JP2012072079A - Dicarboxylic acid monoester derivative and method for producing acrylic acid ester derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a synthetic intermediate which can safely be produced from industrially available raw materials at a low cost in an industrial scale on the production of a (meth)acrylic acid ester derivative which is a raw material for polymers used for resist materials excellent in lithographic characteristics, and to provide a method for producing the (meth)acrylic acid ester derivative using the synthetic intermediate.SOLUTION: There are provided the dicarboxylic acid monoester derivative represented by general formula (1), and the method for producing the (meth)acrylic acid ester derivative using the dicarboxylic acid monoester derivative, [wherein, Ris H or -COOR(Ris a 1 to 5C alkyl, or a 3 to 10C cyclic hydrocarbon group substituted with a 1 to 3C alkyl or not substituted); Y is methylene, O or S; Z is >C=O or >S(=O); n is an integer of 1 to 3].

Description

  The present invention relates to a dicarboxylic acid monoester derivative useful as a monomer synthesis intermediate for resist, and a method for producing an acrylate derivative using the dicarboxylic acid monoester derivative.

In lithography technology, for example, a resist film made of a resist material is formed on a substrate, and the resist film is selectively exposed to radiation such as light and electron beams through a mask on which a predetermined pattern is formed. And performing a developing process to form a resist pattern having a predetermined shape on the resist film. Note that a resist material in which the exposed portion changes to a property that dissolves in the developer is referred to as a positive resist material, and a resist material that changes to a property in which the exposed portion does not dissolve in the developer is referred to as a negative resist material.
In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization has been rapidly progressing due to advances in lithography technology. As a technique for miniaturization, the exposure light source is generally shortened in wavelength (increased energy). Conventionally, ultraviolet rays typified by g-line and i-line have been used, but now mass production of semiconductor elements using KrF excimer laser or ArF excimer laser has been started. In addition, lithography using an F ₂ excimer laser, an electron beam, EUV (extreme ultraviolet), X-ray, or the like having a shorter wavelength (higher energy) than KrF excimer laser or ArF excimer laser is also being studied.

Resist materials are required to have lithography characteristics such as sensitivity to these exposure light sources and resolution capable of reproducing a pattern with fine dimensions. As a resist material satisfying such requirements, a chemically amplified resist composition containing a base material component whose solubility in an alkaline developer is changed by the action of an acid and an acid generator component that generates an acid upon exposure is used. It has been.
For example, as a positive chemically amplified resist composition, a resist composition containing a resin component (base resin) whose solubility in an alkaline developer is increased by the action of an acid and an acid generator component is generally used. It has been. When a resist film formed using such a resist composition is selectively exposed at the time of resist pattern formation, an acid is generated from the acid generator component in the exposed portion, and the alkali developer of the resin component is generated by the action of the acid. As a result, the exposed area becomes soluble in an alkaline developer.

  Currently, as a base resin of a resist material used in ArF excimer laser lithography and the like, a resin having a structural unit derived from a (meth) acrylic acid ester in its main chain, so-called acrylic, is excellent in transparency near 193 nm. System resins are generally used as polymer compounds that are one component of photoresist compositions (see, for example, Patent Document 1).

  In the future, there are demands for the development of new materials that can be used for lithography applications, as further progress in lithography technology and expansion of application fields are expected. For example, as pattern miniaturization progresses, development of resist materials that can improve various lithography characteristics such as resolution and line width roughness (LWR) and pattern shape more than ever is desired. As means for solving these problems, it has been proposed to use a resin having a cyclic structure and an ester group at an ester site in a specific structural unit (see, for example, Patent Documents 2 and 3).

JP 2003-241385 A JP 2010-055084 A JP 2010-134417 A

Resist materials containing a resin having a specific structural unit described in Patent Documents 2 and 3 are excellent in lithography characteristics. However, (meth) acrylic acid ester derivatives from which the specific structural unit is derived are manufactured using expensive and relatively difficult to obtain raw materials such as methacryloloxyethyl succinate and ethyldiisopropylaminocarbodiimide. Since it is difficult to mass-produce on an industrial scale, development of an industrially useful production method is desired.
The present invention has been made in view of the above circumstances, and is an industrially easily available raw material for producing a (meth) acrylic acid ester derivative used as a raw material for a polymer compound used in a resist material having excellent lithography properties. To provide a synthetic intermediate that can be produced safely and inexpensively on an industrial scale, and to provide a method for producing a (meth) acrylic acid ester derivative using the synthetic intermediate And

  As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by using a dicarboxylic acid monoester derivative having a specific structure, and have completed the present invention.

（式中、Ｒ¹は、水素原子または−ＣＯＯＲ²（Ｒ²は、炭素数１〜５のアルキル基を表すか、または炭素数１〜３のアルキル基で置換された若しくは無置換の炭素数３〜１０の環状炭化水素基を表す。）を表す。Ｙは、メチレン基、酸素原子または硫黄原子を表し、Ｚは、＞Ｃ＝Ｏ、＞Ｓ＝Ｏまたは＞Ｓ（＝Ｏ）₂を表す。また、ｎは、１〜３の整数を表す。）
で示されるジカルボン酸モノエステル誘導体。
［２］前記一般式（１）において、ｎが１である、上記［１］に記載のジカルボン酸モノエステル誘導体。 That is, the present invention provides the following [1] to [4].
[1] The following general formula (1)

(In the formula, R ¹ represents a hydrogen atom or —COOR ² (R ² represents an alkyl group having 1 to 5 carbon atoms, or is substituted or unsubstituted with an alkyl group having 1 to 3 carbon atoms) Represents a cyclic hydrocarbon group of 3 to 10. Y represents a methylene group, an oxygen atom or a sulfur atom, and Z represents>C═O,> S═O or> S (═O) ₂ . N represents an integer of 1 to 3.)
A dicarboxylic acid monoester derivative represented by:
[2] The dicarboxylic acid monoester derivative according to the above [1], wherein n is 1 in the general formula (1).

