JP7052612B2 - (Meta) acrylic acid ester and its manufacturing method - Google Patents

Description

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

In general, (meth) acrylic acid esters are useful in a wide range of applications such as plastics, paints, adhesives, paper processing agents, fiber oils, lubricating oil additives, building sealants, and inks. Further, as a resist polymer used in ArF excimer laser lithography, an acrylic polymer transparent to light having a wavelength of 193 nm has been attracting attention. In recent years, as a resist composition that can suitably cope with shortening of the wavelength of irradiation light and miniaturization of a pattern, a polymer in which an acid desorbing group is desorbed by the action of an acid to become alkali-soluble, and a photoacid generator are used. A so-called chemically amplified resist composition containing it has been proposed, and its development and improvement are being promoted. As a tertiary (meth) acrylic acid ester useful as a monomer having an acid desorption group, cycloalkyl (meth) acrylate is known (Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2015-141353 Japanese Unexamined Patent Publication No. 2006-104169

In recent years, the miniaturization of pattern formation by lithography has been rapidly progressing, and the development of a resist material capable of further improving various lithography characteristics such as pattern formability and Rheinwidusroughness (LWR) has been eagerly desired. By increasing the hydrophobicity of the resist material, the pattern-forming property and LWR at the time of forming the resist pattern by lithography can be improved, and for that purpose, a monomer having a larger hydrophobicity is useful.
An object of the present invention is to provide a (meth) acrylic acid ester having excellent hydrophobicity and a method for producing the same.

The present invention has the following aspects.
[1] A (meth) acrylic acid ester represented by the following formula (1).

[In formula (1), R ¹ is a hydrogen atom or a methyl group, R ³ is a linear or branched alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and R ²¹ , R ²² and R ²³ are independent of each other. In addition, a hydrogen atom, a linear or branched alkyl group, or a cycloalkyl group, at least two are linear or branched alkyl groups or cycloalkyl groups, and Z ¹ has 1 to 1 carbon atoms. A substituted or unsubstituted divalent chain hydrocarbon group of 20, a substituted or unsubstituted divalent cyclic hydrocarbon group having 1 to 20 carbon atoms, which may have a hetero atom, or a simple group. Bond, Z ² is a divalent chain hydrocarbon group having 1 to 12 carbon atoms, and Z ³ is a hetero with 3 to 10 carbon atoms together with the carbon atom to which (R ²¹ R ²² R ²³ ) C- is bonded. An atomic group forming a cyclic hydrocarbon group which may have an atom, n is an integer of 0 to 3, and m is an integer of 1 to 18. ]
[2] A ketone compound represented by the following formula (2) is reacted with an alkyl metal compound represented by the following formula (3) to obtain a hydroxy compound represented by the following formula (4).
A method for producing a (meth) acrylic acid ester, which comprises reacting the hydroxy compound with a (meth) acrylic acid chloride to obtain a (meth) acrylic acid ester represented by the following formula (5).

In formula (2), R ³ is a linear or branched alkyl group, cycloalkyl group, aryl group or aralkyl group, and Z ³ is a hetero with 3 to 10 carbon atoms together with a carbon atom to which an oxygen atom is bonded. An atomic group forming a cyclic hydrocarbon group which may have an atom, m is an integer of 1 to 18.
In formula (3), R ²¹ , R ²² , and R ²³ are independently hydrogen atoms, linear or branched alkyl groups, or cycloalkyl groups, and at least two are linear or branched. It is an alkyl group or a cycloalkyl group, and M ¹ is Li or Mg X (X is a halogen atom).
In Eq. (4), R ³ , Z ³ , and m are the same as Eq. (2), and R ²¹ , R ²² , and R ²³ are the same as Eq. (3).
In formula (5), R ¹ is a hydrogen atom or a methyl group, R ³ , Z ³ , and m are the same as in formula (2), and R ²¹ , R ²² , and R ²³ are the same as in formula (3). be.
[3] The ester compound represented by the following formula (6) is reacted with the compound represented by the following formula (7) to obtain a hydroxy compound represented by the following formula (4).
A method for producing a (meth) acrylic acid ester, which comprises reacting the hydroxy compound with a (meth) acrylic acid chloride to obtain a (meth) acrylic acid ester represented by the following formula (5).

