JP2002371072A - Method for manufacturing alicyclic ester including epoxy group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an alicyclic ester including epoxy group in high selectivity, by a transesterification between an organic carboxylic acid ester and 2,3-epoxyalkanol, especially 2,3-epoxycyclohexanol while suppressing naturation of 2,3-epoxycyclohexanol itself or production of a polymer by a sequential naturation of the objective product in the reaction. SOLUTION: In this method for manufacturing the alicyclic ester including epoxy group by carrying out the transesterification between the organic carboxylic acid ester and 2,3-epoxycycloalkanol in the presence of a catalyst, the reaction is carried out in the presence of an inert solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transesterification reaction between an organic carboxylic acid ester compound and a 2,3-epoxycycloalkanol to produce an epoxy-containing alicyclic ester compound which can be usefully used as various crosslinking agents. On how to do it.

[0002]

2. Description of the Related Art Epoxy compounds having a glycidyl group have been widely used as useful crosslinking agents for electric insulating materials, adhesives, paints, matrix resins for composite materials, and the like. Among them, glycidyl ester compounds having a glycidyl group via an ester bond are known to have high curing reactivity.For example, glycidyl methacrylate, glycidyl ester compounds such as triglycidyl trimellitate are often used in the above fields. Used.

In recent years, epoxy-containing alicyclic compounds having an epoxy ring inside an alicyclic group have been proposed for the purpose of improving the water resistance, weather resistance or heat resistance of an epoxy compound having a glycidyl group via an ester bond. ing. They are,
It is a compound represented by the following general formula (1) in which 3,4-epoxycyclohexanemethanol is bonded via an ester bond as an epoxy group, and is partially put into practical use. (In the formula, n represents an integer of 1 or more, and R represents a hydrocarbon group.)

[0004]

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The compound represented by the above formula (1) is obtained by esterifying an organic carboxylic acid such as methacrylic acid with 3,4-epoxycyclohexanemethanol in the presence of an acid catalyst such as sulfuric acid or p-toluenesulfonic acid. Or an organic carboxylic acid alkyl ester such as methyl methacrylate and 3,4-epoxycyclohexanemethanol, the acid catalyst or lithium hydroxide, sodium alcoholate,
A method has been proposed in which a reaction is carried out in the presence of a transesterification catalyst such as aluminum alcoholate or tetrabutoxytitanium (Japanese Patent Laid-Open No. 4-283575).

The present inventors have proposed an epoxy-containing alicyclic compound having an epoxy group inside the alicyclic group as an epoxy-containing alicyclic compound represented by the following formula (2).
An epoxy-containing alicyclic compound having an epoxy group at the 3-position has been proposed (Japanese Patent Application No. 00-09352).

[0007]

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Heretofore, no technique has been reported for performing esterification by transesterification of a cycloalkanol having an epoxy group at the 2,3-position. The present inventors have disclosed in the above-mentioned Japanese Patent Application No. 00-09352 an organic alkyl ester, 2,3-epoxycyclohexanol,
And an epoxy-containing alicyclic ester was obtained by transesterification with a three-component system comprising lithium hydroxide as a catalyst. However, since the 2,3-epoxycyclohexanol used is a secondary alcohol, the transesterification rate is lower than that of primary alcohol compounds such as 3,4-epoxycyclohexanemethanol, and a side reaction tends to occur. Was in In particular, in the above three-component system, when the reaction temperature is increased or the reaction time is increased in order to increase the reaction rate, the selectivity of the target substance tends to further decrease.

[0009]

The present invention relates to an organic carboxylic acid ester and a 2,3-epoxycycloalkanol,
In particular, in the transesterification reaction with 2,3-epoxycyclohexanol, the modification of 2,3-epoxycyclohexanol itself during the reaction and the formation of a high-molecular-weight product due to the successive modification of the target product are suppressed. It is to provide a method for selectively producing an epoxy-containing alicyclic ester.