（式中、Ｒ¹、Ｙ、Ｚおよびｎは、前記定義の通りである。）
で示されるジカルボン酸モノエステル誘導体と、下記一般式（２）

（式中、Ｒ³は、水素原子またはメチル基を表す。）
で示されるヒドロキシエチル（メタ）アクリレートとを反応させることを特徴とする、下記一般式（３）

（式中、Ｒ¹、Ｒ³、Ｙ、Ｚおよびｎは、前記定義の通りである。）
で示されるアクリル酸エステル誘導体の製造方法。
［４］前記一般式（１）および（３）において、ｎが１である、上記［３］に記載のアクリル酸エステル誘導体の製造方法。 [3] The following general formula (1)

(Wherein R ¹ , Y, Z and n are as defined above.)
And a dicarboxylic acid monoester derivative represented by the following general formula (2)

(In the formula, R ³ represents a hydrogen atom or a methyl group.)
The following general formula (3), characterized by reacting with hydroxyethyl (meth) acrylate represented by

(Wherein R ¹ , R ³ , Y, Z and n are as defined above.)
The manufacturing method of the acrylic ester derivative shown by these.
[4] The method for producing an acrylate derivative according to the above [3], wherein in the general formulas (1) and (3), n is 1.

  According to the method using the synthetic intermediate of the present invention, for example, as proposed in Patent Documents 2 and 3, a (meth) acrylic acid ester derivative used as a raw material for a polymer compound used for a resist material having excellent lithography properties Can be produced on an industrial scale safely and inexpensively using raw materials that are industrially easily available.

[Dicarboxylic acid monoester derivative (1)]
The dicarboxylic acid monoester derivative of the present invention (hereinafter referred to as dicarboxylic acid monoester derivative (1)) is represented by the following general formula (1).

R ¹ in the dicarboxylic acid monoester derivative (1) represents a hydrogen atom or COOR ² . R ² represents an alkyl group having 1 to 5 carbon atoms, or represents an unsubstituted or substituted cyclic hydrocarbon group having 3 to 10 carbon atoms with an alkyl group having 1 to 3 carbon atoms.
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ² include a methyl group, an ethyl group, and various propyl groups (“various” means linear and all branched chains, the same shall apply hereinafter). .), Various butyl groups, and various pentyl groups. Among these, a methyl group and an ethyl group are preferable.
Examples of the cyclic hydrocarbon group having 3 to 10 carbon atoms represented by R ² include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 1-adantyl group, and a 2-adamantyl group. Among these, a cyclopentyl group and a 2-adamantyl group are preferable. Examples of the alkyl group having 1 to 3 carbon atoms that the cyclic hydrocarbon group may have include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
Among these, as R ² , methyl group, ethyl group, 1-ethylcyclopentan-1-yl group, 1-isopropylcyclopentan-1-yl group, 2-methyladamantan-2-yl group, 2-ethyl An adamantane-2-yl group and a 2-isopropyladamantan-2-yl group are preferred.
In particular, R ¹ is preferably a hydrogen atom.

Y in the dicarboxylic acid monoester derivative (1) represents a methylene group, an oxygen atom or a sulfur atom. Among these, a methylene group or an oxygen atom is preferable.
Z in the dicarboxylic acid monoester derivative (1) represents>C═O,> S═O or> S (═O) ₂ . Among these, as Z,> C═O or> S (═O) ₂ is preferable.
N in the dicarboxylic acid monoester derivative (1) represents an integer of 1 to 3. n is preferably 1.

  Although the specific example of a dicarboxylic acid monoester derivative (1) is shown, it is not specifically limited to these.

（式中、Ｒ¹、Ｙ、Ｚおよびｎは、前記定義の通りである。） (Method for producing dicarboxylic acid monoester derivative (1))
Although there is no restriction | limiting in particular in the manufacturing method of the dicarboxylic acid monoester derivative (1) of this invention, For example, the alcohol derivative (henceforth an alcohol derivative (a)) shown in the following chemical formula, and a dicarboxylic acid anhydride (henceforth, (Referred to as dicarboxylic anhydride (b)) in the presence of a basic compound.

(Wherein R ¹ , Y, Z and n are as defined above.)

Specific examples of the alcohol derivative (a) include 2-hydroxy-4-oxa-5-thiatricyclo [4.2.1.0 ^3,7 ] nonane-5,5-dioxide, 3-hydroxyhexahydro- 5-oxo-2,6-methanofuro [3,2-b] furan, 6-hydroxyhexahydro-2-oxo-3,5-methano-4H-cyclopenta [2,3-b] furan, 6-hydroxyhexa And hydro-2-oxo-3,5-methano-4H-cyclopenta [2,3-b] furan.

