JPH0827136A - Production of epoxy compound - Google Patents

Abstract

PURPOSE:To obtain an epoxy compound in high selectivity and yield by reacting olefins with hydrogen peroxide in the presence of an alpha-aminomethylphosphonic acid with tungstic acids and a catalyst in an organic solvent. CONSTITUTION:This method for producing an epoxy compound is to carry out the oxidizing reaction of olefins such as an aliphatic olefinic unsaturated hydrocarbon with an equimolar amount or more of aqueous hydrogen peroxide (preferably a molar amount of 1.5-5 times) in the presence of (A) an alpha- aminomethylphosphonic acid of the formula (R1 to R3 are each H, a 1-18C alkyl or aryl), (B) tungstic acids such as tungstic acid (or an alkali tungstate) and (C) a phase-transfer catalyst such as quaternary ammonium salts (containing a nitrogen ring) in an organic solvent comprising preferably an aromatic hydrocarbon.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an epoxy compound from olefins and aqueous hydrogen peroxide, and more particularly to a method for producing an epoxy compound with high yield and high selectivity.

[0002]

2. Description of the Related Art Generally, in a method for producing an epoxy compound by reacting an olefin with a hydrogen peroxide solution, the conversion and the selectivity of the olefin to the epoxy compound are low. A manufacturing method using is proposed. For example, a method using a derivative of a specific element and a phase transfer catalyst (JP-A-57-156475).
Issue gazette). In this method, by using a phase transfer catalyst such as a quaternary ammonium salt, the operation of carrying out the reaction while removing water is unnecessary. However, since a large excess of olefin is used for the reaction, the conversion rate of olefin is inevitably low, and in order to minimize the amount of water introduced into the reaction system, a relatively high concentration (50
%) Hydrogen peroxide solution is used, so it is difficult to handle, and the economical efficiency of equipment is also a disadvantage.

Further, as a method of using a relatively low concentration hydrogen peroxide solution which is easy to handle, a salt of a quaternary ammonium salt with a group V element of the periodic table and a heteropolyacid ion of tungsten or its peroxide is used. There is a method of reacting an olefin and an aqueous hydrogen peroxide in an organic solvent using an oxidation catalyst consisting of (JP-A-62-234550). In this method, the prepared catalyst salt is previously treated with hydrogen peroxide water, or the catalyst is prepared in the presence of hydrogen peroxide, whereby a catalyst having an enhanced activity can be prepared. However, halogenated hydrocarbons are used as the preferred solvent in this method and the use of aromatic hydrocarbon solvents has not been practical. That is, the epoxidation reaction of 1-octene in a water-organic solvent two-layer system using organic tungstophosphoric acid as a catalyst has been reported, but when chloroform is used as an organic solvent, the yield is 80%.
On the other hand, it was found that the yield was as low as 33% when benzene was used (Ishii, et. Al., J. Org.
Chem. 53, 3587 (1988)). In recent years, the use of halogenated hydrocarbons has been banned or restricted due to the needs of the global environment, and an oxidation catalyst with high conversion and selectivity of olefins to epoxy compounds in non-halogenated organic solvents has been demanded. There has been a demand for a method for producing the epoxy compound used.

[0004]

SUMMARY OF THE INVENTION In view of the above circumstances, an object of the present invention is to use a hydrogen peroxide solution having a relatively low concentration, which is easy to handle on an industrial scale, and to use a non-halogen solvent such as a hydrocarbon solvent. Even if used, it is to provide a method for producing an epoxy compound using an oxidation catalyst having a high conversion rate of an olefin to an epoxy compound and a high selectivity.

[0005]

Means for Solving the Problems The present inventors have completed the present invention as a result of extensive studies to solve the above problems. That is, the present invention relates to an olefin and a hydrogen peroxide solution in an organic solvent in the presence of at least one of α-aminomethylphosphonic acid represented by the general formula (1) (formula 2), tungstic acid and a phase transfer catalyst. The present invention relates to a method for producing an epoxy compound that reacts with.

[0006]

Embedded image (Wherein, R _1, R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group or an aryl group having 1 to 18 carbon atoms) In the general formula (1), R ₁ and R ₂ are hydrogen Of the above epoxy compound in which the atom, R ₃ is an α-aminomethylphosphonic acid having an alkyl group or aryl group having 1 to 18 carbon atoms, and the organic solvent is an aromatic hydrocarbon. The present invention relates to a manufacturing method.

