WO2013133009A1 - Method for producing tungsten peroxide compound, and method for producing epoxy compound - Google Patents

Abstract

As a novel method for producing a tungsten peroxide compound useful as a catalyst for the epoxidation of an alkene, a method for producing a tungsten peroxide compound is provided which is characterized by comprising reacting (a) tungstic acid with (b) an ammonium hydroxide compound selected from (H₄N)(OH), (H₃R¹N)(OH), (H₂R¹R²)(OH), (HR¹R²R³N)(OH) and (R¹R²R³R⁴N)(OH). Also provided is a method for producing an epoxy compound using the catalyst. (In the formulae, R¹ to R⁴ may be the same as or different from one another, independently represent a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group or a benzyl group, and may contain nitrogen or oxygen.)

Description

Method for producing tungsten peroxide compound and method for producing epoxy compound

The present invention relates to a novel method for producing a tungsten peroxide compound useful as a catalyst for alkene epoxidation in a method for producing an epoxy compound. The present invention also relates to a method for producing an epoxy compound using the catalyst.

Various catalyst systems have been developed for alkene epoxidation reactions. For example, (1) phase transfer catalyst: a method of epoxidation with hydrogen peroxide in the presence of polyoxometalate (Patent Documents 1 and 2), (2) phase transfer catalyst: a tungsten compound, α-aminomethylphosphonic acid as a catalyst There are known a method of epoxidation using the compound (Patent Document 2), and (3) a method of epoxidation with hydrogen peroxide without a phase transfer catalyst in the presence of a tungsten compound and a phosphorus compound (Patent Document 3).
Especially, in the epoxidation reaction using a tungsten peroxide catalyst, a reaction with high selectivity of epoxide can be advanced (nonpatent literature 1). This tungsten binuclear catalyst is synthesized by purifying a precipitate formed by adding tetrabutylammonium chloride to tungstic acid dispersed in high hydrogen peroxide, but the catalyst yield is low and it is produced industrially. There was a problem that was difficult.

JP 2004-115455 A JP-A-8-27136 JP 2010-168330 A

An object of the present invention is to provide a novel method for producing a tungsten peroxide compound having high catalytic activity in an alkene epoxidation reaction. Moreover, it aims at providing the manufacturing method of an industrially useful epoxy compound using the manufactured catalyst.

As a result of diligent research to solve the above problems, the inventors of the present invention significantly improved the yield of tungsten peroxide compounds when produced by a synthesis method using tungstic acid and an ammonium hydroxide compound as raw materials. It has been found that the yield of the epoxy compound is remarkably improved by using the tungsten peroxide compound as an epoxidation catalyst, and the present invention has been completed.
That is, the present invention is as follows.

[1] (a) Tungstic acid and (b) (H ₄ N) (OH), (H ₃ R ¹ N) (OH), (H ₂ R ¹ R ² ) (OH), (HR ¹ R ² R ^A process for producing a tungsten peroxide compound, comprising reacting an ammonium hydroxide compound selected from ³ N) (OH) and (R ¹ R ² R ³ R ⁴ N) (OH).
(R ¹ to R ⁴ may be the same or different and each represents a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, or a benzyl group, which contains nitrogen or oxygen. May be.)

[2] The production method according to [1], wherein (b) is a compound represented by (R ¹ R ² R ³ R ⁴ N) (OH).

[3] The production method according to [1] or [2], wherein (b) is a compound represented by [(R ¹ ) ₄ N] (OH).

[4] The production method according to any one of [1] to [3], wherein (b) is [(n-C ₄ H ₉ ) ₄ N] (OH).

[5] The production method according to any one of [1] to [4], wherein the produced tungsten peroxide compound is purified by lamination of a poor solvent and a good solvent.

[6] The production method according to any one of [1] to [4], wherein the produced tungsten peroxide compound is purified by vapor diffusion of a poor solvent and a good solvent.

[7] The production method according to [5] or [6] above, wherein the poor solvent is diethyl ether.