Specific examples of the dicarboxylic acid anhydride (b) include succinic anhydride, glutaric anhydride, and adipic anhydride.
The amount of the dicarboxylic acid anhydride (b) used is preferably 0.7 to 3 moles per mole of the alcohol derivative (a), and more preferably 1 to 2 moles from the viewpoint of ease of post-treatment.

As the basic compound used in this reaction, an organic base or an inorganic base may be used.
Examples of the organic base include amines such as triethylamine, tributylamine, trioctylamine, diisopropylethylamine, triethylenetetramine, triethanolamine, piperazine, diazabicyclo [2.2.2] octane; pyridine, 2-methylpyridine, 2 -Nitrogen-containing heterocyclic aromatic compounds such as methyl-5-ethylpyridine and 2,6-dimethylpyridine. Examples of the inorganic base include alkali metal hydrides such as sodium hydride, potassium hydride, and calcium hydride, or alkaline earth metal hydrides. Among these, an organic base is preferable and an amine is more preferable.
0.7-3 mol is preferable with respect to 1 mol of alcohol derivatives (a), and, as for the usage-amount of a basic compound, 1-2 mol is more preferable from a viewpoint of the ease of post-processing.

This reaction is carried out in the presence or absence of a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction. For example, chain saturated hydrocarbons such as hexane and heptane; alicyclic saturated hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated hydrocarbons such as methylene, dichloroethane, chloroform and chlorobenzene; esters such as methyl acetate, ethyl acetate and propyl acetate; nitriles such as acetonitrile, propionitrile and benzonitrile. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types. Among these, nitrile is preferable.
When this reaction is carried out in the presence of a solvent, the amount of the solvent used is preferably 0.5 to 100 parts by mass with respect to 1 part by mass of the alcohol derivative (a), and is 0 from the viewpoint of ease of post-treatment. 0.5 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is even more preferable.

The reaction temperature varies depending on the type of alcohol derivative (a), acid anhydride and base compound used, but is preferably -30 to 100 ° C, more preferably -10 to 60 ° C, and further preferably 5 to 60 ° C. 10 to 50 ° C. is particularly preferable. Moreover, although there is no restriction | limiting in particular in reaction pressure, Usually, implementing under a normal pressure is preferable.
The reaction time varies depending on the types and amounts of the alcohol derivative (a), acid anhydride and base compound used, the reaction temperature, etc., but is preferably about 1 to 50 hours.
The reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

  The method for carrying out this reaction is not particularly limited, but the reactor is charged with an alcohol derivative (a), an acid anhydride, and optionally a solvent, and this mixture is subjected to a desired reaction temperature and a desired reaction pressure. And a method of adding or adding a basic compound dropwise is preferred. The time for dropping or adding the basic compound varies depending on the type and amount of the alcohol derivative (a), acid anhydride and base compound used, but from the viewpoint of reaction temperature control, 1 minute to 2 hours is preferable. 1 minute to 1 hour is more preferable. Such dropping time or addition time is included in the reaction time described above.

Separation and purification of the dicarboxylic acid monoester derivative (1) from the reaction mixture obtained by the above method can be carried out by methods generally used for separation and purification of organic compounds.
For example, after completion of the reaction, the obtained reaction mixture is cooled to 0 to 5 ° C. to precipitate a solid, and after filtering the solid, a mixed solution of solvent (for example, nitrile and the like) and water (mass ratio = The dicarboxylic acid monoester derivative (1) can be obtained by washing the solid with, for example, about 1: 3) and then drying. Furthermore, the purity of the dicarboxylic acid monoester derivative (1) can be increased by purification means such as recrystallization.

In addition, there is no restriction | limiting in particular in the acquisition method of the said alcohol derivative (a). Some are available industrially, and based on the adduct obtained by Diels-Alder reaction of the corresponding diene and dienophile, the desired product is produced by epoxidation via an intermediate as required. Alternatively, after forming an epoxy compound once by an epoxidation reaction, the target compound can be produced by treating the epoxy compound with, for example, a basic substance.
For example, 5-hydroxy-2,6-norbornane sultone in which R ¹ is a hydrogen atom and Z is> S (═O) ₂ in the structural formula of the alcohol derivative (a) is produced as follows. be able to. That is, cyclopentadiene and vinylsulfonyl chloride generated in the system were subjected to Diels-Alder reaction to obtain 5-norbornene-2-sulfonyl chloride, and then contacted with an aqueous sodium hydroxide solution to give 5-norbornene-2-sulfone. By using an acid sodium salt and further subjecting it to an epoxidation reaction with performic acid, the target product can be produced (see JP 2010-83873 A).
In addition, in the structural formula of the alcohol derivative (a), when R ¹ is a hydrogen atom and Z is> C═O, “J. Chem. Soc., H. B. Henbest et al., P. 221-226 (1959) ".
Other alcohol derivatives (a) can also be produced by referring to the above methods and known methods.

