JP2001017864A - Epoxidation catalyst and production of epoxide of olefin using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable recovery/reutilization and the production only of epoxide by reacting a specific activated carbon or an inorg. solid and a silane coupling agent and subsequently reacting a specific amine with the reaction product to obtain a surface-treated carrier and compounding the carrier with a salt obtained by reacting a specific atom and heteropoly-acid. SOLUTION: Activated carbon or an inorg. solid having a functional group capable of being reacted with a silane coupling agent is reacted with the silane coupling agent having an alkyl group substituted with a functional group capable of being reacted with a tertiary amine to form a quaternary ammonium salt. Thereafter, a tertiary amine or cyclic amine represented by formula (wherein one of R1-R3 is a 8-18C alkyl group and the remaining groups of R1-R3 are a 1-18C alkyl group or a benzyl group) is reacted with the reaction product to obtain a surface-treated carrier. A heteropoly-acid having a group V atom and a tungsten atom in its molecule is reacted to obtain a salt and the carrier is combined with the salt to obtain an epoxidation catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxidation catalyst and a method for epoxidizing olefins using the catalyst. More specifically, the present invention relates to a method for producing an epoxy resin raw material and an organic chemical The present invention relates to an epoxidation catalyst used for producing an epoxy compound useful as a synthetic intermediate of a drug, a pharmaceutical, a pesticide, and the like, and a method for epoxidizing olefins using the catalyst.

[0002]

2. Description of the Related Art A method for epoxidizing olefins using hydrogen peroxide is known. This method generally has a problem that both the conversion of olefin and the selectivity to epoxide are low. The reason why the conversion is low is that hydrogen peroxide remains unreacted in a low-temperature reaction, decomposes at a high temperature to generate oxygen, and is not effectively consumed in the reaction. The low selectivity to the epoxide may be caused by water introduced into the reaction system together with hydrogen peroxide and water generated by the reaction, and by-produced polyol by hydrolysis.

[0003] In order to solve the above problems, "Chem. Rev.," [No. 89, No. 43]
Ikko (1989)] proposes a method using a specific catalyst. Also, "Journal of Organic Chemistry (J. Org. Chem.,)"
No. 3587 Tribute (1988) "and JP-A-62-23
No. 4550 proposes a method in which a heteropolyacid having tungsten or molybdenum is used in combination with an interlayer transfer catalyst.

[0004]

However, in the above-mentioned method for producing an epoxide, the catalyst used in (1) the reaction is disposable, and the effluent containing heavy metals needs to be detoxified. As a solvent, chloroform,
Use highly toxic halogen solvents such as 1,2-dichloromethane; (3) For most olefins, selectivity of epoxide is more than 98%, but for epoxidation of allyl alcohols, it is less than 98%. It has a fatal disadvantage from the viewpoint of protection of the global environment and is not preferable from an industrial point of view.

[0005] The problem to be solved by the present invention is to use, as a reaction solvent, water or a low-toxic organic solvent which is environmentally friendly, the catalyst used in the reaction can be recovered and reused, and only the epoxide can be selectively used. It is to provide a method of manufacturing the.

[0006]

The present inventors have conducted intensive studies to solve the above-mentioned problems. As a result, (1) (a) activated carbon or inorganic carbon having a functional group capable of reacting with a silane coupling agent; After reacting the solid with (b) a silane coupling agent having an alkyl group substituted with a functional group capable of forming a quaternary ammonium salt by reacting with a tertiary amine, (c) a general formula (1)

[0007]

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(Wherein at least one of R ¹ , R ² and R ³ is an alkyl group having 8 to 18 carbon atoms, and the remaining groups are an alkyl group having 1 to 18 carbon atoms or a benzyl group) The surface-treated carrier obtained by reacting a tertiary amine or a cyclic amine represented by the formula (1) with (2) a heteropolyacid having a group V atom and a tungsten atom in the periodic table in its molecule. By using the resulting salt as a catalyst, an epoxide alone can be selectively produced by reacting olefins with hydrogen peroxide in water or an organic solvent, and it has been found that the catalyst can be easily recovered and reused. Thus, the present invention has been completed.

That is, the present invention provides (I) (1) (a) activated carbon or an inorganic solid having a functional group capable of reacting with a silane coupling agent, and (b) a tertiary amine. After reacting with a silane coupling agent having an alkyl group substituted with a functional group capable of forming a quaternary ammonium salt by reacting, (c) a tertiary amine or a cyclic compound represented by the above general formula (1) The present invention provides an epoxidation catalyst comprising a salt obtained by reacting a carrier surface-treated by reacting an amine with (2) a heteropolyacid having a group V atom and a tungsten atom in its molecule.

In order to solve the above problems, the present invention provides (II) a method for producing an epoxidized olefin by reacting an olefin with hydrogen peroxide in water or an organic solvent in the presence of a catalyst. , As the catalyst (I)
And a method for producing an epoxidized product using the epoxidation catalyst described in (1).

[0011]

DETAILED DESCRIPTION OF THE INVENTION The catalyst of the present invention comprises (1) (a) activated carbon or an inorganic solid having a functional group capable of reacting with a silane coupling agent, and (b) a quaternary ammonium by reacting with a tertiary amine. After reacting with a silane coupling agent having an alkyl group substituted with a functional group capable of forming a salt, (c) reacting with a tertiary amine or a cyclic amine represented by the above general formula (1) to form a surface A salt obtained by reacting the treated carrier with (2) a heteropolyacid having a group V atom of the periodic table atom and a tungsten atom in the molecule. The method for preparing the catalyst is not particularly limited, but is usually prepared from a silane coupling agent and a tertiary amine in a suitable solvent in advance (hereinafter, this solvent is referred to as a catalyst preparation solvent). A quaternary ammonium salt (hereinafter, this compound is referred to as a quaternary surface treating agent) is prepared, and then an activated carbon or an inorganic solid having a functional group capable of reacting with a silane coupling agent is added thereto. After vigorous stirring at a predetermined temperature, the solvent is distilled off, a heteropolyacid dissolved in a catalyst preparation solvent is further added, and after stirring at a predetermined temperature, the solvent is distilled off and dried. Can be

The inorganic solid having a functional group capable of reacting with the surface treating agent is not particularly limited as long as it can support the heteropolyacid (salt) without decomposition. Examples of such inorganic solids include alumina, silica gel, molecular sieves, florisil, and celite. Among these, silica gel and alumina are preferred. One of these inorganic solids may be used alone, or two or more thereof may be used in combination.