[8] The production method according to [5] or [6], wherein the good solvent is acetone or acetonitrile.

[9] The tungsten peroxide compound to be produced is (R ¹ R ² R ³ R ⁴ N) ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)], (R ¹ R ² R ³ HN) ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)], (R ¹ R ² H ₂ N) ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)], (R ¹ H ₃ N ) ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)] or (H ₄ N) ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)] [1] The production method according to any one of [8].

[10] The above-mentioned [1], wherein the tungsten peroxide compound to be produced is (R ¹ R ² R ³ R ⁴ N) ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)]. The production method according to any one of to [9].

[11] The above [1] to [10], wherein the tungsten peroxide compound to be produced is [(R ¹ ) ₄ N] ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)]. ] The manufacturing method in any one of.

[12] The tungsten peroxide compound to be produced is [(n—C ₄ H ₉ ) ₄ N] ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)]. ] To [11].

[13] An epoxy characterized in that an olefin epoxidation reaction using hydrogen peroxide as an oxidizing agent is performed using the tungsten peroxide compound produced by any one of the methods [1] to [12] as a catalyst. Compound production method.

[14] The method for producing an epoxy compound as described in [13], wherein the olefin is an alicyclic olefin.

[15] The method for producing an epoxy compound according to [14], wherein the alicyclic olefin is tetrahydroindene.

By the method of the present invention, a tungsten peroxide compound can be easily obtained with a much higher yield as compared with a conventionally known synthesis method.
Further, by using the tungsten peroxide compound obtained by the method of the present invention as a catalyst, the yield of the epoxy compound can be remarkably improved in the alkene epoxidation reaction, which has been difficult to epoxidize until now.
Moreover, the epoxy compound obtained by this invention is useful as an intermediate body or raw material in manufacture of various industrial products, a pharmaceutical, an agrochemical, etc. including a semiconductor sealing material, a hardening | curing agent, and a resist material. By producing these using hydrogen peroxide, it is industrially useful as a process with a low environmental load since it has good yield and few by-products.

Hereinafter, the present invention will be described.

In the method of the present invention, a tungsten peroxide compound is produced by reacting (a) tungstic acid and (b) an ammonium hydroxide compound as raw materials.

The (b) ammonium hydroxide compound used in the present invention includes (H ₄ N) (OH), (H ₃ R ¹ N) (OH), (H ₂ R ¹ R ² ) (OH), and (HR ¹ R ² ). R ³ N) (OH), or (R ¹ R ² R ³ R ⁴ N) (OH).
In the above formula, R ¹ to R ⁴ may be the same or different and each represents a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, a benzyl group, etc. It may contain oxygen.

Specific examples of R ¹ to R ⁴ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl , Tetradecyl, pentadecyl and the like, and may be branched or cyclic on the way. In addition, those containing a benzyl group or a hydroxyl group are also possible, such as benzyltrimethyl, benzyltriethyl, 2-hydroxyethyltrimethyl, hexadecyltrimethyl, trimethyl-3-trifluoromethylphenyl, tris (2-hydroxyethyl) methyl. And functional groups such as A cetylpyridinium group or the like can also be used. More preferred are tetraalkylammonium hydroxide and alkylpyridinium hydroxide having 1 to 8 carbon atoms.

(B) The ammonium hydroxide compound is particularly preferably a compound represented by (R ¹ R ² R ³ R ⁴ N) (OH). R ¹ to R ⁴ may be different from each other or all the same, but are preferably all the same alkyl group. The alkyl group is preferably a linear and / or branched alkyl group having 1 to 12 carbon atoms, more preferably a linear alkyl group having 1 to 12 carbon atoms, and 1 to 8 carbon atoms. Are more preferable, and n-butyl is most preferable. Therefore, in the present invention, as the ammonium hydroxide compound (b), tetra-n-butylammonium hydroxide is most preferable.

