JP5573924B2 - (Meth) acrylic acid ester and method for producing the same - Google Patents

Description

  The present invention relates to a (meth) acrylic acid ester having a novel structure and a method for producing the same.

  In the case of producing a vinyl copolymer resin, (meth) acrylic acid ester is one of important monomer groups for copolymerization and is used in various applications. However, polymerization with a single monomer often fails to provide the desired performance. In that case, in order to obtain the required physical properties, it is possible to mix a plurality of different (meth) acrylate monomers and copolymerize them. Done. Among them, imparting polarity to the resin is one of the most important modifications of the resin, and a (meth) acrylate monomer having a polar group in the molecule is used for that purpose. Typical examples thereof include linear hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. Since these can be easily produced industrially from a compound having a corresponding epoxy skeleton or a corresponding diol and (meth) acrylic acid, they have been widely used because they are easily available in large quantities at low cost. However, depending on the application, hydroxy (meth) acrylates having these chain skeletons are not optimal for expressing the desired properties. Rather, although these polar polar monomers are added, these chain polar monomers are added. By doing so, there was a problem that originally necessary functions were weakened or no longer expressed.

  On the other hand, (meth) acrylate, which has been improved in hydrophilicity by having both a heterocyclic ring and a hydrophilic group in the same monomer, is based on the development of physical properties due to the characteristics of the heterocyclic ring and the hydrophilic group, and the hydrophilic group. It is a compound that is expected to have various uses because of its versatility that can be converted into various compounds.

  For example, as a radiation curable resin composition, a hydroxy (meth) acrylate such as hydroxyethyl methacrylate, a polyol, a polyfunctional urethane (meth) acrylate prepared from a mixture of diisocyanate (a component that gives viscosity to the resin), and tetrahydrofurfuryl It is disclosed that a composition in which a component having a heterocyclic compound such as (meth) acrylate is mixed is preferable (Patent Document 1). This is because unless the heterocyclic compound is added, the hardness of the cured coating layer is not sufficiently increased and the desired performance is not achieved. Therefore, if there is a heterocyclic compound (meth) acrylate having a hydroxyl group, urethane acrylate having a heterocyclic structure can be produced, and thus its utility value is considered high.

  In recent years, in the field of ArF photoresist for semiconductors, (meth) acrylate resins are used as the mainstream of resist materials. In manufacturing this ArF photoresist resin, in order to improve the etching resistance. Introduction of a cyclic hydrocarbon structure such as an adamantane skeleton is required (Non-Patent Document 1). However, introduction of a large number of hydrocarbon groups, on the other hand, results in a decrease in the solubility of the resin in the developer, and therefore modification of the resin that increases the solubility in the aqueous developer is required. At present, for this purpose, a resin to which a monomer having a polar group such as hydroxyadamantyl methacrylate is added is used. However, since the affinity of these monomers with water is not sufficient, the addition amount must be increased. There is a problem that the manufacturing cost of the entire resist resin is increased because it is expensive. Therefore, also in this field, development of a (meth) acrylate monomer having a high water affinity capable of efficiently imparting hydrophilicity to a resin has been desired.

  As a (meth) acrylate monomer that satisfies these requirements, Patent Document 2 discloses (meth) acryloyloxytetrahydrofurans. These have a structure that has both a tetrahydrofuran skeleton, which is a heterocyclic ring, and a hydroxyl group, which is a hydrophilic group, and have a high affinity for water, so they are used for modification purposes to impart hydrophilicity to (meth) acrylic resins. Is an expected compound.

Japanese Patent Laid-Open No. 7-48422 JP2007-1112764A

J. et al. Photopolym. Sci. Technol. , 9. 509 (1996).

  However, on the other hand, if the monomer disclosed in Patent Document 2 is used, the resin obtained may dissolve more than necessary in an aqueous solvent due to its high water affinity, and the resin shape cannot be maintained. was there. Therefore, a means for controlling the water affinity of the resin while utilizing the excellent water affinity of this skeleton has been desired.

  Then, this invention makes it a subject to provide the novel (meth) acrylic acid ester which can control the water affinity of resin obtained, and its manufacturing method in view of the said problem.

