JP2008162946A - Method for producing (meth)acrylate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing (meth)acrylate useful as a resin raw material of a constituent component of a coating material, an adhesive, a pressure-sensitive adhesive, a resin for ink, a resist, a molding material, an optical material or the like, especially a raw material for a resin for the resist, in a high yield with a reduced number of steps while hardly leaving a still residue after distillation purification at each step. <P>SOLUTION: The method for producing the (meth)acrylate represented by formula (4a) or (4b) includes carrying out an acid addition step for producing a saturated acid adduct by adding a saturated carboxylic acid to a compound represented by formula (1), and an ester-interchange step for ester-interchanging the saturated carboxylic acid adduct with the (meth)acrylate in order. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a (meth) acrylic acid ester useful as a constituent resin raw material for paints, adhesives, pressure-sensitive adhesives, ink resins, resists, molding materials, optical materials and the like.

  The (meth) acrylic acid ester having an alicyclic structure is useful as a constituent resin material for paints, adhesives, pressure-sensitive adhesives, ink resins, resists, molding materials, optical materials and the like. Among them, in ArF excimer laser lithography, a resist resin having transparency to irradiation light has been searched, and the above (meth) acrylic acid ester is a promising candidate. For example, Patent Document 1 discloses a mixture of 5-cyanobicyclo [2.2.1] heptyl-2-methacrylate and 6-cyanobicyclo [2.2.1] heptyl-2-methacrylate (in this specification, It is described that a polymer obtained by polymerizing this mixture as described in “a mixture of 5- and 6-cyanobicyclo [2.2.1] heptyl-2-methacrylate” is promising as a resist polymer. A method for producing the (meth) acrylic acid ester is described. Specifically, a transesterification step is described in which a carboxylic acid is added to cyanonorbornene and purified by distillation to obtain a purified carboxylic acid adduct, and the carboxylic acid adduct is transesterified with a (meth) acrylic acid ester. ing. However, in the process of distilling the purified carboxylic acid adduct, there is a problem that the purified carboxylic acid adduct obtained has a large amount of high-boiling substances (hereinafter referred to as kettle residue) remaining in the reaction kettle after distillation.

Furthermore, as a monomer that is promising as a monomer for a resist polymer, Patent Document 2 discloses 8- and 9- (meth) acryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] -decane- A process for the preparation of 3-one mixtures is described. In this prior document, a compound obtained by Diels-Alder reaction of cyclopentadiene or a decomposition product of dicyclopentadiene and maleic anhydride is reduced by using a reducing agent such as sodium tetrahydroborate and the following formula ( The following production method is described using 4-oxatricyclo [5.2.1.0 ^2,6 ] -8-decen-3-one represented by 1-1) as a starting material. .

According to this prior document, it is said that it is obtained by synthesizing an alcohol represented by the following formula (2) and converting it to (meth) acryloylation. As a method of synthesizing the alcohol represented by the following formula (2), (i) epoxidizing and reducing a double bond,
(Ii) after hydroboration, hydrolyze oxidatively;
(Iii) hydrolyzing an ester obtained by adding a lower carboxylic acid such as formic acid or acetic acid,
(Iv) adding mercuric acetate to reduce (oxymercuration reaction, demercuration reaction),
The method is mentioned. Among them, a method of producing by synthesizing an alcohol represented by the following formula (2) by the method (iii) and converting it to (meth) acryloyl is considered preferable from the viewpoint of yield, economy, and large scale. .

JP 2005-263757 A International Publication No. 02/46179 Pamphlet

  However, the yield of the (meth) acrylate ester as the final target substance is also low in the production method of (meth) acrylate ester by the synthesis method of (iii) because the yield of the alcohol represented by the formula (2) is low. Is not high enough. In addition, there is a problem that the number of steps is not sufficiently small.

  The present invention provides (meth) acrylic acid esters that are useful as constituent resin raw materials for paints, adhesives, pressure-sensitive adhesives, ink resins, resists, molding materials, optical materials, etc., particularly as resist resin raw materials, in high yields. Another object of the present invention is to provide a production method in which the number of steps is reduced and the residue in the kettle after the distillation production in each step is reduced.

  As a result of intensive investigations in view of the above problems, the present inventors have found that, as a constituent resin material for paints, adhesives, pressure-sensitive adhesives, ink resins, resists, molding materials, optical materials, etc., particularly for resists having excellent stability. The inventors have found a method for producing a (meth) acrylic acid ester useful as a raw material for a resin in a high yield and with a small number of steps, and have reached the present invention.

That is, the first gist of the present invention is an acid addition step for producing a saturated carboxylic acid adduct by adding a saturated carboxylic acid to a compound represented by the following formula (1):
A transesterification step of transesterifying the saturated carboxylic acid adduct and (meth) acrylic acid ester;
Is a method for producing a (meth) acrylic acid ester represented by the following formula (4a) or (4b).

(In Formula (1), A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or A ¹ and A ² together form —O—, —S—. Or an alkylene group having 1 to 6 carbon atoms, wherein R ² and R ³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, a cyano group, or a carbon number. Represents a carboxy group esterified with an alcohol of 1 to 6. In formulas (4a) and (4b), R ¹ represents a hydrogen atom or a methyl group, and A ¹ and A ² , R ² and R ³ represent formula ( It is synonymous with 1).

  Moreover, the 2nd summary of this invention is the manufacturing method of the said (meth) acrylic acid ester which uses the compound represented by following formula (1-1) as a compound represented by said formula (1). is there.

  Moreover, the 3rd summary of this invention is the manufacturing method of the said (meth) acrylic acid ester which uses the compound represented by following formula (1-2) as a compound represented by said formula (1). is there.