In formula (6), R ²¹ , R ²² , and R ²³ are independently hydrogen atoms, linear or branched alkyl groups, or cycloalkyl groups, and at least two are linear or branched. It is an alkyl group or a cycloalkyl group, and R ¹¹ is a linear or branched alkyl group or a cycloalkyl group.
In formula (7), R ³ is a linear or branched alkyl group, cycloalkyl group, aryl group or aralkyl group, and Y ¹ is a linear or branched alkylene group having 2 to 9 carbon atoms or cyclo. The alkylene group, M ² and M ³ are independently MgX (X is a halogen atom), and m is an integer of 1 to 18.
In equation (4), R ²¹ , R ²² , and R ²³ are the same as equation (6), R ³ and m are the same as equation (7), and Z ³ is (R ²¹ R ²² R ²³ ). It is an atomic group forming a cyclic hydrocarbon group which may have a heteroatom having 3 to 10 carbon atoms together with a carbon atom to which C- is bonded.
In formula (5), R ¹ is a hydrogen atom or a methyl group, R ²¹ , R ²² and R ²³ are the same as formula (6), R ³ and m are the same as formula (7), and Z. ³ is the same as the equation (4).

According to the present invention, a (meth) acrylic acid ester having excellent hydrophobicity can be obtained.

The definitions of the following terms apply throughout the specification and claims.
As used herein, "(meth) acrylic acid" means acrylic acid or methacrylic acid.
In the present specification, the compound represented by the formula (1) is referred to as compound (1). Compounds represented by other formulas are also described in the same manner.

<(Meta) acrylic acid ester>
The (meth) acrylic acid ester of the present invention is a compound (1) represented by the following formula (1). Compound (1) is useful as a monomer having an acid desorption group.

In formula (1), R ¹ is a hydrogen atom or a methyl group.
R ³ is a linear or branched alkyl group, cycloalkyl group, aryl group or aralkyl group. m is an integer from 1 to 18.
R ³ is a substituent bonded to the carbon atom constituting Z ³ , and m is the number of substituents (R ³ ) bonded to Z ³ . When m is 2 or more, the plurality of ^R3s bonded to ^Z3 may be the same or different from each other. Two ^R3s may be bonded to the same carbon atom.
Examples of the linear or branched alkyl group as R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, a t-butyl group and the like. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the aryl group include an alkylphenyl group such as a phenyl group and a 4-methylphenyl group, a dimethylphenyl group and a naphthyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. Among these, from the viewpoint of easiness of synthesis ^, R3 is preferably a methyl group, an ethyl group, a propyl group or an isopropyl group.
m is preferably 1 to 10 from the viewpoint of ease of synthesis, and more preferably 1 to 4.

R ²¹ , R ²² , and R ²³ are independently hydrogen atoms, linear or branched alkyl groups, or cycloalkyl groups, and at least two are linear or branched alkyl or cycloalkyl groups. Is.
Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, a t-butyl group and the like.
Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.
Among these, from the viewpoint of ease of synthesis, one of R ²¹ , R ²² , and R ²³ is a hydrogen atom and the other two are methyl groups, or all of R ²¹ , R ²² , and R ²³ are methyl groups. Is preferable.

Z ¹ may have a substituted or unsubstituted divalent chain hydrocarbon group having 1 to 20 carbon atoms and a substituted or unsubstituted heteroatom having 1 to 20 carbon atoms. It is a cyclic hydrocarbon group, or a single bond.
When Z ¹ is a divalent chain hydrocarbon group, it may be linear or branched. The divalent chain hydrocarbon group is preferably an alkylene group. Examples of the substituent include -O-, -S-, -NH-, and -PH-. The number of carbon atoms is preferably 1 to 10, and more preferably 1 to 6.
When Z ¹ is a divalent cyclic hydrocarbon group, it may be monocyclic or polycyclic. As the cyclic hydrocarbon group, a cyclic saturated hydrocarbon group is preferable. Examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. A substituent may be bonded to a carbon atom constituting the ring. Examples of the substituent include a linear or branched alkyl group having 1 to 10 carbon atoms.
Z ¹ is preferably a single bond in that it enhances hydrophobicity while ensuring good solubility in the organic solvent used as the resist solvent.