The silane coupling agent to be reacted with activated carbon or an inorganic solid is a silane coupling agent having an alkyl group substituted with a functional group capable of forming a quaternary ammonium salt by reacting with a tertiary amine. Such silane coupling agents include, for example, chloromethyltrimethoxysilane, bromomethyltrimethoxysilane, iodomethyltrimethoxysilane, chloromethyltriethoxysilane, bromomethyltriethoxysilane, iodomethyltriethoxysilane, chloropropyl Trimethoxysilane, bromopropyltrimethoxysilane, iodopropyltrimethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, iodopropyltriethoxysilane, acetoxymethyltrimethoxysilane, acetoxymethyltriethoxysilane, acetoxypropyltrimethoxy Silane, acetoxypropyltriethoxysilane, and the like. Of these, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, chloropropyltrimethoxysilane, and chloropropyltriethoxysilane are recommended because of the ease of preparation and availability of quaternary ammonium salts.

The tertiary amine used in the reaction with the silane coupling agent having an alkyl group substituted with a functional group capable of forming a quaternary ammonium salt is a tertiary amine represented by the above general formula (1) or a cyclic amine It is. Of these, cyclic amines are preferred.

Examples of the tertiary amine represented by the general formula (1) include dioctylmethylamine, dilauryldimethylamine, lauryldimethylamine, stearyldimethylamine, laurylmethylbenzylamine, and stearyldimethylamine.

As the cyclic amine compound, a pyridine ring,
Tertiary amine compounds having a nitrogen-containing heterocyclic ring such as a picoline ring, a quinoline ring, an imidazoline ring and a morpholine ring are exemplified, and a tertiary amine compound having a quinoline ring is preferred. As the tertiary amine compound having a nitrogen-containing heterocyclic ring, an alkyl group such as quinoline, 2-methylquinoline and 3-ethylquinoline having 1 to 10 carbon atoms (hereinafter, the alkyl group in this section is the same). ), Alkylquinoline, pyridine, alkylpyridine, picoline, alkylpicoline, isoquinoline, alkylisoquinoline, imidazole, alkylimidazole, morpholine, alkylmorpholine, and the like. Among these,
Quinoline, alkylquinoline, isoquinoline, alkylisoquinoline are preferred, and quinoline and alkylquinoline are particularly preferred.

Examples of the combination of a silane coupling agent to be reacted with activated carbon or an inorganic solid and a cyclic amine include a combination of chloromethyltrimethoxysilane and quinoline, a combination of chloromethyltriethoxysilane and quinoline, and a combination of chloropropyltrimethoxysilane. In combination with quinoline, a combination of chloropropyltriethoxysilane and quinoline, a combination of chloromethyltrimethoxysilane and 2-methylquinoline, a combination of chloromethyltriethoxysilane and 2-methylquinoline are preferable, among these, Particularly preferred is a combination of chloromethyltrimethoxysilane and quinoline, and a combination of chloromethyltriethoxysilane and quinoline.

The loading ratio of the silane coupling agent having a quaternary ammonium salt obtained by reacting the activated carbon or the inorganic solid with the cyclic amine with the silane coupling agent ranges from 5 to 500 mmol per 100 g of the carrier. Is preferably in the range of 20 to 400 mmol, more preferably in the range of 50 to 200 mmol.

In the present invention, a mixture of a silane coupling agent having an alkyl group substituted with a functional group capable of forming a quaternary ammonium salt by reacting with a tertiary amine and a silane coupling agent having lipophilicity is used. The use of a catalyst supported on activated carbon or an inorganic solid is particularly effective for low-reactivity olefins.

Examples of the lipophilic silane coupling agent include phenyltrimethoxysilane, diphenyldiethoxysilane, triphenylethoxysilane, para-chlorophenyltrimethoxysilane, benzyltriethoxysilane, phenylmethyldiethoxysilane, and phenyldimethyl. Dimethoxysilane, and the like.
Of these, phenyltrimethoxysilane, diphenyldiethoxysilane, and triphenylethoxysilane are preferred, and triphenylethoxysilane is particularly preferred. These lipophilic silane coupling agents are:
One type may be used alone, or two or more types may be used in combination.

The fourth carbon supported on the above-mentioned activated carbon or inorganic solid
The mixing ratio of the silane coupling agent having lipophilicity to the quaternary ammonium silane compound is 0.5 to 200 parts by weight with respect to 100 parts by weight of the silane coupling agent having a quaternary ammonium salt supported on activated carbon or an inorganic solid. The range is preferred, the range of 5 to 150 parts by weight is particularly preferred, and the range of 10 to 60 parts by weight is more preferred.

Examples of the heteropolyacid having a group V atom and a tungsten atom in the molecule to be reacted with the carrier obtained by the surface treatment include [IV Kozhevnikov, Applied Catalysis (Applied Catalysis);
l. Cat., No. 5, 135-Kitsu (1983)] and the like, for example, phosphonotungstic acid (phosphotungstic acid, 12-tungstophosphoric acid), arsenotungstic acid , And the like. Among these, phosphonotungstic acid is particularly preferred. The heteropolyacid having a group V atom of the periodic table and a tungsten atom in these molecules may be used alone or in combination of two or more.

The amount of the heteropolyacid added to the quaternary ammonium silane compound supported on the activated carbon or the inorganic solid is usually about 1/3 mol per 1 mol of the quaternary ammonium silane compound supported on the activated carbon or the inorganic solid. A slightly larger heteropoly acid may be used.

The predetermined temperature at the time of stirring for preparing the catalyst of the present invention is about room temperature, but is not limited to this, and is arbitrary as long as it is lower than the boiling point of the catalyst preparation solvent used. Also, there is no particular limitation on the stirring time,
Usually, it is about 1 to 10 hours. Further, the drying temperature is not particularly limited as long as it is a temperature at which the used solvent for catalyst preparation can be removed, but if the drying temperature is too high, the activity of the catalyst may be reduced or deactivated. It is preferable that the temperature is slightly higher than the boiling point of the solvent for preparing the catalyst. The drying step may be performed not only under normal pressure but also under reduced pressure, and may be performed under an atmosphere of an inert gas such as argon other than air or nitrogen.

The olefins applicable to the production method of the present invention include those represented by the general formula (2)

[0026]

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(Wherein R ¹ ′, R ² ′, R ³ ′ and R ⁴ ′ represent a monovalent hydrocarbon group which may have a double bond, and R ¹ ′ and R ² ′ Or R ³ ′ and R ⁴ ′ together represent a divalent hydrocarbon group which may have a double bond, or R ¹ ′ and R ³ ′ are
² ′ and R ⁴ ′ together represent a divalent hydrocarbon group which may have a double bond. )).

