JP2003238544A - Method for producing epoxides - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a more economical method for producing epoxides environmentally excellently by using hydrogen peroxide. <P>SOLUTION: This method for producing the epoxide comprises reacting an olefin with hydrogen peroxide in the presence of a tungsten oxide that is obtained by reacting a tungsten compound with hydrogen peroxide, a phase transfer catalyst and a tribasic alkali metal phosphate or an alkali earth phosphate. As the tungsten compound, for example, a tungsten metal, tungsten carbide, tungsten boride, tungsten sulfide, or the like, are cited. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing epoxides.

[0002]

2. Description of the Related Art Epoxides are important compounds as various chemical products such as resins and their synthetic intermediates.
A method of oxidizing with peracids such as m-chloroperbenzoic acid and peracetic acid is known. However, peracid is relatively expensive, requires careful handling, and is troublesome in post-treatment after the reaction. Therefore, development of a method for producing epoxides without using peracid has been desired.

In recent years, hydrogen peroxide has been attracting attention as a clean and excellent oxidizing agent that is inexpensive, easy to handle, and becomes harmless water after the reaction. A method for producing epoxides has been reported. For example, a method of reacting olefins with hydrogen peroxide in the presence of α-aminomethylphosphonic acid, a phase transfer catalyst and tungstic acids (JP-A-8-2
7136), a phosphoric acid, a phase transfer catalyst, and a tungstic acid in the presence of a method of reacting olefins with hydrogen peroxide (J. Org. Chem., 48 ,
3831 (1983)) and the like, but the method is expensive, has high hygroscopicity, and requires careful handling.
-In the point that aminomethylphosphonic acid must be used, the method of (1) uses 1,2-dichloroethane as a solvent, which is problematic in terms of environment and occupational safety and health, and is therefore not sufficiently satisfactory from an industrial viewpoint. It wasn't a feasible method.

[0004]

Under these circumstances, the present inventors have used hydrogen peroxide and are excellent in terms of environment.
As a result of intensive studies to develop a more economical method for producing epoxides, a tungsten oxide and a phase transfer catalyst obtained by reacting easily available tungsten compounds such as tungsten metal or tungsten boride with hydrogen peroxide. And epoxides can be produced by reacting olefins with hydrogen peroxide in the presence of a trialkali metal phosphate such as trisodium phosphate or an alkaline earth metal phosphate such as calcium phosphate. The present invention has been completed and the present invention has been achieved.

[0005]

That is, the present invention is directed to the presence of a tungsten oxide obtained by reacting a tungsten compound with hydrogen peroxide, a phase transfer catalyst, and a trialkali metal phosphate or an alkaline earth metal phosphate. Under,
The present invention provides a method for producing epoxides, which comprises reacting olefins with hydrogen peroxide.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The olefin used as a raw material may be a compound having one or more olefinic carbon-carbon double bonds in the molecule, and two carbon atoms forming the double bond are In addition to the hydrogen atom, it may be substituted with a substituent such as an alkyl group, an aryl group, an aralkyl group, a silyl group and a halogen atom.

The alkyl group includes, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group. , Linear alkyl groups such as n-octyl group, isooctyl group, n-nonyl group, n-decyl group, cyclopentyl group and cyclohexyl group, branched or cyclic alkyl groups. Such an alkyl group may have a substituent, and as the substituent,
For example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an alkoxy group such as an n-butoxy group, a silyl group described later, and a halogen atom described later are exemplified.

As the aryl group, for example, a phenyl group,
Naphthyl group and the like and phenyl group, aromatic ring constituting the naphthyl group, etc., for example, alkyl group, alkoxy group
Substituted by a substituent such as a silyl group, a halogen atom, an acyl group such as an acetyl group or a propionyl group, for example, 2-
Fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-bromophenyl group, 2-methylphenyl group, 4-methylphenyl group,
4-methoxyphenyl group, 4-acetylphenyl group, etc. are mentioned.