Z ² is a divalent chain hydrocarbon group having 1 to 12 carbon atoms. It may be linear or branched. The alkylene group is preferable as the chain hydrocarbon group. The number of carbon atoms is preferably 1 to 6, and more preferably 1 to 3.
n is an integer of 0 to 3, preferably 0 to 2, more preferably 0 or 1.

Z ³ is an atomic group forming a cyclic hydrocarbon group which may have a heteroatom having 3 to 10 carbon atoms together with a carbon atom to which (R ²¹ R ²² R ²³ ) C- is bonded. be. The cyclic hydrocarbon group may be monocyclic or polycyclic. The cyclic hydrocarbon group is preferably a cyclic hydrocarbon group composed of a hydrocarbon (having no heteroatom).
The carbon number of the cyclic hydrocarbon group also includes the carbon atom to which (R ²¹ R ²² R ²³ ) C- is bonded.
Examples of the cyclic hydrocarbon group consisting of a monocyclic hydrocarbon having 3 to 10 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, and a cyclopentenyl. Examples thereof include a group, a cyclohexenyl group, a cyclooctadienyl group and the like. Among these, a cyclopentyl group and a cyclohexyl group are preferable from the viewpoint of availability.
Examples of the cyclic hydrocarbon group composed of a polycyclic hydrocarbon having 3 to 10 carbon atoms include a bicyclo [4.3.0] nonanyl group, a naphthalenyl group, a decahydronaphthalenyl group, a boronyl group, an isobornyl group, and a norbornyl group. Examples include a group, an adamantyl group, a noradamantyl group and the like. Among these, a norbornyl group and an adamantyl group are preferable from the viewpoint of availability.

Preferred embodiments of compound (1) include the following.
R ¹ is a hydrogen atom or a methyl group, and Z ³ is an atomic group forming a cyclopentyl group, a cyclohexyl group, a norbornyl group or an adamantyl group together with a carbon atom to which C- is bonded (R ²¹ R ²² R ²³ ). Yes, R ³ is one or more selected from the group consisting of a methyl group, an ethyl group, a propyl group and an isopropyl group, m is an integer of 1 to 4, and 1 of R ²¹ , R ²² and R ²³ . A compound in which one is a hydrogen atom and the remaining two are methyl groups, or all of R ²¹ , R ²² , and R ²³ are methyl groups, Z ¹ is a single bond, and n = 0.

<Manufacturing method of (meth) acrylic acid ester>
[First aspect]
The hydroxy compound (4) represented by the following formula (4) is obtained by reacting the ketone compound (2) represented by the following formula (2) with the alkyl metal compound (3) represented by the following formula (3). The (meth) acrylic acid ester is obtained by reacting the hydroxy compound (4) with the (meth) acrylic acid chloride to obtain the (meth) acrylic acid ester (5) represented by the following formula (5). Manufacturing method.

In the formulas (2) to (5), R ¹ , R ³ , R ²¹ , R ²² , R ²³ , Z ³ , and m in the formula (1) include R ¹ , R ³ , and R ²¹ , in the formula (1). Same as R ²² , R ²³ , Z ³ , and m.
In the formulas (2) and (4), the carbon atom bonded to the oxygen atom corresponds to the carbon atom to which (R ²¹ R ²² R ²³ ) C- is bonded in the formula (1).
In formula (3), M ¹ is Li or MgX (X is a halogen atom).
Formula (5) corresponds to a compound in formula (1) in which Z ¹ is a single bond and n = 0.