  In this specification, the (meth) acrylic acid ester represented by the above formula (4a) or (4b) is described as the following formula (4).

  The present invention provides (meth) acrylic acid esters that are useful as constituent resin raw materials for paints, adhesives, pressure-sensitive adhesives, ink resins, resists, molding materials, optical materials, etc., particularly as resist resin raw materials, in high yields. Moreover, it can be manufactured by a method in which the number of steps is small and the residue in the pot after distillation production in each step is small.

  This invention is a manufacturing method of the (meth) acrylic acid ester represented by said Formula (4). “(Meth) acrylic acid” is a general term for methacrylic acid and acrylic acid.

  The (meth) acrylic acid ester represented by the formula (4) is a step of adding a saturated carboxylic acid to the compound represented by the formula (1) (acid addition step), and the obtained saturated carboxylic acid adduct. And a step of transesterifying with (meth) acrylic acid ester (transesterification step). A washing step for removing the acid catalyst is preferably performed between the acid addition step and the transesterification step in terms of yield and polymerization prevention in the transesterification step, and the resulting (meth) acrylic ester is constituted. From the viewpoint of storage stability of the resist resin as a unit.

1. Compound represented by the above formula (1) When the (meth) acrylic acid ester represented by the above formula (4) is used for a resist, A ¹ and A ² together represent carbon in terms of etching resistance. It is preferably a C 1-6 alkylene group, or —O—, and more preferably a C 1-2 alkylene group, or —O—. Therefore, the same applies to the compound represented by the formula (1). R ² and R ³ are preferably hydrogen groups from the viewpoint of easy availability of the compound represented by the formula (1).

  Specific examples of particularly preferred compounds include compounds represented by the following formula (1-1) or (1-2).

The compound represented by the formula (1) can be obtained, for example, by a Diels-Alder reaction between cyclopentadiene and dienophile. For example, 4-oxatricyclo [5.2.1.0 ^2,6 ] -8-decen-3-one represented by the formula (1-1) is a Diels-Alder reaction between cyclopentadiene and maleic anhydride. Can be obtained by reacting a compound obtained by the above with a reducing agent such as sodium tetrahydroborate. Cyclopentadiene may be isolated once and then subjected to Diels-Alder reaction, or cyclopentadiene generated after pyrolysis of dicyclopentadiene may be directly subjected to Diels-Alder reaction without isolation.

  The cycloaddition reaction of maleic anhydride and cyclopentadiene proceeds easily, but it is preferable to use a catalyst such as Lewis acid as necessary and without solvent or in a solvent such as methanol.

2. Acid addition step The compound represented by the above formula (1) is a compound (acid adduct) represented by the following formula (3) by adding a saturated carboxylic acid (R ⁴ COOH) according to the following reaction formula (I). Converted to.

(In the reaction formula (I), R ⁴ represents a hydrogen atom or an optionally substituted alkyl group.)
As the saturated carboxylic acid used in the acid addition step, acetic acid, formic acid, and trifluoroacetic acid are preferable. Formic acid is particularly preferred from the viewpoint of high reactivity and economy. Further, since the carboxylic acid has a low boiling point, if it remains after the acid addition step, it can be easily removed by reducing the pressure. Only one kind of saturated carboxylic acid may be used, or two or more kinds may be used in combination.

The remaining saturated carboxylic acid may cause the following problems.
1) Hydrolysis occurs, and the product is converted to a compound represented by the following formula (2), and the yield is lowered.
2) It adversely affects the stability of the resist.
3) It dissolves in the aqueous phase in the next water washing step, and acts as a compatibilizer for dissolving the intermediate ester in the aqueous phase, resulting in a decrease in yield.

  For this reason, it is preferable to remove the excess saturated carboxylic acid remaining after the acid addition step under reduced pressure from the viewpoint of obtaining the desired product in a high yield.

  Although the usage-amount of the saturated carboxylic acid used at an acid addition process is not restrict | limited in particular, It is preferable that it is the range of 2-15 mol with respect to 1 mol of compounds represented by the said Formula (1). When the amount of saturated carboxylic acid used is 2 mol or more, the yield and reaction rate tend to be improved. Moreover, when the usage-amount of saturated carboxylic acid is 15 mol or less, it exists in the tendency which can remove the excess saturated carboxylic acid after reaction easily. The amount of saturated carboxylic acid used is particularly preferably in the range of 3 to 8 mol. In the reaction, the order of adding the compound represented by the formula (1) and the saturated carboxylic acid is arbitrary. Moreover, the whole quantity may be charged at once, and the method of adding in several times may be taken.

  The acid addition step may be performed in the presence of an acid catalyst. Examples of the acid catalyst include Lewis acids such as boron trifluoride; mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid; p-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, and camphorsulfone. Acids, organic acids such as trifluoromethanesulfonic acid; heteropolyacids such as phosphotungstic acid and silicotungstic acid; strong acid ion exchange resins and the like. From the point of high reactivity, sulfuric acid, p-toluenesulfonic acid, camphorsulfone Acid, methanesulfonic acid, and trifluoromethanesulfonic acid are preferable, and p-toluenesulfonic acid is particularly preferable because of easy handling. The acid catalyst may be used alone or in combination of two or more.

  The amount of the acid catalyst used is preferably in the range of 0.03 to 0.3 mol with respect to 1 mol of the compound represented by the formula (1). When the usage-amount of an acid catalyst is 0.03 mol or more, it exists in the tendency which can improve a yield and reaction rate. Moreover, when the usage-amount of an acid catalyst is 0.3 mol or less, it exists in the tendency for the production | generation suppression of a by-product and the refinement | purification after an acid addition reaction to be performed easily. The amount of the acid catalyst used is particularly preferably in the range of 0.05 to 0.25 mol.