[0010]

Means for Solving the Problems In the transesterification reaction, the present inventors have studied the modification of 2,3-epoxycycloalkanol itself used as a raw material and the formation of a high molecular weight compound by successive modification of the target product. Intensive studies were carried out to suppress this and improve the reaction selectivity. As a result, it has been found that the coexistence of an inert solvent dramatically improves the reaction selectivity. Generally, the transesterification reaction is performed in an excess of an alcohol compound serving as a reaction substrate. At this time, the alcohol compound also plays a role as a solvent at the same time, and usually, in a transesterification reaction, an inert solvent which does not participate in the reaction other than the alcohol compound is not used in order to increase purification efficiency after the reaction. . The present invention provides an epoxy-containing alicyclic ring which is difficult to purify, for example, by distillation or recrystallization, by adding an inert solvent to add a step of removing the solvent, while dramatically improving the reaction selectivity. An object of the present invention is to provide a process capable of obtaining a formula ester with high purity. Furthermore, by using an inert solvent having a dielectric constant in a specific range, not only the reaction selectivity but also the decrease in the reaction rate, which is a concern due to dilution with the solvent, can be suppressed, and the reaction rate and selectivity can be balanced. The present inventors have found an efficient and efficient production method, and have reached the present invention.

That is, the present invention is as follows. 1. In a method for producing an epoxy-containing alicyclic ester compound by subjecting an organic carboxylic acid ester compound and a 2,3-epoxycycloalkanol represented by the following general formula to a transesterification reaction in the presence of a catalyst, an inert solvent is used. A method for producing an epoxy-containing alicyclic ester, which is caused to coexist.

Embedded image (In the formula, n represents an integer of 0 to 8.)

2. The method according to the above 1, wherein the 2,3-epoxycycloalkanol is 2,3-epoxycyclohexanol.

3. 3. The production method according to the above 1 or 2, wherein the inert solvent has a dielectric constant of 1.8 to 50.

4. 4. The production method according to any one of the above 1 to 3, wherein an onium salt and / or a tertiary amine compound is allowed to coexist.

Hereinafter, the present invention will be described in detail. As the 2,3-epoxycycloalkanol used in the present invention,
An epoxy group-containing alcohol represented by the following formula (3). In the present invention, n is preferably an integer selected from 1 and 2.

[0016]

Embedded image (In the formula, n represents an integer of 0 to 8.)

In the production method of the present invention, although it depends on the structure of the target compound,
3-epoxycyclohexanol can be used alone or as a mixture of two or more kinds, and further mixed with another alcoholic compound having a hydroxyl group.

In the present invention, 2,3-epoxycyclohexanol can be particularly preferably used as the 2,3-epoxycycloalkanol because the resulting epoxy-containing alicyclic ester compound has high heat resistance.

By the way, 2,3-epoxycycloalkanols are generally represented by the following formulas (4) and (5).
The is isomer (formula (4)) and the trans isomer (formula (5)) exist as stereoisomers.

[0020]

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[0021]

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In the present invention, either one of the 2,3-epoxycycloalkanols represented by the above structure may be used alone, or a mixture of both may be used.

The above-mentioned 2,3- used in the raw material of the present invention
Epoxycycloalkanols are, for example, a method of epoxidizing a 2-hydroxycycloalkene with a known oxidizing agent such as an organic peracid, hydrogen peroxide, oxygen, or the like, or a method of converting a cycloalkene into a molybdenum or vanadium catalyst. Can be easily obtained by a method of oxidation.

Hereinafter, the organic carboxylic acid ester which can be used in the present invention will be described. As the organic carboxylic acid ester used in the production method of the present invention, an ester of an organic carboxylic acid represented by the following general formula (6) with a lower alcohol is preferable.

[0025]

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In the above formula (6), R ₂ may be a linear or branched aliphatic hydrocarbon group which may have an unsaturated bond having 1 to 6 carbon atoms, or 3 to 6 carbon atoms. Represents an alicyclic hydrocarbon group. Examples of these aliphatic hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, tert-butyl, isobutyl, n-pentyl, and the like. In addition, examples of the alicyclic hydrocarbon group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and the like. In the present invention, one of these alkyl groups may be an organic carboxylic acid alkyl ester, or an ester having two or more alkyl groups at the same time may be used. Further, two or more kinds of organic carboxylic acid alkyl esters having these alkyl groups may be used. In the present invention,
R ₂ preferably has 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group, because these alkyl groups can be easily removed as a lower alcohol outside the reaction system by transesterification.

Further, n in the above formula (6) is an integer of 1 to 25.