In the reaction between the compound (2) and the compound (3), the amount of the compound (3) used is not particularly limited, but from the viewpoint of obtaining the compound (4) in good yield, 0. 5 mol or more is preferable, 0.8 mol or more is more preferable, and 1.0 mol or more is further preferable. Further, from the viewpoint of suppressing a side reaction and a load on the treatment step after the reaction, 2 mol or less is preferable, 1.8 mol or less is more preferable, and 1.5 mol or less is further preferable. ..

An inorganic compound may be added from the viewpoint of obtaining the compound (4) in good yield in the reaction between the compound (2) and the compound (3). Examples of the inorganic compound include lithium chloride, zinc chloride, cerium chloride, iron chloride, lanthanum trichloride bislithium chloride complex and the like.
The amount of the inorganic compound used is preferably 0.01 mol or more, more preferably 0.1 mol or more, per 1 mol of the ketone compound (2) from the viewpoint of reaction yield. Further, from the viewpoint of suppressing the load on the treatment step after the reaction, 2.0 mol or less is preferable, and 1.5 mol or less is more preferable.

It is preferable to use a solvent in the reaction between the compound (2) and the compound (3). The solvent is not particularly limited as long as it is a solvent that does not react with the compound (3). Examples thereof include aromatic solvents such as toluene and xylene: hydrocarbon solvents such as hexane, heptane, octane and cyclohexane: ether solvents such as diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran and dioxane. .. One of these solvents may be used alone, or two or more of them may be mixed and used. The amount of the solvent used can be set as appropriate.
The reaction temperature of the compound (2) and the compound (3) may be the reaction temperature in a normal reaction using an alkyl metal compound. From the viewpoint of shortening the reaction time, −100 ° C. or higher is preferable, and −80 ° C. or higher is more preferable. From the viewpoint of suppressing problems such as side reactions, 65 ° C. or lower is preferable, and 45 ° C. or lower is more preferable.
The reaction time varies depending on the reaction temperature and the like, and may be appropriately determined. For example, about 0.5 to 20 hours is preferable.

The compound (4) obtained by the reaction between the compound (2) and the compound (3) may be purified. The purification method of the compound (4) is performed by taking into consideration the physical characteristics of the product, raw materials, the type and amount of the alkyl metal compound (3) and the inorganic compound, the type of the solvent, etc., and washing with alkaline water, washing with water, distillation, crystallization, and filtration. Etc., known purification methods can be appropriately combined.

Compound (5) is obtained by reacting compound (4) with (meth) acrylate acid chloride.
As the (meth) acrylate acid chloride, a commercially available product or a separately synthesized product may be used. The amount of the (meth) acrylate compound used is not particularly limited, but is preferably 0.5 mol or more, preferably 0.7 mol or more, per mol of the compound (4) from the viewpoint of obtaining the compound (5) in good yield. Is more preferable, and 0.9 mol or more is further preferable. Further, in terms of preventing polymerization derived from the (meth) acrylate product, 3 mol or less is preferable, 2.5 mol or less is more preferable, and 2 mol or less is further preferable.

A base may be added from the viewpoint of obtaining the compound (5) in good yield in the reaction between the compound (4) and the (meth) acrylic acid chloride. Examples of bases include n-butyllithium, s-butyllithium, t-butyllithium, methylmagnesium bromide, t-butylmagnesium chloride, triethylamine, 4-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0. ] -7-Undesen and the like.
The amount of the base used is preferably 0.1 mol or more, more preferably 0.5 mol or more, per 1 mol of the compound (4) from the viewpoint of the reaction yield. Further, from the viewpoint of suppressing the load on the treatment step after the reaction, 3 mol or less is preferable and 2 mol or less is more preferable per 1 mol of the compound (4).

A solvent may be used in the reaction of compound (4) with the (meth) acrylate acid chloride. The solvent is not particularly limited as long as it is a solvent that does not react with the (meth) acrylate acid chloride. Examples thereof include aromatic solvents such as toluene and xylene: hydrocarbon solvents such as hexane, heptane, octane and cyclohexane: ether solvents such as diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran and dioxane. .. One of these solvents may be used alone, or two or more of them may be mixed and used. The amount of the solvent used can be set as appropriate.

