JP2003096079A - Method for producing alicyclic epoxy compound with oxetane ring - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing in a high yield and at a lower cost an alicyclic epoxy compound having an oxetanyl group which is used in the fields of coating materials, adhesives, resists or the like. SOLUTION: Alicyclic olefins having an oxetanyl group are oxidized using hydroperoxide and a hydroperoxide compound as an oxidizing agent in the presence of a catalyst, thus epoxidizing a carbon - carbon double bond of the alicyclic olefins.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an alicyclic epoxy compound having an oxetanyl group at a high yield, that is, at a high conversion rate and a high selectivity.

[0002]

2. Description of the Related Art In recent years, there has been an increasing demand for highly heat-resistant resists, sealants, and coating films with a high crosslinking density for electronic parts.
Accordingly, various types of multifunctional epoxy compounds are required.

A polyfunctional compound having both an oxetanyl group and an epoxy group in the molecule is expected to have high heat resistance, and a structure having an oxetane ring is excellent in fast curing property, and thus a compound capable of meeting diversifying needs. Is considered to be.

In US Pat. No. 3,388,105, an alicyclic epoxy compound having an oxetane ring is synthesized. However, since peracetic acid, which is expensive and inconvenient to use, is used, it is economically unfavorable and a special manufacturing facility is required. Moreover, the yield is low. Furthermore, since acetic acid is produced in the reaction system, a complicated operation is required to isolate the epoxy compound.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an alicyclic epoxy compound having an oxetanyl group with a high conversion rate,
It is an object of the present invention to provide a method for producing at a high selectivity with a high yield and at low cost.

[0006]

Means for Solving the Problems As a result of intensive studies on the solution of the above problems, the inventors have found that the above problems can be solved by using hydrogen peroxide or hydroperoxide as an oxidant in the presence of a catalyst. Heading out, the present invention has been completed. That is, the present invention provides the following [1] to [1
3] relates to a method for producing an alicyclic epoxy compound having an oxetane ring.

[1] Oxetane represented by the general formula (2), characterized by oxidizing the compound represented by the general formula (1) with hydrogen peroxide and / or a hydroperoxide compound in the presence of a catalyst. A method for producing an alicyclic epoxy compound having a ring.

[Chemical 3] (In the formula, R ¹ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms or an aryl group, and m is an integer of 0 to 2,
n is 2 when m is 0, and is 1 otherwise. )

[Chemical 4] (In the formula, R ¹ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms or an aryl group, and m is an integer of 0 to 2,
n is 2 when m is 0, and is 1 otherwise. )

[2] The method for producing an epoxy compound according to [1], wherein the hydroperoxide compound is a compound represented by the general formula (3). R ² —OOH (3) (R ² is an aryl group having 6 to 12 carbon atoms, and 7 to 15 carbon atoms.
Represents an aralkyl group or a (cyclo) alkyl group having 1 to 12 carbon atoms. )

[3] The catalyst according to [1] or [2], wherein the catalyst is one or more compounds selected from manganese compounds, rhenium compounds, titanium compounds, vanadium compounds, tungsten compounds and molybdenum compounds. Method for producing epoxy compound. [4] The catalyst is one or more compounds selected from tungstic acid, sodium tungstate, phosphotungstic acid, sodium phosphotungstate, molybdic acid, sodium molybdate, phosphomolybdic acid, and sodium phosphomolybdate. [3] The method for producing an epoxy compound according to [3]. [5] The method for producing an epoxy compound according to [3], wherein the catalyst is methyltrioxorhenium.

[6] The hydroperoxide compound is t
ert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-
Dimethylhexane-2,5-dihydroperoxide,
The method for producing an epoxy compound according to [1], which is at least one selected from 1,1,3,3-tetramethylbutyl hydroperoxide. [7] The compound represented by the general formula (3) is tert-butyl hydroperoxide and / or cumene hydroperoxide [2] to [5]
7. The method for producing an epoxy compound according to any one of 1.

