WO2003101976A1

WO2003101976A1 - Process for producing epoxide

Info

Publication number: WO2003101976A1
Application number: PCT/JP2003/006635
Authority: WO
Inventors: Masaji Hirota; Koji Hagiya
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2002-06-03
Filing date: 2003-05-28
Publication date: 2003-12-11
Also published as: AU2003241811A1

Abstract

A process for producing an epoxide, characterized by comprising reacting an olefin with hydrogen peroxide in the presence of a tungsten oxide, the tungsten oxide obtained through reaction of at least one ammonium salt selected from the group consisting of quaternary ammonium phosphates, quaternary ammonium hydrogen phosphates and quaternary ammonium dihydrogen phosphates, a tungsten compound and hydrogen peroxide.

Description

Specification

Epoxide production method

Technical field

The present invention relates to a method for producing an epoxide. Background art

Epoxides are important compounds for various chemical products such as resins and their synthetic intermediates.For example, olephine is oxidized with peracids such as perbenzoic acid and peracetic acid. There are known ways to do this. However, peracids are relatively expensive, require careful handling, and are difficult to work up after the reaction. Therefore, it has been desired to develop an epoxide production method that does not use peracids. -In recent years, hydrogen peroxide has attracted attention as a clean and excellent oxidizing agent that is inexpensive, easy to handle, and becomes harmless water after the reaction. Have been reported. For example, Japanese Patent Application Laid-Open No. Hei 8-27136 discloses that olefin and hydrogen peroxide are reacted in the presence of phase transfer catalysts such as para-aminomethylphosphonic acid, quaternary ammonium halides and tungstic acids. A method is described. However, aminomethylphosphonic acid, which is expensive, has high hygroscopicity, and requires careful handling, is not industrially and sufficiently satisfactory. Disclosure of the invention

Under such circumstances, the present inventors have studied to develop a method for advantageously producing an epoxide, and have reached the present invention.

That is, the present invention relates to a quaternary ammonium phosphate, at least one ammonium salt selected from the group consisting of a quaternary ammonium hydrogenphosphate and a quaternary ammonium dihydrogenphosphate, and a tungsten metal or tungsten compound and hydrogen peroxide. To provide a method for producing an epoxide, which comprises reacting olefin and hydrogen peroxide in the presence of a tungsten oxide obtained by reacting BEST MODE FOR CARRYING OUT THE INVENTION

The olefin used in the present invention is not particularly limited as long as it has one or more olefinic carbon-carbon double bonds in the molecule.

Such olefins include, for example, formula (1):

(Wherein, RR ² , R ³ and R ⁴ are the same or different and are each a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl) Represents a substituted or unsubstituted aralkyl group, a trisubstituted silyl group or a halogen atom, wherein any two of RR ² , R ³ and R ⁴ are taken together to form a substituted or unsubstituted alkylene May form a group.).

Examples of the unsubstituted linear, branched or cyclic alkyl group represented by RR ² , R ³ or R ⁴ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group Group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, n-nonyl group, n-decyl group, Examples thereof include a linear, branched or cyclic C11-10 alkyl group such as a cyclopentyl group and a cyclohexyl group. Examples of the linear, branched or cyclic substituted alkyl group include an alkoxy group (for example, a C 1-4 alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group and an n-butoxy group). ), A trisubstituted silyl group (for example, a silyl group substituted with three substituents selected from the aforementioned C1-10 alkyl group or aryl group (phenyl group or naphthyl group, etc.)) and a halogen atom (for example, , A chlorine atom, a fluorine atom, a bromine atom, an iodine atom, etc.). Examples of the unsubstituted aryl group represented by R ¹ , R ² , R ³ or R ⁴ include a C 6-10 aryl group such as a phenyl group and a naphthyl group. Examples include linear, branched or cyclic alkyl groups, alkoxy groups, trisubstituted silyl groups, hydroxyl groups, aryl groups substituted with a substituent selected from a halogen atom or an acyl group. Here, a linear, branched or cyclic alkyl group, trisubstituted silyl group and octogen atom are the same as described above, and an alkoxy group is, for example, a methoxy group, an ethoxy group, an n-propoxy group. And a C 1-4 alkoxy group such as an isopropoxy group, an n-butoxy group, and a methylenedioxy group. Specific examples of the acyl group include, for example, an acetyl group, a propionyl group and the like.