  The present inventors freely control the affinity for water even after the novel (meth) acrylic acid ester represented by the general formula (1) into which the acid-dissociable protecting group has been introduced is used as a resin. It has been found to be an excellent monomer that can.

  That is, the first aspect of the present invention provides a (meth) acrylic acid ester having a structure represented by the following general formula (1) to solve the above problems.

（式（１）においてＲ^１は水素原子またはメチル基であり、Ｒ^２は下記一般式（２）または（３）に示される置換基である。）

(In the formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is a substituent represented by the following general formula (2) or (3).)

（式（２）においてＲ^３は炭素数１〜１０のアルキル基またはアリール基であり、式（３）においてＲ^４は水素原子または炭素数１〜１０のアルキル基であり、Ｒ^５は炭素数１〜１０のアルキル基である。Ｒ^４とＲ^５は互いに連結していてもよい。）

(In Formula (2), R ³ is an alkyl group or aryl group having 1 to 10 carbon atoms, and in Formula (3), R ⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ⁵ is a carbon number. An alkyl group of 1 to 10. R ⁴ and R ⁵ may be linked to each other.

In the second aspect of the present invention, a compound represented by the general formula (4) is reacted with a compound represented by the following general formula (5 ) or di-tert-butyl dicarbonate in the presence of a base. The present invention solves the above problems by providing a method for producing a (meth) acrylic acid ester.

(In Formula (4), R ¹ Is a hydrogen atom or a methyl group, R in formula (5) ³ Is an alkyl group having 1 to 10 carbon atoms or an aryl group. )

  The third aspect of the present invention is characterized in that it is produced by reacting a compound represented by the following general formula (4) with a compound represented by the following general formula (7) in the presence of an acid. The manufacturing method of (meth) acrylic acid ester is provided and the said subject is solved.

（式（４）においてＲ^１は水素原子またはメチル基であり、式（７）においてｎは０〜３の整数である。）

(In Formula (4), R ¹ is a hydrogen atom or a methyl group, and in Formula (7), n is an integer of 0 to 3.)

  The (meth) acrylic acid ester obtained in the present invention is an excellent monomer that can freely control its affinity for water even after it is made into a resin. Therefore, it can be widely used as a raw material for vinyl polymer resins in various fields such as electronic component materials, optical applications, recording media, various curing agents, and medical materials. For example, if it is used as a copolymerization monomer for a resist resin, the solubility in water can be controlled, so the range of conditions that can be employed in the drawing process is widened, and its utility value is extremely high.

  Such an operation and a gain of the present invention will be clarified from the best mode for carrying out the invention described below.

  The (meth) acrylic acid ester of the present invention is a compound having a structure represented by the following general formula (1).

In the general formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is a substituent represented by the following general formula (2) or (3).

In the general formula (2), R ³ is an alkyl group or an aryl group having 1 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n- Examples thereof include a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a hexyl group, and an octyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Among them, R ³ is preferably an isopropyl group, a sec-butyl group, or a tert-butyl group because of its high ability to desorb to acids.

In General Formula (3), R ⁴ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ⁵ is an alkyl group having 1 to 10 carbon atoms, and R ⁴ and R ⁵ may be linked to each other. . As the alkyl group for R ⁴ and R ^5, the same groups as those for R ^{3 in} formula (2) can be exemplified. R ⁴ and R ⁵ are preferable because elimination performance when in contact with connection to have the acid increases with each other, in particular, by connecting R ⁴ and R ⁵ together constitute a tetrahydropyranyl group or a tetrahydrofuranyl group It is preferable from the point of easy availability of the raw material at the time of manufacture.

The method for synthesizing the compound represented by the general formula (1) can be arbitrarily selected. In formula (4), R ¹ is a hydrogen atom or a methyl group), and then the hydroxyl group is protected with a group represented by the above general formula (2) or (3). Hereinafter, the synthesis of 3- (meth) acryloyloxy-4-hydroxytetrahydrofuran and the reaction of introducing a protecting group into the hydroxyl group will be described separately.