[Method for producing acrylic ester derivative (2)]
From the dicarboxylic acid monoester derivative (1) of the present invention, the acrylic acid ester derivative (2) can be easily produced on an industrial scale safely and inexpensively (see the following chemical reaction formula). Specifically, the acrylate derivative (2) can be produced by reacting the dicarboxylic acid monoester derivative (1) with hydroxyethyl (meth) acrylate. More specifically, the following production methods (A) and (B) are preferable.
Production method (A): A method in which the dicarboxylic acid monoester derivative (1) is reacted with hydroxyethyl (meth) acrylate in the presence of a catalyst.
Production method (B): After reacting the dicarboxylic acid monoester derivative (1), the basic compound and the activating agent [first reaction], react with hydroxyethyl (meth) acrylate in the presence of the basic compound [first reaction] 2 reaction].
In addition, the said hydroxyethyl (meth) acrylate is the structure described in the following chemical reaction formulas.

（式中、Ｒ¹、Ｒ³、Ｙ、Ｚおよびｎは、前記定義の通りである。）

(Wherein R ¹ , R ³ , Y, Z and n are as defined above.)

<Manufacturing method (A)>
Hereinafter, the manufacturing method (A) will be described.
The catalyst used in the production method (A) is preferably a strong acid, and examples thereof include mineral acids such as hydrogen chloride and sulfuric acid; and acidic organic compounds such as p-toluenesulfonic acid and methanesulfonic acid. Among these, sulfuric acid and p-toluenesulfonic acid are preferable. An acidic compound may be used individually by 1 type, and may mix and use 2 or more types.
The amount of the acidic compound used is preferably from 0.001 to 2 mol, more preferably from 0.001 to 1 mol, based on 1 mol of the dicarboxylic acid monoester derivative (1), and 0 from the viewpoint of ease of post-treatment. More preferably, 0.01-1 mol.

The production method (A) is carried out in the presence of a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction. For example, chain saturated hydrocarbons such as hexane and heptane; alicyclic saturated hydrocarbons such as cyclohexane and methylcyclohexane; aromatic carbons such as benzene, toluene and xylene. Hydrogen; halogenated hydrocarbons such as methylene chloride, dichloroethane, chloroform, chlorobenzene; esters such as methyl acetate, ethyl acetate, and propyl acetate; nitriles such as acetonitrile, propionitrile, and benzonitrile. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types. Among these, aromatic hydrocarbons are preferable, and toluene and xylene are more preferable.
When the reaction is carried out in the presence of a solvent, the amount of the solvent to be used is preferably 0.5 to 100 parts by mass with respect to 1 part by mass of the alcohol derivative (3). 5-20 mass parts is more preferable, and 0.5-10 mass parts is further more preferable.

  In the production method (A), the reaction can be promoted by removing water generated with the progress of the reaction out of the reaction system. As a method for removing generated water from the reaction system, a method of adding a dehydrating agent such as molecular sieves, magnesium sulfate, sodium sulfate, or the like; a method of distilling off water together with a solvent using a solvent azeotropic with water Is mentioned. Among these, a method of distilling off water together with a solvent using a solvent azeotropic with water is preferable. Preferred examples of the solvent azeotropic with water include aromatic hydrocarbons such as toluene and xylene; alicyclic saturated hydrocarbons such as cyclohexane and methylcyclohexane; and chain saturated hydrocarbons such as hexane and heptane. Among these, toluene and xylene are more preferable.

Although reaction temperature changes with kinds of solvent to be used, 50-150 degreeC is generally preferable, 50-110 degreeC is more preferable from a viewpoint which suppresses side reactions, such as superposition | polymerization, and 65-100 degreeC is further more preferable.
There is no restriction | limiting in particular in reaction pressure, Although it changes also with the kind of solvent, reaction temperature, etc., 1-100 kPa is preferable and 10-60 kPa is more preferable.
Although reaction time changes with reaction temperature and the usage-amount of a catalyst, about 1 to 100 hours are preferable, and 1 to 50 hours is more preferable from a viewpoint of suppressing side reactions, such as superposition | polymerization.
The reaction of the production method (A) can be stopped by adding a basic compound. Examples of the basic compound include alkali metal hydroxides or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; alkalis such as sodium carbonate, potassium carbonate, calcium carbonate, and barium carbonate. Examples thereof include metal carbonates and alkaline earth metal carbonates. Among these, alkali metal hydroxide is preferable. In addition, this basic compound may be mixed with water as needed and used as an aqueous solution.

  There is no restriction | limiting in particular in embodiment of reaction of a manufacturing method (A). For example, a dicarboxylic acid monoester derivative (1), hydroxyethyl (meth) acrylate and a catalyst and a solvent as necessary are charged into a reactor, and the resulting mixture is heated to a desired reaction temperature under a desired reaction pressure. The reaction is preferably carried out while removing (preferably distilling off) the solvent.

  Separation and purification of the acrylate derivative (2) from the reaction mixture obtained by the above method can be carried out by methods generally used for separation and purification of organic compounds. For example, after completion of the reaction, the resulting reaction mixture is separated into an organic layer and an aqueous layer, the aqueous layer is extracted with toluene, combined with the organic layer, and concentrated to obtain an acrylate derivative (2). can get. Next, recrystallization using a mixed solvent of ethyl acetate and diisopropyl ether or the like can provide an acrylic ester derivative (2) with high purity.