In order to suppress the polymerization in the reaction between the compound (4) and the (meth) acrylic acid chloride, a polymerization inhibitor may be present in the reaction system. The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone monomethyl ether, hydroquinone, 4-hydroxy-2,2,6,6,-tetramethylpiperidin-N-oxyl, phenothiazine, and copper salt. These may be used alone or in combination of two or more.

The reaction temperature in the step of reacting the compound (4) with the (meth) acrylic acid chloride may be any temperature as long as it is used for ordinary esterification. In terms of shortening the reaction time, −100 ° C. or higher is preferable, and −80 ° C. or higher is more preferable. Further, from the viewpoint of suppressing problems such as side reactions and polymerization, 65 ° C. or lower is preferable, and 45 ° C. or lower is more preferable.
The reaction time varies depending on the reaction temperature and the like, and may be appropriately determined. For example, about 0.5 to 20 hours is preferable.

It is preferable to purify the compound (5) obtained by reacting the compound (4) with the (meth) acrylate acid chloride. As the purification method of the compound (5), a known purification method such as alkaline washing, washing with water, distillation, crystallization, filtration, etc. is used in consideration of the physical characteristics of the product, the raw material, the type and amount of the base, the type of the solvent, and the like. It can be combined as appropriate.

[Second aspect]
The ester compound (6) represented by the following formula (6) is reacted with the compound (7) represented by the following formula (7) to obtain the hydroxy compound (4) represented by the formula (4). Then, the hydroxy compound (4) is reacted with the (meth) acrylic acid chloride to obtain the (meth) acrylic acid ester (5) represented by the above formula (5), and the (meth) acrylic acid ester is produced. Method.

In the formulas (6) and (7), R ³ , R ²¹ , R ²² , R ²³ , and m are the same as R ³ , R ²¹ , R ²² , R ²³ , and m in the formula (1), including preferred embodiments. Is.
In formula (6), R ¹¹ is a linear or branched alkyl group or a cycloalkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, a t-butyl group and the like. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Among these, a methyl group, an ethyl group, a propyl group and an isopropyl group are preferable from the viewpoint of easy availability.

In the formula (7), Y ¹ is a linear or branched alkylene group having 2 to 9 carbon atoms or a cycloalkylene group, and M ² and M ³ are independently Mg X (X is a halogen atom). ..
Examples of the alkylene group of Y ¹ include an ethylene group, a propylene group, an isopropylene group, a butylene group, a pentylene group and a hexylene group. Examples of the cycloalkylene group include a cyclohexylene group and the like. Among these, a butylene group and a pentylene group are preferable from the viewpoint of easy availability.

In the reaction between the compound (6) and the compound (7), the amount of the compound (7) used is not particularly limited, but from the viewpoint of obtaining the compound (4) in good yield, 0. 5 mol or more is preferable, 0.8 mol or more is more preferable, and 1.0 mol or more is further preferable. Further, from the viewpoint of suppressing a side reaction and a load on the treatment step after the reaction, 5 mol or less is preferable, 4 mol or less is more preferable, and 3 mol or less is further preferable.

A solvent may be used in the reaction between the compound (6) and the compound (7). The solvent is not particularly limited as long as it is a solvent that does not react with the compound (7). Examples thereof include aromatic solvents such as toluene and xylene: hydrocarbon solvents such as hexane, heptane, octane and cyclohexane: ether solvents such as diethyl ether, diisopropyl ether, t-butyl methyl ether, tetrahydrofuran and dioxane. .. One of these solvents may be used alone, or two or more of them may be mixed and used. The amount of the solvent used can be set as appropriate.

The reaction temperature of the compound (6) and the compound (7) may be the temperature in a normal cyclization reaction using the compound (7). In terms of shortening the reaction time, −100 ° C. or higher is preferable, and −80 ° C. or higher is more preferable. Further, 100 ° C. or lower is preferable, and 80 ° C. or lower is more preferable, in terms of suppressing problems such as side reactions.
The reaction time varies depending on the reaction temperature and the like, and may be appropriately determined. For example, about 0.5 to 30 hours is preferable.