Specific examples of the substituted or unsubstituted aryl group include, for example, 2-fluorophenyl group, 3_fluorophenyl group, 4_fluorophenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-methylphenyl, 2-bromophenyl, 2-methylphenyl, 4-methylphenyl, 4-methoxyphenyl, 3-methoxy-4-hydroxyphenyl, 3,4-dimethoxyphenyl And a 3,4-methylenedioxyphenyl group and a 4-acetylphenyl group. Specific examples of the trisubstituted silyl group in the present invention include a trimethylsilyl group, a triethylsilyl group, a dimethylphenylsilyl group, and a methyldiphenylsilyl group.

Examples of the unsubstituted or substituted aralkyl group include an alkyl group (for example, a C1-10 alkyl group) substituted with the above-mentioned substituted or unsubstituted aralkyl group. Specific examples include a benzyl group and a phenylethyl group. Group, 4-fluorobenzyl group, 4-methoxybenzyl group, 4-methylbenzyl group, 2-methylbenzyl group, 3-methoxy-4-hydroxybenzyl group, 3,4-dimethoxybenzyl group, 3,4 —Methylenedioxybenzyl group and the like.

In the formula of the olefin represented by the above formula (1), as the unsubstituted alkylene group represented by any two of R ¹ R ² , R ³ and R ⁴ together, trimethylene, tetramethylene, pentamethylene And alkylene groups such as hexamethylene, heptamethylene and octamethylene groups. Examples of the substituted alkylene group include those described above. An unsubstituted alkyl group, an alkoxy group, a trisubstituted silyl group, an unsubstituted aryl group or an alkylene group or a cycloalkylene group substituted with an octane atom, such as a cyclopentylene group, a cyclohexylene group Etc.) are exemplified.

Specific examples of such an olefin include, for example, ethylene. Further, propylene, 1-butene, 1_pentene, 4,4_dimethyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-octene, -Nonene, 1-decene, 1-decene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pendecene, 1-hexadecene, 1-octadecene, 3,3-dimethyl-1-butene, Monosubstituted olefins such as vinyl cyclopentane, vinylcyclohexane, arylcyclohexane, styrene, 4- (tert-butyl) styrene, arylbenzene, 4-methoxystyrene, safrole, eugenol, 3,4-dimethoxy-1-arylbenzene, etc. Table in the formula (1), RR ^2, third group of R ³ and R ⁴ represent a hydrogen atom, the remaining one group a group other than hydrogen .),

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, 3-nonene, 4-nonene, 5-decene, 2-methyl-1-indenecene, cyclopentene, cyclohexene, 4- Disubstituted olefins such as methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, methylenecyclohexane, / 3-methylstyrene, stilbene, isosaflor, isoeugenol, / 3-pinene, norbornene (Formula (1) In, ^{two of} R ¹ , R ² , R ³ and R ⁴ represent a hydrogen atom, and the remaining two represent groups other than hydrogen.)

For example, 2-methyl-2-butene, 2-methyl-2-pentene, 2-methyl-2-hexene, 2-methyl-1-heptene, 2-methyl-1-nonene, 1-methylcyclopentene, 1-methylcyclohexene , 1_ (tert-butyl) cyclohexene, 1-isopropylcyclohexene, 2-carene, 3-carene, α-pinene and other tri-substituted olefins (in the formula (1), RR ² , R ³ and R ⁴ One of them represents a hydrogen atom, and the remaining groups represent groups other than a hydrogen atom.), For example, tetrasubstituted olefins such as 2,3-dimethyl-2-butene and 2,3,4-trimethyl-2-pentene (in the formula (1), RR ² , R ³ and R ⁴ are not hydrogen atoms). Is exemplified.

Further, examples of the olefin include diolefins such as 2,5-dimethyl-2,4-hexadiene.