In the method of the present invention, tungstic acid is first added to hydrogen peroxide water and stirred to obtain a solution in which tungstic acid is suspended or dissolved. Next, the reaction is carried out by adding an ammonium hydroxide compound.
The concentration of the hydrogen peroxide solution used at this time is arbitrary, but 10% to 70% hydrogen peroxide solution is preferable from the viewpoint of safety and efficiency.
The amount of tungstic acid can be appropriately set according to the concentration of the hydrogen peroxide solution. For example, when 30% hydrogen peroxide solution is used, the amount used is 30 ml of 30% hydrogen peroxide solution. The amount is usually 5 to 50 g, preferably 10 to 30 g. The stirring time is not particularly limited, but is a time sufficient for the tungstic acid to be sufficiently suspended or dissolved in the hydrogen peroxide solution, and is usually 10 minutes to 10 hours.
The ratio of tungstic acid and ammonium hydroxide compound is not particularly limited, but the ion equivalent ratio of (anion of tungstic acid) / (counter cation) is preferably in the range of 0.01 to 100, more preferably 0.1 to 10. It is a range.

After the reaction, the insoluble matter is filtered, and the filtrate in which the reaction product is dissolved is added to a solvent (hereinafter referred to as precipitation solvent) to precipitate a tungsten peroxide compound insoluble in the precipitation solvent as a precipitate. Can be recovered.
In addition, it is preferable from the viewpoint of efficiency that the filtrate is concentrated before being added to the precipitation solvent. The degree of concentration is arbitrary, but it is preferably 2 to 10 times concentrated.
The precipitation solvent is not particularly limited as long as it can precipitate the tungsten peroxide compound, but a mixed solution of diethyl ether and isopropyl alcohol is particularly preferably used.

The precipitate obtained as described above is preferably subjected to a purification treatment. As the purification method, a lamination method using a good solvent and a poor solvent, or a vapor diffusion method is preferable.
The lamination method using a good solvent and a poor solvent is a technique in which a poor solvent is added little by little to a solution in which a precipitate is dissolved in a good solvent, and crystals are grown using the difference in solubility.
In the vapor diffusion method, a solution in which a precipitate is dissolved in a good solvent is put in a container with an open top, and the whole container is put in a container containing a poor solvent and sealed. After a while, both containers have the same solvent ratio due to the vapor pressure equilibrium of both solvents, and this is also a method of crystal growth utilizing the difference in solubility.

The good solvent is not particularly limited as long as the tungsten peroxide compound is dissolved. For example, the first, second, and third carbon atoms having 1 to 6 carbon atoms such as methanol, ethanol, normal or isopropanol, and tertiary butanol can be used. Grade monohydric alcohols; polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, diethylene glycol, and triethylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetyl acetone; methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate , Esters such as n-butyl acetate, iso-butyl acetate, sec-butyl acetate, tert-butyl acetate, methyl benzoate, etc .; ethylene carbonate, propylene carbonate, etc., dimethyl carbonate carbonate Over preparative like; dimethylformamide, dimethylacetamide, nitromethane, acetonitrile, nitrogen compounds such as benzonitrile and the like. Among these, methanol, ethanol, normal or isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, dimethyl carbonate, dimethylformamide, dimethylacetamide, acetonitrile, and benzonitrile are preferably used. Acetone and acetonitrile are particularly preferred.

The poor solvent is not particularly limited. For example, ethers such as diethyl ether, diisopropyl ether, dioxane, and tetrahydrofuran; halogenated hydrocarbons such as chloroform and dichloromethane; aliphatic hydrocarbons such as normal hexane and normal heptane; Examples include aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane and cyclopentane; norbornene compounds such as ethylidene norbornene, vinyl norbornene, and dicyclopentadiene. Among these, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, normal hexane, normal heptane, and normal octane are preferably used, and diethyl ether is particularly preferable.

The use ratio of the good solvent and the poor solvent is arbitrary, and if the amount of the good solvent that dissolves the precipitate is too large, crystals do not precipitate. On the other hand, if there are too many poor solvents, sufficient crystal growth cannot be achieved, so an appropriate amount is required. Therefore, the good solvent / poor solvent has a volume ratio of preferably 0.001 to 1000, more preferably 0.01 to 100.