The compound (4) obtained by the reaction of the compound (6) and the compound (7) may be purified.
As the purification method, known purification methods such as alkaline water washing, water washing, distillation, crystallization, and filtration can be appropriately combined in consideration of the physical characteristics of the product, the type and amount of the raw material, the type of solvent, and the like.
The step of reacting the compound (4) with the (meth) acrylate acid chloride to obtain the compound (5) can be carried out in the same manner as in the first aspect.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Reaction tracking was performed by gas chromatography.

<Synthesis Example 1: Synthesis of compound (4)>
In this example, t-butylmagnesium chloride was used as the compound (3) and reacted with the compound (2) to synthesize the compound (4).
To a glass flask, 5.4684 g (22 mmol) of cerium chloride and 12.2 mL of tetrahydrofuran were added, and the mixture was stirred at room temperature for 1.8 hours under a nitrogen flow. The mixture was cooled to 0 ° C., 12.2 mL of t-butylmagnesium chloride (23 mass% tetrahydrofuran solution, 24 mmol) was added, and the mixture was stirred for 1 hour. Subsequently, the mixture was cooled to −40 ° C., 2.815 g (22 mmol) of 2-methylcyclopentanone was added dropwise, and the mixture was stirred at −25 ° C. for 21 hours. The reaction yield was 48%. After adding 20 mL of saturated ammonium chloride aqueous solution and 20 mL of ethyl acetate and separating the liquids, the aqueous layer was extracted twice with 20 mL of ethyl acetate. To the organic layer, 20 mL of a saturated aqueous sodium hydrogen carbonate solution and then 10 mL of a saturated saline solution were added and washed. After drying with magnesium sulfate, the solvent was distilled off. The obtained crude product was distilled to obtain 399.3 mg of 2-methyl-t-butylcyclopentanol.

<Synthesis Example 2: Synthesis of compound (4)>
In this example, t-butyllithium was used as the compound (3) and reacted with the compound (2) to synthesize the compound (4).
To a glass flask, 8.0 mL of t-butyllithium (18 mass% pentane solution, 15 m mmol) and 5 mL of tetrahydrofuran were added, and the mixture was cooled to −50 ° C. under a nitrogen flow. Subsequently, 504.2 mg (5.1 mmol) of 2-methylcyclopentanone dissolved in 2.5 mL of tetrahydrofuran was added dropwise, and the mixture was stirred for 1 hour. The yield of 2-methyl-t-butylcyclopentanol was 30%.

<Synthesis Example 3: Synthesis of compound (4)>
In this example, compound (6) was reacted with compound (7) to synthesize compound (4).
To a glass flask, 6.0290 g (248 mmol) of shaving magnesium and 100 mL of tetrahydrofuran were added, and 12.5 mL (92 mmol) of 1,4-dibromopentane dissolved in 100 mL of tetrahydrofuran was added dropwise at room temperature in 1.2 hours. bottom. Then, the mixture was stirred for 2.8 hours. The mixture was cooled to −5 ° C., and 10.9 mL (82 mmol) of methyl pivalate dissolved in 84 mL of tetrahydrofuran was added dropwise over 1 hour. Subsequently, the temperature was raised to 0 ° C., the mixture was stirred for 0.6 hours, and then stirred overnight at room temperature. The yield of 2-methyl-t-butylcyclopentanol was 72%.

<Synthesis Example 4: Synthesis of compound (4)>
In Synthesis Example 1, 3-methyl-t-butylcyclopentanol was obtained in the same manner as in Synthesis Example 1 except that 3-methylcyclopentanone was used instead of 2-methylcyclopentanone.