The present invention will be described in more detail below. The catalyst used in the production method of the present invention contains α-aminomethylphosphonic acids represented by the general formula (1), tungstic acids and a phase transfer catalyst. In the general formula (1), R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group. As alkyl, methyl, ethyl, n
-Propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, lauryl, cetyl, stearyl, etc., and aryl may have a substituent. Examples thereof include phenyl and naphthyl.

The amino group of the α-aminomethylphosphonic acid represented by the general formula (1) may be substituted with an alkyl group, an aryl group, etc., but the hydrogen atom on the nitrogen atom participates in some form to react. Among the α-aminomethylphosphonic acids, which are believed to activate active species, α-aminomethylphosphonic acids having at least one hydrogen atom on the nitrogen are particularly useful. Specific examples of α-aminomethylphosphonic acids include aminomethylphosphonic acid,
α-aminoethylphosphonic acid, α-aminopropylphosphonic acid, α-aminobutylphosphonic acid, α-aminopentylphosphonic acid, α-aminoheptylphosphonic acid, α-
Examples thereof include aminohexylphosphonic acid, α-aminoheptylphosphonic acid, α-aminooctylphosphonic acid, α-aminononylphosphonic acid and α-amino-α-phenylmethylphosphonic acid. These α-aminomethylphosphonic acids may be used alone or in combination of two or more.

The tungstic acid is generally a compound capable of forming a tungstic acid anion in water, and examples thereof include tungstic acid, alkali tungstate, ammonium tungstate, tungsten trioxide, tungsten trisulfide, tungsten hexachloride, and tungsten phosphonate. Acid, silicotungstic acid, borotungstic acid, etc. can be mentioned. The tungstic acids may be used alone or in combination of two or more.

Examples of the phase transfer catalyst include quaternary ammonium salts, nitrogen ring-containing quaternary ammonium salts, quaternary phosphonium salts, macrocyclic polyethers and the like, and quaternary ammonium salts or nitrogen ring-containing catalysts. Quaternary ammonium salts are preferred. Specific examples of the quaternary ammonium salts include trioctylmethylammonium chloride, trioctylethylammonium chloride, dilauryldimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, lauryldimethylbenzylammonium chloride, stearyldimethylammonium chloride and trioctyldimethylammonium chloride. Caprylmethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride and the like can be mentioned. Also,
These bromides, iodides, sulfites or sulfates may be used.

Examples of the nitrogen ring-containing quaternary ammonium salts include quaternary ammonium salts in which the nitrogen ring is a pyridine ring, a picoline ring, a quinoline ring, an imidazoline ring, a morpholine ring, or the like. Quaternary ammonium compounds are preferable, and specific examples include the following. Alkyl (8 to 20 carbon atoms
A straight-chain or branched alkyl of, and the like below) pyridinium salt (for example, N-laurylpyridinium chloride, N
-Cetylpyridinium chloride, etc.), alkylpicorium salt (eg, N-laurylpicolinium chloride, etc.), alkylquinolium chloride, alkylisoquinolium chloride, alkylhydroxyethylimidazoline chloride, alkylhydroxymorpholine chloride, etc. , Iodide or sulfate may be used. The phase transfer catalyst may be used alone or in combination of two or more kinds.

In the production method of the present invention, generally, the α-aminomethylphosphonic acid represented by the general formula (1), the tungstic acid and the phase transfer catalyst are
Each is used in an approximately equimolar amount, and the amount of each used is 0.01 to 10 mol%, more preferably 0.1 to 5 mol%, and most preferably 0.5 to 2 mol% with respect to the olefins.
used. In the production method of the present invention, the α-aminomethylphosphonic acid represented by the general formula (1) and tungstic acid may be treated with hydrogen peroxide water, added with a phase transfer catalyst, and extracted with an organic solvent for use. . However, the α represented by the general formula (1) can be obtained without extraction and isolation.
-There is no problem in reactivity even if a mixture of aminomethylphosphonic acid, tungstic acid and a phase transfer catalyst is added with an organic solvent and aqueous hydrogen peroxide to react.

Examples of the olefins in the present invention include aliphatic olefinic unsaturated hydrocarbons, aromatic olefinic hydrocarbons and alicyclic olefinic hydrocarbons.
Specifically, ethylene, propylene, butene, butene, pentene, hexene, hexene, heptene, octene, nonene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, aicosene, diisobutylene,
Propylene trimer or tetramer, cycloalkene or cyclopolyene (eg cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene,
Cyclopentadiene, cyclooctadiene, cyclododecatriene), dicycloalkapolyene (dicyclopentadiene, tetrahydroindene, etc.), alkylenedicycloalkane (methylenecyclopropane, methylenecyclopentane, methylenecyclohexene, etc.), vinylcycloalkene (vinylcyclohexene, etc.) These can also be used as a mixture of two or more kinds.The concentration of hydrogen peroxide water that can be used in the present invention is 5 to 50%, and the concentration of hydrogen peroxide water is 10% to 35% in terms of handling. The amount of hydrogen peroxide solution used is equimolar or more, preferably 1.5 to 5 times the amount of olefins.