<Synthesis of 3- (meth) acryloyloxy-4-hydroxytetrahydrofuran>
The production route of 3- (meth) acryloyloxy-4-hydroxytetrahydrofuran represented by the general formula (4) is not particularly limited, and any production method can be adopted. Among them, the method using erythritol as a raw material is preferable because erythritol can be obtained in an industrial amount at low cost. In this case, either erythritol is first monoesterified and then cyclized, or conversely cyclized first to 3,4-dihydroxytetrahydrofuran and then one of the hydroxyl groups is (meth) acrylated. It can be used arbitrarily.

  The (meth) acrylated reaction in the next step in the method via 3,4-dihydroxytetrahydrofuran can be arbitrarily selected. Typical methods include esterifying a hydroxyl group using (meth) acrylic acid halide or (meth) acrylic anhydride, transesterification using an ester of a lower alcohol of (meth) acrylic acid, ( And a direct esterification reaction of dehydrating and condensing (meth) acrylic acid and erythritan.

  In addition, as a method for converting one hydroxyl group to (meth) acrylate, step by step, first protecting one of the hydroxyl groups of 3,4-dihydroxytetrahydrofuran and then deprotecting the hydroxyl group after (meth) acrylate conversion, A mono (meth) acrylate is selectively used, such as a method in which two hydroxyl groups are modified to a carbonate structure, and selectively one is nucleophilically converted to a (meth) acrylate group, followed by a post-treatment with water. The method for producing can be employed without any particular limitation.

  In the following, typical reaction conditions for esterification of 3,4-dihydroxytetrahydrofuran are described.

(1. Transesterification method)
A compound that can be used as a (meth) acrylate agent in the case of (meth) acrylate-converting 3,4-dihydroxytetrahydrofuran by transesterification is a lower alcohol ester of (meth) acrylic acid. The lower alcohol is preferably a C1-C4 aliphatic alcohol, and the number of alcohol residues is selected from 1 to 3. Particularly preferred are (meth) acrylic acid methyl ester, ethyl ester, n-propyl ester and i-propyl ester.

  The lower limit of the amount of (meth) acrylic acid ester used relative to the number of moles of the raw material 3,4-dihydroxytetrahydrofuran is usually 0.1 molar equivalents or more, preferably 0.2 molar equivalents or more, more preferably 0.8. The upper limit is usually 10 mol equivalent or less, preferably 5 mol equivalent or less, more preferably 1 mol equivalent or less.

  There is no particular limitation on the method of adding these (meth) acrylic acid esters, and it can be added to the total amount of 3,4-dihydroxytetrahydrofuran when the reaction is charged, or can be added in portions during the reaction. It can be adopted.

  The reaction can be carried out without solvent or using a solvent. When using a solvent, the solvent to be used is not particularly limited, but an aromatic hydrocarbon solvent such as toluene and xylene, an aliphatic hydrocarbon solvent such as hexane and heptane, diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol Ether solvents such as dimethyl ether, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester solvents such as ethyl acetate, butyl acetate, and gamma butyrolactone, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone Are preferably used. These solvents may be used alone, or a plurality of arbitrary solvents may be mixed and used.

  In the case of using a solvent, the amount of 3,4-dihydroxytetrahydrofuran as a raw material is such that the lower limit is usually 0.1% or more, preferably 1% or more, and the upper limit is not particularly limited, but usually 80 % Or less, preferably 50% or less.

  The transesterification reaction is usually performed in the presence of a catalyst. As the usable catalyst, those generally usable in transesterification can be applied. For example, transition metal compounds such as titanium tetraisopropoxide, alkali metal or alkaline earth metal alcoholates such as sodium methoxide, etc. And aluminum alkoxides such as aluminum triisopropoxide, alkali metal or alkaline earth metal hydroxides such as lithium hydroxide and sodium hydroxide, and tin compounds such as dibutyltin oxide and dioctyltin oxide.

  The lower limit of the amount of these catalysts used is usually 0.01 mol% or more, preferably 0.1 mol% or more, more preferably 0.5 mol% or more, relative to the number of moles of 3,4-dihydroxytetrahydrofuran as a raw material. The upper limit is usually 50 mol% or less, preferably 20 mol% or less, and more preferably 10 mol% or less.