[8] The method for producing an epoxy compound according to any one of [1] to [7], characterized in that an onium salt represented by the general formula (4) is added. R ³ R ⁴ R ⁵ R ⁶ M + Q- (4) (wherein R ^{3 to} R ⁶ are each independently a hydrogen atom or a carbon number 1
To 30 alkyl groups, and R ^{3 to} R ⁶ may form a ring with adjacent groups. M is a nitrogen atom or a phosphorus atom, and Q ⁻ represents an anion. )

[9] The method for producing an epoxy compound according to any one of [1] to [8], wherein the oxidation reaction is carried out in the presence of a phosphate anion. [10] The method for producing an epoxy compound according to any one of [1] to [9], wherein the solvent for the oxidation reaction is substantially water. [11] The method for producing an epoxy compound according to any one of [1] to [9], wherein the oxidation reaction is performed in a two-phase system of water and an organic solvent. [12] The method for producing an epoxy compound according to [10] or [11], characterized in that the oxidation reaction is carried out when the pH of the aqueous phase is 3 to 6. [13] The epoxy compound having an oxetane ring represented by the general formula (2) is 7,8-epoxy-2-oxa-
The epoxy compound according to any one of [1] to [12], which is 5-methylspiro [3.5] nonane or 6,7-epoxy-2-oxaspiro [3.5] nonane. Production method.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION General formula (2) produced by the present invention.

[Chemical 5] (In the formula, R ¹ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms or an aryl group, and m is an integer of 0 to 2,
n is 2 when m is 0, and is 1 otherwise. Examples of the alicyclic epoxy compound having an oxetanyl group represented by the following). That is, 7,
8-epoxy-2-oxa-5-methylspiro [3.
5] nonane, 7,8-epoxy-2-oxa-5-ethylspiro [3.5] nonane, 7,8-epoxy-2-oxa-5-phenylspiro [3.5] nonane, 6,7-
Epoxy-2-oxaspiro [3.5] nonane, spiro [5,6-epoxynorbornane-2,3'-oxetane], spiro [5,6-epoxy-3-methylnorbornane-2,3'-oxetane], etc. Is.

These compounds are represented by the corresponding general formula (1)

[Chemical 6] (In the formula, R ¹ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms or an aryl group, and m is an integer of 0 to 2,
n is 2 when m is 0, and is 1 otherwise. ) It can be obtained by oxidizing the carbon-carbon double bond of the compound represented by the formula (4) to form an epoxy ring.

R ¹ in the general formulas (1) and (2) represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms or an aryl group. The alkyl group and the aryl group may have a substituent. Further, m = 0 means that there is no crosslinking by a methylene group.

The catalysts used in the present invention are manganese compounds, rhenium compounds, titanium compounds, vanadium compounds, tungsten compounds and molybdenum compounds.

Specifically, tungstic acid such as tungstic acid, sodium tungstate, potassium tungstate, lithium tungstate, ammonium tungstate or a salt thereof; phosphotungstic acid, sodium phosphotungstate, silicotungstic acid, sodium silicotungstate. , Phosphorus vanadotungstic acid, phosphomolybdotungstic acid, and other heteropolyacids containing a tungsten atom, or salts thereof, molybdic acid, sodium molybdate, potassium molybdate, lithium molybdate, ammonium molybdate, or other salts thereof; phosphorus; Molybdic acid, sodium phosphomolybdate, silicomolybdic acid, sodium silicomolybdate,
Heteropoly acids containing molybdenum atoms such as phosphovanadomolybdic acid and phosphomolybdomolybdic acid, or salts thereof; dioxobis (acetylacetonato) molybdenum, molybdenum oxide, bis (2,4-pentanedionato) vanadium oxide, titanium tetraethoxide , Titanium tetraisoprooxide, methyltrioxorhenium, and the like. Among these, sodium tungstate, phosphotungstic acid, sodium phosphotungstate, silicotungstic acid, sodium molybdate, phosphomolybdic acid, sodium phosphomolybdate and silicomolybdic acid are preferred, and sodium tungstate, phosphotungstic acid, molybdic acid are preferred. Sodium and phosphomolybdic acid are more preferable.

These compounds may be used alone or in admixture of two or more.

The amount of catalyst used is 0.001 to 0.1 mol per 1 mol of the compound represented by the general formula (1).
Is preferred.

In the present invention, hydrogen peroxide and / or hydroperoxide compounds are used as the oxidizing agent. The oxidizing agent may be used alone or in combination of two or more kinds. The hydroperoxide compound has the general formula (3)
Those represented by are preferred. R ² —OOH (3) (R ² is an aryl group having 6 to 12 carbon atoms, and 7 to 15 carbon atoms.
Represents an aralkyl group or a (cyclo) alkyl group having 1 to 12 carbon atoms. ) The (cyclo) alkyl group means that either an alkyl group or a cycloalkyl group may be used.