<Synthesis Example 5: Synthesis of 1,4-dibromo-2-methylbutane>
2-Methyl-1,4-butanediol was synthesized by the method described in paragraphs 0032 to 0033 of JP2011-11139.
To a glass flask, 101.2 g (766 mmol) of methyl succinic acid was added, and 400 mL of acetyl chloride was added dropwise. After stirring for 2 hours, the mixture was concentrated and purified by vacuum distillation to obtain 83.6 g of methylsuccinic anhydride.
26.3 g (705 mmol) of lithium aluminum hydride and 800 mL of tetrahydrofuran were added to a glass flask, and 41.0 g (359 mmol) of methyl succinic anhydride dissolved in 200 mL of tetrahydrofuran was added dropwise over 1 hour. After stirring for 2 days, a mixture of 100 mL of tetrahydrofuran and 100 mL of water was added dropwise, and 500 mL of tetrahydrofuran was added to the obtained slurry. After drying with sodium sulfate, the solvent was distilled off. The obtained crude product was distilled to obtain 28.5 g of 2-methyl-1,4-butanediol.
To a glass flask, 5.5698 g (53.5 mmol) of 2-methyl-1,4-butanediol and 72.18 g (428 mmol) of 48% hydrobromic acid were added, and the mixture was stirred at 90 ° C. for 5 hours. After adding 100 mL of toluene and separating the liquids, the aqueous layer was extracted once with 100 mL of toluene. 50 mL of a saturated aqueous sodium hydrogen carbonate solution and then 25 mL of a saturated saline solution were added to the organic layer for washing. After drying with magnesium sulfate, the solvent was distilled off to obtain 8.2690 g of 1,4-dibromo-2-methylbutane.

<Synthesis Example 6: Synthesis of Compound (4)>
In Synthesis Example 3, the same procedure as in Synthesis Example 3 was carried out except that 1,4-dibromo-2-methylbutane was used instead of 1,4-dibromopentane to obtain 3-methyl-t-butylcyclopentanol. ..

<Synthesis Example 7: Synthesis of Compound (4)>
In Synthesis Example 3, the same procedure as in Synthesis Example 3 was carried out except that methyl isobutyrate was used instead of methyl pivalate to obtain 2-methyl-isopropylcyclopentanol.

<Example 1: Production of compound (5)>
In this example, compound (5) was produced by reacting compound (4) with methacrylic acid chloride.
To a glass flask, 199.3 mg (1.3 mmol) of 2-methyl-t-butylcyclopentanol obtained in Synthesis Example 3 and 2.6 mL of tetrahydrofuran were added, and the mixture was cooled to −40 ° C. under a nitrogen flow. 1.12 mL of n-butyllithium (15 mass% hexane solution, 1.8 mmol) was added dropwise, and the mixture was stirred at 0 ° C. for 1 hour. The mixture was cooled to −40 ° C. again, 225 μL (2.3 mmol) of methacrylic acid chloride was added dropwise, and the mixture was stirred at 0 ° C. for 2 hours. 1.1 g of a 10 mass% lithium hydroxide aqueous solution was added, and the mixture was stirred at 50 ° C. for 1 hour and then separated. The aqueous layer was extracted twice with 5 mL of ethyl acetate, and 5 mL of a saturated aqueous sodium hydrogen carbonate solution and then 5 mL of saturated brine were added to the organic layer for washing. After drying with magnesium sulfate, the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography to obtain 234.0 mg of the target compound.
¹ It was confirmed that the compound obtained by 1 H-NMR analysis was 2-methyl-t-butylcyclopentyl methacrylate (the structural formula is shown in Table 1).
^{1 1} H NMR (270 MHz, CDCl ₃ ) (cis + trans): δ6.05 ppm (m, 1H) 5.48 ppm (m, 1H) 1.94 ppm (s, 3H) 2.68-1.30 ppm (m, 7H), 1.01 ppm (s, 9H), 0.98 ppm (d, 3H).

<Example 2: Production of compound (5)>
In Example 1, the same procedure as in Example 1 was carried out except that 3-methyl-t-butylcyclopentanol obtained in Synthesis Example 4 was used instead of 2-methyl-t-butylcyclopentanol. Compound was obtained.
¹ It was confirmed that the compound obtained by 1 H-NMR analysis was 3-methyl-t-butylcyclopentyl methacrylate (the structural formula is shown in Table 1).
^{1 1} H NMR (270 MHz, CDCl ₃ ) (cis + trans): δ6.02 ppm (m, 1H), 5.47 ppm (m, 1H), 1.92 ppm (s, 3H), 2.78-1.41 ppm (m, 7H), 0.99ppm (s, 9H), 1.06, 0.98ppm (d, 3H).