In the general formula (2), R ¹ ′, R ² ′, R
³ ′ and R ⁴ ′ are a monovalent hydrocarbon group which may have a double bond. Examples of the hydrocarbon group include a linear or branched alkyl group having 1 to 30 carbon atoms, Aliphatic hydrocarbon group such as alkenyl group; alicyclic hydrocarbon group having 3 to 12 carbon atoms which may be branched, such as cycloalkyl group, cycloalkenyl group and polycycloalkyl group; aryl group and alkaliol group Aromatic hydrocarbon groups such as
And the like. Examples of the divalent hydrocarbon group which may have a double bond represented by R ¹ ′ and R ² ′ or R ³ ′ and R ⁴ ′ together include, for example, carbon Examples thereof include an alkylene group and an alkenylene group having 3 to 11 atoms. Further, R ¹ ′ and R ³ ′ or R
Examples of the divalent hydrocarbon group which may have a double bond represented by ² ′ and R ⁴ ′ together include an alkylene group having 1 to 10 carbon atoms, an alkenylene group, and the like. No.

The olefins represented by the general formula (2) can be classified into aliphatic olefinically unsaturated hydrocarbons, aromatic olefinic hydrocarbons, alicyclic olefinic hydrocarbons and the like.

Examples of the aliphatic olefinically unsaturated hydrocarbon include ethylene, propylene, butene, pentene, 1-hexene, 3-hexene, 1-heptene, 1-
Octene, 1-nonene, 1-undecene, 1-dodecene, 1-tridecene, 1-etradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-icosene, diisobutylene, propylene Alkenes such as trimers or tetramers of
Terpenes such as myrcene; polyenes such as polybutadiene; and the like.

Examples of the aromatic olefinic hydrocarbon include styrene, α-methylstyrene, divinylbenzene, stilbene and the like.

Examples of the alicyclic olefinic hydrocarbon include cyclopentene, cyclohexene, 1-phenyl-1-cyclohexene, 1-methyl-1-cyclohexene, cycloheptene, cyclooctene, cyclodecene,
Cycloalkenes or cyclopolyenes such as cyclopentadiene, cyclooctadiene, cyclododecatriene; dicycloalkapolyenes such as dicyclopentadiene, tetrahydroindene; methylenecyclopropane;
Alkylenecycloalkanes such as methylenecyclopentane and methylenecyclohexene; vinylcycloalkenes such as vinylcyclohexene; cyclic terpenes such as α-limonene, pyrene and camphene; norbornene compounds such as norbornene, methylnorbornene, ethylnorbornene, vinylnorbornene and ethylidene norbornene , And the like.

The olefins applicable to the production method of the present invention are not limited to the compounds exemplified above. The olefins exemplified above can also be used as a mixture of two or more. Another feature of the present invention is that an epoxide which is very unstable to acids, such as an epoxide of 1-phenyl-1-cyclohexene, can be selectively synthesized.

The hydrogen peroxide used in the production method of the present invention may be a conventional one, and an aqueous solution having a concentration of usually 3 to 70% by weight can be used. When hydrogen peroxide having a concentration of 35% or more is used, the reaction time can be reduced. However, since the selectivity of the epoxide decreases due to a side reaction, a material having a concentration of 35% or less that is easy to handle is preferably used. It is preferred to use When using hydrogen peroxide having a concentration of 35% or more, the epoxide can be selectively synthesized by lowering the reaction temperature and lengthening the reaction time. As described above, one of the features of the present invention is that the reaction proceeds more efficiently by using hydrogen peroxide having a concentration of 35% or less as compared with the conventional method.

The ratio of the olefins to hydrogen peroxide may be equimolar, but one of the raw materials may be too small or too large. For example, the usage ratio of hydrogen peroxide per mole of olefin is preferably in the range of 0.1 to 5 moles, and particularly preferably in the range of 0.7 to 2 moles.

The amount of the catalyst used is preferably in the range of 0.0005 to 0.5 mol per mol of olefin,
The range of 001 to 0.1 mol is particularly preferred, and 0.004 to 0.1 mol.
The range of -0.05 mol is more preferred.

The solvent used in the production method of the present invention is
Although it is water or an organic solvent, regarding the reactivity of olefin, a system using an organic solvent as a reaction solvent is a little higher in reactivity, and from the viewpoint of protecting the global environment, a system using water as a reaction solvent is recommended. You. The amount of water or organic solvent used is arbitrary, but is usually 100 to 50 per mol of olefin.
00cm is about ^3.

It is necessary to use an organic solvent which is as inert as possible to the reactants (olefins, hydrogen peroxide) and the produced epoxide. As organic solvents,
For example, C1-C6 first, second, and the like, such as methanol, ethanol, normal or isopropanol, tertiary butanol, amyl alcohol, and cyclohexanol,
Tertiary monohydric alcohols; polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; oligomers of ethylene oxide or propylene oxide such as diethylene glycol, triethylene glycol and dipropylene glycol, dimethoxyethylene glycol, diethoxyethylene glycol, dimethoxy Polyhydric alcohol derivatives such as ethers of oligomers of ethylene oxide or propylene oxide such as diethylene glycol; ethers such as ethyl ether, isopropyl ether, dioxane and tetrahydrofuran; alcohols such as ethyl acetate; formic acid esters or acetate esters of polyhydric alcohols; Esters: acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl Propyl ketone, cyclohexanone, such as ketones acetylacetone;

Nitrogen compounds such as dimethylformamide and nitromethane; phosphorus compounds such as triethyl phosphate, trioctyl phosphate and phosphate esters such as diethylhexyl phosphate; halogenated hydrocarbons such as chloroform, dichloromethane and ethylene dichloride; normal hexane , Normal heptane; aliphatic hydrocarbons; toluene, xylene; aromatic hydrocarbons; cyclohexane;
From among alicyclic hydrocarbons such as cyclopentane, etc.,
Those which are as inert as possible to the reactants and epoxides are mentioned. Among them, aliphatic hydrocarbons, aromatic hydrocarbons and alicyclic hydrocarbons, which are non-hydrophilic solvents, are preferred, and aromatic hydrocarbons are particularly preferred. These solvents may be used alone or in combination of two or more.

The production method of the present invention is desirably performed in an oxygen-containing gas atmosphere or an inert gas atmosphere. However, when the reaction scale is large, there is a danger of explosion in the oxygen-containing gas atmosphere. In this case, it is preferable that the treatment be performed in an inert gas atmosphere.