Some of these olefins include geometric isomers and optical isomers. In the present invention, a single geometric isomer or optical isomer may be used, or a mixture of geometric isomers may be used. Alternatively, a mixture of optical isomers may be used.

Examples of the tungsten metal or the tungsten compound include tungsten metal, a tungsten compound composed of tungsten and a group 13 element, a tungsten compound composed of tungsten and a group 14 element, a tungsten compound composed of tungsten and a group 15 element, and tungsten. And a simple substance or a mixture of a tandasten compound or the like consisting of a group 16 element.

A tungsten compound composed of tungsten and a Group 13 element is, for example, tungsten boride, and a tungsten compound composed of tungsten and a Group 14 element is, for example, tungsten carbide is composed of tungsten and a Group 15 element. Examples of the tungsten compound include tungsten phosphide and tungsten nitride, and examples of the tungsten compound composed of tungsten and the Group 16 element include tungsten oxide, tungsten sulfide, tungstic acid, and disodium tungstate. . Among such tungsten compounds, when a hydrate is present, an anhydride or a hydrate may be used.

Among such tungsten metals or tungsten compounds, tungsten metal, tungsten carbide, tungsten boride, tungsten sulfide, tungstic acid, tungsten oxide, and disodium tungstate are preferred. The particle size of the tungsten metal or the tungsten compound is not particularly limited, but it is preferable to use a tungsten metal or a tungsten compound having a small particle size from the viewpoint of facilitating the preparation of the tungsten oxide.

The tungsten oxide is prepared by reacting the tungsten metal or the tandasten compound with hydrogen peroxide. Hydrogen peroxide is usually water Although a solution is used, an organic solvent solution may be used. It is preferable to use an aqueous solution of hydrogen peroxide in that handling is easier. The concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution or in the organic solvent solution of hydrogen peroxide is not particularly limited, but is practically 1 to 60% by weight in consideration of volumetric efficiency, safety and the like. The aqueous hydrogen peroxide solution may be used as it is, or may be used as it is or after adjusting the concentration by dilution, concentration, or the like as necessary. The hydrogen peroxide organic solvent solution can be prepared by, for example, extracting an aqueous hydrogen peroxide solution with an organic solvent, or distilling the aqueous solution in the presence of an organic solvent.

The amount of hydrogen peroxide used for preparing the tungsten oxide is usually at least 3 moles, preferably at least 5 moles, per mole of the tandasten metal or tungsten compound, and the upper limit is not particularly limited.

The reaction of tungsten metal or tandastene compound with hydrogen peroxide is usually carried out in water. Of course, ether solvents such as getyl ether, methyl tert-butyl ether, tetrahydrofuran, etc .; ester solvents such as ethyl acetate; tertiary alcohol solvents such as tert-butanol; nitrile solvents such as acetonitrile It may be carried out in an organic solvent such as a solvent or a mixed solvent of the organic solvent and water. The reaction temperature is usually from −10 to 100.

When tungsten metal or a tungsten compound is reacted with hydrogen peroxide in water, an organic solvent, or an organic solvent Z-water mixed solvent, all or a part of the tungsten metal or tungsten compound is dissolved, and the tungsten oxide is dissolved. A solution or suspension containing the same is obtained. Tungsten oxide may be taken out of the solution or suspension and used as a catalyst for the reaction between olefin and hydrogen peroxide. May be used as a catalyst as it is.

During the preparation of the tandastene oxide, the reaction is carried out with stirring so that the tungsten metal or tandastene compound is sufficiently dispersed in the tungsten oxide preparation liquid in order to improve the contact efficiency between the tungsten metal or the tandastene compound and hydrogen peroxide. Is preferred. In addition, in order to increase the contact efficiency between the tungsten metal or the tungsten compound and the hydrogen peroxide and to facilitate the control during the preparation of the tungsten oxide, for example, particles of the tungsten metal or the tundastene compound such as powdery tungsten metal or the like. It is preferable to use a fine stainless steel metal or fine stainless steel compound. In the present invention, at least one selected from the group consisting of quaternary ammonium phosphate, quaternary ammonium hydrogenphosphate and quaternary ammonium dihydrogenphosphate (hereinafter abbreviated as quaternary ammonium salt). Is used.