Examples of the hydroperoxide compound include tert-butyl hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide and 2,5-dimethylhexane-
2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, ethylbenzene hydroperoxide, bisdiisobutyl-2.5-
Dihydroperoxide, α, α-dimethylheptyl hydroperoxide, trityl hydroperoxide,
Examples thereof include cyclohexyl peroxide and cumene hydroperoxide. Preferred is tert-butyl hydroperoxide or cumene hydroperoxide.

The amount of the oxidizing agent used is appropriately 1 to 2 times the molar equivalent of the compound represented by the general formula (1), and more preferably about 1.1 to 1.5 equivalents. As for the method of charging the oxidizing agent, it is desirable that the oxidizing agent is gradually added dropwise in accordance with the reaction rate and the removal rate of the reaction heat.

The oxidant is preferably added to the reaction system after being dissolved or diluted in water or an organic solvent. The concentration is appropriately selected and determined in consideration of the reaction rate and the heat removal capacity of the reaction apparatus.

When hydrogen peroxide is used as an oxidizing agent, the concentration is not particularly limited, but a commercially available product of about 30 to 70% by mass is preferable because it is easily available and industrially handled. .

Onion used in the oxidation reaction of the present invention
The formula (4) R³R^FourR^FiveR⁶M + Q- (4) (R in the formula³~ R⁶Are each independently a hydrogen atom or a carbon number of 1.
~ 30 alkyl groups, and R³~ R⁶Next to each
You may form a ring with the group which contacts. M is a nitrogen atom or
Q atom^-Indicates an anion. ) Represented by four
Primary ammonium salts or quaternary phosphonium salts are preferred
Yes. Where Q ^-As Cl^-, Br^-, I^-Halogen of etc.
Ion and OH^-, HSO_Four ^-Inorganic anions such as
It

As the quaternary ammonium salt, trioctylmethylammonium chloride, tetradodecylammonium chloride, didecyldimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, dioctadecyldimethylammonium chloride,
Hexadecyldimethylbenzylammonium chloride, dioctadecyldimethylammonium bromide,
Examples thereof include cetylpyridinium ammonium chloride, ethylpicolinium chloride, n-butylpicolinium chloride and ethylimidazoline chloride. Examples of the quaternary phosphonium salt include tetrabutylphosphonium chloride. Of these, dioctadecyldimethylammonium chloride, cetylpyridinium ammonium chloride and hexadecyldimethylbenzylammonium chloride are preferred.

The amount of the onium salt used is 0.001 to 0.1 mo based on 1 mol of the compound represented by the general formula (1).
It is preferably l.

More preferably, the oxidation reaction of the present invention is carried out in the presence of a phosphate anion. The phosphate anion is added as phosphoric acid or phosphate, and the addition amount thereof is about 0.5 to 10 times mol, preferably about 1 to 5 times mol, of the catalyst to be applied. Too little,
If the amount is too large, the catalytic activity is lowered, which is not preferable.

The aqueous phase containing the catalyst and phosphate anion is adjusted to pH 3 with mineral acid or alkali hydroxide or alkali carbonate.
-6, preferably 4-6, more preferably 5-5.5.
It is desirable to be prepared. The lower the pH, the higher the reaction rate, but on the contrary, the selectivity of the target compound decreases.

The solvent used in the oxidation reaction of the present invention may be substantially water, or in some cases, an organic solvent may be used simultaneously with water. "Substantially only water" means that a small amount of organic solvent or the like for dissolving a reagent may be contained, and may be 100%, but is not completely 100%. Not requesting. The amount of water used as a solvent can be appropriately selected.

The type of organic solvent is not particularly limited as long as it is incompatible with water and can be separated from water with a separating funnel or the like. Specific examples thereof include benzene, toluene, xylene, chloroform, dichloroethane, dichloromethane, ethyl acetate, butyl acetate, dibutyl ether and the like. From an industrial point of view, aromatic hydrocarbons such as toluene and xylene are preferable.

The amount of the organic solvent used is appropriately 0 to 10 times the weight of the compound represented by the general formula (1). If it is more than this, the reaction rate may be slowed down, which is not preferable.

The temperature of the oxidation reaction is about 30 to 80 ° C, preferably 40 to 60 ° C.

At the above reaction temperature, the reaction time is 2 to 7
Time is appropriate.