  The temperature for the acid addition step is preferably in the range of 50 to 150 ° C. When the reaction temperature is 50 ° C. or higher, the yield and reaction rate tend to be improved. Moreover, when reaction temperature is 150 degrees C or less, it exists in the tendency which can suppress the production | generation of a by-product. The reaction temperature is particularly preferably in the range of 70 to 130 ° C.

  A solvent can be used in the acid addition step. The solvent is not particularly limited, but ether solvents such as tetrahydrofuran, tetrahydropyran, dimethyl ether, diethyl ether, diisopropyl ether, and methyl-t-butyl ether; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, and cyclohexane An aromatic hydrocarbon solvent such as benzene, toluene and xylene. These solvents are preferably dehydrated beforehand by a conventional method because a high reaction yield can be obtained. A solvent may use only 1 type and may use 2 or more types together. However, it is preferable to perform the acid addition reaction without a solvent from the viewpoint of good yield.

  The time required for the acid addition reaction varies depending on the batch size, acid catalyst, and reaction conditions, but is preferably in the range of 1 to 12 hours. When the reaction time is 1 hour or longer, the yield tends to be improved, and when the reaction time is 12 hours or shorter, the production of by-products tends to be suppressed. The reaction time is particularly preferably in the range of 2 to 8 hours.

In the acid addition step, since polymerization may occur, it is preferable that a polymerization inhibitor coexists. The polymerization inhibitor is not particularly limited as long as it inhibits polymerization, but hydroquinone, hydroquinone monomethyl ether, 2,4-dimethyl-6-t-butylphenol, p-benzoquinone, 2,5-diphenyl-p-benzoquinone. , Phenothiazine, N-nitrosodiphenylamine, copper salt, copper metal, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4- [H— (OCH ₂ CH ₂ ) _n —O] — Examples include 2,2,6,6-tetramethylpiperidine-N-oxyl (where n = 1 to 18). Only one type of polymerization inhibitor may be used, or two or more types may be used in combination. It is also effective to suppress the polymerization by carrying out the reaction while blowing air or oxygen.

  After completion of the acid addition step, it is preferable to remove at least a part, preferably substantially all of the unreacted saturated carboxylic acid remaining in the reaction solution from the viewpoint of yield.

  Since the saturated carboxylic acid used in the acid addition step has a low boiling point, it is preferably removed under reduced pressure. Usually, it can be removed under reduced pressure at a temperature of 40 to 100 ° C. and a pressure of 5 to 50 torr (666.5 to 6665 Pa). When the temperature is 40 ° C. or more and the pressure is 50 torr (6665 Pa) or less, the removal time tends to be shortened. When the temperature is 100 ° C. or less and the pressure is 5 torr (666.5 Pa) or more, it is generated. There is a tendency that the acid adduct is not easily dissipated. A temperature range of 50 to 70 ° C. and a pressure of 10 to 30 torr (1333 to 3999 Pa) are particularly preferable.

  On the other hand, when an acid addition reaction is performed in the presence of an acid catalyst, the acid catalyst remaining after the reaction cannot be easily removed under reduced pressure.

  For this reason, a method of removing the acid catalyst by washing the reaction solution with water or an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, etc., and removing the acid catalyst; sodium carbonate, sodium hydrogen carbonate, oxidation A method of adding an alkali powder such as magnesium and stirring, and then removing the acid catalyst by filtering the neutralized salt; a method of adding an amine such as triethylamine, triethanolamine, morpholine and the like to neutralize the acid catalyst. It is preferred to remove the catalyst. Among these, from the viewpoint of effectively removing the acid catalyst, a method of neutralizing and washing with an aqueous alkali solution to remove the acid catalyst and then extracting with an organic solvent is more preferable. Examples of the organic solvent used for extraction include toluene, benzene, hexane, cyclohexane, ethyl acetate, diethyl ether, diisopropyl ether, etc. From the viewpoint that extraction efficiency is high and the amount of solvent used can be reduced, toluene, ethyl acetate, diethyl Ether is preferred, and toluene and a mixed solvent of toluene and ethyl acetate are particularly preferred because the purity of the compound represented by the formula (3) can be increased.

  The compound represented by the following formula (2) is produced as a by-product in this step.

  The by-product can be inhibited from being produced, for example, by performing an acid addition reaction under dehydrating conditions. Moreover, you may refine | purify by well-known methods, such as distillation and column chromatography. However, since the compound represented by the formula (2) can be used as a raw material of the compound represented by the formula (4) in the next transesterification step, such generation suppression and reduction measures are omitted. By doing so, the manufacturing cost can be reduced.

  The obtained compound represented by the formula (3) may be purified by a known method such as distillation or column chromatography, or may be used directly in the next step without being purified. From the viewpoint of increasing the reactivity in the next step, it is preferable to carry out distillation purification, and from the viewpoint of increasing the yield, it is preferable not to perform purification.

  In the case of distillation purification, it is desirable to use thin film distillation because the distillation yield is high. Furthermore, it is preferable to mix and distill a substance having a boiling point higher than that of the saturated carboxylic acid adduct with the saturated carboxylic acid adduct in terms of increasing the distillation yield. As a substance having a boiling point higher than that of the saturated carboxylic acid adduct, for example, polyethylene glycol such as polyethylene glycol 400, polyethylene glycol 600, and polyethylene glycol 800 can be used, and polyethylene glycol 600 is preferable.

3. Transesterification Step In the present invention, the compound represented by the formula (4) is an ester for transesterifying the acid adduct and one or more (meth) acrylic acid esters represented by the formula (11). It is produced by an exchange reaction (reaction formula (II)).