Examples of quaternary ammonium phosphates include triphosphate (methyltrioctyl ammonium), triphosphate (ethyltrioctyl ammonium), triphosphate (butyl trioctyl ammonium), and triphosphate (tetraethylammonium). Octylammonium), triphosphate [methyltri (decyl) ammonium], triphosphate [ethylethyl (decyl) ammonium], triphosphate [butylethyl (decyl) ammonium], triphosphate [tetra (decyl) ammonium] ], Triphosphate [methyltri (dodecyl) ammonium], triphosphate [dimethyldi (dodecyl) ammonium], triphosphate [trimethyl (dodecyl) ammonium], triphosphate [tetra (dodecyl) ammonium], phosphoric acid Tri [trimethyl (tetradecyl) ammonium], La Defense Sil) Anmoniumu], tricalcium phosphate [trimethyl (tetradecyl) Anmoniumu], tricalcium phosphate [tetra (tetradecyl) Anmoniumu,

Triphosphate (lauryl dimethyl pendant ammonium), triphosphate (methyltrihexyl ammonium), triphosphate (dimethyldihexyl ammonium), triphosphate (trimethylhexyl ammonium), phosphorus Triphosphate (tetrahexyl ammonium), Triphosphate (tetrabutylammonium), Triphosphate (benzyltrimethylammonium), Triphosphate (benzyltriethylammonium), Triphosphate (N _Lauryl pyridinium), triphosphate (N-cetylpyridinium), triphosphate (N_lauryl picolinium) and the like.

Examples of the quaternary ammonium hydrogen phosphate include dihydrogen phosphate (methyltrioctyl ammonium), dihydrogen phosphate (ethyltrioctylammonium), and dihydrogen phosphate (butyltrioctylammonium). ), Dihydrogen phosphate (tetraoctyl ammonium), dihydrogen phosphate [methyltri (decyl) ammonium], dihydrogen phosphate [ethylethyl (decyl) ammonium], dihydrogen phosphate [butylbutyl (decyl) ammonium], phosphorus Dihydrogen phosphate [tetra (decyl) ammonium], dihydrogen phosphate [methyltri (dodecyl) ammonium], dihydrogen phosphate [dimethyldi (dodecyl)] Ammonium], dihydrogen phosphate [trimethyl (dodecyl) ammonium], dihydrogen phosphate [tetra (dodecyl) ammonium], dihydrogen phosphate [trimethyl (tetradecyl) ammonium], dihydrogenphosphate [dimethyldi (tetradecyl) ammonium] ], Dihydrogen phosphate [trimethyl (tetradecyl) ammonium], dihydrogen phosphate [tetra (tetradecyl) ammonium],

Dihydrogen phosphate (lauryl dimethyl pendenyl ammonium), dihydrogen phosphate (methyl trihexyl ammonium), dihydrogen phosphate (dimethyl dihexyl ammonium), dihydrogen phosphate ( Trimethylhexylammonium, dihydrogenphosphate (tetrahexylammonium), dihydrogenphosphate (tetrabutylammonium), dihydrogenphosphate (benzyltrimethylammonium), dihydrogenphosphate ( Benzyltriethylammonium), dihydrogen phosphate (N-laurylpyridinium), dihydrogen hydrogen phosphate (N-cetylbiridinium), dihydrogen phosphate (N-laurylpicolinium), and the like. .

Examples of the quaternary ammonium dihydrogen phosphate include, for example, dihydrogen phosphate (methyltrioctyl ammonium), dihydrogen phosphate (ethyltrioctyl ammonium), and dihydrogen phosphate (butyltrioctyl ammonium). ), Dihydrogen phosphate (tetraoctylammonium), dihydrogen phosphate [methyltri (decyl) ammonium], dihydrogen phosphate [ethylethyl (decyl) ammonium], dihydrogen phosphate [butylethyl (decyl) ammonium], phosphoric acid Dihydrogen [tetra (decyl) ammonium], dihydrogen phosphate [methyltri (dodecyl) ammonium], dihydrogen phosphate [dimethyldi (dodecyl) ammonium], dihydrogen phosphate [trimethyl (dodecyl) ammonium], phosphoric acid Dihydrogen [tetra (dodecyl) ammonium], dihydrogen phosphate [trimethyl (Tetradecyl) ammonium], dihydrogen phosphate [dimethyldi (tetradecyl) ammonium], dihydrogen phosphate [trimethyl (tetradecyl) ammonium], dihydrogenphosphate [tetra (tetradecyl) ammonium],

