the elution of Pd into the reaction system measured by ICP emission spectroscopy was 9 ppm.

Example 15 (Example 2 of reaction between methyl methacrylate and acetic acid) Example 15 was repeated except that 1.0 g of lithium acetate was further added.
The same operation as in 14 was performed.

After completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was measured by GC. As a result, the yield of the target methyl α-acetoxymethyl acrylate was 8%.
It was 6 mol%. At this time, elution of Pd into the reaction system measured by ICP emission spectroscopy was 8 ppm.

Example 16 (Example 3 of reaction between methyl methacrylate and acetic acid) The same operation as in Example 14 was performed except that the catalyst was changed to 2.0 g of an acyloxylation reaction catalyst C.

After completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was measured by GC. As a result, the yield of the target α-acetoxymethyl acrylate was 7%.
It was 6 mol%. At this time, the elution of Pd into the reaction system measured by ICP emission spectroscopy was 2 ppm.

Example 17 (Reaction Example 4 of Methyl Methacrylate and Acetic Acid) The same operation as in Example 14 was performed, except that the catalyst was changed to 2.0 g of an acyloxylation reaction catalyst E.

After completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was measured by GC. As a result, the yield of the target methyl α-acetoxymethyl acrylate was 7%.
It was 1 mol%. At this time, elution of Pd into the reaction system measured by ICP emission spectroscopy was not detected.

Example 18 (Reaction Example 5 of Methyl Methacrylate and Acetic Acid) The same operation as in Example 14 was carried out except that the catalyst used was 2.0 g of an acyloxylation catalyst G.

After completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was measured by GC. As a result, the yield of the target α-acetoxymethyl acrylate was 7%.
It was 4 mol%. At this time, elution of Pd into the reaction system measured by ICP emission spectroscopy was not detected.

Example 19 (Example of reaction between para-xylene and methacrylic acid) In a 100 ml Hastelloy C autoclave equipped with a thermometer, a stirrer, a pressure gauge, and a gas inlet tube, p was added.
-Xylene 10.6 g, methacrylic acid 17.2 g, phenothiazine 17 mg, and catalyst H for acyloxylation reaction
After adding 2.0 g, 10 mol% in the autoclave was added.
It was completely replaced by a mixed gas of oxygen and 90 mol% of nitrogen.
After adding 50 atm of a mixed gas of 10 mol% oxygen-90 mol% nitrogen, the mixture was gradually heated with mixing and stirring to raise the internal temperature to 14%.
5 ° C.

Next, the reaction was completed by stirring for 15 hours while adding oxygen so that the pressure at 145 ° C. was maintained at 65 atm.

After completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was measured by GC. As a result, the yield of 4-methylbenzyl methacrylate was 51 mol%.
The yield of 1,4-dimethacryloxymethylbenzene is 22
Mole%. At this time, elution of Pd into the reaction system measured by ICP emission spectroscopy was not detected.

Example 20 (Example of reaction between propylene and methacrylic acid) In a 100 ml Hastelloy C autoclave equipped with a thermometer, a stirrer, a pressure gauge, and a gas inlet tube, 17.2 g of methacrylic acid, 17 mg of phenothiazine, and After adding 2.0 g of the acyloxylation reaction catalyst F, the inside of the autoclave was completely replaced with a mixed gas of 10 mol% oxygen-90 mol% nitrogen. 4.2 g of propylene there
Was added to the mixture, and the mixture was pressurized to 30 atm with a mixed gas of 10 mol% oxygen and 90 mol% nitrogen.

Next, the reaction was completed by stirring for 8 hours while adding oxygen so that the pressure at 120 ° C. was maintained at 65 atm.

After completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was measured by GC. As a result, the yield of the target allyl methacrylate was 51 mol%.
At this time, Pd was added to the reaction system measured by ICP emission spectroscopy.
Was not detected.

Example 21 (Reaction Example 1 of Cyclohexene and Methacrylic Acid) 16.4 g of cyclohexene and 17.4 g of methacrylic acid were placed in a 100 ml Hastelloy C autoclave equipped with a thermometer, a stirrer, a pressure gauge, and a gas inlet tube. After adding 2 g, 17 mg of methoxyhydroquinone, and 2.0 g of an acyloxylation reaction catalyst D, 1 g
It was completely replaced by a 0 mol% oxygen-90 mol% nitrogen mixed gas. 10 mol% oxygen-90 mol% nitrogen mixed gas
After adding 0 atm, the mixture was gradually heated with mixing and stirring, and the internal temperature was set to 125 ° C.

Next, the reaction was completed by stirring for 8 hours while adding oxygen so that the pressure at 125 ° C. was maintained at 60 atm.

After completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was measured by GC. As a result, the yield of cyclohexene methacrylate was 71 mol%. At this time, elution of Pd into the reaction system measured by ICP emission spectroscopy was not detected.