(In the reaction formula (II), R ⁵ is an arbitrary substituent)
R ⁵ usually represents an alkyl group having 1 to 4 carbon atoms or an alkenyl group. Specific examples include a methyl group, an ethyl group, a butyl group, a propyl group, an isopropyl group, and a vinyl group. From the viewpoint of high reactivity, a methyl group, an ethyl group, a butyl group, and a vinyl group are preferable. The isopropyl group is preferable from the point of few things.

  Moreover, the (meth) acrylic acid ester represented by the formula (11) may be used alone or in combination of two or more. When using 2 or more types, you may mix and use a (meth) acrylic acid ester from the beginning, and you may add one afterwards.

  It is preferable that the usage-amount of the (meth) acrylic acid ester represented by said Formula (11) is the range of 2-15 mol with respect to a total of 1 mol of the compound represented by said Formula (3). When the amount of (meth) acrylic acid ester used is 2 mol or more, the yield and reaction rate tend to be improved. Moreover, when the usage-amount of (meth) acrylic acid ester is 15 mol or less, it exists in the tendency for the removal time of the (meth) acrylic acid ester represented by (11) to be shortened. The amount of the (meth) acrylic acid ester is particularly preferably in the range of 3 to 10 mol.

  In conducting the transesterification reaction, a catalyst is usually used. The catalyst is not particularly limited as long as it allows the transesterification reaction to proceed. For example, tetraalkoxy titaniums such as tetrabutoxy titanium, tetraisopropoxy titanium, and tetramethoxy titanium; dialkyls such as dibutyl tin oxide and dioctyl tin oxide Tin oxides: Aluminum alkoxylates and alkali metal alkoxylates are mentioned. From the viewpoint of reactivity, tetrabutoxy titanium, tetraisopropoxy titanium and tetramethoxy titanium are preferable, and dibutyl tin oxide and dioctyl are preferable from the viewpoint of few by-products. Tin oxide and tetramethoxytitanium are preferable, and tetramethoxytitanium is particularly preferable in terms of excellent reactivity and few side reactions. Further, tetraisopropoxy titanium is preferable from the viewpoint of excellent reactivity, and it is particularly preferable to use two or more kinds of catalysts containing tetraisopropoxy titanium in order to reduce by-products. As the catalyst used in combination, tetramethoxytitanium, dibutyltin oxide, and dioctyltin oxide can be preferably used because there are few by-products.

  When the amount of such a transesterification catalyst is small, the reaction does not proceed easily. When the amount is large, a by-product increases, and it is difficult to dissolve the transesterification catalyst after the reaction. The amount of the transesterification catalyst used is preferably in the range of 0.01 to 0.2 mol with respect to 1 mol of the compound represented by the formula (3) as a raw material. When the transesterification catalyst is used in an amount of 0.01 mol or more, the yield and reaction rate tend to be improved. Moreover, when the transesterification catalyst amount is 0.2 mol or less, the production of by-products tends to be suppressed. The transesterification catalyst amount is particularly preferably in the range of 0.05 to 0.15 mol.

  Further, the transesterification catalyst may be charged all at once, or may be added in several portions. In order to allow the transesterification reaction to proceed sufficiently, it is preferable to add after the reaction temperature shown below is reached. When two or more transesterification catalysts are used, the whole amount may be charged at once, or any transesterification catalyst may be added at an arbitrary timing.

  The reaction temperature of the transesterification reaction is preferably in the range of 50 to 150 ° C. When the reaction temperature is 50 ° C. or higher, the yield and reaction rate tend to be improved. Moreover, when reaction temperature is 150 degrees C or less, there exists a tendency to suppress the production | generation and superposition | polymerization of a by-product. The reaction temperature is particularly preferably in the range of 80 to 130 ° C.

  The transesterification time varies depending on the batch size, the transesterification catalyst, and the reaction conditions, but is preferably in the range of 1 to 12 hours. When the reaction time is 1 hour or longer, the yield and reaction rate tend to be improved. Moreover, when reaction time is 12 hours or less, there exists a tendency which can suppress the production | generation and superposition | polymerization of a by-product. The reaction time is particularly preferably in the range of 2 to 8 hours.

  During the transesterification reaction, if the water content in the system is large, the catalytic activity decreases or the by-products increase. Therefore, it is preferable to remove the water content in the system before starting the transesterification reaction. . The amount of water in the system before starting the transesterification reaction is preferably 1000 ppm or less, more preferably 500 ppm or less, and even more preferably 200 ppm or less. The method for removing moisture is not particularly limited, and examples thereof include a method of azeotropically boiling with a high boiling point solvent such as toluene using an apparatus such as a Dean Stark trap or a decanter.

  Moreover, when performing transesterification, since superposition | polymerization may occur, it is preferable to make a polymerization inhibitor coexist. The polymerization inhibitor is not particularly limited as long as it suppresses polymerization, and the same polymerization inhibitor as that used in the acid addition step can be used. It is also effective to carry out the reaction while blowing air or oxygen.

  After completion of the transesterification reaction, the reaction solution may be concentrated as it is and purified by distillation, column chromatography, etc. However, since the transesterification catalyst may remain after the purification, purify after dissolving the transesterification catalyst. It is preferable to do. To dissolve the transesterification catalyst, the reaction solution is diluted with an organic solvent as necessary, and the reaction solution is washed with water or an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, or neutralized water. Or by adding an alkali powder such as sodium carbonate, sodium hydrogen carbonate, magnesium oxide, stirring, and then filtering the neutralized salt, or using water, hydrochloric acid, sulfuric acid, or other acid. May be added to dissolve the transesterification catalyst. Since the process is simple and the yield of the product is good, a method in which water and an acid are added to dissolve the transesterification catalyst is preferable.