Dihydrogen phosphate (lauryl dimethyl pendyl ammonium), dihydrogen phosphate (methyl trihexyl ammonium), dihydrogen phosphate (dimethyl dihexyl ammonium), dihydrogen phosphate (trimethyl hexyl ammonium) Dihydrogen phosphate (tetrahexylammonium), dihydrogen phosphate (tetrabutylammonium), dihydrogen phosphate (benzyltrimethylammonium), dihydrogenphosphate (benzyltriethylammonium)ゥ ), Dihydrogen phosphate (N_laurylpyridinium), dihydrogen phosphate (N-cetylbiridinium), dihydrogen phosphate (N-laurylpicolinium) and the like. The amount of the quaternary ammonium salt used may be 0.25 mol or more with respect to 1 mol of tungsten oxide, and there is no particular upper limit, but in consideration of economical aspects, practically, It is at most 2 moles with respect to tungsten oxide. Such a quaternary ammonium salt may be used in advance in the preparation of the above-mentioned tungsten oxide, but is preferably used in the reaction between olefin and hydrogen peroxide described later.

As the hydrogen peroxide used for the reaction with Orefin, an aqueous solution is usually used. Of course, an organic solvent solution of hydrogen peroxide may be used. The concentration of hydrogen peroxide in the aqueous solution of hydrogen peroxide or the solution of hydrogen peroxide in an organic solvent is not particularly limited, but is practically 1 to 60% by weight in consideration of volumetric efficiency and safety.

The amount of hydrogen peroxide used is usually at least 0.8 mol, preferably at least 1 mol per mol of olefin, and there is no particular upper limit. Practically, the amount is practically 5 mol or less, preferably 3 mol or less, based on the olefin. When a solution or suspension containing tungsten oxide is used, the amount of hydrogen peroxide to be used may be determined in consideration of the amount of hydrogen peroxide contained in the solution or suspension.

The amount of the tungsten oxide to be used is generally 0.01 to 0.95 mol, preferably 0.05 to 0.1 mol, per mol of olefin as tungsten metal.

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

This reaction is usually carried out with tungsten oxide, quaternary ammonium salt, Contacting and mixing hydrogen peroxide and hydrogen peroxide, for example, by contacting and mixing tungsten metal or a tungsten compound, quaternary ammonium salt, orefin and hydrogen peroxide, preparing tungsten oxide, The reaction with hydrogen peroxide may be performed simultaneously and in parallel.

The reaction temperature of the reaction between olefin and hydrogen peroxide is usually from 0 to 13 O, and the reaction is usually carried out under normal pressure, but may be carried out under reduced pressure or increased pressure.

The pH in the reaction system is preferably in the range of 1-4, more preferably in the range of 2-3.5, and more preferably in the range of 2-3, The range is more preferred. Therefore, if the pH range in the reaction system is not within the above range, the pH in the reaction system is adjusted to the above range using an acid such as sulfuric acid or an alkali metal hydroxide such as sodium hydroxide. Preferably, the reaction is carried out.

After completion of the reaction, the resulting reaction solution is decomposed as it is or, if necessary, the remaining hydrogen peroxide is decomposed with a reducing agent such as sodium sulfite, followed by concentration treatment, crystallization treatment, etc. Can be taken out. The epoxide can also be taken out by adding water and / or an organic solvent insoluble in water to the reaction solution, if necessary, performing an extraction treatment, and concentrating the obtained organic layer. The extracted epoxide may be further purified by ordinary purification means such as distillation, column chromatography, recrystallization and the like.

The epoxide thus obtained has the following formula (2):

(Wherein, Ri-R ⁴ has the same meaning as defined for formula (1)).