After completion of the reaction, the organic phase is separated, the organic component in the aqueous phase is further extracted, and then the residual excess is washed by washing with an aqueous solution of sodium hydrogen sulfite, sodium thiosulfate, sodium sulfite, or the like. It is desirable to decompose the oxide, neutralize with an alkaline aqueous solution, and wash with pure water. Then, after removing the solvent under reduced pressure, a highly pure product can be obtained by recrystallization, distillation, or the like.

Since some of the starting olefins (compounds represented by the general formula (1)) and the obtained epoxy compounds have high polymerizability, they are used in the epoxidation reaction and in the post-treatment and distillation steps. A polymerization inhibitor may be used. However, when a polymerization inhibitor is added during the epoxidation reaction, the catalyst activity is lowered, so that it is preferably 500 ppm or less with respect to the raw material olefins.

[0037]

EXAMPLES The effects of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Reagents] Among the materials used in Examples and Comparative Examples, the main commercially available products are as follows. Commercial products, including the following, were used as they were without purification.

As the sodium carbonate, dioctadecyldimethylammonium chloride, cetylpyridinium chloride, 85 mass% phosphoric acid solution, sodium hydroxide, molybdenum oxide and pyrazole, products manufactured by Tokyo Chemical Industry Co., Ltd. were used. As the 30% by mass hydrogen peroxide solution, t-butyl hydroperoxide and phosphotungstic acid, products manufactured by Kanto Chemical Co., Inc. were used. As the sodium tungstate, a product of Junsei Chemical Co., Ltd. was used. As peracetic acid and trioxomethyl rhenium, products manufactured by Aldrich Japan Co., Ltd. were used.

[Production Example of Raw Material] <Synthesis of 2-oxa-9-methylspiro [3.5] non-6-ene> 1) Synthesis of 6-methyl-3-cyclohexene-1,1-dimethanol 3-port In a flask with butadiene and crotonaldehyde
Dimethyl-Alder reaction product 2-methyl-4-cyclohexene-1-carbaldehyde (327 g), methanol (600 ml) and 37% formalin water (729 g) were added, and the solution was heated to 60 ° C. with stirring. Subsequently, a solution prepared by dissolving 252 g of KOH in 600 ml of distilled water was added dropwise over 2 hours. After continuing stirring for 7 hours, the reaction solution was concentrated under reduced pressure to obtain a bilayer residue. The oil layer concentrated to about 150 ml was washed with 300 ml of distilled water. After the oil layer was concentrated under reduced pressure, 50 mg of 3,5-di (t-butyl) -4-hydroxytoluene (BHT) was added and distilled under reduced pressure to give colorless crystals of 6-methyl-3-cyclohexene-1,1. -311 g of dimethanol (yield 82%) was obtained.

2) 6-methyl-3-cyclohexene-
Synthesis of 1,1-dimethanol cyclic carbonate 6-methyl-3-cyclohexene-
310 g (1.99 mol) of 1,1-dimethanol, 894 g of dimethyl carbonate (DMC) and 0.9 of potassium carbonate
3 g was charged, the temperature was raised to 90 ° C., and the mixture was refluxed for 4 hours. The reaction solution was returned to room temperature and potassium carbonate was filtered off. After adding 120 mg of BHT, the remaining DMC and methanol were removed under reduced pressure of 2 kPa (15 mmHg), and then vacuum distillation was performed to perform 6-methyl-3-cyclohexene-1,1-dimethanol cyclic reaction at room temperature as colorless crystals. 326 g (yield 89.4%) of carbonic acid ester was obtained.

3) 2-oxa-9-methyl-spiro
Synthesis of [3.5] non-6-ene 6-Methyl-3-cyclohexene-
1,1-dimethanol cyclic carbonic acid ester 321.15
g, BHT 642 mg (0.2 mass%), LiCl 1.9
3 g was charged, and the mixture was heated and stirred at 275 ° C. using a mantle heater. Immediately transfer the product to approximately 8 kPa (60 mmH
Under reduced pressure of g), draw out from the system, until it stops distilling 4
Heating was continued for an hour. 600 mg of BHT was added to the product,
It was distilled under reduced pressure to give 187 g of 2-oxa-9-methylspiro [3.5] non-6-ene as a colorless transparent liquid (yield 7
1%) was obtained.

