JP2009292751A - Method for producing 5-oxo-4-oxatricyclo[4.2.1.03,7]nonan-2-yl (meth)acrylate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To industrially produce 5-oxo-4-oxatricyclo[4.2.1.0<SP>3,7</SP>]nonan-2-yl ester having a low impurity content and a low metal content in a high yield. <P>SOLUTION: The method for producing 5-oxo-4-oxatricyclo[4.2.1.0<SP>3,7</SP>]nonan-2-yl (meth)acrylate comprises reacting 2-hydroxy-4-oxatricyclo[4.2.1.0<SP>3,7</SP>]nonan-5-one with (meth)acrylic acid or its derivative and crystallizing the obtained reaction product using a mixed solvent of a carbonyl compound and an aliphatic hydrocarbon. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a process for producing (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester. The (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester obtained by the present invention is useful as a raw material monomer for a resist resin.

Conventionally, as a method for producing (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester, (1) 2-hydroxy-4-oxatri Cyclo [4.2.1.0 ^3,7 ] nonan-5-one is dissolved in tetrahydrofuran and reacted with acrylic acid chloride in the presence of N, N-dimethylaniline, and then the reaction solution is washed with a solvent. And then recrystallizing with diisopropyl ether (see Patent Document 1), (2) 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonane-5 The reaction mixture obtained by dissolving ON in toluene and heating with methacrylic acid in the presence of sulfuric acid is neutralized with alkali, and then adsorbed. Then, the filtrate is concentrated, and diisopropyl ether is added to the concentrate to re-activate. Crystallizer (See Patent Document 2), (3) 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7] nonan-5-one was dissolved in toluene, and methacrylic acid in the presence of sulfuric acid A method of neutralizing the heated reaction solution with 2.9% aqueous ammonia and ethyl acetate and recrystallizing crude crystals obtained by concentration and crystallization from the extracted organic layer in a mixed solvent of ethyl acetate and diisopropyl ether (patent References 3), (4) 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one is dissolved in toluene and heated with methacrylic acid in the presence of sulfuric acid. The reaction solution was neutralized with 2.9% ammonia water and butyl acetate, and the extracted organic layer was washed with ion-exchanged water, and after solvent replacement with butyl acetate, recrystallization was performed (Patent Document 4). Etc. are known.

(Meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester is known to be useful as a raw material monomer for resist resins, In order to make full use of its performance, specific examples include reduction of organic impurities including polymers such as metal impurities, halogens, oligomers derived from raw materials and products, among them, substrates. With the progress of circuit miniaturization, reduction of organic impurities including polymers such as oligomers has been demanded. However, in the above methods (1) and (2) and (3) and (4), the resulting (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] The purity of nonan-2-yl ester is 99.0%, which does not sufficiently satisfy the quality required for the raw material monomer of the resist resin. Also, the cooling temperature at the time of crystallization is −20 to 10 ° C., and a special cooling device is required for cooling, which is disadvantageous as an industrial production method.
Japanese Patent Laid-Open No. 2000-026446 JP 2001-192355 A JP 2005-255583 A JP 2005-255586 A

The object of the present invention is to yield (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester with low impurity content and low metal content. It is to be manufactured industrially well.

The present invention relates to a reaction product obtained by reacting 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one with (meth) acrylic acid or a derivative thereof. Is crystallized using a mixed solvent of a carbonyl compound and an aliphatic hydrocarbon (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl It is a manufacturing method of ester.

According to the production method of the present invention, (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester with low impurity content and low metal content Can be industrially produced with good yield.

  Hereinafter, the present invention will be described in detail.

(Meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester obtained by the production method of the present invention has the following general formula (I):

(In the formula, R represents a hydrogen atom or a methyl group)
Indicated by

In the production method of the present invention, 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one as a raw material is, for example, a Diels-Alder of cyclopentadiene and acrylic acid. The product obtained by the reaction can be obtained by oxidizing with formic acid and hydrogen peroxide (see J. Chem. Soc., Pages 221-226 (1959)).