  In particular, tetraalkoxytitanium widely used as a transesterification catalyst generates a large amount of insoluble matter when contacted with water, and it is difficult to dissolve this. On the other hand, tetraalkoxytitanium generates an insoluble matter by contacting with an acid, but since it is a water-soluble salt, it dissolves when water is added. Therefore, in the present invention, in order to dissolve the tetraalkoxytitaniums, it is preferable to add an acid to the reaction solution and then add and dissolve water to dissolve it. For this purpose, the acid to be added is not particularly limited, but a strong acid such as sulfuric acid, nitric acid and hydrochloric acid is preferable from the viewpoint that the amount used can be reduced, and sulfuric acid is particularly preferable from the viewpoint of easy handling.

  When dissolving the transesterification catalyst, examples of the organic solvent used for dilution include toluene, benzene, hexane, cyclohexane, ethyl acetate, diethyl ether, diisopropyl ether, and the like, and the extraction efficiency is high and the amount of solvent used can be reduced. From the viewpoint of good yield, toluene and ethyl acetate are more preferable.

  The obtained mixture of compounds represented by the formula (4) is preferably purified by column chromatography, (reduced pressure) distillation or the like. From the point that impurities such as solvents and trace metals can be reduced, simple distillation, thin film It is more preferable to purify by distillation under reduced pressure such as distillation. Since polymerization may occur during the distillation, it is preferable that a polymerization inhibitor coexists. The polymerization inhibitor is not particularly limited as long as it suppresses polymerization, and the same polymerization inhibitor as that used in the acid addition step can be used. It is also effective to suppress the polymerization by carrying out the reaction while blowing air or oxygen.

Specific examples of the (meth) acrylic acid ester obtained by the production method of the present invention are shown below. In the formula, R ¹ represents a hydrogen atom or a methyl group.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. The intermediates and products obtained in the examples were identified by ¹ H-NMR.

<Measurement of ¹ H-NMR>
Using a JNM-GX270 type FT-NMR (trade name) manufactured by JEOL Ltd., put a deuterated chloroform solution of a sample of about 5% by mass into a test tube having a diameter of 5 mmφ, measuring temperature 25 ° C., observation frequency The measurement was performed 16 times in a single pulse mode at 270 MHz.

<Gas chromatography>
The sampled sample was diluted in acetone and analyzed using a gas chromatograph 5890 series II (trade name) manufactured by Hewlett-Packard equipped with a capillary column DB-5 manufactured by J & W Scientific.

<Example 1>
Synthesis of a mixture of 8- and 9-formoxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one (Part 1)
To a 2 L glass three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 130 g (0.87 mol) of 4-oxatricyclo [5.2.1.0 ^2,6 ] -8-decen-3-one Then, 208.6 g (4.35 mol) of formic acid was charged, 7.7 ml (0.087 mol) of trifluoromethanesulfonic acid was gradually added with stirring, and then the temperature was raised to 100 ° C. with stirring. Then, it was made to react for 6 hours, keeping the temperature in a flask at 100 degreeC.

After completion of the reaction, the reaction solution was cooled, and unreacted formic acid was removed under the conditions of 60 ° C. and 2660 Pa. Thereafter, the reaction solution was cooled in an ice bath, and 400 ml of ethyl acetate and 400 ml of a saturated aqueous sodium hydrogen carbonate solution were added while stirring. This was transferred to a separatory funnel and separated, and then extracted from the aqueous layer three times with 400 ml of ethyl acetate. The ethyl acetate layers were combined and washed with 400 ml of 20% brine. The ethyl acetate layer was concentrated with an evaporator at 40 ° C. and 2660 Pa, and then the concentrated solution was distilled under reduced pressure. As a result, 8- and 9-formoxy-4-oxatricyclo [5.2. 1.08.4 g (0.45 mol, yield 51.8%) of a mixture of 1.0 ^2,6 ] decan-3-one was obtained. At this time, the balance of the pot was 5.6 g.

Synthesis of a mixture of 8- and 9-acryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one (Part 1)
The resulting 8- and 9-formoxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decane was added to a 2 L glass three-necked flask equipped with a stirrer, thermometer, Dean Stark and reflux condenser. To the mixture of 7-one, 78.5 g (0.40 mol), ethyl acrylate 200.2 g (2.00 mol), hydroquinone monomethyl ether 0.12 g was charged up to 100 ° C. while performing air bubbling and stirring. The temperature was raised. Thereafter, 70.1 g (0.02 mol) of tetraisopropoxytitanium was added, and the reaction was allowed to proceed for 5.5 hours while maintaining the temperature of the flask at 100 ° C. (transesterification step). When the reaction solution was analyzed by gas chromatography, the conversion rate was 93.6%, and 8- and 9-acryloyloxy-4-oxatricyclo [5.2.1.0 ^2, represented by the following formula (6) ^{. 6} ] It was confirmed that a mixture of decan-3-one was formed.

After completion of the reaction, the reaction solution was cooled in an ice bath, diluted with 243 ml of ethyl acetate with stirring, and 6.92 ml of concentrated sulfuric acid was added to form a precipitate. When 264 ml of water was added thereto, the precipitate was dissolved. This was transferred to a separatory funnel, the aqueous layer was removed, and then the ethyl acetate layer was washed with 264 ml of a saturated aqueous sodium bicarbonate solution. After concentrating this with an evaporator at 40 ° C. and 2660 Pa, the concentrated solution was purified by distillation under reduced pressure. As a result, 8- and 9-acryloyloxy-4-oxatricyclo [5.2 represented by the following formula (6) was obtained. .1.0 ^2,6] decane-3-one 62.2 g (0.28 mol 70.0% yield) were obtained. At this time, the balance of the kettle was 0.62 g.