R ₁ is an oxygen atom having 1 to 50 carbon atoms;
A hydrocarbon group that may contain at least one hetero atom selected from the group consisting of a nitrogen atom and a halogen atom. The hydrocarbon group is an aromatic hydrocarbon group, an aliphatic hydrocarbon group which may contain a linear or branched aromatic ring or a carbon-carbon unsaturated double bond, or an alicyclic hydrocarbon group.

The organic carboxylic acid used in the present invention
The ester is a COOR of the above formula (6) ₁Group is the above hydrocarbon
Attached to the carbon atom of the elementary group.

The organic carboxylic acid ester used in the present invention is an ester of the organic carboxylic acid having the structure described above with a lower alcohol, and specifically, an aromatic hydrocarbon as exemplified below. Organic carboxylic acid consisting of a group, an organic carboxylic acid consisting of an aliphatic hydrocarbon group, an organic carboxylic acid consisting of an alicyclic hydrocarbon group, or an ester of an organic carboxylic acid consisting of a hydrocarbon group having a hetero atom and a lower alcohol. is there.

Examples of the organic carboxylic acid comprising an aromatic hydrocarbon group include benzoic acid and its nuclear-substituted derivatives, naphthalene mono- or dicarboxylic acids and their nuclear-substituted derivatives, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid,
Trimesic acid, hemmellitic acid, pyromellitic acid, benzophenone polycarboxylic acid, biphenyl polycarboxylic acid and the like.

Examples of the organic carboxylic acid comprising an aliphatic hydrocarbon group include monocarboxylic acids of saturated hydrocarbons such as acetic acid, butyric acid, isobutyric acid, valeric acid, caproic acid and stearic acid, oxalic acid, malonic acid, and the like. Saturated hydrocarbon polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, sebacic acid, decanedicarboxylic acid, hexanetricarboxylic acid, and butanetetracarboxylic acid.

In the organic carboxylic acid having an aliphatic hydrocarbon group, compounds having a carbon-carbon unsaturated bond include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, vinyl acetic acid, fumaric acid, maleic acid, and itaconic acid. Acid, glutaconic acid and the like.

The alicyclic hydrocarbon group includes cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanecarboxylic acid,
Examples thereof include cyclohexanecarboxylic acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, and nuclear-substituted products thereof.

Examples of the organic carboxylic acid comprising a hydrocarbon group having a hetero atom such as an oxygen atom, a nitrogen atom and a halogen atom include chloroacetic acid, chlorobutyric acid, tris (2-carboxyethyl) isocyanurate, bis ( 2
-Carboxyethyl) isocyanurate and the like.

Hereinafter, the catalyst used in the present invention will be described. In the method for producing an alicyclic ester compound of the present invention, generally known transesterification catalysts shown below can be suitably used.

For example, hydrides, oxides, hydroxides, alcoholates, amides or salts of alkali metals can be suitably used. The alkali metals include lithium, sodium, potassium, rubidium and cesium. Further, the salts of the alkali metals are those of organic acids or inorganic acids, for example, acetate,
Organic carboxylates such as propionate, benzoate and stearate, salts with phenolic compounds, carbonates, bicarbonates, cyanate, cyanate, phosphate,
Borate, stannous acid salts or antimonate salts of C ₁ -C _4, salts, and the like with inorganic acids stannic salt. In addition, a substance that forms a complex with an alkali metal compound such as crown ethers or polyethylene glycols may be added and used.

Further, as a catalyst that can be used in the production method of the present invention, a thallium compound, for example, oxides,
Hydroxides, carbonates, bromides, chlorides, fluorides, cyanates, phosphonates, acetates, nitrates, thallium methylate, thallium ethylate, and the like.

Further, as a catalyst which can be used in the present invention,
Ion exchange resins having tertiary amines or quaternary ammonium groups as functional groups, antimony compounds such as antimony oxide, manganese compounds such as manganese acetate,
Phosphines such as tributylphosphine and triphenylphosphine; arsines such as trimethylarsine, tributylarsine and triphenylarsine; stibines such as triphenylstibine; sulfur compounds such as diphenylsulfide and diphenyldisulfide; and selenium such as diphenylselenide. And the like.