In the production method of the present invention, (meth) acrylic acid or a derivative thereof is used. The derivative of (meth) acrylic acid is a derivative capable of reacting with the hydroxyl group of 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one. Derivatives of (meth) acrylic acid typically react with the hydroxyl group of 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one to form an ester. Derivatives of (meth) acrylic acid include, for example, (meth) acrylic acid halides such as (meth) acrylic acid chloride and (meth) acrylic acid bromide; acid anhydrides such as anhydrous (meth) acrylic acid; (meth) acrylic acid Examples thereof include alkyl esters or alkenyl esters of (meth) acrylic acid such as methyl, ethyl (meth) acrylate, vinyl (meth) acrylate, and 2-propenyl (meth) acrylate, preferably (meth) acrylic acid. (Meth) acrylic acid chloride and anhydrous (meth) acrylic acid.

An esterification reaction between 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one and (meth) acrylic acid will be described.

The amount of (meth) acrylic acid used is preferably equimolar or more with respect to 1 mol of 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one. More preferably, it is 2 moles or more.

The reaction of 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one with (meth) acrylic acid or a derivative thereof is usually in a solvent inert to the reaction. Done in Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbons such as hexane, cyclohexane, heptane, octane, and decane; methylene chloride, chloroform, 1,2-dichloropropane, chlorobenzene, And halogenated hydrocarbons such as trifluoromethylbenzene; ethers such as diethyl ether, diisopropyl ether, dibutyl ether, anisole and tetrahydrofuran; and mixed solvents thereof. As the solvent, a solvent that is azeotropic with the by-product water and can be separated from water (solvent capable of azeotropic dehydration), for example, toluene is preferable.

The amount of the solvent used is based on 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one in consideration of reaction efficiency, operability, economy and the like. 1 to 20 times the weight is preferable. When the solvent is distilled azeotropically, the solvent of the distilled water is added to the system as needed, or when an excessive amount of solvent is charged beyond the amount necessary for azeotropic dehydration from the beginning of the reaction. The solvent may not be added until the end of the reaction. The solvent distilled by azeotropic distillation can be returned to the reaction system after being separated from water.

The reaction of 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one with (meth) acrylic acid or a derivative thereof is preferably performed in the presence of a catalyst. . Examples of the catalyst include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and heteropolyacid (for example, silicotungstic acid, silicomolybdic acid, phosphotungstic acid, phosphomolybdic acid, etc.); benzenesulfonic acid, p-toluenesulfone Sulfonic acids such as acid, naphthalene sulfonic acid, methane sulfonic acid, trifluoromethane sulfonic acid, ethane sulfonic acid, camphor sulfonic acid; Amberlyst 15 (manufactured by Tokyo Organic Chemical Industry Co., Ltd.), Amberlite IR-118 (Tokyo Organic Chemical Industry) Acid-type ion exchange resins such as those manufactured by Co., Ltd .; Lewis acids such as boron fluoride diethyl etherate. These are used alone or in combination of two or more. The amount of the esterification catalyst used is in the range of 0.001 to 100 mol% with respect to 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one. In consideration of the efficiency of the reaction, it is more preferably in the range of 0.1 to 20 mol%.

  The reaction temperature is preferably in the range of 20 to 130 ° C, and more preferably in the range of 50 to 120 ° C. When the reaction temperature is less than 20 ° C., the progress of the reaction becomes extremely slow and the residence time becomes long, so that the reaction efficiency tends to deteriorate, and when the reaction temperature exceeds 130 ° C., There is a tendency that (meth) acrylic acid, a product esterified product, or a mixture thereof is polymerized and a compound having a high boiling point is by-produced.

  The reaction time is preferably in the range of 0.1 to 50 hours, more preferably in the range of 10 to 30 hours. When the reaction time is less than 0.1 hour, the reaction does not proceed sufficiently and the reaction efficiency tends to be low, and when it exceeds 50 hours, the compound having a high boiling point to be suppressed is not a secondary component. It tends to be born.