As the reaction solvent, those inert to olefins, hydrogen peroxide and the produced epoxy compound can be used. Aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, ethers, esters, Examples thereof include ketones and halogenated hydrocarbons. Specifically, n-hexane, benzene, toluene, xylene, cyclohexane,
Propyl ether, dioxane, tetrahydrofuran,
Acetate ester of ethyl ether, alcohol (1 to 3 carbon atoms having 1 to 3 carbon atoms, polyhydric alcohol, polyhydric alcohol derivative), acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl propyl ketone, chloroform, dichloroethane , Trichlorethane, perchlorethane and the like.

From an industrial point of view, aromatic hydrocarbons such as benzene, toluene and xylene are preferred unless the olefins are insoluble in the solvent. The method of the present invention is
Although it can be carried out in halogenated hydrocarbons, the use of halogenated hydrocarbons is demanded to be prohibited or restricted in view of recent needs for the global environment as described above, which is not preferable.

A general embodiment of the invention is that the reactor comprises:
Α-Aminomethylphosphonic acid represented by the general formula (1), tungstic acid and hydrogen peroxide water are added and mixed,
After adjusting the pH, a phase transfer catalyst, olefins and an organic solvent are charged, the temperature is raised, and the reaction and aging are performed. Incidentally, industrially, a method of gradually dropping hydrogen peroxide solution in accordance with the reaction rate and the reaction heat removal rate may be adopted. In the method of the present invention, the reaction is performed by adjusting the pH of the reaction mixture. The pH is between 1.0 and 4.0, preferably p
It is preferably between H1.5 and 2.5, particularly preferably about pH 2.0. The pH of the reaction mixture can be adjusted by adding an aqueous solution of an acid such as sulfuric acid or phosphoric acid.

The reaction temperature is usually about 0 to 120 ° C., preferably 20 to 1 considering the reaction rate and the decomposition of hydrogen peroxide.
It is about 00 ° C. The reaction time varies depending on the reaction conditions such as the amount of the catalyst used, the reaction temperature and the reactivity of the olefins, but is usually several minutes to 50 hours. In the production method of the present invention, the production of by-products is small, and after the reaction, excess hydrogen peroxide, catalyst,
The target epoxy compound of olefins can be obtained by removing water and the reaction solvent.

[0018]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 A 100 ml eggplant-shaped flask equipped with a Dimro cooler and a magnetic stirrer was placed in a sodium tungstate dihydrate (660
mg, 2.00 mmol), hydrogen peroxide solution (30%, 2
2.7 g, 200 mmol) and aminomethylphosphonic acid (222 mg, 2.00 mmol) were added, and 8 wt
The pH was adjusted to 2.0 with% sulfuric acid. Toluene (20 ml), 1-octene (11.2 g, 100 mm)
ol), trioctylmethylammonium chloride (808 mg, 2.00 mmol) and n-nonane (621.8 mg, 4.85 mmol) as an internal standard, and the mixture was stirred at 90 ° C. for 4 hours. When the reaction was traced by gas chromatography, 1,2-epoxyoctane was obtained with a yield of 98%.

EXAMPLE 2 Sodium tungstate dihydrate (330) was placed in a 100 ml eggplant-shaped flask equipped with a Dimro condenser and a magnetic stirrer.
mg, 1.00 mmol), hydrogen peroxide solution (30%, 2
2.7 g, 200 mmol) and aminomethylphosphonic acid (111 mg, 1.00 mmol) were added, and 8 wt
The pH was adjusted to 2.0 with% sulfuric acid. Toluene (20 ml), cis-3-octene (11.2 g, 1
00 mmol), trioctylmethylammonium chloride (404 mg, 1.00 mmol) and n-nonane as an internal standard (670.5 mg, 5.23 mmo).
1) was added, and the mixture was stirred at 90 ° C. for 1.5 hours. The reaction was traced by gas chromatography, yielding 99% yield of 3, 4
-Epoxy octane is obtained. The obtained 3,4-epoxyoctane was isolated and purified, and its NMR was measured.
It was s-3,4-epoxy octane. .