(Example 1) 3 equipped with a stirrer and a thermometer
Using a 00 ml three-necked flask, phosphotungstic acid (0.837 g, 3 mmol in terms of W) was dissolved in 60 g of pure water (ion-exchanged water), and then 85% by mass phosphoric acid aqueous solution (1.38 g, 12 mmol) was added. The mixture was stirred at 25 ° C for 20 minutes. Subsequently, sodium carbonate was added to adjust the pH of the aqueous solution to 5.0, and then the mixture was stirred at 25 ° C for 30 minutes. 2-Oxa-9-methylspiro [3.5] nano-6
-Ene (13.82 g, 100 mmol) was added and the reaction was heated to 60 ° C. While stirring, 30% by mass hydrogen peroxide solution (13.6 g, 120 mmol) was added over 1.5 hours, and the mixture was further stirred at 40 ° C. for 2 hours for reaction.
After the reaction was completed, the mixture was cooled to below 30 ° C and toluene (100g)
Was added to extract 7,8-epoxy-2-oxa-5-methylspiro [3.5] nonane. After separating the organic phase, the aqueous phase was extracted again with toluene (50 g),
This was added to the first organic phase. It was washed with a 10 mass% sodium sulfite aqueous solution, a 5 mass% sodium hydrogen carbonate aqueous solution and pure water. Conversion rate, selectivity and yield (= conversion rate x
Selectivity × 0.01) was determined by gas chromatographic analysis of the organic phase. The results are shown in Table 1. afterwards,
The low-boiling component of this organic phase was distilled off using an evaporator, and then high-purity 7,8-epoxy-2-oxa-5-methylspiro [3.5] nonane (purity was obtained by vacuum distillation (12 mmHg, 114 ° C.). 99.5 mass% or more) was isolated.

(Example 2) 3 equipped with a stirrer and a thermometer
Using a 00 ml three-necked flask, phosphotungstic acid (0.837 g, W conversion 3 mmol) was dissolved in pure 60 g, and then 85% by mass of phosphoric acid solution (1.38 g, 12
mmol) was added and the mixture was stirred at 25 ° C. for 20 minutes. Subsequently, sodium carbonate was added to adjust the pH of the aqueous solution to 4.5, and then the mixture was stirred at 25 ° C for 30 minutes. Toluene (30 g), 2-oxa-9-methylspiro [3.5]
Nano-6-ene (13.82 g, 100 mmol), dioctadecyldimethylammonium chloride (3 mm
ol) was added and the reaction was heated to 40 ° C. 30 mass% hydrogen peroxide solution (13.6 g, 120 mm) with stirring
ol) was added over 1.5 hours, and the mixture was further stirred at 40 ° C. for 2 hours for reaction. After completion of the reaction, the mixture was cooled to 30 ° C. or lower, toluene (100 g) was added, and 7,8-epoxy-2-oxa-5-methylspiro [3.5] nonane was extracted.
After separating the organic phase, the aqueous phase was again added with toluene (50 g).
The extraction operation was carried out with and this was added to the first organic phase. 10
It was washed with an aqueous solution of sodium sulfite of 5% by mass, an aqueous solution of sodium hydrogencarbonate of 5% by mass and pure water. The conversion rate, selectivity and yield were determined by gas chromatographic analysis of the organic phase, and the results are shown in Table 1. Then, the low boiling point component of this organic phase was distilled off using an evaporator, followed by high-purity 7,8-epoxy-2-oxa-5-methylspiro [3.5] nonane by vacuum distillation (12 mmHg, 114 ° C.). (Purity of 99.5 mass% or more) was isolated.

Example 3 The same procedure as in Example 2 was repeated except that cetylpyridinium chloride was used instead of dioctadecyldimethylammonium chloride.

Example 4 Example 4 was repeated except that dichloromethane was used instead of toluene.

Example 5 The procedure of Example 2 was repeated except that the pH was adjusted to 5.5.

(Example 6) The procedure of Example 2 was repeated except that the oxidation reaction was carried out at 50 ° C.