  The reaction may be carried out under normal pressure or reduced pressure. However, if the azeotropic point of the solvent used and water exceeds 130 ° C. at the vapor pressure at which the reaction is carried out, the reaction temperature becomes high and the by-product Since generation | occurrence | production may be anxious, it is preferable to carry out under reduced pressure.

  The reaction is preferably performed in the presence of a polymerization inhibitor. By allowing the polymerization inhibitor to be present in the reaction system, it is possible to prevent polymerization of the raw material (meth) acrylic acid, the product esterified product, or a mixture thereof. As the polymerization inhibitor, known polymerization inhibitors can be used. For example, hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, phenothiazine, p-phenylenediamine, benzidine and the like can be used. In order to suppress polymerization in the gas phase part in the reaction system, it is preferable to carry out the reaction while blowing air or oxygen into the reaction system.

On the other hand, the reaction of 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one with a derivative of (meth) acrylic acid depends on the type of the derivative, The reaction can be performed in the presence of a base or a transesterification catalyst. For example, when (meth) acrylic acid halide or acid anhydride is used as a derivative of (meth) acrylic acid, in the presence of a base (acid scavenger) such as triethylamine or pyridine, for example, 0-100 ° C. in the solvent. The reaction is carried out at a moderate temperature. In addition, when (meth) acrylic acid ester is used as a derivative of (meth) acrylic acid, a periodic table is used particularly when a conventional transesterification catalyst or alkenyl (meth) acrylate is used as the reactive derivative. In the presence of a Group 3 element compound catalyst (for example, a samarium compound such as samarium acetate, samarium trifluoromethanesulfonate, or a samarium complex), the reaction is performed, for example, in the solvent at a temperature of about 0 to 150 ° C.

By reacting 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one with (meth) acrylic acid or a derivative thereof, (meth) acrylic acid 5-oxo-4 -Oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester is formed. In addition, as a component to be reacted with 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one, a halogen that lowers performance when used as a resist resin is reacted. Since it is not contained in a product, (meth) acrylic acid etc. are more preferable.

The reaction product (reaction mixture) thus obtained may be subjected to crystallization as it is, but before that, it is preferably washed with at least one washing liquid selected from water, an alkaline aqueous solution and an acidic aqueous solution. By this washing treatment, 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one or (meth) acrylic which is an unreacted raw material contained in the reaction mixture. Acids, catalysts, oligomers derived from (meth) acrylic acid, other water-soluble impurities, and metals such as iron and nickel can be efficiently removed.

  As said water, the thing with little metal content according to the objective of this invention, for example, ion-exchange water etc., is preferable.

  As the alkaline aqueous solution, for example, an alkaline solution added to water to adjust the pH to about 8 to 14 is preferable. A more preferable pH range is about 8 to 12, and further preferably about pH 8 to 11. Examples of the alkali used for preparing the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like, among which sodium carbonate and sodium hydrogen carbonate are preferable.

  As said acidic aqueous solution, what added the acid to water and made pH into about 0-5 is preferable, for example. A more preferable pH range is about 0 to 4, more preferably about pH 1 to 3. Examples of the acid used for forming the acidic aqueous solution include formic acid, succinic acid, acetic acid, hydrochloric acid, sulfuric acid and the like, and among them, succinic acid is preferable.

  The cleaning may be performed using one or two cleaning liquids of water, an alkaline aqueous solution, and an acidic aqueous solution, but is preferably performed by combining the three cleaning liquids. The order of cleaning in the case of using a plurality of cleaning liquids is not particularly limited, but the order of acidic aqueous solution cleaning-alkaline aqueous solution cleaning-water cleaning is desirable. The number of washings may be once or plural times for each washing solution. The number of times of the washing treatment may be one time or a plurality of times, but is preferably 2 times or more, more preferably about 2 to 10 times, and particularly preferably about 3 to 8 times. Although there is no special restriction | limiting in the usage-amount of a washing | cleaning liquid, it is preferable that it is 10-200 weight part with respect to 100 weight part of to-be-washed | cleaned objects (reaction mixture) per washing | cleaning process, and about 20-100 weight part is preferable. It is more preferable that The temperature of the cleaning treatment is preferably about 10 to 60 ° C.