Examples of the aralkyl group include those composed of the above-mentioned alkyl group and the above-mentioned aryl group. For example, benzyl group, phenylethyl group, 4-fluorobenzyl group, 4-methoxybenzyl group, 2-chloro group. Examples thereof include a benzyl group.

Examples of the silyl group include trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group and methyldiphenylsilyl group. Examples of the halogen atom include fluorine atom, chlorine atom and bromine atom. Etc.

Further, the substituents of the carbon atoms constituting the olefinic carbon-carbon double bond may be joined together to form a part of a ring structure. Examples of the ring structure include a cyclobutane ring and a cyclobutane ring. Pentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring,
Examples thereof include a cyclodecane ring and a cyclododecane ring. Of course, such a ring structure may be substituted with the alkyl group, the alkoxy group, the silyl group, the halogen atom or the like.

Examples of such olefins include ethylene, propylene, 1-butene, 1-pentene, 4,4
-Dimethyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene , 1-octadecene, 3,3-dimethyl-1-butene, vinylcyclopentane, vinylcyclohexane, allylcyclohexane, styrene, 4- (tert-butyl) styrene,
Allylbenzene, 4-methoxystyrene, safrole,
Monosubstituted olefins such as eugenol and 3,4-dimethoxy-1-allylbenzene,

For example, 2-butene, isobutylene, 2-methyl-1-butene, 2-pentene, 2-hexene, 2-
Methyl-1-hexene, 3-hexene, 2-heptene,
2-methyl-1-heptene, 3-heptene, 2-octene, 3-octene, 4-octene, 2-nonene, 2-methyl-2-nonene, 3-nonene, 4-nonene, 5-decene, 2- Disubstituted olefins such as methyl-1-undecene, cyclopentene, cyclohexene, 4-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, methylenecyclohexane, β-methylstyrene, stilbene, isosafurol, isoeugenol, β-pinene, norbornene. ,

For example, 2-methyl-2-butene, 2-methyl-2-pentene, 2-methyl-2-hexene, 2,5
-Dimethyl-2,4-hexadiene, 2-methyl-2-
Heptene, 1-methylcyclopentene, 1-methylcyclohexene, 1- (tert-butyl) cyclohexene, 1-isopropylcyclohexene, 2-carene, 3
Examples include trisubstituted olefins such as -calene and α-pinene, and tetrasubstituted olefins such as 2,3-dimethyl-2-butene and 2,3,4-trimethyl-2-pentene.

Some of these olefins have geometrical isomers and optical isomers. In the present invention, a single geometrical isomer or optical isomer may be used, or a geometrical isomer may be used. You may use the mixture of and the mixture of optical isomers.

Examples of the tungsten compound include tungsten metal, a tungsten compound containing tungsten and a Group IIIb element, a tungsten compound containing tungsten and a Group IVb element, a tungsten compound containing tungsten and a Group Vb element, and tungsten. VIb
Examples thereof include a tungsten compound containing a group element, or a mixture thereof.

Examples of the compound of the group IIIb element with tungsten include tungsten boride and the like.
Examples of the tungsten compound composed of the IVb group element compound include tungsten carbide and the like and tungsten and Vb
Examples of the tungsten compound containing the group element include tungsten phosphide and tungsten nitride, and examples of the tungsten compound containing the tungsten and the group VIb element include tungsten oxide, tungsten sulfide and tungstic acid.

Among these tungsten compounds, tungsten metal, tungsten carbide, tungsten boride and tungsten sulfide are preferable. In addition, it is preferable to use a tungsten compound having a small particle size, because it facilitates the preparation of the tungsten oxide.