<Example 2>
Synthesis of a mixture of 8- and 9-formoxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one (part 2)
To a 2 L glass three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 130 g (0.87 mol) of 4-oxatricyclo [5.2.1.0 ^2,6 ] -8-decen-3-one 208.6 g (4.35 mol) of formic acid and 17.7 g (0.17 mol) of methanesulfonic acid were charged, and the temperature was raised to 100 ° C. while stirring. Then, it was made to react for 6 hours, keeping the temperature in a flask at 100 degreeC.

After completion of the reaction, the reaction mixture was worked up in the same manner as in Example 1 to obtain 8- and 9-formoxy-4-oxatricyclo [5.2.1.0 ^2,6 ] represented by the above formula (5). 86.1 g (0.44 mol, yield 50.4%) of a mixture of decan-3-one was obtained. At this time, the balance of the kettle was 5.2 g.

Synthesis of a mixture of 8- and 9-acryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one (part 2)
The resulting 8- and 9-formoxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decane was added to a 2 L glass three-necked flask equipped with a stirrer, thermometer, Dean Stark and reflux condenser. -3-one mixture 78.5 g (0.40 mol), methyl acrylate 172.2 g (2.00 mol), hydroquinone monomethyl ether 0.10 g, tetraisopropoxy titanium 70.1 g (0.02 mol) Then, 4 ml of n-hexane was charged, and the temperature was raised to 80 ° C. while performing air bubbling and stirring. Then, it was made to react for 5 hours, keeping the temperature of a flask at 80 degreeC (transesterification process). The reaction solution was analyzed by gas chromatography. As a result, 8- and 9-acryloyloxy-4-oxatricyclo [5.2.1.0 ^2, represented by the above formula (6) with a conversion rate of 88.3% was obtained ^{. 6} ] It was confirmed that a mixture of decan-3-one was formed.

After completion of the reaction, the reaction mixture was post-treated in the same manner as in Example 1 to obtain 8- and 9-acryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 represented by the above formula (6). 57.8 g (0.26 mol, yield 65.0%) of a mixture of decan-3-one was obtained. At this time, the balance of the kettle was 0.50 g.

<Example 3>
Synthesis of mixtures of 8- and 9-formoxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one (part 3)
To a 2 L glass three-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 130 g (0.87 mol) of 4-oxatricyclo [5.2.1.0 ^2,6 ] -8-decen-3-one 208.6 g (4.35 mol) of formic acid and 33.1 g (0.17 mol) of p-toluenesulfonic acid were added, and the temperature was raised to 100 ° C. while stirring. Then, it was made to react for 5 hours, keeping the temperature in a flask at 100 degreeC.

After completion of the reaction, the reaction mixture was worked up in the same manner as in Example 1 to obtain 8- and 9-formoxy-4-oxatricyclo [5.2.1.0 ^2,6 ] represented by the above formula (5). 86.5 g (0.44 mol, yield 50.7%) of a mixture of decan-3-one was obtained. At this time, the balance of the kettle was 5.2 g.

Synthesis of a mixture of 8- and 9-methacryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one (Part 1)
The resulting 8- and 9-formoxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decane was added to a 2 L glass three-necked flask equipped with a stirrer, thermometer, Dean Stark and reflux condenser. A mixture of 3-8.5 was charged with 78.5 g (0.40 mol), t-butyl methacrylate 284.4 g (2.00 mol), and hydroquinone monomethyl ether 0.17 g. Reacted at ~ 120 ° C. Thereafter, 70.1 g (0.02 mol) of tetraisopropoxytitanium was added, and the reaction was performed for 6 hours while maintaining the temperature of the flask at 80 ° C. (transesterification step). When the reaction solution was analyzed by gas chromatography, 8- and 9-methacryloyloxy-4-oxatricyclo [5.2.1.0 ^2, represented by the following formula (7) with a conversion rate of 89.9% ^{. 6} ] It was confirmed that a mixture of decan-3-one was formed.

After completion of the reaction, the reaction mixture was post-treated in the same manner as in Example 1 to obtain 8- and 9-methacryloyloxy-4-oxatricyclo [5.2.1.0 ^2, represented by the following formula (7) ^{. 6} ] 68.0 g (0.29 mol, yield 72.0%) of a mixture of decan-3-one was obtained. At this time, the balance of the kettle was 0.5 g.

<Example 4>
Synthesis of a mixture of 8- and 9-formoxy-4,10-dioxatricyclo [5.2.1.0 ^2,6 ] decan-3-one made of 3 L glass equipped with a stirrer, thermometer and reflux condenser. In a three-necked flask, 264.7 g (1.74 mol) of 4,10-dioxatricyclo [5.2.1.0 ^2,6 ] -8-decen-3-one and 417.2 g of formic acid (8.7 15.4 ml (0.174 mol) of trifluoromethanesulfonic acid was gradually added with stirring, and the temperature was raised to 100 ° C. with stirring. Then, it was made to react for 6 hours, keeping the temperature in a flask at 100 degreeC.

After completion of the reaction, the reaction solution was cooled, and unreacted formic acid was removed under the conditions of 60 ° C. and 2660 Pa. Thereafter, the reaction solution was cooled in an ice bath, and 800 ml of ethyl acetate and 800 ml of a saturated aqueous sodium hydrogen carbonate solution were added while stirring. This was transferred to a separatory funnel and separated, and then extracted from the aqueous layer three times with 800 ml of ethyl acetate. The ethyl acetate layers were combined and washed with 800 ml of 20% brine. The ethyl acetate layer was concentrated with an evaporator at 40 ° C. and 2660 Pa, and then the concentrated solution was distilled under reduced pressure. As a result, 8- and 9-formoxy-4,10-dioxatricyclo [5] represented by the following formula (8) was obtained. 24.8 (2,8, 10.1% yield) of a mixture of .2.1.0 ^2,6 ] decan-3-one. At this time, the balance of the pot was 0.9 g.