In the conventionally known method, impurities are generated in addition to the tungsten peroxide compound, and sorting is necessary while observing the crystal form using a microscope or the like. Therefore, it is difficult to manufacture industrially and the yield is low. It was. In addition, since the raw material containing halogen is used in the conventional method, it has been an industrially limited catalyst that the epoxy compound contains halogen.
Tungsten peroxide compounds can be easily produced in a higher yield than the method of the present invention, and the obtained tungsten peroxide compounds do not contain halogen. Therefore, low halogen products can be easily produced by using them as epoxidation catalysts. can do.

By the method of the present invention, for example, (R ¹ R ² R ³ R ⁴ N) ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)], (R ¹ R ² R ³ HN) ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)], (R ¹ R ² H ₂ N) ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)], (R ¹ H ₃ N) ₂ [ Tungsten peroxide compounds such as {WO (O ₂ ) ₂ } ₂ (μ-O)] and (H ₄ N) ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)] can be produced. However, it is not limited to these compounds. In the chemical formula, μ represents a bridging atom.

The tungsten peroxide compound according to the present invention can possess cations such as protons, alkali metal cations, alkaline earth metal cations, ammonium cations and quaternary alkyl ammonium cations. Of these, quaternary alkyl ammonium cations are preferred. This is because it has high catalytic activity in the epoxidation reaction of unsaturated bond compounds.

The tungsten peroxide compound produced by the method of the present invention is suitably used as a catalyst for the alkene epoxidation reaction.
The alkene epoxidation reaction using the catalyst produced by the method of the present invention will be described below.

The alkene epoxidation reaction is carried out by contacting the alkene with an oxidizing agent in the presence of a tungsten peroxide catalyst.

In the present invention, the alkene used for the epoxidation reaction is not particularly limited, and can be used regardless of whether it is acyclic or cyclic. Specifically, ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1 -Tetradecene, 1-pentadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 1,3-butadiene, isoprene, isobutene, diisobutylene, propylene trimer, tetramers, styrene, vinyltoluene, divinylbenzene Terminal olefins such as 2-butene, 2-octene, 2-methyl-1-hexene, 2,3-dimethyl-2-butene, and the like; cyclopentene, cyclohexene, 1-phenyl-1-cyclohexene, 1- Methyl-1-cyclohexene, cycloheptene, cyclooctene, Fats such as clodecene, cyclopentadiene, cyclodecatriene, cyclooctadiene, dicyclopentadiene, methylenecyclopropane, methylenecyclopentane, methylenecyclohexane, vinylcyclohexane, norbornene, tetrahydroindene, indene, 4-vinyl-1-cyclohene And terpenes such as cyclic olefin, limonene, α-pinene, β-pinene, and ferrandrene. Alkenes may have various functional groups. Examples of the functional group include —CHO, —COOH, —CN, —COOR, —OR (R represents an alkyl group, a cycloalkyl group, an aryl group, or an arylalkyl group). Moreover, you may have functional groups, such as an aryl group, a halogen group, a nitro group, a sulfonic acid group, a carbonyl group, and a hydroxyl group. Among these alkenes, it is preferable to use aliphatic hydrocarbons, and among them, the catalyst according to the present invention can be used for epoxidation of easily hydrolyzable alkenes such as epoxides of cyclohexene ring. Cyclic olefin compounds are more preferred. More preferred is tetrahydroindene. One or two olefin moieties can be arbitrarily used in the compound.

The oxidizing agent for the epoxidation reaction is not particularly limited as long as it is a peroxide, but is preferably hydrogen peroxide. The concentration thereof is arbitrary, but 10% to 70% hydrogen peroxide water is preferable from the viewpoint of safety and efficiency. The ratio of hydrogen peroxide to alkene is arbitrary, but the ratio of the number of moles of hydrogen peroxide to the number of moles of olefin in the alkene is preferably in the range of 0.1 to 10.
In addition, hydrogen peroxide may be added in an amount necessary for the reaction from the beginning or may be sequentially added.