<Manufacturing method (B)>
Hereinafter, the first reaction and the second reaction of the production method (B) will be described in order.
-First reaction-
As the basic compound used in the first reaction of the production method (B), either an organic base or an inorganic base can be used. Examples of the organic base include amines such as triethylamine, trioctylamine, tributylamine, triethylenetetramine, triethanolamine, piperazine, diazabicyclo [2.2.2] octane; pyridine, 2-methylpyridine, 2-methyl-5 -Nitrogen-containing heterocyclic aromatic compounds such as ethylpyridine and 2,6-dimethylpyridine. Examples of the inorganic base include alkali metal hydrides such as sodium hydride and potassium hydride. Among these, an organic base is preferable, and triethylamine and pyridine are more preferable.
0.7-3 mol is preferable with respect to 1 mol of dicarboxylic acid monoester derivative (1), and, as for the usage-amount of a basic compound, 1-2 mol is more preferable.

The activator used in the first reaction of the production method (B) reacts with the carboxylic acid of the dicarboxylic acid monoester derivative (1) in the presence of a basic compound to form an acid anhydride structure or an O-acylisourea structure. The desired esterification reaction is promoted by forming. Examples of the activator include pivaloyl chloride, 2,4,6-trichlorobenzoyl chloride, methanesulfonyl chloride, p-toluenesulfonyl chloride, dicyclohexylcarbodiimide and the like. Among these, pivaloyl chloride and methanesulfonyl chloride are preferable.
0.7-3 mol is preferable with respect to 1 mol of dicarboxylic acid monoester derivative (1), and, as for the usage-amount of an activator, 1-2 mol is more preferable.

The 1st reaction of a manufacturing method (B) is implemented in presence of a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction. For example, chain saturated hydrocarbons such as hexane and heptane; alicyclic saturated hydrocarbons such as cyclohexane and methylcyclohexane; aromatic carbons such as benzene, toluene and xylene. Hydrogen; halogenated hydrocarbons such as methylene chloride, dichloroethane, chloroform, chlorobenzene; esters such as methyl acetate, ethyl acetate, and propyl acetate; nitriles such as acetonitrile, propionitrile, and benzonitrile. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
When the reaction is carried out in the presence of a solvent, the amount of the solvent used is preferably 0.5 to 100 parts by mass with respect to 1 part by mass of the dicarboxylic acid monoester derivative (1), from the viewpoint of ease of post-treatment. 0.5-20 mass parts is more preferable, and 0.5-10 mass parts is still more preferable.

Although the reaction temperature of the 1st reaction of a manufacturing method (B) changes with kinds of activator to be used, -50-100 degreeC is generally preferable, and -20-70 degreeC is more preferable.
There is no restriction | limiting in particular in the reaction pressure of 1st reaction of a manufacturing method (B), Although it changes also with reaction temperature etc., a normal pressure is preferable from a viewpoint of the simplicity of operation in implementation.
The reaction time of the first reaction in the production method (B) varies depending on the reaction temperature and the type of activator used, but is generally preferably 0.1 to 50 hours, more preferably 0.5 to 30 hours.
The first reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon.
The reaction mixture obtained as described above is preferably used as a raw material for the second reaction in the production method (B) as it is.

-Second reaction-
Specific examples of hydroxyethyl (meth) acrylate used in the second reaction of the production method (B) include hydroxyethyl acrylate and hydroxyethyl methacrylate.
1-10 mol is preferable with respect to 1 mol of dicarboxylic acid monoester derivative (1) used by 1st reaction, and, as for the usage-amount of hydroxyethyl (meth) acrylate, 1-5 mol is more preferable.

As the basic compound used in the second reaction of the production method (B), either an organic base or an inorganic base can be used. Examples of the organic base include amines such as triethylamine, trioctylamine, tributylamine, triethylenetetramine, triethanolamine, piperazine, diazabicyclo [2.2.2] octane; pyridine, 2-methylpyridine, 2-methyl-5 -Nitrogen-containing heterocyclic aromatic compounds such as ethylpyridine and 2,6-dimethylpyridine. Examples of the inorganic base include alkali metal hydrides such as sodium hydride and potassium hydride. Among these, an organic base is preferable, and triethylamine and pyridine are more preferable.
1-3 mol is preferable with respect to 1 mol of dicarboxylic acid monoester derivative (1) used by 1st reaction, and, as for the usage-amount of a basic compound, 1-2 mol is more preferable. It is more preferable to select the same basic compound as the basic compound used in the first reaction of the production method (B).

The second reaction in the production method (B) is carried out in the presence of a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction. For example, chain saturated hydrocarbons such as hexane and heptane; alicyclic saturated hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; Halogenated hydrocarbons such as methylene, dichloroethane, chloroform and chlorobenzene; esters such as methyl acetate, ethyl acetate and propyl acetate; nitriles such as acetonitrile, propionitrile and benzonitrile. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
When the reaction is carried out in the presence of a solvent, the amount of the solvent used is preferably 0.5 to 100 parts by mass with respect to the dicarboxylic acid monoester derivative (1) used in the first reaction, and easy post-treatment. From the viewpoint, 0.5 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is more preferable.

Although the reaction temperature of the 2nd reaction of a manufacturing method (B) changes with kinds of activator to be used, -50-100 degreeC is generally preferable, and -20-70 degreeC is more preferable.
There is no restriction | limiting in particular in the reaction pressure of the 2nd reaction of a manufacturing method (B), Although it changes also with reaction temperature etc., a normal pressure is preferable from a viewpoint of the simplicity of operation in implementation.
The reaction time of the second reaction in the production method (B) varies depending on the reaction temperature and the type of the activator used, but is generally preferably 0.1 to 50 hours, and more preferably 0.5 to 30 hours.
The second reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon.
In the second reaction of the production method (B), the reaction can be stopped by adding water.