Among the catalysts described above, catalysts which can be particularly preferably used in the method of the present invention include lithium, potassium, sodium, rubidium, cesium,
It is a hydroxide, bicarbonate, carbonate, cyanide, cyanate, alcoholate, or organic acid salt of an alkali metal or alkaline earth metal ion selected from magnesium, calcium, strontium, and barium.

The alcoholate has 1 to 20 carbon atoms.
And an alcoholate comprising the above-mentioned metal ion of an alcoholic compound having a hydroxyl group such as methoxide, ethoxide, propoxide and butoxide of the above-mentioned alkali metal or alkaline earth metal. Further, an alcoholate composed of 2,3-epoxycycloalkanol and an alkali metal used as a raw material in the production method of the present invention may be used.

As the organic acid salt, a carboxylate comprising the above alkali metal or alkaline earth metal and a hydrocarbon having 1 to 20 carbon atoms and optionally containing an aromatic ring,
And salts with aromatic compounds having a phenolic OH of 20.

Among the catalysts described above, the catalysts particularly preferably used in the present invention include, specifically, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, and hydroxide. Calcium, hydroxide which is strontium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, hydrogen carbonate such as cesium hydrogen carbonate, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, Strontium carbonate, carbonate which is barium carbonate, sodium cyanide,
Cyanide such as potassium cyanide, sodium cyanate, cyanate such as potassium cyanate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, sodium benzoate, potassium benzoate, sodium phenolate, potassium Organic acid salts such as phenolate; and alcoholates such as sodium methoxide, sodium ethoxide, sodium butoxide, potassium methoxide, and potassium butoxide.

In the present invention, a hydroxide of a metal ion selected from lithium, sodium and potassium, which has a sufficient reaction rate, a high selectivity for the target compound, and is easily available industrially, It is further preferred to use bicarbonates, carbonates, cyanides, cyanates, alcoholates, and organic acid salts.

In the production method of the present invention, the ratio of the amount of the organic carboxylic acid ester used as a raw material to the amount of 2,3-epoxycycloalkanol is usually 2,3 to the alkyl ester group of the organic carboxylic acid alkyl ester used.
An equivalent of epoxycycloalkanol of 0.01 to 20;
The range of equivalents. In the present invention, the larger the amount of the 2,3-epoxycyclohexanol used, the higher the reaction rate tends to be. However, on the other hand, the modification of the 2,3-epoxycyclohexanol itself and the product, Modifications with epoxycyclohexanol tend to occur. Therefore, the corresponding amount is preferably in the range of 0.01 to 10 equivalents,
It is particularly preferably in the range of 0.01 to 2 equivalents, and more preferably in the range of 0.01 to 1.6 equivalents.

In the present invention, the reaction may be carried out by simultaneously charging these raw materials, or the reaction may be carried out while adding either one. For example, 2,3-epoxycyclohexanol is dropped into a reactor containing an organic carboxylic acid ester, and the 2,3-epoxycyclohexanol stays in the reaction system.
The reaction may be carried out while adjusting the amount of epoxycyclohexanol to the above-mentioned preferred equivalent range.

The use amount of the above catalyst is 0.04 to 2,3-epoxycycloalkanol used as a raw material.
0001 to 1 times mol, desirably 0.0001 to 0.5
The molar amount is twice as much, more preferably 0.0001 to 0.2 times. When the molar ratio is less than 0.00001 times, the reaction rate is reduced and the productivity is low. On the other hand, when the molar ratio exceeds 1-fold, side reactions tend to occur simultaneously, and, for example, when the catalyst forms a heterogeneous layer in a solid state in the reaction system, the stirring efficiency decreases. These catalysts may be added to the reaction system in their entirety from the beginning or may be added in portions. Furthermore, by mixing in advance with one of the organic carboxylic acid ester and 2,3-epoxycycloalkanol, and further heating it in the range of, for example, 20 ° C. to 150 ° C., and then mixing it with the other raw material A reaction may be performed.