Tungsten oxide is prepared by reacting such a tungsten compound with hydrogen peroxide. Hydrogen peroxide is usually used as an aqueous solution, but an organic solvent solution may be used. It is preferable to use an aqueous hydrogen peroxide solution because it is easier to handle. The hydrogen peroxide concentration in the aqueous hydrogen peroxide solution or the organic solvent solution is not particularly limited, but is practically 1 to 60% by weight in consideration of volume efficiency, safety and the like. As the hydrogen peroxide aqueous solution, a commercially available hydrogen peroxide aqueous solution may be used as it is, or if necessary, after adjusting the concentration by dilution, concentration, etc., and an organic solvent solution of hydrogen peroxide may be, for example, an aqueous solution of hydrogen peroxide. By means such as extraction treatment with a solvent or distillation treatment in the presence of an organic solvent,
It can be prepared.

The amount of hydrogen peroxide used in preparing the tungsten oxide is usually 3 with respect to the tungsten compound.
The molar ratio is not less than 5 times, preferably not less than 5 times, and there is no particular upper limit.

The reaction between the tungsten compound and hydrogen peroxide is usually carried out in an aqueous solution. Of course, for example, ether solvents such as diethyl ether, methyl tert-butyl ether and tetrahydrofuran, ester solvents such as ethyl acetate, tertiary alcohol solvents such as tert-butanol, nitrile solvents such as acetonitrile and propionitrile. It may be carried out in an organic solvent such as or a mixed solvent of the organic solvent and water.

The temperature for preparing the tungsten oxide is usually -10 to 100 ° C.

By reacting the tungsten compound with hydrogen peroxide in water or an organic solvent, all or part of the metal compound is dissolved to prepare a homogeneous solution or suspension containing the metal oxide. However, the metal oxide may be taken out from the preparation liquid by, for example, concentration treatment and used as a catalyst, or the preparation liquid may be directly used as a catalyst.

In order to improve the contact efficiency between the tungsten compound and hydrogen peroxide, it is preferable to carry out the reaction while stirring so that the tungsten compound is sufficiently dispersed in the tungsten oxide preparation liquid. From the viewpoint of increasing the contact efficiency between the tungsten compound and hydrogen peroxide and facilitating the control during the preparation of the metal oxide, it is preferable to use a tungsten compound having a small particle size such as a powdery tungsten compound.

Examples of the trialkali metal phosphate include trisodium phosphate, tripotassium phosphate, etc.
Examples of the alkaline earth metal phosphate include calcium phosphate, calcium pyrophosphate, magnesium phosphate,
Examples include magnesium pyrophosphate and the like. Either one of these trialkali metal phosphates or alkaline earth metal phosphates may be used, or a mixture thereof may be used. Further, as the alkali metal phosphate or alkaline earth metal phosphate, an anhydride or a hydrate may be used.

The amount of trialkali metal phosphate or alkaline earth metal phosphate used is usually 0.1 to 4 times, preferably 0.3 to 2 times the mol of the tungsten oxide.

The trialkali metal phosphate or the alkaline earth metal phosphate may be used in the above-mentioned preparation of the tungsten oxide.

Examples of the phase transfer catalyst include quaternary ammonium salts, quaternary phosphonium salts, macrocyclic polyethers and the like, and quaternary ammonium salts are preferable.

Examples of the quaternary ammonium salt include trioctylmethylammonium chloride, trioctylethylammonium chloride, dilauryldimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride,
Lauryldimethylbenzylammonium chloride, tricaprylmethylammonium chloride, tridecylmethylammonium chloride, trihexylmethylammonium chloride, tridodecylmethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, N-laurylpyridinium chloride , N-cetylpyridinium chloride, quaternary ammonium chlorides such as N-laurylpicolinium chloride, and chlorine ions constituting the quaternary ammonium chlorides, quaternary ammonium bromides in which bromine ions are replaced, Chloride ions that make up quaternary ammonium chlorides are quaternary ammonium iodides that have replaced iodine ions, Chlorine ion constituting the quaternary ammonium chloride is a quaternary ammonium sulfite salt replacing sulfite ion, chlorine ion constituting the quaternary ammonium chloride is a quaternary ammonium sulfate replacing sulfate ion. Examples thereof include salts and quaternary ammonium hydrogensulfates in which the chlorine ions constituting the quaternary ammonium chlorides are replaced with hydrogensulfate ions.