  The reaction is preferably carried out in a reactor equipped with a normal stirring device. Further, the reaction may be carried out while transferring the equilibrium to the production system while distilling off the alcohol generated during the reaction. At this time, if the (meth) acrylic acid ester used as the reagent and the alcohol azeotropes and the (meth) acrylic acid ester is removed from the system, the (meth) acrylic acid ester is sequentially added as necessary. You may replenish and react.

  It is preferable to carry out the reaction with heating in order to obtain a sufficient reaction rate. Specifically, the lower limit is usually −10 ° C. or higher, preferably 0 ° C. or higher, and the upper limit is usually 200 ° C. or lower, preferably 150 ° C. or lower.

  The reaction time is arbitrarily selected, but since alcohol is produced as the reaction proceeds, it is preferable to continue the reaction until a predetermined amount of alcohol is produced. In general reaction time, the lower limit is usually 10 minutes or longer, preferably 30 minutes or longer, and the upper limit is not particularly limited, but is usually 50 hours or shorter, preferably 30 hours or shorter.

(2. (Meth) acrylic acid halide method and (meth) acrylic anhydride method)
3,4-Dihydroxytetrahydrofuran can be (meth) acrylated using (meth) acrylic acid halide or (meth) acrylic anhydride as a (meth) acrylating agent. The compounds that can be used as the (meth) acrylic acid halide in that case are chloride, bromide, and iodide of (meth) acrylic acid.

  The lower limit of the amount of (meth) acrylic acid halide or (meth) acrylic anhydride used is usually 0.01 mol equivalent or more, preferably 0.05 mol, relative to the number of moles of the raw material 3,4-dihydroxytetrahydrofuran. The upper limit is usually 10 mol equivalents or less, preferably 5 mol equivalents or less, more preferably 1 mol equivalents or less.

  It is a method of adding these (meth) acrylic acid halides or (meth) acrylic acid anhydrides, but avoiding direct contact with these (meth) acrylic reagents and basic substances for a long time before the reaction, There is no restriction | limiting in particular in the method of addition. For example, 3,4-dihydroxytetrahydrofuran and (meth) acrylic acid halide or (meth) acrylic anhydride may be charged into the reactor at the same time, and a basic substance may be added later, or charged into the reactor in advance. The reaction may be carried out by dropping (meth) acrylic acid halide or (meth) acrylic acid anhydride into the basic substance and 3,4-dihydroxytetrahydrofuran or its solution, but the latter addition method is adopted. It is preferable for suppressing the production of by-product dimethacrylate.

  The reaction can be carried out without solvent or using a solvent. When using a solvent, the solvent to be used is not particularly limited, but an aromatic hydrocarbon solvent such as toluene and xylene, an aliphatic hydrocarbon solvent such as hexane and heptane, diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol Ether solvents such as dimethyl ether, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ester solvents such as ethyl acetate, butyl acetate, and gamma butyrolactone, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone Are preferably used. These solvents may be used alone, or a plurality of arbitrary solvents may be mixed and used.

  In the case of using a solvent, the amount of 3,4-dihydroxytetrahydrofuran as a raw material is such that the lower limit is usually 0.1% or more, preferably 1% or more, and the upper limit is not particularly limited, but usually 80 % Or less, preferably 50% or less.

  The (meth) acrylation reaction with (meth) acrylic acid halide or (meth) acrylic anhydride is usually performed in the presence of a basic substance. Usable basic substances include metal hydroxides such as sodium hydroxide and barium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, metal phosphates such as monosodium phosphate and potassium phosphate It is possible to use salts, hydrogen phosphates, basic ion exchange resins, organic tertiary amines such as triethylamine and tributylamine, and aromatic amines such as pyridine. Of these, pyridine, triethylamine, and potassium carbonate are preferably used.

  Although it is the usage-amount of these basic substances, with respect to the (meth) acrylic acid halide or (meth) acrylic anhydride used, the lower limit is usually 0.1 mol equivalent or more, preferably 0.5 mol. Equal amount or more, more preferably 1 mol equivalent or more, and the upper limit is usually 10 mol equivalent or less, preferably 5 mol equivalent or less, more preferably 2 mol equivalent or less.