  Washing can be performed by a known or conventional method such as a batch system, a continuous system, or a multistage system. Unreacted raw materials such as (meth) acrylic acid can be recovered from the aqueous layer after washing and reused.

In the present invention, a reaction product obtained by reacting 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one with (meth) acrylic acid or a derivative thereof. Is crystallized using a mixed solvent of a carbonyl compound and an aliphatic hydrocarbon.

  The mixed solvent of the carbonyl compound and the aliphatic hydrocarbon is preferably mixed in the reaction mixture after the washing treatment, after replacing the solvent used for the esterification reaction with the carbonyl compound and then adding the aliphatic hydrocarbon. Crystallize after using as solvent. Therefore, the carbonyl compound preferably has a boiling point higher than that of the esterification reaction solvent.

  Examples of carbonyl compounds used for solvent substitution and crystallization solvents include acetone, methyl ethyl ketone, 2-pentanone, 2-hexanone, methyl isobutyl ketone, 2-hexanone, cyclohexanone, 2-heptanone, 4-heptanone, diisobutyl ketone, 2- Octanone, 3-octanone, 4-octanone, acetophenone, propiophenone and the like are preferable, and aliphatic ketones are preferable. Among them, methyl isobutyl ketone is preferable in consideration of purification efficiency in crystallization after solvent substitution and drying efficiency of crystals. Particularly preferred.

The distillation of the reaction solvent in the solvent replacement operation varies depending on the type of the reaction solvent, but is performed, for example, at a pressure of about 665 to 13300 Pa (5 to 100 mmHg) and a temperature of about 10 to 60 ° C. When the temperature is too high, (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester may be polymerized, which is not preferable. The reaction solvent distilled off can be reused.

In the crystallization step, the reaction product preferably contains (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester after the solvent substitution. Aliphatic hydrocarbons are added to, and crystallization is performed in a mixed solvent of a carbonyl compound and an aliphatic hydrocarbon.

  Examples of the aliphatic hydrocarbon include pentane, hexane, cyclohexane, heptane, octane, nonane, decane, dodecane, and the like. Of these, cyclohexane and the like are preferable.

  The mixed solvent of the carbonyl compound and the aliphatic hydrocarbon is particularly preferably a mixed solvent of methyl isobutyl ketone and cyclohexane.

The ratio of the carbonyl compound to the aliphatic hydrocarbon is, for example, carbonyl compound / aliphatic hydrocarbon (weight ratio) = 5/95 to 95/5, preferably 20/80 to 90/10, more preferably 35/65. It is about 85/15. When the proportion of the carbonyl compound is too high, crystallization tends to be difficult, and when the proportion of the ketone is too low, 5-methacrylic acid 5-oxo-4-oxatricyclo [4.2.1. The quality of 0 ^3,7 ] nonan-2-yl ester tends to deteriorate.

The amount of crystallization solvent used varies depending on the type of solvent, but (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester 100 wt. The amount is preferably in the range of 20 to 1000 parts by weight, more preferably in the range of 25 to 800 parts by weight, and particularly preferably in the range of 30 to 500 parts by weight. The crystallization operation is performed, for example, by cooling from a temperature of about 30 to 70 ° C. to a temperature of about 10 to 20 ° C. The cooling time is, for example, about 0.1 to 10 hours, preferably about 0.3 to 6 hours, and the aging time is, for example, about 0.5 to 15 hours, preferably about 1 to 5 hours.

By-product such as oligomers derived from (meth) acrylic acid can be efficiently removed by crystallization treatment, and high-purity (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^{3 , 7} ] nonan-2-yl ester can be obtained.

  The drying conditions for the crystals obtained by crystallization can be set as appropriate within a range that does not impair the quality and work efficiency. For example, the temperature is about 10 to 70 ° C. (preferably about 10 to 60 ° C.) 13.3-101000 Pa (0.1-760 mmHg)]. The drying time is, for example, about 0.1 to 24 hours. Drying may be performed in an inert gas stream such as nitrogen.