Hereinafter, the inert solvent used in the present invention will be described. The inert solvent referred to in the present invention refers to an organic carboxylic acid ester used as a raw material, and a reaction for forming a covalent bond with the raw material under a reaction condition with 2,3-epoxycycloalkanol. It means a compound that is dissolved at a reaction temperature of 0.1% or more, preferably 1% or more, and is liquid at the reaction temperature. Such solvents include, for example, pentane,
Hexane, octane, aliphatic hydrocarbons such as cyclohexane, benzene, toluene, xylene, aromatic hydrocarbons such as ethylbenzene, diethyl ether, dipropyl ether, methyl butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, ethers such as dioxane, Examples thereof include halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, nitriles such as acetonitrile and propionitrile, nitro compounds such as nitrobenzene, and amides such as dimethylformamide and dimethylacetamide.

Generally, in a chemical reaction using a solvent,
When the concentration of the reaction substrate is reduced, the reaction rate, that is, the conversion rate of the reaction substrate tends to decrease, and in the present invention, the reaction rate is reduced by using the inert solvent as compared with the case where the reaction is not used. Tend to. However, among the above inert solvents, not only the effect of improving the reaction selectivity, but also the reaction rate is not significantly reduced despite being diluted with the solvent, as a solvent that provides an industrially sufficient reaction rate Inert solvents having a dielectric constant in the range of 1.8 to 50 are preferred. More preferably, the dielectric constant is in the range of 1.8 to 10, particularly preferably 1.8 to 10.
The range is 4.5. Inert solvents having a dielectric constant in the above range and particularly preferably used in the production method of the present invention include hexane, heptane, octane, methylcyclohexane, cyclohexane, decalin, dioxane, benzene, xylene, toluene, n-butyl ether, and isopropylbenzene. , Ethylbenzene, anisole and the like. The dielectric constant of the solvent used in the present invention described above is a value described in "Solvent Handbook" (published by Sangyo Tosho Co., Ltd., revised edition, 1970).

In the present invention, one kind of the above-mentioned inert solvent may be used, or a mixture of two or more kinds may be used. These solvents may be charged into the reactive group together with the raw materials, or may be added during the reaction, for example, when the conversion of the organic carboxylic acid ester becomes 10% or more. Further, one raw material or a mixture of the raw material and the inert solvent is charged into a reactor, and then the reaction is performed while adding the other raw material or a mixture of the other raw material and the inert solvent to the reactor. May be implemented.

In the present invention, the weight of the inert solvent used is usually 0.01 to 100 times the total weight of the organic carboxylic acid ester and the 2,3-epoxycycloalkanol as the raw materials. Can be Preferably,
0.1 to 50 times, particularly preferably 0.5 to 0.5 times.
The range is 10 to 10 times. If it is less than 0.01, the effect of the reaction selectivity tends not to be exhibited, and if it exceeds 100 times, the reaction rate is remarkably reduced, the productivity is low and the efficiency is low.

In the production method of the present invention, when an organic carboxylic acid ester which is easily polymerized is used as a raw material,
It is desirable to add a polymerization inhibitor. As the polymerization inhibitor, those generally used can be used, and examples thereof include hydroquinone, hydroquinone monomethyl ether, a nucleus-substituted product with an alkyl group such as a tert-butyl group of phenol, phenothiazine, and catechol. The addition amount of the polymerization inhibitor is suitably from 10 to 3000 ppm based on the total weight of the organic carboxylic acid ester and 2,3-epoxycycloalkanol used as the raw materials.

In the present invention, when an onium salt and / or a tertiary amine compound coexist in the reaction system, not only the selectivity but also the reaction rate tends to be improved, which is preferable. In the present invention, either one of an onium salt and a tertiary ammonium salt may be used, or both may be used simultaneously.

The onium salt in the present invention is represented by the general formula A
_{1 A 2 A 3 A 4 M} + Q - (A 1 ~A 4 oxygen having 1 to 50 carbon atoms,
A hydrocarbon group that may contain at least one heteroatom selected from nitrogen, and may be the same or different. M represents nitrogen or phosphorus, Q _- represents a halogen ion or an inorganic anion. ) Is a quaternary ammonium salt or a quaternary phosphonium salt. Examples of the hydrocarbon group in the onium salt include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a cyclohexyl group, and the like. Examples of the halogen ion include chlorine ion, bromide ion and iodine ion, and examples of the inorganic ion include hydroxyl ion and sulfite ion.
Specific examples of the quaternary ammonium salt include cetylpyridinium salt, trioctylmethylammonium salt, tetrahexylammonium salt, tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, alkylpicoliniumammonium salt And alkyl imidazoline salts. Specific examples of the quaternary phosphonium salt include a tetrabutylphosphonium salt, a tetrapropylphosphonium salt, a trioctylmethylphosphonium salt, a trioctylethylphosphonium salt, and a tetrahexylphosphonium salt. These alone,
Alternatively, two or more kinds may be used. The amount of these onium salts is 0.0001 to 1 times the total weight of the organic carboxylic acid alkyl ester and 2,3-epoxycycloalkanol used as the raw materials.