The amount of the tungsten peroxide catalyst can be used in an arbitrary amount of 0.01 mol% to 1000 mol% with respect to the olefin content of the alkene. More preferably, it is 0.05 mol% to 100 mol%.

The epoxidation reaction may be performed in a water-soluble organic compound, or may be performed in a two-phase system with a water-insoluble organic compound or a mixture thereof. Examples of usable organic solvents include primary, secondary and tertiary monohydric alcohols having 1 to 6 carbon atoms such as methanol, ethanol, normal or isopropanol, and tertiary butanol; ethylene glycol, propylene glycol, glycerin, Polyhydric alcohols such as diethylene glycol and triethylene glycol; Ethers such as ethyl ether, isopropyl ether, dioxane and tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and acetyl acetone; Methyl acetate, ethyl acetate, propyl acetate and isopropyl acetate , Esters such as n-butyl acetate, iso-butyl acetate, sec-butyl acetate, tert-butyl acetate, methyl benzoate; ethylene carbonate, propylene carbonate, etc., dimethyl carbonate Carbonates; nitrogen compounds such as dimethylformamide, dimethylacetamide, nitromethane, acetonitrile and benzonitrile; phosphorus compounds such as phosphate esters such as triethyl phosphate and diethylhexyl phosphate; halogenated hydrocarbons such as chloroform and dichloromethane; Aliphatic hydrocarbons such as hexane and normal heptane; aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane and cyclopentane; norbornene compounds such as ethylidene norbornene, vinyl norbornene, and dicyclopentadiene .

Among the solvents, alcohols having 1 to 4 carbon atoms, chloroform, dichloromethane, hexane, heptane, nonane, indane, indene, hydrindan, acetonitrile, benzonitrile, dimethyl sulfoxide, dimethylformamide, ethyl acetate, propyl acetate, isopropyl acetate, It is preferable to use dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dimethyl carbonate, ethylene carbonate, propylene carbonate, or a mixture thereof.

In addition, a mixture of the above compound and water can be used, and a neat reaction can be performed without using a solvent.
A phase transfer catalyst or a surfactant can also be used for the epoxidation reaction. Although these are arbitrary compounds, More preferably, cetylpyridinium chloride, cetylpyridinium bromide, methyltrioctyl hydrogen sulfate, etc. are mentioned.

The epoxidation reaction is preferably performed at a reaction temperature of 0 ° C. or higher and 100 ° C. or lower, more preferably 10 ° C. or higher and 80 ° C. or lower. The reaction time is preferably from 1 minute to 400 hours. More preferably, it is 60 minutes or more and 300 hours or less. Although reaction pressure is arbitrary, 20 atmospheres or less are preferable, More preferably, it is 10 atmospheres or less, and it can also react under reduced pressure. *

The tungsten peroxide catalyst obtained by the method of the present invention can significantly improve the yield of an epoxy compound in a reaction that has been difficult to epoxidize so far, so that it is possible to produce an industrially useful epoxy compound. Become.
In addition, in industrial products using epoxy compounds as raw materials, the lifetime may be deteriorated or break down due to the contained halogen, and reduction of halogen is desired. Since the tungsten peroxide catalyst obtained by the method of the present invention does not contain a halogen, a low halogen epoxy compound can be easily produced, so that this problem can be solved.
Therefore, the halogen content contained in the epoxy compound obtained by the method of the present invention is usually 100 mass ppm or less, and the halogen content can be made 10 mass ppm or less by using a purification method such as distillation. .

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.