Synthesis of a mixture of 8- and 9-methacryloyloxy-4,10-dioxatricyclo [5.2.1.0 ^2,6 ] decan-3-one. Stirrer , thermometer, Dean Stark and reflux condenser. 29.7 g of the obtained mixture of 8- and 9-formoxy-4,10-dioxatricyclo [5.2.1.0 ^2,6 ] decan-3-one was put into a 1 L glass three-necked flask attached. (0.15 mol), methyl methacrylate 75.1 g (0.75 mol), hydroquinone monomethyl ether 0.05 g, tetraisopropoxy titanium 2.13 g (0.0075 mol) were charged while air bubbling and stirring were performed. The temperature was raised to 100 ° C. The reaction was carried out for 5 hours while maintaining the temperature of the flask at 100 ° C. (transesterification step). When the reaction solution was analyzed by gas chromatography, the conversion rate was 91.5%, and 8- and 9-methacryloyloxy-4,10-dioxatricyclo [5.2.1. It was confirmed that a mixture of 0 ^2,6 ] decan-3-one was formed.

After completion of the reaction, the reaction solution was cooled in an ice bath, diluted with 91 ml of ethyl acetate with stirring, and 6.92 ml of concentrated sulfuric acid was added to form a precipitate. When 99 ml of water was added thereto, the precipitate was dissolved. This was transferred to a separatory funnel, the aqueous layer was removed, and the ethyl acetate layer was washed with 99 ml of saturated aqueous sodium hydrogen carbonate solution. After concentrating this with an evaporator at 40 ° C. and 2660 Pa, the concentrated solution was purified by distillation under reduced pressure. As a result, 8- and 9-methacryloyloxy-4,10-dioxatricyclo [ Thus, 25.3 g (0.11 mol, yield 70.8%) of a mixture of 5.2.1.0 ^2,6 ] decan-3-one was obtained. At this time, the balance of the kettle was 0.30 g.

<Comparative Example 1>
Synthesis of a mixture of 8- and 9-hydroxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one In a ² L glass three-necked flask equipped with a stirrer, thermometer and reflux condenser. , 4-oxatricyclo [5.2.1.0 ^2,6 ] -8-decen-3-one 52.6 g (0.35 mol) and 71.7 g formic acid (1.56 mol) were stirred and stirred. While gradually adding 5.3 g (0.035 mol) of trifluoromethanesulfonic acid, the temperature was raised to 100 ° C. with stirring. Then, it was made to react for 6 hours, keeping the temperature in a flask at 100 degreeC.

After completion of the reaction, the reaction solution was cooled, and unreacted formic acid was removed under the conditions of 60 ° C. and 2660 Pa. Thereafter, the reaction solution was cooled in an ice bath, and 160 ml of ethyl acetate and 160 ml of a saturated aqueous sodium hydrogen carbonate solution were added while stirring. This was transferred to a separatory funnel and separated, and then extracted from the aqueous layer three times with 160 ml of ethyl acetate. The ethyl acetate layers were combined and washed with 160 ml of 20% brine. The ethyl acetate layer was concentrated by an evaporator at 40 ° C. and 2660 Pa, and then the concentrated solution was distilled under reduced pressure. As a result, 8- and 9-formoxy-4-oxatricyclo [5.2. As a result, 35.3 g (0.18 mol, yield 51.4%) of a mixture of 1.0 ^2,6 ] decan-3-one was obtained. At this time, the remaining amount of the kettle was 2.20 g.

Then, the obtained 8- and 9-formoxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decane-3 was added to a 1 L glass three-necked flask equipped with a stirrer, a thermometer and a reflux condenser. -35.3 g (0.18 mol) of the ON mixture and 100 ml of methanol. While stirring, 100 g of a 10% aqueous potassium hydroxide solution was added thereto, and the mixture was stirred at room temperature for 12 hours for alkali hydrolysis, and methanol was distilled off with an evaporator at 30 ° C. and 3990 Pa. This was extracted three times with 100 ml of ethyl acetate, the ethyl acetate layers were combined, washed with 150 ml of water, dried over sodium sulfate, and concentrated with an evaporator at 40 ° C. and 2660 Pa. When the concentrated liquid was purified by silica gel column chromatography, 8- and 9-hydroxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one represented by the following formula (10) was obtained. Of 24.3 g (0.14 mol, 80.3% yield) was obtained. At this time, the balance of the kettle was 0.23 g.

Synthesis of a mixture of 8- and 9-methacryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one (part 2)
The obtained 8- and 9-hydroxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decane-3 was added to a 0.5 L glass three-necked flask equipped with a stirrer, a thermometer and a reflux condenser. -18.5 g (0.11 mol) of the ON mixture and 90 ml of dehydrated dichloromethane. One of the dropping funnels was charged with 14.5 g (0.14 mol) of triethylamine and 13.8 g (0.13 mol) of methacrylic acid chloride on the other, and the inside of the flask was purged with nitrogen, and the internal temperature was adjusted with an ice bath. The temperature was about 2 ° C. Then, while stirring in the flask, triethylamine and methacrylic acid chloride were added to the methacrylic acid chloride and added dropwise over 50 minutes while adjusting the ethylamine to be slightly excessive. After completion of the dropwise addition, 0.27 g (0.002 mol) of dimethylaminopyridine was added, and the reaction was allowed to proceed for 24 hours while allowing the internal temperature to return to room temperature.