The order in which the raw materials such as olefins, catalyst, reaction solvent, hydrogen peroxide and the like are charged into the reaction tank (order of charging) is arbitrary, and they may be charged all at once.
When epoxidation of olefins having low reactivity is performed, the reaction can be efficiently advanced by adopting a method of dropping olefins into a mixture of a catalyst, a reaction solvent and hydrogen peroxide. .

[0042] The reaction temperature is preferably in the range of 0 to 120 ° C, particularly preferably in the range of 20 to 110 ° C. When the reaction temperature is higher than 110 ° C., self-decomposition of hydrogen peroxide is remarkable, and the selectivity of epoxide tends to decrease. If the reaction temperature is lower than 0 ° C., the reaction tends to be extremely slow. The reaction time can be variously changed depending on the concentration of the catalyst, solvent, olefin and hydrogen peroxide used, but is usually in the range of several minutes to 24 hours. After the reaction, after separating the catalyst by filtration, water and the solvent are removed by means such as extraction or / and distillation to obtain the desired epoxide. The catalyst separated by filtration can be repeatedly used by washing or / and drying.

[0043]

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

(Example 1) Capacity 30 cm^Three Round bottom flask
In addition, quinoline 0.387 g (3 mmol), chloromethy
0.512 g (3 mmol) of rutrimethoxysilane and
Petroleum ether 5cm ^Three And in a hot water bath at 70 ° C in a nitrogen atmosphere.
The mixture was stirred vigorously for 5 hours under an atmosphere. After stirring, dry
Knoll 5cm^Three And 3 g of silica gel, and at the same temperature
Stirred vigorously for 1 hour. After stirring, cool the reaction solution to room temperature.
Rejected. Then dry ethanol 5cm^Three 1 dissolved in
2.88 g (1 mmol) of 2-tungstophosphoric acid was added.
Then, the mixture was vigorously stirred at room temperature for 5 hours under a nitrogen atmosphere. Stirring
After completion, the solvent was distilled off at 50 ° C. under reduced pressure (133 Pa).
Was. Then, under reduced pressure (133 Pa), under nitrogen atmosphere for 5 hours
After drying, the catalyst was prepared. After drying,
The medium was stored in a desiccator.

To a round bottom flask having a capacity of 10 cm ³ , 0.021 mmol of the catalyst, 1 cm ^{3 of} distilled water, 0.246 g (3 mmol) of cyclohexene and 0.68 g (6 mmol) of 30% hydrogen peroxide were added. Atmosphere, 80
Stir vigorously at 7 ° C. for 7 hours. After the completion of the reaction, the reaction solution was cooled to room temperature. Thereafter, the mixture was filtered to separate the reaction solution and the catalyst. Unreacted hydrogen peroxide was decomposed by adding 10 cm ³ of a saturated aqueous solution of sodium thiosulfate dropwise to the filtrate. After the aqueous phase was extracted twice with 10 cm ³ of dichloromethane, anhydrous magnesium sulfate was added to the extract and dried. After concentrating the extract,
Tetradecane (internal standard substance) was added to the concentrate and analyzed by gas chromatography. As a result, the conversion of cyclohexene and the corresponding epoxide (cyclohexene oxide) were determined.
Was 100%.

Comparative Example 1 3 g of silica gel and 2.88 of 12-tungstophosphoric acid were placed in a 30 cm ³ round bottom flask.
g (1 mmol) and 10 cm ³ of dry ethanol,
The mixture was vigorously stirred in a 70 ° C. water bath under a nitrogen atmosphere for 5 hours. After completion of the stirring, the solvent was distilled off at 50 ° C. under reduced pressure (133 Pa). Thereafter, the catalyst was dried under reduced pressure (133 Pa) under a nitrogen atmosphere for 5 hours to prepare a catalyst. After drying, the catalyst was stored in a desiccator.

To a round bottom flask having a capacity of 10 cm ³ , 0.021 mmol of the catalyst, 1 cm ^{3 of} distilled water, 0.246 g (3 mmol) of cyclohexene and 0.68 g (6 mmol) of 30% hydrogen peroxide were added. Atmosphere, 80
Stir vigorously at 7 ° C. for 7 hours. After the completion of the reaction, the reaction solution was cooled to room temperature. Thereafter, the mixture was filtered to separate the reaction solution and the catalyst. Unreacted hydrogen peroxide was decomposed by adding 10 cm ³ of a saturated aqueous solution of sodium thiosulfate dropwise to the filtrate. After the aqueous phase was extracted twice with 10 cm ³ of dichloromethane, anhydrous magnesium sulfate was added to the extract and dried. After concentrating the extract,
As a result of adding tetradecane (internal standard substance) to the concentrate and analyzing by gas chromatography, the conversion of cyclohexene was 4%, and the selectivity of the corresponding epoxide (cyclohexene oxide) was 85%.

Comparative Example 2 Capacity 30 cm^ThreeRound bottom flask
In addition, quinoline 0.387 g (3 mmol), chloromethy
0.512 g (3 mmol) of rutrimethoxysilane and
Petroleum ether 5cm ^Three And in a hot water bath at 70 ° C in a nitrogen atmosphere.
The mixture was stirred vigorously for 5 hours under an atmosphere. After stirring, dry
Knoll 5cm^Three And 3 g of silica gel, and at the same temperature
Stirred vigorously for 1 hour. After stirring, cool the reaction solution to room temperature.
Rejected. Then dry ethanol 5cm^Three 1 dissolved in
1.83 g (1 mmol) of 2-molybdophosphoric acid was added,
The mixture was vigorously stirred at room temperature for 5 hours under a nitrogen atmosphere. End of stirring
Thereafter, the solvent was distilled off at 50 ° C. under reduced pressure (133 Pa). So
After drying under reduced pressure (133 Pa) under nitrogen atmosphere for 5 hours
Thus, a catalyst was prepared. After drying, the catalyst is decomposed.
Saved in the siccate.

To a round-bottomed flask having a capacity of 10 cm ³ , 0.021 mmol of the catalyst, 1 cm ^{3 of} distilled water, 0.246 g (3 mmol) of cyclohexene and 0.68 g (6 mmol) of 30% hydrogen peroxide were added. Atmosphere, 80
Stir vigorously at 7 ° C. for 7 hours. After the completion of the reaction, the reaction solution was cooled to room temperature. Thereafter, the mixture was filtered to separate the reaction solution and the catalyst. Unreacted hydrogen peroxide was decomposed by adding 10 cm ³ of a saturated aqueous solution of sodium thiosulfate dropwise to the filtrate. After the aqueous phase was extracted twice with 10 cm ³ of dichloromethane, anhydrous magnesium sulfate was added to the extract and dried. After concentrating the extract,
As a result of adding tetradecane (internal standard substance) to the concentrate and analyzing by gas chromatography, the conversion of cyclohexene was 2%, and the selectivity of the corresponding epoxide (cyclohexene oxide) was 82%.