(Example 1)
1 g of tungstic acid was stirred in 10 ml of 30% hydrogen peroxide solution for 1.5 hours to obtain a white suspension solution (A). To this suspension solution (A) was added 4 ml of tetrabutylammonium hydroxide 1M aqueous solution to obtain a pale yellow suspension solution (B). The insoluble matter was filtered through membrane cellulose acetate, and the filtrate was concentrated to 2 ml. When this solution was added dropwise to a diethyl ether / isopropyl alcohol (150 ml / 20 ml) solution, a pale yellow powder (C) was produced. The powder (C) was separated by filtration and washed with diethyl ether to obtain 1.4 g of a white powder (D).
After 0.5 g of white powder (D) was dissolved in acetone, this solution was put into a screw tube and diethyl ether was slowly laminated. When this was left still in the refrigerator for 1 day, 0.37 g of plate crystals (E) were obtained. The yield of (E) relative to (D) was 75%, and the overall yield was 52%. The crystal (E) was recovered and measured by IR, and it was confirmed that it was [(n-C ₄ H ₉ ) ₄ N] ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)]. The yield comparison of catalyst synthesis is shown in Table 1.

(Example 2)
1 g of tungstic acid was stirred in 10 ml of 30% hydrogen peroxide solution for 1.5 hours to obtain a white suspension solution (A). To this suspension solution (A) was added 4 ml of tetrabutylammonium hydroxide 1M aqueous solution to obtain a pale yellow suspension solution (B). The insoluble matter was filtered through membrane cellulose acetate, and the filtrate was concentrated to 2 ml. When this solution was added dropwise to a diethyl ether / isopropyl alcohol (150 ml / 20 ml) solution, a pale yellow powder (C) was produced. The powder (C) was separated by filtration and washed with diethyl ether to obtain 1.4 g of a white powder (D).
After 16.9 mg of white powder (D) was dissolved in acetone, this solution was placed in a small screw tube (model No. 1 volume 4 ml) and screwed into a screw tube (model No. 6 volume 30 ml) to which diethyl ether was added. The small tube was added and the lid was covered and left in the refrigerator. After standing for 22 days, 10.7 mg of plate-like crystals (F) were obtained. The yield of (F) relative to (D) was 63%, and the overall yield was 43%. This crystal (F) was recovered and measured by IR, and it was confirmed that it was [(n-C ₄ H ₉ ) ₄ N] ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)]. The yield comparison of catalyst synthesis is shown in Table 1.

(Example 3)
Using the crystal (E) obtained in Example 1, tetrahydroindene (hereinafter referred to as THI) was epoxidized. In a test tube, THI (1 mmol) was dissolved in 5 ml of acetonitrile, 2 equivalents of 30% aqueous hydrogen peroxide was added, and then 5 mol% of the catalyst was added. The reaction was performed at a stirring speed of 800 rpm and 293 K using a ChemiStation of Tokyo Science Instrument Co., Ltd. Quantification using gas chromatography (GC) after the reaction for 8 hours gave a THI conversion of 67.8%, a monoepoxide yield of 25.2%, and a diepoxide yield of 13.8%. After the 216h reaction, the THI conversion was 94.7%, the monoepoxide yield was 23.9%, and the diepoxide yield was 65.7%. The epoxide yield comparison is shown in Table 2.

(Example 4)
The THI epoxidation reaction was performed using the crystal (F) obtained in Example 2. In a test tube, THI (1 mmol) was dissolved in 5 ml of acetonitrile, 2 equivalents of 30% aqueous hydrogen peroxide was added, and then 5 mol% of the catalyst was added. The reaction was performed at a stirring speed of 800 rpm and 293 K using a ChemiStation of Tokyo Science Instrument Co., Ltd. Quantification using GC after the reaction for 8 hours gave a THI conversion of 66.2%, a monoepoxide yield of 25.0%, and a diepoxide yield of 12.5%. After 120 hours of reaction, the THI conversion was 87.4%, the monoepoxide yield was 33.0%, and the diepoxide yield was 45.1%. The epoxide yield comparison is shown in Table 2.