Specific examples of such epoxides include ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, 4,4-dimethyl-1,2-epoxypentane, and 1,2-epoxypentane. Epoxy hexane, 1,2-eppo Xyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxypandecane, 1,2-epoxidedodecane, 1,2-epoxytridecane, 1,2 _Epoxytetradecane, 1,2-epoxybenzenedecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, 3,3-dimethyl-1,2_epoxybutane, cyclopentylethylene oxide, cyclohexane Xylethylene oxide, 3-cyclohexyl-1,2-epoxypropane, styreneoxide, 4_ (tert-butyl) styreneoxide, 3-phenyl-1,2-epoxypropane, 4-methoxystyreneoxide, safrrooxide, 3_ (4-Hydroxy-3-methoxyphenyl) 1-1,2-epoxypropane, 3- (3,4-dimethoxyphenyl) — 1,2-E Xypropane, 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-epoxy Dexdecane, cyclopentenoxide, cyclohexenoxide, 4-methylcyclohexenoxide, cycloheptene oxide, cyclooctenoxide, cyclodeceneoxide, cyclodode Nokishido, / 3-methylstyrene O sulfoxide, stilbene O dimethylsulfoxide, Isosa Flore O dimethylsulfoxide, 1- (4-hydroxy-one 3- main Tokishifueniru) -1, 2-epoxypropane, 3- Binenokishido, norbornene Nenokishido,

2-methyl-2,3-epoxybutane, 2-methyl-2,3-epoxypentane, 2-methyl-2,3-epoxyhexane, 2,5-dimethyl-2,3-epoxyhexane 4- 1, 2-methyl-2,3-epoxyheptane, 1-methyl-1,2-epoxycyclopentane, 1_methyl-1,2-epoxycyclohexane, 1- (tert-butyl) -1,2 —Epoxycyclohexane, 1-isopyl pill 1,2 _epoxycyclohexane, 2-force lenoxide, 3 _carene Oxide, α-pinenoxoxide, 2,3-dimethyl-2,3-epoxybutane, 2,3,4-trimethyl-2,3-epoxypentane and the like are exemplified. Example

Hereinafter, 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

A 10 OmL Schlenk tube equipped with a reflux condenser was purged with nitrogen, and at room temperature, 0.26 g of disodium tandestenate · decahydrate and 7.2 g of 30% by weight hydrogen peroxide solution were charged. After stirring and reacting for a minute, a tungsten oxide preparation was obtained. A solution consisting of 4.4 g of 1-octene, 0.19 g of trioctylmethylammonium dihydrogen phosphate and 8 mL of toluene was added to the prepared solution, and sulfuric acid was further added to adjust the pH in the reaction system to 2%. Adjusted to 5. Thereafter, the mixture was stirred and reacted at an internal temperature of 9 for 4 hours. After cooling the obtained reaction solution, liquid separation treatment was performed to obtain an organic layer containing 1,2-epoxysiloxane. When the organic layer was analyzed by gas chromatography (internal standard method), the yield of 1,2-epoxyoctane was 85%. Example 2

Example 1 was repeated, except that the reaction was carried out at an internal temperature of 90 for 6 hours. Thus, 1,2-epoxyoctane was obtained at a yield of 90%.

Example 3

A 10 OmL Schlenk tube equipped with a reflux condenser was purged with nitrogen, and at room temperature, 0.26 g of disodium tandestenate · decahydrate and 7.2 g of 30% by weight hydrogen peroxide solution were charged. After stirring and reacting for a minute, a tungsten oxide preparation was obtained. A solution consisting of 4.4 g of cyclooctene, 0.19 g of trioctylmethylammonium dihydrogen phosphate and 8 mL of toluene was added to the preparation, and sulfuric acid was added to adjust the pH in the reaction system to 2.8. did. Thereafter, the mixture was stirred and reacted at an internal temperature of 90 for 3 hours. After the obtained reaction solution was cooled, liquid separation treatment was performed to obtain an organic layer containing cyclooctenoxide. When the organic layer was analyzed by gas chromatography (internal standard method), the yield of cyclooctenoxide was 95%. Example 4