Examples of the quaternary phosphonium salt include tetrabutylphosphonium bromide and the like, and examples of the macrocyclic polyethers include 12-crown-4, 18-crown-6 and benzo-18-crown-6. To be

When using such a phase transfer catalyst, the amount used is usually 0.0005 mol times or more with respect to the olefins, and there is no particular upper limit, but in view of economical aspects, it is practical. Is 1 mol times or less with respect to the olefins. Further, such a phase transfer catalyst may be used in the above-described preparation of the tungsten oxide.

Hydrogen peroxide is usually used as the hydrogen peroxide reacted with the olefins. Of course, hydrogen peroxide / organic solvent solution may be used. The hydrogen peroxide concentration in the hydrogen peroxide solution or hydrogen peroxide / organic solvent solution is not particularly limited, but considering volume efficiency, safety, etc.,
Practically, it is 1 to 60% by weight.

The amount of hydrogen peroxide used is usually 0.8 mol times or more, preferably 1 mol times or more with respect to the olefins, and there is no particular upper limit, but too much amount is economically disadvantageous. Therefore, it is practically 5 mol times or less, preferably 3 mol times or less, with respect to the olefins.

The amount of the metal oxide catalyst used is
It is usually 0.001 to 0.95 mol times, and preferably 0.005 to 0.1 mol times, relative to olefins.

The reaction between the olefins and hydrogen peroxide may be carried out without a solvent or in a water solvent or an organic solvent. Examples of the organic solvent include an aromatic hydrocarbon solvent such as toluene and xylene, an aliphatic hydrocarbon solvent such as hexane and heptane, an ether solvent such as diethyl ether, methyl tert-butyl ether, tetrahydrofuran, and diglyme. An ester solvent such as ethyl acetate, for example, a tertiary alcohol solvent such as tert-butanol, for example, acetonitrile,
Examples thereof include nitrile solvents such as propionitrile.
The amount of water solvent or organic solvent used is not particularly limited.

This reaction is usually carried out by contacting and mixing a tungsten compound, a phase transfer catalyst, a trialkali metal phosphate or an alkaline earth metal phosphate, an olefin and hydrogen peroxide. Not limited. In addition, for example, a tungsten compound, hydrogen peroxide, a trialkali metal phosphate or an alkaline earth metal phosphate, a phase transfer catalyst and olefins are brought into contact with each other and mixed to prepare a tungsten oxide, and olefins and peroxides are mixed. The reaction with hydrogen may be carried out simultaneously.

The reaction temperature is usually 0 to 130 ° C. and is usually carried out under normal pressure conditions, but it may be carried out under reduced pressure or increased pressure.

Epoxides are formed with the progress of the reaction, and the progress of the reaction can be confirmed by usual analytical means such as gas chromatography, high performance liquid chromatography, thin layer chromatography, NMR, IR and the like.

After completion of the reaction, the reaction solution is left as it is or, if necessary, residual hydrogen peroxide is decomposed with a reducing agent such as sodium sulfite, and then concentrated and crystallized to obtain the desired epoxide. The kind can be taken out. In addition, epoxides can be taken out by adding water and / or an organic solvent insoluble in water to the reaction liquid, if necessary, and subjecting it to an extraction treatment and concentrating the obtained organic layer. The taken out epoxides may be further purified by a conventional purification method such as distillation, column chromatography, recrystallization and the like.