Comparative Example 3 Capacity 30 cm^ThreeRound bottom flask
In addition, quinoline 0.387 g (3 mmol), chloromethy
0.512 g (3 mmol) of rutrimethoxysilane and
Petroleum ether 5cm ^Three And in a hot water bath at 70 ° C in a nitrogen atmosphere.
The mixture was stirred vigorously for 5 hours under an atmosphere. After stirring, dry
Knoll 5cm^Three And 3 g of silica gel, and at the same temperature
Stirred vigorously for 1 hour. After stirring, cool the reaction solution to room temperature.
Rejected. Then dry ethanol 5cm^Three 1 dissolved in
3.31 g (1 mmol) of 2-tungstosilicic acid was added.
Then, the mixture was vigorously stirred at room temperature for 5 hours under a nitrogen atmosphere. Stirring
After completion, the solvent was distilled off at 50 ° C. under reduced pressure (133 Pa).
Was. Then, under reduced pressure (133 Pa), under nitrogen atmosphere for 5 hours
After drying, the catalyst was prepared. After drying,
The medium was stored in a desiccator.

To a round bottom flask having a capacity of 10 cm ³ , 0.021 mmol of the catalyst, 1 cm ^{3 of} distilled water, 0.246 g (3 mmol) of cyclohexene and 0.68 g (6 mmol) of 30% hydrogen peroxide were added. Atmosphere, 80
Stir vigorously at 7 ° C. for 7 hours. After the completion of the reaction, the reaction solution was cooled to room temperature. Thereafter, the mixture was filtered to separate the reaction solution and the catalyst. Unreacted hydrogen peroxide was decomposed by adding 10 cm ³ of a saturated aqueous solution of sodium thiosulfate dropwise to the filtrate. After the aqueous phase was extracted twice with 10 cm ³ of dichloromethane, anhydrous magnesium sulfate was added to the extract and dried. After concentrating the extract, tetradecane (internal standard substance) was added to the concentrate and analyzed by gas chromatography. As a result, the conversion of cyclohexene was 0%, and the corresponding epoxide (cyclohexene oxide) was not detected at all. .

Comparative Example 4 A round bottom flask having a capacity of 30 cm ³ was charged with 0.304 g (3 mmol) of triethylamine, 0.512 g (3 mmol) of chloromethyltrimethoxysilane and 5 cm ³ of petroleum ether. The mixture was stirred vigorously in a bath under a nitrogen atmosphere for 5 hours. After completion of the stirring, 5 cm ^{3 of} dry ethanol and 3 g of silica gel were added,
The mixture was vigorously stirred at the same temperature for 1 hour. After completion of the stirring, the reaction solution was cooled to room temperature. Thereafter, 2.88 g (1 mmol) of 12-tungstophosphoric acid dissolved in 5 cm ³ of dry ethanol was added, and the mixture was vigorously stirred at room temperature for 5 hours under a nitrogen atmosphere. After completion of the stirring, the solvent was distilled off at 50 ° C. under reduced pressure (133 Pa). Thereafter, the catalyst was dried under reduced pressure (133 Pa) under a nitrogen atmosphere for 5 hours to prepare a catalyst. After drying, the catalyst was stored in a desiccator.

To a round bottom flask having a capacity of 10 cm ³ , 0.021 mmol of the catalyst, 1 cm ^{3 of} distilled water, 0.246 g (3 mmol) of cyclohexene and 0.68 g (6 mmol) of 30% hydrogen peroxide were added. Atmosphere, 80
Stir vigorously at 7 ° C. for 7 hours. After the completion of the reaction, the reaction solution was cooled to room temperature. Thereafter, the mixture was filtered to separate the reaction solution and the catalyst. Unreacted hydrogen peroxide was decomposed by adding 10 cm ³ of a saturated aqueous solution of sodium thiosulfate dropwise to the filtrate. After the aqueous phase was extracted twice with 10 cm ³ of dichloromethane, anhydrous magnesium sulfate was added to the extract and dried. After concentrating the extract,
As a result of adding tetradecane (internal standard substance) to the concentrate and analyzing by gas chromatography, the conversion of cyclohexene was 25%, and the selectivity of the corresponding epoxide (cyclohexene oxide) was 75%.

Example 2 Example 1 was repeated except that 3 g of activated carbon was used in place of 3 g of silica gel.
A catalyst was prepared in the same manner as described above. After drying, the catalyst was stored in a desiccator.

The epoxidation reaction was carried out in the same manner as in Example 1 except that the catalyst using silica gel as a carrier (0.7 mol%) was used.
The reaction was carried out in the same manner as in Example 1 except that the catalyst using the activated carbon as a carrier (0.7 mol%) was used. As a result of analyzing the extract by gas chromatography, the conversion of cyclohexene was 97%, and the selectivity of the corresponding epoxide (cyclohexene oxide) was 100%.

Example 3 A catalyst was prepared in the same manner as in Example 1, except that 3 g of neutral alumina was used instead of 3 g of silica gel. After drying, the catalyst was stored in a desiccator.

The epoxidation reaction was carried out in the same manner as in Example 1, except that the catalyst using neutral alumina as a carrier (0.021 mmol) was used instead of the catalyst using silica gel as a carrier (0.021 mmol).
The reaction was carried out in the same manner as in Example 1 except that (mmol) was used. Analysis of the extract by gas chromatography showed that the conversion of cyclohexene was 98% and the selectivity of the corresponding epoxide (cyclohexene oxide) was 1
00%.

Example 4 A round bottom flask having a capacity of 30 cm ³ was charged with 0.387 g (3 mmol) of quinoline, 0.596 g (3 mmol) of chloropropyltrimethoxysilane and 5 cm ³ of petroleum ether. The mixture was stirred vigorously in a bath under a nitrogen atmosphere for 5 hours. After completion of the stirring, 5 cm ^{3 of} dry ethanol and 3 g of silica gel were added, and the mixture was further vigorously stirred at the same temperature for 1 hour. After completion of the stirring, the reaction solution was cooled to room temperature. Thereafter, 2.88 g (1 mmol) of 12-tungstophosphoric acid dissolved in 5 cm ³ of dry ethanol was added, and the mixture was vigorously stirred at room temperature for 5 hours under a nitrogen atmosphere. After completion of the stirring, the solvent was distilled off at 50 ° C. under reduced pressure (133 Pa). Thereafter, the catalyst was dried under reduced pressure (133 Pa) under a nitrogen atmosphere for 5 hours to prepare a catalyst. After drying, the catalyst was stored in a desiccator.