  There is no restriction | limiting in particular as embodiment of the 2nd reaction of a manufacturing method (B). For example, the reaction mixture obtained in the first reaction of the production method (B), hydroxyethyl (meth) acrylate, and a solvent as necessary are charged into a reactor, and a base is added at a desired reaction pressure and a desired reaction temperature. A method of adding a functional compound is preferred.

Separation and purification of the acrylate derivative (2) from the reaction mixture obtained by the above method can be carried out by methods generally used for separation and purification of organic compounds.
For example, after completion of the reaction, the resulting reaction mixture is separated into an organic layer and an aqueous layer, the aqueous layer is extracted with toluene, combined with the organic layer, and concentrated to obtain an acrylate derivative (2). can get. Next, recrystallization using a mixed solvent of ethyl acetate and diisopropyl ether or the like can provide an acrylic ester derivative (2) with high purity.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these examples.

<Synthesis Example 1> Synthesis of 5-hydroxy-2,6-norbornane sultone In a four-necked flask with an internal volume of 1 L equipped with a stirrer and a thermometer, 0.40 g of phenothiazine, 1154.0 g of tetrahydrofuran (THF), cyclopentadiene 87.0 g (1.32 mol) was charged and cooled to 5 ° C. or lower with stirring. Then, 195.7 g (1.20 mol) of 2-chloroethanesulfonyl chloride and 146.0 g (1.45 mol) of 2-chloroethanesulfonyl chloride were placed in separate dropping funnels, respectively, and dripped simultaneously over 5 hours at an internal temperature of 5 to 10 ° C. It was.
After completion of the dropwise addition, the reaction mixture was stirred at 5 to 10 ° C. for 3 hours, and then the precipitated salt was filtered under reduced pressure. Subsequently, 600.0 g of THF was poured into the filtered salt to obtain 1632.8 g of filtrate ( The filtrate is referred to as “filtrate (A)”). When the filtrate (A) was analyzed by gas chromatography, it contained 178.2 g (0.925 mol) of 5-norbornene-2-sulfonyl chloride (yield: 77.1% based on 2-chloroethanesulfonyl chloride). ).
920 g of water was put into a 3 L three-necked flask equipped with a stirrer and a thermometer, and cooled to 20 ° C. or lower. While stirring, 80.30 g (2.01 mol) of sodium hydroxide was added so that the internal temperature was 20 ° C. or lower. Here, 1300 g of “filtrate (A)” (5-norbornene-2-sulfonyl chloride was 141.9 g, 0.737 mol) was added dropwise at an internal temperature of 20 to 25 ° C. over 4 hours.
One hour after the completion of the dropwise addition, the reaction mixture was analyzed by gas chromatography. As a result, 5-norbornene-2-sulfonyl chloride had completely disappeared. The reaction mixture was concentrated under reduced pressure to remove THF, then transferred to a 2 L separatory funnel and washed three times with 300 g of toluene to obtain 1065.3 g of an aqueous solution containing 5-norbornene-2-sulfonic acid sodium salt. (This aqueous solution is referred to as “aqueous solution (A)”).
All of the “aqueous solution (A)” was placed in a three-necked flask having an internal volume of 3 L equipped with a stirrer and a thermometer, and cooled to 10 ° C. After dropping 93.27 g (2.01 mol) of 99% formic acid at an internal temperature of 11 to 15 ° C. and heating to an internal temperature of 50 to 53 ° C., 162.50 g (1. 43 mol) was added dropwise over 3 hours. The internal temperature was maintained at around 50 ° C. even after completion of the dropwise addition, and the reaction mixture was analyzed by high performance liquid chromatography (HPLC) 17 hours after the completion of the dropwise addition. As a result, the conversion of 5-norbornene-2-sulfonic acid was 98. 7%.
After cooling the reaction mixture to 15 ° C., 36.55 g (0.29 mol) of sodium sulfite was slowly added at an internal temperature of 15 to 18 ° C., and it was confirmed that hydrogen peroxide was not detected by starch paper. 95 g (1.68 mol) was slowly added at an internal temperature of 15 to 17 ° C. to adjust the pH of the reaction mixture to 7.3. Extraction was performed twice with 900 g of ethyl acetate, and the obtained organic layers were combined and concentrated under reduced pressure to obtain 69.15 g of a yellowish white solid. This solid was dissolved in 140 g of ethyl acetate at 50 ° C., and then slowly cooled to 10 ° C., and the precipitated crystals were filtered. The crystals separated by filtration were washed with 30 g of ethyl acetate at 5 ° C. and dried under reduced pressure at 40 ° C. for 2 hours, whereby 53.9 g of 5-hydroxy-2,6-norbornane sultone having the following structure (purity: 99.1%) 0.28 mol) (yield 38.1% based on 5-norbornene-2-sulfonyl chloride).

¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm): 1.72 (1H, dd, J = 11.6, 1.6 Hz), 2.06-2.10 (3H, m), 2.22 (1H, dd, J = 11.2, 1.6 Hz), 2.44 (1H, m), 3.44 (1H, m), 3.50-3.53 (1H, m), 3.93 (1H, brs), 4.61 (1H, d, J = 4.8 Hz)

<Example 1> Preparation of 4-oxa-5-thiatricyclo [4.2.1.0 ^3,7 ] nonane-5,5-dioxido-2-yl succinate Internal volume of 2000 mL equipped with a stirrer and a thermometer Was charged with 180.0 g (946.3 mmol) of 5-hydroxy-2,6-norbornane sultone, 104.2 g (1041.2 mmol) of succinic anhydride, and 274.7 g of acetonitrile. Subsequently, 58.0 g (567.4 mmol) of triethylamine was added dropwise over 30 minutes at an internal temperature of 39 to 45 ° C. while stirring. Then, after stirring for 1 hour at 39 to 45 ° C., 820.6 g (556.4 mmol) of 0.676 mol / kg hydrochloric acid was added dropwise over 23 minutes at an internal temperature of 45 to 34 ° C.
After confirming that the internal temperature was 40 ° C. and the inside of the system was a homogeneous solution, the internal temperature was lowered to 1 ° C. over 4 hours to precipitate a solid. Then, after stirring at 1 degreeC for 3 hours, it filtered with the filter paper. After washing the solid with 274.8 g of a mixed solution of acetonitrile and water (acetonitrile / water = 1/3 (mass ratio)), the solid was dried at 40 ° C. for 8 hours, and the following 4-oxa-5- 221.4 g (yield 80.6%) of a white solid of thiatricyclo [4.2.1.0 ^3,7 ] nonane-5,5-dioxido-2-yl succinate was obtained.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 1.83 (1H, d, J = 11.6 Hz), 2.01-2.09 (2H, m), 2.20 (1H, ddd, 13.6, 10.7, 4.4 Hz), 2.52 (1 H, d, J = 3.6 Hz), 2.60 (4 H, s), 3.49-3.52 (1 H, m ), 3.65 (1H, ddd, J = 10.7, 4.4, 2.4 Hz), 4.63 (1H, d, J = 1.6 Hz), 4.76 (1H, d, J = 4.8Hz)

<Synthesis Example 2> Synthesis of 5-hydroxy-2,6- (7-oxanorbornane) carbolactone Into a 100 mL four-necked flask equipped with a stirrer and a thermometer, 48.0 g (0.705 mol) of furan was added. Then, 20.0 g (0.232 mol) of methyl acrylate was added and cooled to -20 ° C. The boron trifluoride diethyl ether complex 3.0mL was dripped there, maintaining internal temperature -15--18 degreeC. After completion of the dropwise addition, stirring was continued for 14 hours at an internal temperature of 0 to 5 ° C. The reaction mixture was concentrated under reduced pressure, and the resulting concentrate was dissolved in 300 g of ethyl acetate, washed successively with 50 g of water, 50 g of a saturated aqueous sodium hydrogen carbonate solution and 50 g of saturated brine, and then concentrated under reduced pressure. 28.3 g of oil was obtained.
To this oily substance was added 93.6 g (0.234 mol) of a 10% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 24 hours, and then adjusted to pH 2.0 with concentrated hydrochloric acid. After extracting three times with 300 g of ethyl acetate, the obtained extracted layers were combined and concentrated under reduced pressure to obtain 21.5 g of a solid.
The total amount of the solid obtained above was placed in a 200 mL four-necked flask equipped with a stirrer, thermometer and dropping funnel, and 12.0 g (0.232 mol) of 88% formic acid was mixed at 20 to 30 ° C. Then, it heated and the internal temperature was 45-46 degreeC. Next, 26.1 g (0.232 mol) of 30% aqueous hydrogen peroxide was added dropwise over 6 hours. After completion of dropping, the mixture was stirred for 20 hours while maintaining the internal temperature at around 45 ° C. After cooling the reaction mixture to 15 ° C., 9.7 g of sodium sulfite was added at an internal temperature of 15 to 20 ° C. After confirming that hydrogen peroxide was not detected by starch paper, the reaction was performed with 20% aqueous sodium hydroxide solution. The pH of the mixture was 7.8. Extraction was performed 3 times with 400 g of ethyl acetate, and the obtained organic layers were combined and concentrated under reduced pressure. 30 g of ethanol was added to the obtained solid, heated, and after the solid was completely dissolved, the solid was slowly cooled to 0 ° C., and the precipitated crystals were filtered. The crystals separated by filtration were washed with 10 g of ethanol at 0 ° C., and dried under reduced pressure at 40 ° C. for 2 hours, whereby 10.8 g of 5-hydroxy-2,6- (7-oxanorbornane) carbolactone having the following structure ( Purity 98.9%, 0.068 mol) was obtained.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 1.97 (1H, dd, J = 13.4, 1.8 Hz), 2.11 (1H, d, J = 8.4 Hz), 2.23 (1H, ddd, J = 13.6, 11.2, 5.6 Hz), 2.71 (1 H, m), 3.89 (1 H, d, J = 8.8 Hz), 4.51 (1H, d, J = 4.8 Hz), 4.58 (1H, d, J = 5.2 Hz), 5.32 (1H, t, J = 4.8 Hz)