The tertiary amine compound referred to in the present invention is a compound of the general formula B ₁ B ₂ B ₃ N (B ₁ , B ₂ and B _{3 each} having 1 carbon atom)
To 20 hydrocarbon groups which may contain at least one heteroatom selected from oxygen and nitrogen, which may be the same or different. N represents a nitrogen atom. )). Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, a cyclohexyl group and the like.
Specific examples of the tertiary amine compound include trimethylamine, triethylamine, tripropylamine, tributylamine, triphenylamine, benzyldimethylamine and the like. These may be used alone or in combination of two or more. The amount of the tertiary amine compound used is determined by the amount of the organic carboxylic acid ester used as a raw material and the amount of 2,3
-0.1% based on the total weight of the epoxycycloalkanol.
It is 0001 to 10 times the weight.

In the production method of the present invention, the reaction temperature is usually in the range of 10 to 180 ° C., preferably 30 to 140 ° C.
Particularly preferably, the temperature is in the range of 50 to 120 ° C. Further, the reaction pressure may be any of pressurized, normal pressure, or reduced pressure,
In order to allow the reaction to proceed advantageously, it is preferable to carry out the reaction while distilling off the generated alcohol outside the reaction system. Therefore, for example, the alcohol produced by a method of performing the reaction under reduced pressure in the range of 0.1 to 700 torr or a method of performing the reaction while introducing an inert gas such as nitrogen into the surface of the reaction solution or the reaction solution under normal pressure is used. Is preferably distilled out of the reaction system. In this case, the inert solvent to be used may be distilled off together with the produced alcohol within a range not departing from the above-mentioned use range. Further, an inert solvent azeotropic with the alcohol to be produced may be selected and inevitably distilled as a composition with the alcohol.

When the target substance is taken out from the reaction solution obtained by the production method of the present invention, it depends on the properties of the target substance at room temperature and physical properties such as boiling point. It can be easily obtained by a general purification method such as precipitation.
Hereinafter, the present invention will be described with reference to examples.

[0058]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Gas chromatography was performed with the following equipment and conditions. Apparatus: GC-14B manufactured by Shimadzu Corporation Column: GL Science Inc. Capillary column TC-1 (0.25 mm ID, length 30 m) Carrier gas: He Detection: FID Column temperature conditions: 20 ° C./mi after holding at 60 ° C. for 2 minutes
n to 300 ° C and hold at 300 ° C for 15 minutes Sample dissolution solvent: toluene

2. GPC Measurement Each compound (2.0 mg) was dissolved in tetrahydrofuran (2.0 g), filtered through a 0.5 μm filter, developed and detected under the following conditions, and analyzed. Measuring device: Tosoh HLC-8120GPC Detector: RI Developing solution: Tetrahydrofuran Developing solution flow rate: 1.0 ml / min Column: Tosoh TSKgel GMH _HR- N
One and G1000H _XL 2 present in series installation Column temperature: 40 ° C.

[0060]

EXAMPLE 1 34.8 g (0.2 mol) of dimethyl adipate was placed in a 500 ml four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a T-shaped tube with a condenser for distillation.
l), 2,3-epoxycyclohexanol (mixture consisting of 95% of cis form and 5% of trans form)
2 g (0.8 mol), toluene (dielectric constant 2.379)
300 ml and lithium carbonate 0.48 g (2
0 mmol). Next, the tip of the nitrogen introduction tube was set so as to enter the reaction solution, and the solution was bubbled by flowing a nitrogen gas.