To a round bottom flask having a capacity of 10 cm ³ , 0.021 mmol of the catalyst, 1 cm ^{3 of} distilled water, 0.246 g (3 mmol) of cyclohexene and 0.68 g (6 mmol) of 30% hydrogen peroxide were added. Atmosphere, 80
Stir vigorously at 7 ° C. for 7 hours. After the completion of the reaction, the reaction solution was cooled to room temperature. Thereafter, the mixture was filtered to separate the reaction solution and the catalyst. 10 cm ³ of a saturated aqueous solution of sodium thiosulfate was added dropwise to the filtrate to decompose unreacted hydrogen peroxide. After the aqueous phase was extracted twice with 10 cm ³ of dichloromethane, anhydrous magnesium sulfate was added to the extract and dried. After concentrating the extract, tetradecane (internal standard) was added to the concentrate, and the mixture was analyzed by gas chromatography. As a result, the conversion of cyclohexene and the selectivity of the corresponding epoxide (cyclohexene oxide) were both 100%.

(Example 5) Capacity 30 cm^ThreeRound bottom flask
Pyridine 0.237 g (3 mmol), chloromethy
0.512 g (3 mmol) of rutrimethoxysilane and
Petroleum ether 5cm ^Three And in a hot water bath at 70 ° C in a nitrogen atmosphere.
The mixture was stirred vigorously for 5 hours under an atmosphere. After stirring, dry
Knoll 5cm^Three And 3 g of silica gel, and at the same temperature
Stirred vigorously for 1 hour. After stirring, cool the reaction solution to room temperature.
Rejected. Then dry ethanol 5cm^Three 1 dissolved in
2.88 g (1 mmol) of 2-tungstophosphoric acid was added.
Then, the mixture was vigorously stirred at room temperature for 5 hours under a nitrogen atmosphere. Stirring
After completion, the solvent was distilled off at 50 ° C. under reduced pressure (133 Pa).
Was. Then, under reduced pressure (133 Pa), under nitrogen atmosphere for 5 hours
After drying, the catalyst was prepared. After drying,
The medium was stored in a desiccator.

To a round bottom flask having a capacity of 10 cm ³ , 0.021 mmol of the catalyst, 1 cm ^{3 of} distilled water, 0.246 g (3 mmol) of cyclohexene and 0.68 g (6 mmol) of 30% hydrogen peroxide were added. Atmosphere, 80
Stir vigorously at 7 ° C. for 7 hours. After the completion of the reaction, the reaction solution was cooled to room temperature. Thereafter, the mixture was filtered to separate the reaction solution and the catalyst. Unreacted hydrogen peroxide was decomposed by adding 10 cm ³ of a saturated aqueous solution of sodium thiosulfate dropwise to the filtrate. After the aqueous phase was extracted twice with 10 cm ³ of dichloromethane, anhydrous magnesium sulfate was added to the extract and dried. After concentrating the extract,
As a result of adding tetradecane (internal standard substance) to the concentrate and analyzing by gas chromatography, the conversion of cyclohexene was 90%, and the selectivity of the corresponding epoxide (cyclohexene oxide) was 100%.

Example 6 The reaction was performed in the same manner as in Example 1 except that the reaction temperature was changed from 80 ° C. to 60 ° C., and the reaction time was changed from 7 hours to 22 hours. went. Analysis of the extract by gas chromatography showed that the conversion of cyclohexene and the selectivity of the corresponding epoxide (cyclohexene oxide) were both 100.
%Met.

Example 7 Example 1 was repeated except that water was not added, the reaction temperature was changed from 80 ° C. to 50 ° C., and the reaction time was changed from 7 hours to 15 hours. The reaction was carried out in the same manner as described above. Analysis of the extract by gas chromatography showed that the conversion of cyclohexene and the selectivity of the corresponding epoxide (cyclohexene oxide) were both 100%.

(Example 8) In Example 1, the amount of water was changed from 1 g to 2 g, and the reaction temperature was changed from 80 ° C to 90 ° C.
The reaction was carried out in the same manner as in Example 1 except that the temperature was changed to 7 ° C. and the reaction time was changed from 7 hours to 15 hours.
Analysis of the extract by gas chromatography showed that the conversion of cyclohexene and the selectivity of the corresponding epoxide (cyclohexene oxide) were both 100%.

Example 9 A reaction was carried out in the same manner as in Example 1 except that 1 g of toluene was used instead of 1 g of water as a reaction solvent. Analysis of the extract by gas chromatography showed that the conversion of cyclohexene was 98% and the selectivity for the corresponding epoxide (cyclohexene oxide) was 100%.

Example 10 A reaction was carried out in the same manner as in Example 1 except that 1 g of xylene was used instead of 1 g of water as a reaction solvent. As a result of analyzing the extract by gas chromatography, the conversion of cyclohexene was 97%, and the selectivity of the corresponding epoxide (cyclohexene oxide) was 100%.

Example 11 In Example 1, 1 g of hexane was used as the reaction solvent instead of 1 g of water, the reaction temperature was changed from 80 ° C. to 60 ° C., and the reaction time was 7 minutes.
The reaction was carried out in the same manner as in Example 1 except that the time was changed from 18 hours to 18 hours. As a result of analyzing the extract by gas chromatography, the conversion of cyclohexene was 94%, and the selectivity of the corresponding epoxide (cyclohexene oxide) was 100%.

Example 12 A reaction was carried out in the same manner as in Example 1 except that 1 g of decalin was used instead of 1 g of water as a reaction solvent. Analysis of the extract by gas chromatography showed that the conversion of cyclohexene was 95% and the selectivity of the corresponding epoxide (cyclohexene oxide) was 100%.

Example 13 A round bottom flask having a capacity of 30 cm ³ was charged with 3.87 g (30 mmol) of quinoline, 5.12 g (30 mmol) of chloromethyltrimethoxysilane and 50 cm ³ of petroleum ether. The mixture was vigorously stirred in a bath under a nitrogen atmosphere for 7 hours. After completion of the stirring, 50 cm ^{3 of} dry ethanol and 30 g of silica gel were added, and the mixture was further vigorously stirred at the same temperature for 1 hour. After completion of the stirring, the reaction solution was cooled to room temperature. Thereafter, 28.8 g (10 mmol) of 12-tungstophosphoric acid dissolved in 50 cm ³ of dry ethanol was added, and the mixture was vigorously stirred at room temperature under a nitrogen atmosphere for 7 hours. After completion of the stirring, the solvent was distilled off at 50 ° C. under reduced pressure (133 Pa). Thereafter, the catalyst was dried under reduced pressure (133 Pa) under a nitrogen atmosphere for 5 hours to prepare a catalyst. After drying, the catalyst was stored in a desiccator.