(Comparative Example 1)
The catalyst was synthesized according to Non-Patent Document 1. 6 g of tungstic acid was stirred in 30% hydrogen peroxide water at 50 ° C. for 1 hour. After adding 3.3 g of tetrabutylammonium chloride, the insoluble matter was filtered and washed with pure water and diethyl ether to obtain 3.5 g of a light yellow powder (G). 1.5 g of powder (G) was dissolved in acetone, and diethyl ether was layered and allowed to stand for 1 week to obtain plate crystals and granular crystals. While only the plate crystal (H) was sorted using tweezers while observing the crystal in which both were mixed with a microscope, 0.2 g could be recovered. The yield of (H) relative to (G) was 12%, and the overall yield was 3.5%. When this crystal (H) was measured by IR, it was confirmed to be [(n-C ₄ H ₉ ) ₄ N] ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)]. The yield comparison of catalyst synthesis is shown in Table 1.

(Comparative Example 2)
The reaction was performed in the same manner as in Example 3 except that the crystal (H) was used. Quantification using GC after the reaction for 8 hours revealed a THI conversion rate of 55.4%, a monoepoxide yield of 30.2%, and a diepoxide yield of 12.0%. After the 292h reaction, the THI conversion was 98.4%, the monoepoxide yield was 12.8%, and the diepoxide yield was 60.9%. The epoxide yield comparison is shown in Table 2.

According to the method of the present invention, a tungsten peroxide compound can be easily obtained in a much higher yield as compared with a conventionally known method, and an epoxidation reaction using this as a catalyst makes it difficult to epoxidize until now. Since the compound can be produced in a high yield, it is extremely useful industrially.

Claims (15)

1. (A) tungstic acid and ^{_{(b) (H 4 N)}} (OH), (H 3 R 1 N) (OH), (H 2 R 1 R 2) (OH), (HR 1 R 2 R 3 N) A method for producing a tungsten peroxide compound, comprising reacting an ammonium hydroxide compound selected from (OH) and (R ¹ R ² R ³ R ⁴ N) (OH).
   (R ¹ to R ⁴ may be the same or different and each represents a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group, or a benzyl group, which contains nitrogen or oxygen. May be.)
2. The production method according to claim 1, wherein (b) is a compound represented by (R ¹ R ² R ³ R ⁴ N) (OH).
3. The production method according to claim 1 or 2, wherein (b) is a compound represented by [(R ¹ ) ₄ N] (OH).
4. The production method according to any one of claims 1 to 3, wherein (b) is [(n-C ₄ H ₉ ) ₄ N] (OH).
5. The production method according to any one of claims 1 to 4, wherein the produced tungsten peroxide compound is purified by lamination of a poor solvent and a good solvent.
6. 5. The production method according to claim 1, wherein the produced tungsten peroxide compound is purified by vapor diffusion of a poor solvent and a good solvent.
7. The production method according to claim 5 or 6, wherein the poor solvent is diethyl ether.
8. The production method according to claim 5 or 6, wherein the good solvent is acetone or acetonitrile.
9. The tungsten peroxide compound to be produced is (R ¹ R ² R ³ R ⁴ N) ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)], (R ¹ R ² R ³ HN) ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)], (R ¹ R ² H ₂ N) ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)], (R ¹ H ₃ N) ₂ [ {WO (O ₂ ) ₂ } ₂ (μ-O)] or (H ₄ N) ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)] The manufacturing method in any one of 8.
10. 10. The tungsten peroxide compound to be produced is (R ¹ R ² R ³ R ⁴ N) ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)] The manufacturing method of crab.
11. 11. The tungsten peroxide compound to be produced is [(R ¹ ) ₄ N] ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)]. Manufacturing method.
12. The tungsten peroxide compound to be produced is [(n-C ₄ H ₉ ) ₄ N] ₂ [{WO (O ₂ ) ₂ } ₂ (μ-O)]. The manufacturing method in any one.
13. 13. A method for producing an epoxy compound, wherein an olefin epoxidation reaction using hydrogen peroxide as an oxidizing agent is carried out using the tungsten peroxide compound produced by the method according to any one of claims 1 to 12 as a catalyst.
14. The method for producing an epoxy compound according to claim 13, wherein the olefin is an alicyclic olefin.
15. The method for producing an epoxy compound according to claim 14, wherein the alicyclic olefin is tetrahydroindene.