Example 2 Production of 5-oxo-4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl = succinate Four-necked volume of 1000 mL with a stirrer and thermometer attached A flask was charged with 73.2 g (468.8 mmol) of 5-hydroxy-2,6- (7-oxanorbornane) carbolactone, 51.6 g (515.7 mmol) of succinic anhydride, and 162.5 g of acetonitrile. Subsequently, 28.4 g (281.3 mmol) of triethylamine was added over 5 minutes at an internal temperature of 15 to 30 ° C. with stirring. Then, after stirring for 1 hour at 43 ° C., 487.8 g (281.3 mmol) of 0.577 mol / kg hydrochloric acid was added dropwise over 7 minutes at an internal temperature of 43 to 28 ° C.
After confirming that the internal temperature was 43 ° C. and the inside of the system was a homogeneous solution, the internal temperature was lowered to 1 ° C. over 4 hours to precipitate a solid. Then, after stirring at 1 degreeC for 1 hour, it filtered with the filter paper. After washing the solid with 120 g of a mixed solution of acetonitrile and water (acetonitrile / water = 1/3 (mass ratio)), the solid was dried at 41 ° C. over 2.5 hours, and 5-oxo- 98.1 g (81.6%) of a white solid of 4-oxatricyclo [4.2.1.0 ^3,7 ] nonan-2-yl succinate was obtained.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 2.04 (1H, dd, J = 13.6, 2.0 Hz), 2.21 (1H, ddd, 13.6, 11.2 5.6 Hz), 2.62 (4H, s), 2.72 (1H, dddd, J = 11.2, 4.8, 2.0, 0.8 Hz), 4.63 (1H, dd, J = 4.8, 0.8 Hz), 4.67 (1H, d, J = 5.6 Hz), 4.74 (1H, s), 5.38 (1H, t, J = 4.8 Hz)

Example 3 Production of 2′-methacryloyloxyethyl-4-oxa-5-thiatricyclo [4.2.1.0 ^3,7 ] nonane-5,5-dioxido-2-yl succinate Dean Stark, stirring 4-oxa-5-thiatricyclo [4.2.1.0 ^3,7 ] nonane-5,5-dioxide- obtained in Example 1 was placed in a four-necked flask having an internal volume of 500 ml equipped with a device and a thermometer. 2.9 g (10 mmol) of 2-yl = succinate, 1.0 g (5 mmol) of p-toluenesulfonic acid monohydrate, 10 g of toluene and 1.4 g (11 mmol) of hydroxyethyl methacrylate were added, and the inside of the system was adjusted to 33.2 kPa. The pressure was reduced.
Subsequently, the internal temperature was raised to 80 ° C., and heating was continued for 30 hours while appropriately removing water accumulated in the Dean Stark.
After cooling the internal temperature to 25 ° C., the reduced pressure was released, and 2.2 g (5.5 mmol) of 10% by mass-sodium hydroxide aqueous solution was added. The reaction mixture was transferred to a separatory funnel and separated. The aqueous layer was extracted with 10 g of toluene, the organic layer and the extract were mixed, and then concentrated under reduced pressure.
To the obtained concentrate, 10 g of ethyl acetate and 20 g of diisopropyl ether were added, and the internal temperature was raised to 50 ° C. to dissolve the crystals. Subsequently, the internal temperature was cooled to 0 ° C. over 5 hours and stirred at 0 ° C. for 2 hours, and then the precipitated crystals were separated by filtration with a glass filter.
The obtained crystals were dried under the conditions of 0.3 kPa and 40 ° C. to give 2′-methacryloyloxyethyl-4-oxa-5-thiatricyclo [4.2.1.0 ^3,7 ] nonane having the following structure. 3.3 g (white solid, yield 82.0%) of -5,5-dioxido-2-yl succinate was obtained.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 1.93 (3H, s), 2.15-1.75 (5H, m), 2.66-2.54 (4H, m) 3.48 (1H, m), 3.55 (1H, m), 4.34 (4H, s), 4.73-4.71 (2H, m), 5.60 (1H, s), 6.12 (1H, s)

  From the above, by using the dicarboxylic acid monoester derivative (1) of the present invention, the (meth) acrylic acid ester derivative derived from the specific structural unit proposed in Patent Documents 2 and 3 is easily industrially available. It has been proved that it can be manufactured safely and inexpensively on an industrial scale using simple raw materials.

  The dicarboxylic acid ester derivative (1) of the present invention is useful as a synthetic intermediate for the raw material of the polymer compound to be contained in the resist composition.

Claims (4)

The following general formula (1)

(In the formula, R ¹ represents a hydrogen atom or —COOR ² (R ² represents an alkyl group having 1 to 5 carbon atoms, or is substituted or unsubstituted with an alkyl group having 1 to 3 carbon atoms) Represents a cyclic hydrocarbon group of 3 to 10. Y represents a methylene group, an oxygen atom or a sulfur atom, and Z represents>C═O,> S═O or> S (═O) ₂ . N represents an integer of 1 to 3.)
A dicarboxylic acid monoester derivative represented by:   The dicarboxylic acid monoester derivative according to claim 1, wherein n is 1 in the general formula (1). The following general formula (1)

(Wherein R ¹ , Y, Z and n are as defined above.)
And a dicarboxylic acid monoester derivative represented by the following general formula (2)

(In the formula, R ³ represents a hydrogen atom or a methyl group.)
The following general formula (3), characterized by reacting with hydroxyethyl (meth) acrylate represented by

(Wherein R ¹ , R ³ , Y, Z and n are as defined above.)
The manufacturing method of the acrylic ester derivative shown by these.   The method for producing an acrylate derivative according to claim 3, wherein n is 1 in the general formulas (1) and (3).