In a round bottom flask having a capacity of 10 cm ³ , 2.1 mmol of the catalyst, 100 cm ^{3 of} distilled water, and cyclohexene 2 were added.
4.6 g (300 mmol) and 30% hydrogen peroxide solution 6
8 g (600 mmol) and 90 ° C. under a nitrogen atmosphere
For 13 hours. After the completion of the reaction, the reaction solution was cooled to room temperature. Thereafter, the mixture was filtered to separate the reaction solution and the catalyst.

The separated catalyst was washed three times with 10 cm ³ of water and three times with 10 cm ³ of acetone, dried, and stored in a desiccator.

On the other hand, 100 cm ³ of a saturated aqueous solution of sodium thiosulfate was added dropwise to the filtrate to decompose unreacted hydrogen peroxide. After the aqueous phase was extracted twice with 100 cm ³ of dichloromethane, anhydrous magnesium sulfate was added to the extract and dried. After concentrating the extract, tetradecane (internal standard) was added to the concentrate, and the mixture was analyzed by gas chromatography. As a result, the conversion of cyclohexene and the selectivity of the corresponding epoxide (cyclohexene oxide) were both 100%. Cyclohexene oxide 2 was obtained by distillation under reduced pressure.
6.5 g (90%) were obtained.

Using the recovered catalyst, a reaction was carried out in the same manner as the above reaction. Analysis of the extract by gas chromatography showed that the conversion of cyclohexene and the selectivity of the corresponding epoxide (cyclohexene oxide) were both 100%.

Example 14 The procedure of Example 1 was repeated except that 0.289 g (3 mmol) of cycloheptene was used instead of 0.246 g (3 mmol) of cyclohexene.
The reaction was carried out in the same manner as in Example 1. As a result of analyzing the extract by gas chromatography, the conversion of cycloheptene and the selectivity of the corresponding epoxide (cycloheptene oxide) were both 100%.

Example 15 The procedure of Example 1 was repeated, except that 0.331 g (3 mmol) of cyclooctene was used instead of 0.246 g (3 mmol) of cyclohexene.
The reaction was carried out in the same manner as in Example 1. As a result of analyzing the extract by gas chromatography, the conversion of cyclooctene and the selectivity of the corresponding epoxide (cyclooctene oxide) were both 100%.

Example 16 A reaction was carried out in the same manner as in Example 1 except that 0.286 g (3 mmol) of cyclohexene was replaced with 0.282 g (3 mmol) of norbornene. Was. Analysis of the extract by gas chromatography showed the conversion of cycloheptene and the corresponding epoxide (cycloheptene oxide)
Was 100%.

Example 17 The procedure of Example 1 was repeated, except that 0.171 g (3 mmol) of allyl alcohol was used instead of 0.246 g (3 mmol) of cyclohexene, and the reaction time was changed from 7 hours to 12 hours. The reaction was carried out in the same manner as in Example 1. As a result of analyzing the extract by gas chromatography, the conversion of allyl alcohol and the selectivity of the corresponding epoxide (3-hydroxy-1,2-epoxypropane) were both 100%.

Example 18 The procedure of Example 1 was repeated, except that 0.246 g (3 mmol) of cyclohexene was replaced by 2,3.
The reaction was carried out in the same manner as in Example 1 except that 0.252 g (3 mmol) of -dimethyl-2-butene was used.
As a result of analyzing the extract by gas chromatography,
Both the conversion of 3-dimethyl-2-butene and the selectivity of the corresponding epoxide (2,3-dimethyl-2,3-epoxybutane) were 100%.

Example 19 Example 1 was repeated except that 0.475 g (3 mmol) of 1-phenyl-1-cyclohexene was used instead of 0.246 g (3 mmol) of cyclohexene. Then, the reaction was performed. As a result of analyzing the extract by gas chromatography, both the conversion of 1-phenyl-1-cyclohexene and the selectivity of the corresponding epoxide (1-phenyl-1,2-epoxycyclohexane) were 100%.

Example 20 In Example 1, 0.285 g (3 mmol) of 1-methyl-1-cyclohexene was used instead of 0.246 g (3 mmol) of cyclohexene.
The reaction was carried out in the same manner as in Example 1 except that was used. As a result of analyzing the extract by gas chromatography,
The conversion of 1-methyl-1-cyclohexene and the selectivity of the corresponding epoxide (1-methyl-1,2-epoxycyclohexane) were both 100%.

Example 21 A reaction was carried out in the same manner as in Example 1 except that 0.312 g (3 mmol) of styrene was used instead of 0.246 g (3 mmol) of cyclohexene. Was. Analysis of the extract by gas chromatography showed that the conversion of styrene and the selectivity of the corresponding epoxide (styrene oxide) were both 1
00%.

(Example 22) Capacity 30 cm^Three Round bottom frus
In coconut, 0.387 g (3 mmol) of quinoline, chlorome
0.512 g (3 mmol) of tiltrimethoxysilane
And petroleum ether 5cm ^Three And in a 70 ° C hot water bath
The mixture was vigorously stirred for 5 hours under an atmosphere. After stirring, dry
Tanol 5cm^Three And 3 g of silica gel.
For 1 hour. After stirring, bring the reaction solution to room temperature.
Cool. Then dry ethanol 5cm^Three Dissolved in
2.88 g (1 mmol) of 12-tungstophosphoric acid was added.
Then, the mixture was vigorously stirred at room temperature for 5 hours under a nitrogen atmosphere. That
Thereafter, 1 g of triphenylethoxysilane was added and the mixture was placed in a nitrogen atmosphere.
The mixture was vigorously stirred at the same temperature. After completion of stirring, under reduced pressure
(133 Pa), the solvent was distilled off at 50 ° C. Then decompress
(133 Pa) under a nitrogen atmosphere for 5 hours.
A medium was prepared. After drying, the catalyst is desiccated.
Saved inside.