Example 22 (Example 2 of reaction between cyclohexene and methacrylic acid) The same operation as in Example 21 was carried out except that the catalyst was changed to 2.0 g of an acyloxylation catalyst G.

After completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was measured by GC. As a result, the yield of cyclohexene methacrylate was 74 mol%. At this time, elution of Pd into the reaction system measured by ICP emission spectroscopy was not detected.

Example 23 (Reaction Example 1 of Toluene and Acetic Acid) In a 100 ml Hastelloy C autoclave equipped with a thermometer, a stirrer, a pressure gauge, and a gas inlet tube, 36.9 g of toluene, 12.0 g of acetic acid, After adding 2.0 g of the catalyst for acylation reaction B, the inside of the autoclave was completely replaced with a mixed gas of 10 mol% oxygen-90 mol% nitrogen. After adding 50 atm of a 10 mol% oxygen-90 mol% nitrogen mixed gas, the mixture was gradually heated while mixing and stirring to adjust the internal temperature to 145 ° C.

Next, the reaction was completed by stirring for 8 hours while adding oxygen so that the pressure at 145 ° C. was maintained at 70 atm.

After the completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was measured by GC. As a result, the yield of benzyl acetate was 90 mol%. At this time, the elution of Pd into the reaction system measured by ICP emission spectroscopy was 7 ppm.
Met.

Example 24 (Reaction Example 2 of Toluene and Acetic Acid) The same operation as in Example 23 was performed, except that the catalyst was changed to 2.0 g of an acyloxylation catalyst H.

After completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was measured by GC. As a result, the yield of the target benzyl acetate was 86 mol%. At this time, elution of Pd into the reaction system measured by ICP emission spectroscopy was not detected.

Example 25 (Reaction Example 1 of Paraxylene with Acetic Acid) A 100 ml Hastelloy C autoclave equipped with a thermometer, a stirrer, a pressure gauge, and a gas inlet tube was charged with p.
After adding 10.6 g of xylene, 12.0 g of acetic acid, and 2.0 g of catalyst E for acylation reaction, the inside of the autoclave was completely replaced with a mixed gas of 10 mol% oxygen and 90 mol% nitrogen. After adding 50 atm of a 10 mol% oxygen-90 mol% nitrogen mixed gas, the mixture was gradually heated while mixing and stirring to adjust the internal temperature to 145 ° C.

Then, the reaction was completed by stirring for 8 hours while adding oxygen so that the pressure at 145 ° C. was maintained at 70 atm.

After completion of the reaction, the catalyst was removed from the reaction solution by filtration, and the filtrate was measured by GC.
-The yield of xylene monoacetate is 25 mol%,
The yield of 1,4-xylene diacetate was 60 mol%. At this time, elution of Pd into the reaction system measured by ICP emission spectroscopy was not detected.

[0124]

According to the present invention, the activity does not sharply decrease in a short time, the elution of the metal catalyst active component can be suppressed, and no co-catalyst is required. An acyloxylation reaction can advantageously be carried out.

The acyloxylation product obtained by the present invention can be used in a wide range of fragrances, raw materials for medicines and agrochemicals, organic synthesis intermediates, and polymerizable materials.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C07C 67/035 C07C 67/055 67/055 67/313 67/313 69/157 69/157 69/54 Z 69/54 B C07B 61/00 300 // C07B 61/00 300 B01J 23/64 101Z

Claims (5)

[Claims] 1. A catalyst for an acyloxylation reaction in which a carrier is supported on a carrier, wherein the carrier comprises at least one element belonging to Groups 8 to 11 of the periodic table and has a particle size of 10 nm or less. A catalyst for an acyloxylation reaction containing particles. 2. The catalyst for an acyloxylation reaction according to claim 1, wherein the catalyst contains at least one element from Groups 1 to 2 of the periodic table. 3. The catalyst for an acyloxylation reaction according to claim 1, wherein the catalyst contains at least one element of Groups 12 to 16 of the periodic table or tellurium. 4. In the presence of the catalyst according to claim 1, a compound represented by the following general formula (1): CHR ¹ R ² —X (wherein R ¹ and R ² are each independently hydrogen. X represents an atom or an organic residue, and X represents an aromatic hydrocarbon residue which may have a substituent or an olefin residue which may have a substituent); A carboxylic acid represented by the formula (2): R ³ —COOH (wherein R ³ represents a hydrogen atom or an organic residue) is reacted with oxygen to obtain a compound represented by the following general formula (3): R ³ —COO -CR ¹ R ² -X (wherein R ¹ , R ² and R ³ each independently represent a hydrogen atom or an organic residue, and X represents an aromatic hydrocarbon residue which may have a substituent. Or an olefin residue which may have a substituent). Reaction method. 5. The acyloxylation reaction method according to claim 5, wherein the reaction is carried out in the presence of at least one substance selected from the group consisting of a basic compound, a nitrogen-containing compound and a phosphorus-containing compound.