  The reaction temperature adopted is carried out in the range where the lower limit is usually −50 ° C. or higher, preferably −20 ° C. or higher, and the upper limit is usually 100 ° C. or lower, preferably 70 ° C. or lower. In the case of producing mono (meth) acrylate of 3,4-dihydroxytetrahydrofuran, the upper limit temperature is preferably set low, and the upper limit is usually 50 ° C. or lower, preferably 30 ° C. or lower.

  The reaction time is arbitrarily selected, but the lower limit is usually 10 minutes or more, preferably 30 minutes or more, and the upper limit is not particularly limited, but usually 20 hours or less, including the dropping time of general reaction time reagents. , Preferably 10 hours or less.

(3. Direct dehydration method)
When esterifying with (meth) acrylic acid, the reaction proceeds rapidly when a dehydrating condensing agent is allowed to coexist. As the condensing agent, any condensing agent generally known for esterification can be used without particular limitation. For example, N, N′-dicyclohexylcarbodiimide, 2-chloro-1,3-dimethylimidazolium chloride can be used. Propanephosphonic anhydride is preferably used. In this case, an organic basic substance such as pyridine, 4-dimethylaminopyridine or triethylamine may be used in combination. The lower limit of the reaction temperature usually employed in this reaction is usually −20 ° C., preferably −10 ° C., and the upper limit is usually 150 ° C., preferably 100 ° C.

  The amount of the dehydrating condensing agent used is theoretically sufficient if it is used in an equivalent amount or more with respect to 3,4-dihydroxytetrahydrofuran as a substrate, but may be used in excess. Preferably, it is 1.0 molar equivalent or more, more preferably 1.1 molar equivalent or more.

  When a dehydrating condensing agent is not used, (meth) acrylic acid and 3,4-dihydroxytetrahydrofuran are reacted in the presence of an acid while distilling off generated water.

  Any acid can be used without particular limitation as long as it is an acid used in a normal esterification reaction. For example, inorganic acids such as sulfuric acid and hydrochloric acid, p-toluenesulfonic acid, organic sulfonic acids such as methanesulfonic acid and camphorsulfonic acid, acid type ion exchange resins, Lewis acids such as fluorinated boron and ether complexes, lanthanides And water-soluble Lewis acids such as triflate. These acids may be used alone or in combination of two or more.

  The minimum of the usage-amount of an acid is 0.001 mol% or more with respect to 3, 4- dihydroxytetrahydrofuran, Preferably it is 0.01 mol% or more, More preferably, it is 0.1 mol% or more. On the other hand, the upper limit is not limited and is 10 mol equivalent or less, preferably 1 mol equivalent or less.

  The reaction can be carried out without solvent or using a solvent. When using a solvent, the solvent to be used is not particularly limited, but an aromatic hydrocarbon solvent such as toluene and xylene, an aliphatic hydrocarbon solvent such as hexane and heptane, diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol Ether solvents such as dimethyl ether, halogen solvents such as methylene chloride, chloroform, carbon tetrachloride, and the like are preferably used. These solvents may be used alone, or a plurality of arbitrary solvents may be mixed and used.

  In the case of using a solvent, the concentration of 3,4-dihydroxytetrahydrofuran as a raw material is such that the lower limit is usually 0.1% or more, preferably 1% or more, and the upper limit is not particularly limited, but usually 80% Hereinafter, it is preferably 50% or less.

  The reaction is usually carried out at or above the boiling point of the solvent used, and the reaction is carried out while distilling off the produced water.

  The reaction time is arbitrarily selected, but the end point of the reaction can be recognized by measuring the amount of water produced. In general reaction time, including the dropping time of the reagent, the lower limit is usually 10 minutes or longer, preferably 30 minutes or longer, and the upper limit is not particularly limited, but is usually 20 hours or shorter, preferably 10 hours or shorter.

<Introduction of protecting group to hydroxyl group>
The 3- (meth) acryloyloxy-4-hydroxytetrahydrofuran represented by the general formula (4) produced by the above reaction continues to have a protecting group represented by the above general formula (2) or (3) on the hydroxyl group. It is used for the reaction to be introduced. In this reaction, the synthesized 3- (meth) acryloyloxy-4-hydroxytetrahydrofuran may be once isolated and purified, or the protective group is directly introduced in the same reactor following the (meth) acrylate formation. A reaction may be performed.