90 ml of water was carefully added to the reaction solution, stirred for a while, separated with a separatory funnel, washed with 90 ml of a saturated aqueous solution of sodium bicarbonate, the organic layer was dried over magnesium sulfate, and concentrated at 40 ° C. and 2660 Pa with an evaporator. did. The concentrated solution was purified by distillation under reduced pressure. As a result, 8- and 9-methacryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one represented by the above formula (7) was obtained. Of 17.5 g (0.07 mol, 67.3% yield) was obtained. At this time, the balance of the kettle was 1.30 g.

<Comparative example 2>
Synthesis of a mixture of 5- and 6-cyanobicyclo [2.2.1] heptyl-2-formate A 3-L glass three-necked flask equipped with a stirrer, thermometer and reflux condenser was charged with 2-cyanobicyclo [2.2. 1] 350.0 g of hept-5-ene (manufactured by Aldrich, 2.9 mol), 676.5 g of formic acid (14.7 mol), 111.7 g of p-toluenesulfonic acid (0.59 mol) were charged and stirred. The temperature was raised to 100 ° C. Then, it was made to react for 3 hours, keeping the temperature of a flask at 100 degreeC (acid addition process). After completion of the reaction, the reaction solution was cooled and unreacted formic acid was removed under the conditions of 60 ° C. and 18 torr (2399 Pa) (acid removal step). Thereafter, the reaction solution was cooled in an ice bath, and 900 ml of toluene, 900 ml of ethyl acetate, and 720 ml of water were added with stirring. This was transferred to a separatory funnel, the aqueous layer was removed, and then the toluene / ethyl acetate layer was concentrated and distilled under reduced pressure. As a result, 5- and 6-cyanobicyclo [2.2.1] represented by the following formula (11) was obtained. 135.7 g of heptyl-2-formate was obtained. At this time, the remaining amount of the kettle was 65.0 g.

  When this composition was sampled and analyzed by gas chromatography, it contained 92.5% of a mixture of 5- and 6-cyanobicyclo [2.2.1] heptyl-2-formate represented by the following formula (11). The mixture of 5- and 6-cyanobicyclo [2.2.1] heptyl-2-formate represented by the following formula (11) in terms of pure content is 2.3 mol (yield 79%). I found out.

Synthesis of a mixture of 5- and 6-cyanobicyclo [2.2.1] heptyl-2-methacrylate A 3 L glass three-necked flask equipped with a stirrer, thermometer and reflux condenser was prepared. 135.7 g of a composition containing a mixture of bicyclo [2.2.1] heptyl-2-formate, 411.2 g (3.1 mol) of methyl methacrylate, 23.4 g (0.08 mol) of tetraisopropoxytitanium, Hydroquinone monomethyl ether (0.14 g) was charged, and the temperature was raised to 100 ° C. while performing air bubbling and stirring. Then, it was made to react for 2 hours, keeping the temperature of a flask at 100 degreeC (transesterification process). When the reaction solution was analyzed by gas chromatography, 93.5% of the product was a mixture of 5- and 6-cyanobicyclo [2.2.1] heptyl-2-methacrylate represented by the following formula (12). It was confirmed that there was.

  After completion of the reaction, the reaction solution was cooled in an ice bath, diluted with 410 ml of ethyl acetate with stirring, and 53 g of sulfuric acid was added to form a precipitate. When 410 ml of water was added thereto, the precipitate was dissolved. This was transferred to a separatory funnel, the aqueous layer was removed, and then the toluene layer was concentrated. When this concentrate was purified by distillation under reduced pressure, 145.0 g (2.12) of a mixture of 5- and 6-cyanobicyclo [2.2.1] heptyl-2-methacrylate represented by the following formula (12) was obtained. Mol, total yield 73%). At this time, the remaining amount of the kettle was 4.35 g.

According to the production method of the present invention (Examples 1, 2, 3 and 4), 8- and 9-acryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one A mixture of 8- and 9-methacryloyloxy-4-oxatricyclo [5.2.1.0 ^2,6 ] decan-3-one, and 8- and 9-methacryloyloxy-4,10- A mixture of dioxatricyclo [5.2.1.0 ^2,6 ] decan-3-one could be produced with good yield and with a small number of steps.

  According to the present invention, a (meth) acrylic acid ester useful as a component resin raw material for paints, adhesives, pressure-sensitive adhesives, ink resins, resists, molding materials, optical materials, etc. can be obtained in a high yield and the number of steps can be reduced. It is possible to provide a manufacturing method with less.

Claims (3)

An acid addition step of producing a saturated carboxylic acid adduct by adding a saturated carboxylic acid to a compound represented by the following formula (1);
A transesterification step of transesterifying the saturated carboxylic acid adduct and (meth) acrylic acid ester;
A method for producing a (meth) acrylic acid ester represented by the following formula (4a) or (4b).

(In Formula (1), A ¹ and A ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, or A ¹ and A ² together form —O—, —S—. Or an alkylene group having 1 to 6 carbon atoms, wherein R ² and R ³ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, a cyano group, or a carbon number. Represents a carboxy group esterified with an alcohol of 1 to 6. In formulas (4a) and (4b), R ¹ represents a hydrogen atom or a methyl group, and A ¹ and A ² , R ² and R ³ represent formula ( It is synonymous with 1). The method for producing a (meth) acrylic acid ester according to claim 1, wherein a compound represented by the following formula (1-1) is used as the compound represented by the formula (1).

The method for producing a (meth) acrylic acid ester according to claim 1, wherein a compound represented by the following formula (1-2) is used as the compound represented by the formula (1).