A 10 OmL Schlenk tube equipped with a reflux condenser was purged with nitrogen, and at room temperature, 0.26 g of disodium tungstostenate · 12 hydrate and 7.2 g of 30% by weight hydrogen peroxide solution were charged. After stirring and reacting for a minute, a tungsten oxide preparation was obtained. A solution consisting of 4.4 g of 1-octene, 0.126 g of dimethyl dihydrogen dioctadecyl ammonium phosphate and 8 mL of toluene was added to the prepared solution, and sulfuric acid was further added to adjust the pH in the reaction system to 2%. Adjusted to 5. Thereafter, the mixture was stirred and reacted at an internal temperature of 90 for 4 hours. After cooling the obtained reaction solution, liquid separation treatment was performed to obtain an organic layer containing 1,2-epoxy octene. When the organic layer was analyzed by gas chromatography (internal standard method), the yield of 1,2-epoxyoctene was 82%. Example 5

A 10 OmL Schlenk tube equipped with a reflux condenser was purged with nitrogen, and at room temperature, 0.26 g of sodium disodium stenoate decahydrate and 7.2 g of 30% by weight hydrogen peroxide solution were charged. The mixture was stirred and reacted for 1 minute to obtain a tungsten oxide preparation. A solution consisting of 4.5 g of 1-octene, 0.23 g of tetraoctylammonium dihydrogen phosphate and 8 mL of toluene was added to the prepared solution, and sulfuric acid was further added to adjust the pH in the reaction system to 2.5. Was adjusted. Thereafter, the mixture was stirred and reacted at an internal temperature of 90 for 4 hours. After cooling the obtained reaction solution, it was subjected to liquid separation treatment to obtain an organic layer containing 1,2-epoxyoctene. When the organic layer was analyzed by gas chromatography (internal standard method), the yield of 1,2-epoxyoctene was 80%.

Example 6

Example 1 was repeated in the same manner as in Example 5 except that 0.25 g of trioctylbutylammonium dihydrogen phosphate was used in place of tetraoctylammonium dihydrogen phosphate. An organic layer containing epoxy octene was obtained. When the organic layer was analyzed by gas chromatography (internal standard method), the yield of 1,2-epoxyoctene was 80%.

Example 7

Example 5 Same as Example 5 except that instead of tetraoctylammonium dihydrogen phosphate, 0.19 g of trioctylethylammonium dihydrogen phosphate was used. In this manner, an organic layer containing 1,2-epoxyoctene was obtained. When the organic layer was analyzed by gas chromatography (internal standard method), the yield of 1,2-epoxyoctene was 87%. Industrial applicability

According to the present invention, a tungsten oxide which can be easily prepared from readily available tungsten metal or a tandasten compound such as disodium ungstostenate and hydrogen peroxide is used as a catalyst. The use of grade ammonium phosphate, etc., is industrially advantageous since an epoxide compound can be obtained from orefin in a high yield. Moreover, since the phase transfer catalyst does not contain a halogen atom, it can be said that it is a preferable production method in terms of occupational health and environment.

Claims

The scope of the claims

1. Reaction of at least one ammonium salt selected from the group consisting of quaternary ammonium phosphate, quaternary ammonium hydrogenphosphate and quaternary ammonium dihydrogenphosphate and a tungsten metal or tungsten compound with hydrogen peroxide A method for producing an epoxide, comprising reacting an olefin and hydrogen peroxide in the presence of at least tungsten oxide.

2. Tungsten compound composed of tungsten and a Group 13 element, tungsten compound composed of tungsten and a Group 14 element, tungsten compound composed of tungsten and a Group 15 element, and tungsten and a Group 16 element 2. The production method according to claim 1, wherein the production method is at least one selected from the group consisting of tungsten compounds consisting of:

3. The method according to claim 2, wherein the Group 13 element is boron.

4. The method according to claim 2, wherein the Group 14 element is carbon.

5. The method according to claim 2, wherein the Group 15 element is phosphorus.

6. The method according to claim 2, wherein the Group 16 element is oxygen or sulfur.