While stirring, the flask was heated so that the temperature of the reaction solution became 88 ° C., and the reaction was carried out at 90 ° C. for 8 hours. During this time, methanol and toluene containing 2,3-epoxycyclohexanol flowed out through the distillation condenser. In addition, 20 ml of toluene was added every hour from the start of the reaction.

As a result of analyzing the reaction solution by gas chromatography, the conversion of dimethyl adipate was 91%. In addition, the selectivity obtained by GPC analysis (the ratio of the total area of mono- and di-substituted 2,3-epoxycyclohexanol to dimethyl adipate to the total area of the product obtained from the GPC chart) ) Is 94%
Met.

[0063]

Example 2 In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, and a T-shaped tube with a condenser for distillation, 34.8 g of dimethyl adipate (0.2 mol) was added.
l), 2,3-epoxycyclohexanol (mixture consisting of 95% of cis form and 5% of trans form)
2 g (0.8 mol), toluene (dielectric constant 2.379)
300 ml and 0.276 g of potassium carbonate as a catalyst
(2 mmol). Next, the tip of the nitrogen introduction tube was set so as to enter the reaction solution, and the solution was bubbled by flowing a nitrogen gas.

While stirring, the flask was heated so that the temperature of the reaction solution became 83 ° C., and the reaction was carried out at 90 ° C. for 8 hours. During this time, methanol and toluene containing 2,3-epoxycyclohexanol flowed out through the distillation condenser. Further, 15 ml of toluene was added every hour from the start of the reaction.

As a result of analyzing the reaction solution by gas chromatography, the conversion of dimethyl adipate was 94%. In addition, the selectivity obtained by GPC analysis (the ratio of the total area of mono- and di-substituted 2,3-epoxycyclohexanol to dimethyl adipate to the total area of the product obtained from the GPC chart) ) Is 95%
Met.

[0066]

Comparative Example 1 Example 1 was repeated except that toluene was not used.
The same operation as described above was performed. As a result of analyzing the reaction solution by gas chromatography, the conversion of dimethyl adipate was 98%.
%Met. In addition, the selectivity (GP
With respect to the area of the entire product obtained by the C chart,
Ratio of total area of mono-substituted and di-substituted 2,3-epoxycyclohexanol to dimethyl adipate)
Was 83%.

[0067]

Example 3 The same operation as in Example 2 was carried out except that 300 ml of chloroform (dielectric constant: 4.806) and a reaction temperature of 60 ° C. were used instead of toluene.

As a result of analyzing the reaction solution by gas chromatography, the conversion of dimethyl adipate was 55%. In addition, the selectivity obtained by GPC analysis (the ratio of the total area of mono- and di-substituted 2,3-epoxycyclohexanol to dimethyl adipate to the total area of the product obtained from the GPC chart) ) Is 98%
Met.

[0069]

Example 4 Except that 0.119 g (1 mmol) of tetramethylammonium chloride was added at the time of charging,
The same operation as in Example 2 was performed.

As a result of analyzing the reaction solution by gas chromatography, the conversion of dimethyl adipate was 98%. In addition, the selectivity obtained by GPC analysis (the ratio of the total area of mono- and di-substituted 2,3-epoxycyclohexanol to dimethyl adipate to the total area of the product obtained from the GPC chart) ) Is 96%
Met.

[0071]

According to the production method of the present invention, in the transesterification reaction between an organic carboxylic acid ester and 2,3-epoxycycloalkanol, 2,3-epoxycyclohexanol itself is modified during reaction, The formation of a high-molecular-weight product by the successive modification of the compound can be suppressed, and an epoxy-containing alicyclic ester can be produced with high selectivity.

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Claims (4)

[Claims] 1. A method for producing an epoxy-containing alicyclic ester compound by subjecting an organic carboxylic acid ester compound and a 2,3-epoxycycloalkanol represented by the following general formula to a transesterification reaction in the presence of a catalyst. A method for producing an epoxy-containing alicyclic ester, characterized by coexisting with an inert solvent. Embedded image (In the formula, n represents an integer of 0 to 8.) 2. The method according to claim 1, wherein the 2,3-epoxycycloalkanol is 2,3-epoxycyclohexanol. 3. The method according to claim 1, wherein the inert solvent has a dielectric constant of 1.8 to 50. 4. The production method according to claim 1, wherein an onium salt and / or a tertiary amine compound coexist.