There is no particular limitation on the reaction reagent used for the protective group introduction, for example, by Ru using the compounds and di -tert- butyl, such as the following general formula (5) or (7), introducing a protecting group into a hydroxyl group can do.

Oite general formula (5), ^{R 3} is an alkyl or aryl group having 1 to 10 carbon atoms. Definitive ^{R 3} in the general formula (5) are the same as ^{R 3} in the general formula (2). Moreover, in General formula (7), n is an integer of 0-3, and 2, 3- dihydrofuran, 3, 4- dihydro-2H- pyran, etc. are mentioned.

It is theoretically sufficient that the compound represented by the general formula (5) or (7) or di-tert-butyl dicarbonate is used in an equivalent amount or more with respect to 3,4-dihydroxytetrahydrofuran as a substrate. It can be used excessively. Preferably, it is 1.0 molar equivalent or more, more preferably 1.2 molar equivalent or more.

The reaction using the compound represented by the general formula (5) or di-tert-butyl dicarbonate is usually carried out in the presence of a basic substance. Usable basic substances include metal hydroxides such as sodium hydroxide and barium hydroxide, metal carbonates such as sodium carbonate and potassium carbonate, metal phosphates such as monosodium phosphate and potassium phosphate Salts, hydrogen phosphates, basic ion exchange resins, organic tertiary amines such as triethylamine and tributylamine, and aromatic amines such as pyridine and dimethylaminopyridine can be used. Of these, pyridine, dimethylaminopyridine, triethylamine, and potassium carbonate are preferably used. These bases may be used alone or in combination of a plurality of arbitrary bases.
The minimum of the usage-amount of a base is 0.001 mol% or more with respect to the compound shown by General formula (4), Preferably it is 0.01 mol% or more, More preferably, it is 0.1 mol% or more. On the other hand, the upper limit is not limited and is 10 mol equivalent or less, preferably 1 mol equivalent or less.

  On the other hand, the reaction using the general formula (7) is performed in the presence of an acidic substance. However, since a reverse reaction in which the protecting group is removed occurs under strong acidic conditions, a relatively weak acidic substance is used. Examples of acids used include p-toluenesulfonic acid, organic sulfonic acids such as methanesulfonic acid and camphorsulfonic acid, salts of organic sulfonic acids and weak bases such as pyridinium-p-toluenesulfonate, acid-type ion exchange resins, Examples thereof include Lewis acids such as fluorinated boron / ether complexes, and water-soluble Lewis acids such as lanthanide triflate. Of these, salts of organic sulfonic acids such as pyridinium-p-toluenesulfonate and weak bases are preferred because the acidity is sufficient for the progress of the reaction and side reactions can be suppressed. These acids may be used alone or in combination of two or more. The minimum of the usage-amount of an acid is 0.001 mol% or more with respect to the compound shown by General formula (4), Preferably it is 0.01 mol% or more, More preferably, it is 0.1 mol% or more. On the other hand, the upper limit is 10 molar equivalents or less, preferably 1 molar equivalent or less.

  The reaction can be carried out without solvent or using a solvent. When using a solvent, the solvent to be used is not particularly limited, but an aromatic hydrocarbon solvent such as toluene and xylene, an aliphatic hydrocarbon solvent such as hexane and heptane, diethyl ether, tetrahydrofuran, monoethylene glycol dimethyl ether, diethylene glycol Ether solvents such as dimethyl ether, halogen solvents such as methylene chloride, chloroform, carbon tetrachloride, and the like are preferably used. These solvents may be used alone or in combination with a plurality of arbitrary solvents.

  When using a solvent, the amount of the compound represented by the general formula (4) as a raw material is such that the lower limit is usually 0.1% or more, preferably 1% or more, and the upper limit is not particularly limited. Usually, it is 80% or less, preferably 50% or less.