The epoxides thus obtained include
For example, ethylene oxide, propylene oxide, 1,2
-Epoxy butane, 1,2-epoxy pentane, 4,4
-Dimethyl-1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxy Undecane, 1,2-
Epoxydodecane, 1,2-epoxytridecane, 1,
2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 3,3-dimethyl-1,2-epoxybutane, cyclopentylethylene oxide, cyclohexylethylene oxide, 3-cyclohexyl-1. , 2-
Epoxy propane, styrene oxide, 4- (tert
-Butyl) styrene oxide, 3-phenyl-1,2-
Epoxy propane, 4-methoxystyrene oxide, safrole oxide, 3- (4-hydroxy-3-methoxyphenyl) -1,2-epoxypropane, 3- (3,
4-dimethoxyphenyl) -1,2-epoxypropane, 2,3-epoxybutane, 2-methyl-1,2-epoxypropane, 2-methyl-1,2-epoxybutane, 2,3-epoxypentane, 2 , 3-epoxyhexane, 2-methyl-1,2-epoxyhexane, 3,4
-Epoxyhexane, 2,3-epoxyheptane, 3,
4-epoxyheptane, 2,3-epoxyoctane,
3,4-epoxyoctane, 4,5-epoxyoctane, 2,3-epoxynonane,

2-methyl-1,2-epoxynonane,
3,4-epoxynonane, 4,5-epoxynonane,
5,6-epoxydecane, 2-methyl-1,2-epoxyundecane, cyclopentene oxide, cyclohexene oxide, 4-methylcyclohexene oxide, cycloheptene oxide, cyclooctene oxide, cyclodecene oxide, cyclododecene oxide, β- Methyl styrene oxide, stilbene oxide, isosafluor oxide, 1- (4-hydroxy-3-methoxyphenyl) -1,2-epoxypropane, β-pinene oxide, norbornene oxide, 2-methyl-2,3-epoxybutane, 2-methyl-2,3-epoxypentane,
2-Methyl-2,3-epoxyhexane, 2,5-dimethyl-2,3-epoxyhex-4-ene, 2-methyl-2,3-epoxyheptane, 1-methyl-1,2-epoxycyclopentane , 1-methyl-1,2-epoxycyclohexane, 1- (tert-butyl) -1,2-
Epoxycyclohexane, 1-isopropyl-1,2-
Epoxy cyclohexane, 2-carene oxide, 3-carene oxide, α-pinene oxide, 2,3-dimethyl-2,3-epoxybutane, 2,3,4-trimethyl-
2,3-epoxypentane and the like can be mentioned.

[0042]

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

Example 1 A 100 mL Schlenk tube equipped with a reflux condenser was replaced with nitrogen, and 0.15 g of tungsten metal and 7.2 g of 30% by weight hydrogen peroxide were charged at room temperature, and the internal temperature was 50 ° C. for 15 minutes.
The mixture was stirred for a minute to obtain a tungsten oxide preparation liquid. The prepared solution was cooled to room temperature, 0.2 g of trisodium phosphate dodecahydrate was added, and the mixture was stirred for 3 minutes, after which 4.4 g of cyclooctene and 0.19 g of trioctylmethylammonium hydrogensulfate were added. A solution consisting of 8 mL of toluene and 8 mL of toluene was charged, and the mixture was stirred and held at an internal temperature of 90 ° C. for 2 hours to cause a reaction. The obtained reaction liquid was cooled and then subjected to liquid separation treatment to obtain an organic layer containing cyclooctene oxide. When the organic layer was analyzed by gas chromatography (internal standard method), the yield of cyclooctene oxide was 98% (based on cyclooctene).

Example 2 A 100 mL Schlenk tube equipped with a reflux condenser was replaced with nitrogen, and 0.15 g of tungsten metal and 7.2 g of 30% by weight hydrogen peroxide solution were charged at room temperature, and an internal temperature of 50 ° C. was applied for 15 minutes.
The mixture was stirred for a minute to obtain a tungsten oxide preparation liquid. The prepared solution was cooled to room temperature, 0.2 g of trisodium phosphate dodecahydrate was added, and the mixture was stirred for 3 minutes, and then 4.5 g of 2-octene and trioctylmethylammonium hydrogensulfate 0. A solution consisting of 19 g and 8 mL of toluene was charged, and the mixture was stirred and held at an internal temperature of 70 ° C. for 4 hours to cause a reaction.
The obtained reaction liquid was cooled and then subjected to liquid separation treatment to obtain an organic layer containing 2,3-epoxyoctane. When the organic layer was analyzed by gas chromatography (internal standard method),
The yield of 2,3-epoxyoctane was 75% (based on 2-octene).