Example 3 Sodium tungstate dihydrate (330) was placed in a 100 ml eggplant-shaped flask equipped with a Dimro condenser and a magnetic stirrer.
mg, 1.00 mmol), hydrogen peroxide solution (30%, 2
2.7 g, 200 mmol) and aminomethylphosphonic acid (111 mg, 1.00 mmol) were added, and 8 wt
The pH was adjusted to 2.0 with% sulfuric acid. Toluene (20 ml), trans-3-octene (11.2
g, 100 mmol), trioctylmethylammonium chloride (404 mg, 1.00 mmol) and n-nonane (676.1 mg, 5.23) as an internal standard.
mmol) was added and the mixture was stirred at 90 ° C. for 5 hours. When the reaction was traced by gas chromatography, the yield was 98%, 3,
4-epoxy octane was obtained. The obtained 3,4-epoxyoctane was isolated and purified, and the NMR was measured.
It was trans-3,4-epoxy octane. .

Example 4 Epoxidation reaction of geraniol Sodium tungstate dihydrate (66.0) was placed in a 20 ml eggplant type flask equipped with a Dimro condenser and a magnetic stirrer.
mg, 0.20 mmol), aminomethylphosphonic acid (22.2 mg, 0.20 mmol), and hydrogen peroxide solution (30%, 3.40 g, 30.0 mmol) were added, and the pH was adjusted to 2 with 8 wt% sulfuric acid. Adjusted to 0. Toluene (4 ml), trioctylmethylammonium chloride (80.8 mg, 0.20 mmol) and geraniol (3.85 g, 20.0 mmol) were added to this, and 9
The mixture was stirred at 0 ° C for 30 minutes. After the reaction, the organic layer was separated, and the aqueous layer was extracted twice with 10 ml of ethyl acetate. Combine the organic layers,
The extract was washed with 10 ml of saturated saline and then dried over anhydrous sodium sulfate. The solvent was distilled off with a rotary evaporator, and the residue was chromatographed on silica gel (BW-820M, 150 g,
It was purified by hexane / ether = 10: 1) to obtain 2.73 g (yield 80.0%) of the following target compound (Chemical Formula 3).

[0022]

Embedded image Example 5 The reaction was performed in the same manner as in Example 1 except that the reaction time in Example 1 was changed to 3 hours, and the yield of 1,2-epoxyoctane was analyzed by gas chromatography. The results shown in () are obtained. Examples 6 to 7 The reaction was performed in the same manner as in Example 5 except that the aminomethylphosphonic acid of Example 5 was replaced with α-aminoethylphosphonic acid and α-amino-α-phenylmethylphosphonic acid, respectively. When the yield of 2-epoxyoctane was analyzed, the results shown in Table 1 were obtained.

Comparative Example 1 Reaction was carried out in the same manner as in Example 5, except that the aminomethylphosphonic acid of Example 5 was replaced with β-aminoethylphosphonic acid.
When the yield of 1,2-epoxyoctane was analyzed by gas chromatography, the results shown in Table 1 were obtained. Comparative Examples 2 to 4 The β-aminoethylphosphonic acid of Comparative Example 1 was converted into γ
-Aminopropylphosphonic acid, α-dimethylamino-α
-A reaction was performed in the same manner as in Comparative Example 1 except that phenylmethylphosphonic acid and phenylphosphonic acid were used, and the yield of 1,2-epoxyoctane was analyzed by gas chromatography. The results shown in Table 1 were obtained.

[0024]

[Table 1] From Table-1, it can be seen that among the aminophosphonic acids, the substitution position of the amino group is the α-position, that a hydrogen atom is present on the nitrogen atom of the amino group, and the like are essential for increasing the reaction activity. .

[0025]

Industrial Applicability By producing an epoxy compound by the production method according to the present invention, the desired epoxy compound can be produced in a high yield under industrially advantageous conditions. The epoxy compound obtained by the method for producing an epoxy compound of the present invention is useful as a raw material for producing an epoxy resin useful as a sealing material for electronic parts, an intermediate for organic chemicals, agricultural medicine, and the like.

Claims (3)

[Claims] 1. At least one general formula (1)
Α-aminomethylphosphonic acid represented by: (In the formula, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group.) In the presence of a tungstic acid and a phase transfer catalyst, an olefin is used in an organic solvent. A method for producing an epoxy compound, which comprises reacting a salt with aqueous hydrogen peroxide. 2. In the general formula (1), R ₁ and R ₂
The method for producing an epoxy compound according to claim 1, wherein is a hydrogen atom and R ₃ is an α-aminomethylphosphonic acid in which an alkyl group or an aryl group having 1 to 18 carbon atoms is used. 3. The method for producing an epoxy compound according to claim 1, wherein the organic solvent is an aromatic hydrocarbon.