The mother liquor obtained by crystallization contains (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester, which is added to the next batch. The secondary crystals of (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester are recovered as such or by, for example, concentrated crystallization, Can be reused. The solvent recovered by the concentrated crystallization can be reused.

  Hereinafter, the present invention will be described in detail with reference to examples.

Example 1
To a 1 L four-necked flask equipped with a reflux condenser, a water separator, a 3% oxygen inlet tube, a thermometer, and a stirrer was added 2-hydroxy-4-oxatricyclo [4.2.1.0 ^{3. , 7} ] Nonane-5-one 120 g (0.778 mol), methacrylic acid 80.4 g (0.934 mol), sulfuric acid 4.6 g (0.047 mol), methoquinone 0.43 g and toluene 600 g were put in the solution. An oxygen-nitrogen mixed gas having an oxygen concentration of 3% was supplied at a flow rate of 10 ml / min. The temperature of the liquid was raised to 110 ° C., water produced as a by-product in the reaction was distilled off by azeotropy with toluene, and the reaction was carried out for about 15 hours while returning only toluene to the reactor. The reaction solution was subjected to high performance liquid chromatography (hereinafter HPLC) (column: Inertsil ODS-2 4.6 mmφ × 250 mm, manufactured by GL Sciences Inc., carrier solvent: acetonitrile / 0.05 wt% phosphoric acid water, gradient conditions: 5/95 → 90 / 10 (volume ratio), flow rate: 1 ml / min, detection: 210 nm), conversion of 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one The yield was 94% and the yield of methacrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester was 90%.

This reaction solution was transferred to a 2 L four-necked flask equipped with a stirrer and a thermometer, and washed once with a 5 wt% aqueous sodium carbonate solution and once with ion-exchanged water under a temperature of 40 to 50 ° C. In each case, about 50 parts by weight of the cleaning liquid was used with respect to 100 parts by weight of the liquid to be cleaned. By this washing operation, unreacted 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one, methacrylic acid, sulfuric acid and the like are removed, and methacrylic acid is used as the organic layer. A toluene solution of 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester was obtained.

The organic layer was concentrated under reduced pressure while adding methyl isobutyl ketone, toluene was removed from the system, and the solvent was replaced with methyl isobutyl ketone. 5-oxo-4-oxatricyclomethacrylate [4.2 .1.0 ^3,7] to obtain 40 wt% methyl isobutyl ketone solution nonane-2-yl ester. After cyclohexane was added to 30% by weight, the solution was heated to 60 ° C. to completely dissolve the crystals, allowed to cool, and then stirred at 10 to 15 ° C. for 1 hour. . The precipitated crystals were separated by filtration to obtain 149 g of crude crystals of methacrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester. Methyl isobutyl ketone was charged so that the obtained crude crystals were 35% by weight, and the mixture was treated twice with 0.1% by weight aqueous oxalic acid solution and at 1% by weight with 0.1% by weight aqueous sodium hydrogen carbonate solution at 60-65 ° C. And further washed three times with ion-exchanged water. In each case, about 30 parts by weight of the cleaning liquid was used with respect to 100 parts by weight of the liquid to be cleaned. This washing operation removes metals such as iron and nickel, and other water-soluble impurities. After cyclohexane was added to the organic layer so as to be 30% by weight, the solution was heated to 60 ° C. to completely dissolve the crystals, and then allowed to cool, and then at 10 to 15 ° C. for 1 hour. Stir. The precipitated crystals were separated by filtration, and the obtained crystals were vacuum-dried to obtain white methacrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester. 123 g were obtained.

The HPLC purity of the resulting methacrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester is 99.9%, and iron which is a metal component of impurities The nickel content was 20 ppb or less, respectively. The crystallization yields in the two crystallizations were 89 and 84%, respectively.