  It is preferable to carry out the reaction with heating in order to obtain a sufficient reaction rate. Specifically, the lower limit is usually −10 ° C. or higher, preferably 0 ° C. or higher, and the upper limit is usually 200 ° C. or lower, preferably 150 ° C. or lower.

  The reaction time is arbitrarily selected, but the lower limit is usually 10 minutes or more, preferably 30 minutes or more, and the upper limit is not particularly limited, but usually 20 hours or less, including the dropping time of general reaction time reagents. , Preferably 10 hours or less.

  The purification method of the compound represented by the general formula (1) obtained by the reaction can be employed without any particular limitation. For example, a distillation method, a recrystallization method, an extraction cleaning method, and the like. When performing distillation, the form can be arbitrarily selected from simple distillation, precision distillation, thin film distillation, molecular distillation and the like.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples.

Example 1
In a reactor in which nitrogen was circulated, 0.50 g (2.9 mmol) of erythritan monomethacrylate (3-methacryloyloxy-4-hydroxytetrahydrofuran), 0.76 g (3.5 mmol) of di-t-butyl dicarbonate, toluene A solution prepared by dissolving 35.7 mg (0.292 mmol) of 4-dimethylaminopyridine in 2.5 ml of toluene was slowly added dropwise at 25 ° C. while stirring, and stirred at 25 ° C. for 1 hour. After completion of the reaction, the reaction solution was washed twice with 5 ml of 1N hydrochloric acid and then with 5 ml of water, and toluene was concentrated and dried to obtain a target product in which the hydroxyl group was protected with a t-butyl carbonate group. The structure of the obtained target product was identified by mass spectrum and 1H-NMR. The measurement results are as follows.

GC-mass (CI method) 290 (M + NH4)
1H-NMR (400 MHz, CDCl3) δ (ppm) 6.16 (1H, s), 5.61 (1H, s), 5.38 (1H, ddd), 5.22 (1H, ddd), 4. 14 (1H, dd), 4.10 (1H, dd), 3.91 (1H, dd), 3.84 (1H, dd), 1.95 (3H, s), 1.47 (9H, s) )

(Example 2)
A reactor in which nitrogen was passed was charged with 0.50 g (2.9 mmol) of erythritan monomethacrylate, 0.37 g (4.4 mmol) of 3,4-dihydro-2H-pyran and 5 ml of tetrahydrofuran and stirred at 25 ° C. , 74.0 mg (0.294 mmol) of pyridinium-p-toluenesulfonate was added, and the mixture was stirred at 25 ° C. for 9 hours. 15 ml of ethyl acetate was added to the reaction solution, and the mixture was washed 3 times with 15 ml of water. The solvent was concentrated, and the resulting crude product was purified by preparative TLC to obtain the desired product (mixture of two isomers) in which the hydroxyl group was protected with a tetrahydropyran group. The structure of the obtained target product was identified by mass spectrum and 1H-NMR. The measurement results are as follows.

GC-mass (CI method) 274 (M + NH4)
1H-NMR (400 MHz, CDCl3) δ (ppm) 6.20, 6.16 (each 1H, s), 5.60 (1H, s, br), 5.34 (1H, m), 4.72, 4.65 (each 1H, t), 4.45 (1H, m), 3.46-4.13 (6H, m), 1.98, 1.96 (each 3H, s), 1.45 1.80 (6H, m)

  Although the present invention has been described with reference to the most practical and preferred embodiments at the present time, the present invention is not limited to the embodiments disclosed herein. The (meth) acrylic acid ester and the method for producing the same are also within the technical scope of the present invention, and can be changed as appropriate without departing from the spirit or idea of the invention that can be read from the claims and the entire specification. It should be understood as encompassed by the scope.

Claims (1)

A method for producing a (meth) acrylic acid ester having a structure represented by the following general formula (1):

(In Formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² is a substituent represented by the following General Formula (2).)

(In the formula (2), R ³ is an alkyl group having 1 to 10 carbon atoms or an aryl group.)
A method for producing a (meth) acrylic acid ester, which is produced by reacting a compound represented by the following general formula (4) with di-tert-butyl dicarbonate in the presence of a base.

^{(R 1} in the formula (4) is a hydrogen atom or a methyl group.)