(Example 7) 3 equipped with a stirrer and a thermometer
Phosphotungstic acid (0.837 g, 3 mmol in terms of W) was dissolved in 60 g of pure water using a 00 ml three-necked flask, and then 85% by mass of phosphoric acid solution (1.38 g, 12
mmol) was added and the mixture was stirred at 25 ° C. for 20 minutes. Subsequently, sodium carbonate was added to adjust the pH of the aqueous solution to 4.6, and the mixture was stirred at 25 ° C for 30 minutes. Here 2-oxa
9-Methylspiro [3.5] nano-6-ene (13.8
2 g, 100 mmol) and dioctadecyldimethylammonium chloride (1.759 g, 3 mmol) were added, and the reaction solution was heated to 40 ° C. While stirring, 30% by mass hydrogen peroxide solution (13.6 g, 120 mmol) was added over 1.5 hours, and the mixture was further stirred at 40 ° C. for 2 hours for reaction. After completion of the reaction, the mixture was cooled to 30 ° C. or lower, toluene (100 g) was added, and 7,8-epoxy-2-oxa-
5-Methylspiro [3.5] nonane was extracted. After separating the organic phase, the aqueous phase was extracted again with toluene (50 g), and this was added to the first organic phase. 10 mass%
Was washed with an aqueous solution of sodium sulfite, a 5% by mass aqueous solution of sodium hydrogen carbonate and pure water. The conversion rate, selectivity and yield were determined by GC analysis of the organic phase, and the results are shown in Table 1. Then, the low boiling point component of this organic phase was distilled off using an evaporator, followed by vacuum distillation (12 mmHg, 114 mm
7,8-epoxy-2-oxa-5-methylspiro [3.5] nonane was isolated by (.degree. C.).

Example 8 Example 8 was repeated except that sodium tungstate was used instead of phosphotungstic acid.

Example 9 The procedure of Example 7 was repeated except that the pH was adjusted to 5.5.

Example 10 Example 10 was repeated except that sodium hydroxide was used instead of sodium carbonate and the pH was adjusted to 5.5.

Example 11 A 300 ml three-necked flask equipped with a stirrer and a thermometer was charged with dichloromethane (100 ml).
g), 2-oxa-9-methylspiro [3.5] nano-
6-ene (100 mmol), methyltrioxorhenium (1 mmol), and pyrazole (10 mm) as a cocatalyst.
ol) was added. While stirring at 30 ° C., 30 mass% hydrogen peroxide solution (150 mmol) was added over 1.5 hours, and the mixture was further stirred at 40 ° C. for 1 hour to cause a reaction. After completion of the reaction, the mixture was cooled to 30 ° C. or lower, dichloromethane (50 g) was added, and 7,8-epoxy-2-oxa-5-methylspiro [3.5] nonane was extracted. After separating the organic phase, the aqueous phase was extracted again with dichloromethane (50 g), and this was added to the first organic phase. It was washed with a 10 mass% sodium sulfite aqueous solution, a 5 mass% sodium hydrogen carbonate aqueous solution and pure water. The conversion, selectivity and yield were determined by gas chromatographic analysis of the organic phase. As a result, the conversion was 98%, the selectivity was 99%, and the yield was 97%. Then, the low boiling point component of this organic phase was distilled off using an evaporator, followed by vacuum distillation (12 mmHg, 114 mm
C.) with high purity 7,8-epoxy-2-oxa-5
Methylspiro [3.5] nonane (purity 99.5% by mass or more) was isolated.

Example 12 Toluene (100 g) was added to a 300 ml three-necked flask equipped with a stirrer and a thermometer.
2-Oxa-9-methylspiro [3.5] nano-6-ene (100 mmol), molybdenum oxide (3 mmol)
Was added. While stirring at 60 ° C., a toluene solution of 30 mass% t-butyl hydroperoxide (150 mmo
1) was added over 1.5 hours, and the mixture was further stirred at 70 ° C. for 1 hour for reaction. After cooling to 30 ° C. or less, the reaction solution was washed with a 10 mass% reaction aqueous sodium sulfite solution, a 5 mass% sodium hydrogen carbonate aqueous solution and pure water. The conversion, selectivity and yield were determined by gas chromatographic analysis of the organic phase. As a result, conversion rate 70%, selectivity 90%,
The yield was 63%. Then, the low boiling point component of this organic phase was distilled off using an evaporator, followed by vacuum distillation (12
mmHg, 114 ℃) High purity 7,8-epoxy-2
-Oxa-5-methylspiro [3.5] nonane (purity 9
9.5 mass% or more) was isolated

(Comparative Example 1) 3 equipped with a stirrer and a thermometer
In a 00 ml three-necked flask, add toluene (100 g) and 2
-Oxa-9-methylspiro [3.5] nano-6-ene (13.82 g, 100 mmol) was added and the reaction mixture was-
Cooled to 10 ° C. Peracetic acid (150 mmol) was added over 1.5 hours with stirring so that the temperature did not exceed 0 ° C. Then, the mixture was stirred and reacted at 25 ° C. for 2 hours. After the reaction was completed, the organic phase was separated, and the aqueous phase was again added with toluene (5
The extraction operation was carried out on 0 g) and this was added to the first organic phase. It was washed with a 10 mass% sodium sulfite aqueous solution, a 5 mass% sodium hydrogen carbonate aqueous solution and pure water. As a result of analysis by gas chromatography, the yield of 7,8-epoxy-2-oxa-5-methylspiro [3.5] nonane was 40.
%Met.