Example 3 A 100 mL Schlenk tube equipped with a reflux condenser was replaced with nitrogen, and 0.15 g of tungsten metal and 7.2 g of 30% by weight hydrogen peroxide solution were charged at room temperature, and the internal temperature was 50 ° C. for 15 minutes.
The mixture was stirred for a minute to obtain a tungsten oxide preparation liquid. The prepared solution was cooled to room temperature, 0.2 g of trisodium phosphate dodecahydrate was added, and the mixture was stirred for 3 minutes, then, 5.5 g of 3-carene, trioctylmethylammonium hydrogensulfate 0.1. A solution consisting of 19 g and 8 mL of toluene was charged, and the mixture was stirred and held at an internal temperature of 70 ° C. for 4 hours to cause a reaction. The obtained reaction liquid was cooled and then subjected to liquid separation treatment to obtain an organic layer containing 3-carene oxide. When the organic layer was analyzed by gas chromatography (internal standard method), the yield of 3-carene oxide was 80% (based on 3-carene).

Example 4 A 100 mL Schlenk tube equipped with a reflux condenser was replaced with nitrogen, and 0.15 g of tungsten metal and 7.2 g of 30% by weight hydrogen peroxide solution were charged at room temperature, and the internal temperature was 50 ° C. for 15 minutes.
The mixture was stirred for a minute to obtain a tungsten oxide preparation liquid. The prepared solution was cooled to room temperature, 0.2 g of trisodium phosphate dodecahydrate was added, and the mixture was stirred for 3 minutes, then, 5.5 g of 3-carene, trioctylmethylammonium hydrogensulfate 0.1. A solution consisting of 19 g and 8 mL of toluene was charged, and the mixture was stirred and held at room temperature for 96 hours to be reacted. The obtained reaction liquid was cooled and then subjected to liquid separation treatment to obtain an organic layer containing 3-carene oxide. When the organic layer was analyzed by gas chromatography (internal standard method), the yield of 3-carene oxide was 97% (based on 3-carene).

Example 5 A 100 mL Schlenk tube equipped with a reflux condenser was replaced with nitrogen, and at room temperature, 0.16 g of tungsten boride and 30
Charge 7.2% by weight hydrogen peroxide solution, and set the internal temperature at 50 ° C to 1
The mixture was stirred for 5 minutes to obtain a tungsten oxide preparation liquid. The prepared solution was cooled to room temperature, 0.2 g of trisodium phosphate dodecahydrate was added, and the mixture was stirred for 3 minutes, after which 4.4 g of cyclooctene and 0.19 g of trioctylmethylammonium hydrogensulfate were added. A solution consisting of 8 mL of toluene and 8 mL of toluene was charged, and the mixture was stirred and held at an internal temperature of 90 ° C. for 4 hours to cause a reaction. The obtained reaction liquid was cooled and then subjected to liquid separation treatment to obtain an organic layer containing cyclooctene oxide. When the organic layer was analyzed by gas chromatography (internal standard method), the yield of cyclooctene oxide was 88% (based on cyclooctene).

Example 6 A 100 mL Schlenk tube equipped with a reflux condenser was replaced with nitrogen, and 0.16 g of tungsten carbide and 7.2 g of 30% by weight hydrogen peroxide solution were charged at room temperature, and the internal temperature was 50 ° C. for 15 minutes.
The mixture was stirred for a minute to obtain a tungsten oxide preparation liquid. The prepared solution was cooled to room temperature, 0.2 g of trisodium phosphate dodecahydrate was added, and the mixture was stirred for 3 minutes, after which 4.4 g of cyclooctene and 0.19 g of trioctylmethylammonium hydrogensulfate were added. A solution consisting of 8 mL of toluene and 8 mL of toluene was charged, and the mixture was stirred and held at an internal temperature of 90 ° C. for 4 hours to cause a reaction. The obtained reaction liquid was cooled and then subjected to liquid separation treatment to obtain an organic layer containing cyclooctene oxide. When the organic layer was analyzed by gas chromatography (internal standard method), the yield of cyclooctene oxide was 91% (based on cyclooctene).