Example 2
To a 1 L four-necked flask equipped with a reflux condenser, a water separator, a 3% oxygen inlet tube, a thermometer, and a stirrer was added 2-hydroxy-4-oxatricyclo [4.2.1.0 ^{3. , 7} ] Nonane-5-one (263 g, 1.706 mol), methacrylic acid (177 g, 2.056 mol), sulfuric acid (10 g, 0.109 mol), phenothiazine (0.5 g) and toluene (527 g) were added. Was supplied at a flow rate of 10 ml / min. The temperature of the liquid was raised to 110 ° C., water produced as a by-product in the reaction was distilled off by azeotropy with toluene, and the reaction was carried out for about 12 hours while returning only toluene to the reactor. The reaction solution was subjected to high performance liquid chromatography (hereinafter HPLC) (column: Inertsil ODS-2 4.6 mmφ × 250 mm, manufactured by GL Sciences Inc., carrier solvent: acetonitrile / 0.05 wt% phosphoric acid water, gradient conditions: 5/95 → 90 / 10 (volume ratio), flow rate: 1 ml / min, detection: 210 nm), conversion of 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one The yield was 99% and the yield of methacrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester was 92%.

This reaction solution was transferred to a 2 L four-necked flask equipped with a stirrer and a thermometer, and washed once with a 7 wt% aqueous sodium carbonate solution and once with ion-exchanged water under the condition of a temperature of 60 to 70 ° C. In each case, about 50 parts by weight of the cleaning liquid was used with respect to 100 parts by weight of the liquid to be cleaned. By this washing operation, unreacted 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one, methacrylic acid, sulfuric acid and the like are removed, and methacrylic acid is used as the organic layer. A toluene solution of 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester was obtained.

The organic layer was concentrated under reduced pressure while adding methyl isobutyl ketone, toluene was removed from the system, and the solvent was replaced with methyl isobutyl ketone. 5-oxo-4-oxatricyclomethacrylate [4.2 .1.0 ^3,7] to obtain 50 wt% methyl isobutyl ketone solution nonane-2-yl ester. After cyclohexane was added to 35% by weight, the solution was heated to 70 ° C. to completely dissolve the crystals, allowed to cool, and then stirred at 10 to 15 ° C. for 1 hour. . The precipitated crystals were separated by filtration to obtain 342 g of crude crystals of methacrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester. Methyl isobutyl ketone was charged so that the obtained crude crystals would be 40% by weight, and once at a temperature of 60 to 65 ° C. with a 0.1% by weight aqueous oxalic acid solution and once with a 0.1% by weight aqueous sodium bicarbonate solution. And further washed three times with ion-exchanged water. In each case, about 30 parts by weight of the cleaning liquid was used with respect to 100 parts by weight of the liquid to be cleaned. This washing operation removes metals such as iron and nickel, and other water-soluble impurities. After cyclohexane was added to the organic layer so as to be 30% by weight, the liquid temperature was heated to 70 ° C. to completely dissolve the crystals, and then allowed to cool, and then at 10 to 15 ° C. for 1 hour. Stir. The precipitated crystals were separated by filtration, and the obtained crystals were vacuum-dried to obtain 307 g of white methacrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester. Got.

The HPLC purity of the resulting methacrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester is 99.9%, and iron which is a metal component of impurities The nickel content was 20 ppb or less, respectively. The crystallization yields in the two crystallizations were 90 and 90%, respectively.

The high-quality (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester produced by the present invention is a resist resin. It is useful as a raw material monomer.

Claims (3)

A reaction product obtained by reacting 2-hydroxy-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-5-one with (meth) acrylic acid or a derivative thereof is converted into a carbonyl compound. Of (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester that crystallizes using a mixed solvent of olefin and aliphatic hydrocarbon . The method for producing (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl ester according to claim 1, wherein the carbonyl compound is an aliphatic ketone. The mixed solvent of a carbonyl compound and an aliphatic hydrocarbon is a mixed solvent of methyl isobutyl ketone and cyclohexane. The (meth) acrylic acid 5-oxo-4-oxatricyclo [4.2. 1.0 ^3,7 ] Method for producing nonan-2-yl ester.