[0056]

[Table 1]

[0057]

According to the manufacturing method of the present invention, a resist,
An alicyclic epoxy compound having an oxetanyl group, which is useful for a sealant, a paint, etc., can be produced at low cost and in high yield.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4C048 TT08                 4C071 AA04 AA08 BB01 CC12 EE02                       FF13 KK02 LL03

Claims (13)

[Claims] 1. A compound represented by the general formula (2), which comprises oxidizing a compound represented by the general formula (1) with hydrogen peroxide and / or a hydroperoxide compound in the presence of a catalyst.
A method for producing an alicyclic epoxy compound having an oxetane ring represented by: [Chemical 1] (In the formula, R ¹ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms or an aryl group, and m is an integer of 0 to 2,
n is 2 when m is 0, and is 1 otherwise. ) [Chemical 2] (In the formula, R ¹ is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 12 carbon atoms or an aryl group, and m is an integer of 0 to 2,
n is 2 when m is 0, and is 1 otherwise. ) 2. The method for producing an epoxy compound according to claim 1, wherein the hydroperoxide compound is a compound represented by the general formula (3). R ² —OOH (3) (R ² is an aryl group having 6 to 12 carbon atoms, and 7 to 15 carbon atoms.
Represents an aralkyl group or a (cyclo) alkyl group having 1 to 12 carbon atoms. ) 3. A catalyst comprising a manganese compound, a rhenium compound,
The method for producing an epoxy compound according to claim 1 or 2, which is one or more compounds selected from titanium compounds, vanadium compounds, tungsten compounds and molybdenum compounds. 4. The catalyst is one or more compounds selected from tungstic acid, sodium tungstate, phosphotungstic acid, sodium phosphotungstate, molybdic acid, sodium molybdate, phosphomolybdic acid and sodium phosphomolybdate. Claim 3 characterized by
The method for producing an epoxy compound according to 1. 5. The method for producing an epoxy compound according to claim 3, wherein the catalyst is methyltrioxorhenium. 6. A hydroperoxide compound is tert-
Butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide,
p-menthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,
The method for producing an epoxy compound according to claim 1, wherein the epoxy compound is at least one selected from 3,3-tetramethylbutyl hydroperoxide. 7. The compound represented by the general formula (3) is tert.
-Butyl hydroperoxide and / or cumene hydroperoxide.
5. The method for producing an epoxy compound according to any one of 5 above. 8. The method for producing an epoxy compound according to any one of claims 1 to 7, wherein an onium salt represented by the general formula (4) is added. R ³ R ⁴ R ⁵ R ⁶ M + Q- (4) (wherein R ^{3 to} R ⁶ are each independently a hydrogen atom or a carbon number 1
To 30 alkyl groups, and R ^{3 to} R ⁶ may form a ring with adjacent groups. M is a nitrogen atom or a phosphorus atom, and Q ⁻ represents an anion. ) 9. The method for producing an epoxy compound according to claim 1, wherein the oxidation reaction is carried out in the presence of a phosphate anion. 10. The method for producing an epoxy compound according to claim 1, wherein the solvent for the oxidation reaction is substantially water. 11. The method for producing an epoxy compound according to any one of claims 1 to 9, wherein the oxidation reaction is carried out in a two-phase system of water and an organic solvent. 12. The method for producing an epoxy compound according to claim 10, wherein the oxidation reaction is carried out when the pH of the aqueous phase is 3 to 6. 13. The epoxy compound having an oxetane ring represented by the general formula (2) is 7,8-epoxy-2-oxa-5-methylspiro [3.5] nonane or 6,7-.
Epoxy-2-oxaspiro [3.5] nonane, The manufacturing method of the epoxy compound as described in any one of Claims 1-12 characterized by the above-mentioned.