Example 7 A 100 mL Schlenk tube equipped with a reflux condenser was replaced with nitrogen, 0.20 g of tungsten sulfide and 7.2 g of 30% by weight hydrogen peroxide were charged at room temperature, and an internal temperature of 50 ° C. was applied for 15 minutes.
The mixture was stirred for a minute to obtain a tungsten oxide preparation liquid. The prepared solution was cooled to room temperature, 0.2 g of trisodium phosphate dodecahydrate was added, and the mixture was stirred for 3 minutes, after which 4.4 g of cyclooctene and 0.19 g of trioctylmethylammonium hydrogensulfate were added. A solution consisting of 8 mL of toluene and 8 mL of toluene was charged, and the mixture was stirred and held at an internal temperature of 90 ° C. for 4 hours to cause a reaction. The obtained reaction liquid was cooled and then subjected to liquid separation treatment to obtain an organic layer containing cyclooctene oxide. When the organic layer was analyzed by gas chromatography (internal standard method), the yield of cyclooctene oxide was 62% (based on cyclooctene).

Example 8 A 100 mL Schlenk tube equipped with a reflux condenser was replaced with nitrogen, and 0.15 g of tungsten metal and 7.2 g of 30% by weight hydrogen peroxide were charged at room temperature, and the internal temperature was 50 ° C. for 15 minutes.
The mixture was stirred for a minute to obtain a tungsten oxide preparation liquid. The prepared liquid was cooled to room temperature, 0.2 g of trisodium phosphate dodecahydrate was added, and the mixture was stirred for 3 minutes, and then 4.5 g of 1-octene and trioctylmethylammonium hydrogen sulfate. A solution consisting of 19 g and 8 mL of toluene was charged, and the mixture was stirred and held at an internal temperature of 90 ° C. for 4 hours to cause a reaction.
The obtained reaction liquid was cooled and then subjected to a liquid separation treatment to obtain an organic layer containing 1,2-epoxyoctane. When the organic layer was analyzed by gas chromatography (internal standard method),
The yield of 1,2-epoxyoctane was 27% (based on 1-octene). The conversion rate of 1-octene is 30
%Met.

[0051]

INDUSTRIAL APPLICABILITY According to the present invention, tungsten oxide, a phase transfer catalyst, and a trialkali metal salt of phosphoric acid or an alkali which can be easily prepared from a tungsten compound such as tungsten metal or tungsten boride and hydrogen peroxide are readily available. Epoxides are obtained by reacting olefins with hydrogen peroxide in the presence of an earth metal salt, which is industrially advantageous.

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Claims (6)

[Claims] 1. An olefin and hydrogen peroxide in the presence of a tungsten oxide obtained by reacting a tungsten compound with hydrogen peroxide, a phase transfer catalyst, and a trialkali metal phosphate or an alkaline earth metal phosphate. A method for producing epoxides, which comprises reacting with 2. A tungsten compound, a tungsten compound containing tungsten metal, a tungsten compound containing tungsten and a Group IIIb element, a tungsten compound containing tungsten and a Group IVb element, a tungsten compound containing tungsten and a Group Vb element, and tungsten. The method for producing epoxides according to claim 1, wherein the method is at least one selected from the group consisting of tungsten compounds containing a Group VIb element. 3. The method for producing epoxides according to claim 2, wherein the Group IIIb element is boron. 4. The method for producing an epoxide according to claim 2, wherein the Group IVb element is carbon. 5. The method for producing epoxides according to claim 1, wherein the Group Vb element is phosphorus. 6. The method for producing epoxides according to claim 1, wherein the Group VIb element is oxygen or sulfur.