To a round bottom flask having a capacity of 10 cm ³ , 0.021 mmol of the catalyst, 1 cm ^{3 of} distilled water, 0.541 g (3 mmol) of trans-stilbene and 0.68 g (6 mmol) of 30% hydrogen peroxide were added. , Under nitrogen atmosphere, 8
Stir vigorously at 0 ° C. for 7 hours. After the completion of the reaction, the reaction solution was cooled to room temperature. Thereafter, the mixture was filtered to separate the reaction solution and the catalyst. Unreacted hydrogen peroxide was decomposed by adding 10 cm ³ of a saturated aqueous solution of sodium thiosulfate dropwise to the filtrate. After the aqueous phase was extracted twice with 10 cm ³ of dichloromethane, anhydrous magnesium sulfate was added to the extract and dried. After concentrating the extract,
As a result of adding tetradecane (internal standard substance) to the concentrate and analyzing by gas chromatography, the conversion of trans-stilbene and the selectivity of the corresponding epoxide (trans-stilbene oxide) were both 100%.

Example 23 The procedure of Example 22 was repeated, except that 0.541 g (3 mmol) of cis-stilbene was used instead of 0.541 g (3 mmol) of trans-stilbene. The reaction was performed.
Analysis of the extract by gas chromatography showed that the conversion of cis-stilbene and the corresponding epoxide (cis-
The selectivity of both (stilbene oxide) was 100%.

Example 24 Example 22 was the same as Example 22 except that 0.537 g (3 mmol) of trans-stilbene was replaced by 0.337 g (3 mmol) of trans-4-octene. Then, the reaction was performed. Analysis of the extract by gas chromatography showed that the conversion of trans-4-octene and the selectivity of the corresponding epoxide (4,5-epoxyoctane) were both 1
00%.

(Example 25) In Example 22, 0.463 g of trans-2-oxy-3-decene was used in place of 0.541 g (3 mmol) of trans-stilbene.
(3 mmol), and the reaction was carried out in the same manner as in Example 22 except that the reaction time was changed from 7 hours to 20 hours. Analysis of the extract by gas chromatography showed the conversion of trans-2-oxy-3-decene and the corresponding epoxide (3,4-epoxy-2-decanone)
Was 100%.

(Example 26) In Example 22, 0.337 g (3 mmol) of 1-octene was used in place of 0.541 g (3 mmol) of trans-stilbene.
The reaction was carried out in the same manner as in Example 22, except that the reaction temperature was changed from 80 ° C. to 90 ° C., and the reaction time was changed from 7 hours to 15 hours. As a result of analyzing the extract by gas chromatography, the conversion of 1-nonene and the selectivity of the corresponding epoxide (1,2-epoxyoctane) were both 100%.

(Example 27) In Example 22, 0.379 g (3 mmol) of 1-nonene was used in place of 0.541 g (3 mmol) of trans-stilbene, and the reaction temperature was changed from 80 ° C to 90 ° C. The reaction was carried out in the same manner as in Example 22 except that the reaction time was changed from 7 hours to 18 hours. As a result of analyzing the extract by gas chromatography, the conversion of 1-nonene and the selectivity of the corresponding epoxide (1,2-epoxynonane) were both 100%.

(Example 28) In Example 22, 0.21 g (3 mmol) of methyl vinyl ketone was used instead of 0.541 g (3 mmol) of trans-stilbene, and the reaction time was changed from 7 hours to 15 hours. Other than
The reaction was carried out in the same manner as in Example 22. Analysis of the extract by gas chromatography showed the conversion of methyl vinyl ketone and the corresponding epoxide (3-oxo-1,
The selectivity of both (2-epoxybutane) was 100%.

(Example 29) In Example 22, 0.403 g (3 mmol) of phenylallyl ether was used instead of 0.541 g (3 mmol) of trans-stilbene, and the reaction time was changed from 7 hours to 15 hours. The reaction was carried out in the same manner as in Example 22 except that the reaction was performed. Analysis of the extract by gas chromatography showed that the conversion of phenylallyl ether and the corresponding epoxide (3-
The selectivity of both phenoxy-1,2-epoxypropane) was 100%.

[0091]

The epoxidation catalyst of the present invention can produce an epoxide with a selectivity of 99% or more irrespective of the type of olefin and even with a low concentration of hydrogen peroxide. This has the advantage that the catalyst can be recovered and reused.

Continued on the front page F-term (reference) 4G069 AA01 AA03 AA04 AA08 AA09 BA01A BA01B BA02A BA02B BA07A BA08A BA08B BA13A BA21A BA21B BA21C BB07A BB07B BB07C BC60A BC60B BC60C BD06A BE06B BE17B BEB37BE07B BE33B BE33C BE36A BE36C BE37A BE37B BE37C BE38A BE38B BE38C CB07 CB08 CB73 DA05 FA01 FA02 FB05 FB14 FB17 FB57 FB78 FC01 FC04

Claims (4)

[Claims] (1) (a) activated carbon or an inorganic solid having a functional group capable of reacting with a silane coupling agent, and (b) a functional group capable of reacting with a tertiary amine to form a quaternary ammonium salt. After reacting with a silane coupling agent having a substituted alkyl group, (c) general formula (1) (In the formula, at least one of R ¹ , R ² and R ³ is an alkyl group having 8 to 18 carbon atoms, and the remaining groups are an alkyl group having 1 to 18 carbon atoms or a benzyl group.) An epoxy comprising a salt obtained by reacting a carrier surface-treated by reacting a tertiary amine or a cyclic amine represented by the formula with (2) a heteropolyacid having a group V atom and a tungsten atom in the molecule in the molecule. Catalyst. (1) (a) activated carbon or an inorganic solid having a functional group capable of reacting with a silane coupling agent, and (b) (b-
1) reacting with a mixture of a silane coupling agent having an alkyl group substituted with a functional group capable of forming a quaternary ammonium salt by reacting with a tertiary amine and (b-2) a lipophilic silane coupling agent After that, (c) general formula (wherein,
R ¹ , R ² and R ³ are at least one group being an alkyl group having 1 to 18 carbon atoms or a benzyl group), and a surface-treated carrier obtained by reacting with a tertiary amine or a cyclic amine represented by the formula: (2) An epoxidation catalyst comprising a salt obtained by a reaction with a heteropolyacid having a Group V atom and a tungsten atom in the molecule of the periodic table. 3. The epoxidation catalyst according to claim 1, wherein the group V atom of the periodic table is a nitrogen atom or a phosphorus atom. 4. The method according to claim 1, wherein the olefin is reacted with hydrogen peroxide in water or an organic solvent in the presence of a catalyst to produce an epoxidized olefin. A method for producing an epoxidized product, comprising using the epoxidation catalyst described in 1 above.