<Example 3: Production of compound (5)>
Example 3 is a reference example.
In Example 1, the compound of interest was obtained in the same manner as in Example 1 except that 2-methyl-isopropylcyclopentanol obtained in Synthesis Example 7 was used instead of 2-methyl-t-butylcyclopentanol. Got
¹ It was confirmed that the compound obtained by 1 H-NMR analysis was 2-methyl-isopropylcyclopentyl methacrylate (the structural formula is shown in Table 1).
^{1 1} H NMR (270 MHz, CDCl ₃ ) (cis + trans): δ 5.60 ppm (m, 1H) 5.45 ppm (m, 1H) 1.90 ppm (s, 3H), 2.57-1.23 ppm (m, 8H), 1.03ppm (d, 3H), 0.98 (d, 3H), 0.95ppm (d, 3H).

<Comparative Example 1>
T-Butylcyclopentyl methacrylate (the structural formula is shown in Table 1) was synthesized by the method described in paragraphs 0405 to 0409 of JP2015-141353A.
Cyclopentanone (8.4 g) and tetrahydrofuran (200 mL) were added to the three-necked flask, and the mixture was cooled to 0 ° C. 166 mL of lanthanum trichloride bislithium chloride complex (0.6 mol / L tetrahydrofuran solution) was added dropwise at 0 ° C., and the mixture was stirred for 30 minutes. Then, 100 mL of t-butylmagnesium bromide (1.0 mol / L tetrahydrofuran solution) was added dropwise at 0 ° C., and the mixture was stirred for 2 hours. Subsequently, 100 mL of a saturated aqueous solution of ammonium chloride was added, the aqueous phase was extracted twice with 200 mL of ethyl acetate, the organic phases were combined, washed with a saturated aqueous sodium hydrogen carbonate solution and a saturated brine, and then the solvent was distilled off. The obtained crude product was purified by silica gel chromatography to obtain 12.6 g of 1-t-butylcyclopentanol (yield 88%).
1-t-Butylcyclopentanol (12.6 g) was added to 200 mL of tetrahydrofuran and cooled to −40 ° C. 55 mL of normal butyllithium (1.6 mol / L hexane solution) was added dropwise at −40 ° C., and the mixture was stirred at 0 ° C. for 1 hour. After cooling the reaction solution to −40 ° C. again, 8.4 g of methacrylic acid chloride was added dropwise, and the temperature was raised to room temperature. After stirring for 1 hour, the mixture was cooled to 0 ° C. and 100 mL of water was added. The aqueous phase was extracted twice with 200 mL of ethyl acetate, the organic phases were combined, washed with water and saturated brine, and the solvent was distilled off. The obtained crude product was purified by silica gel chromatography to obtain t-butylcyclopentyl methacrylate (13.2 g) (yield 86%).

<Comparative Example 2>
In Comparative Example 1, isopropylmagnesium bromide was used instead of t-butylmagnesium bromide in the same manner as in Comparative Example 1 to obtain isopropylcyclopentyl methacrylate (the structural formula is shown in Table 1).

<Test example: Evaluation of hydrophobicity>
Using the methacrylic acid esters obtained in the above Examples and Comparative Examples as samples and silica gel surface-treated with a hydrocarbon group having 18 carbon atoms as a column packing material, reverse phase liquid chromatography measurement was performed under the following conditions. ..
[Measurement condition]
Equipment: Waters, liquid chromatography system ACQUITY UPLC H-Class (product name).
Column: ACQUITY UPLC BEH C18 (product name) manufactured by Waters, 1.7 μm (particle size).
Moving layer: acetonitrile / water = 3/1.
Flow rate: 0.5 mL / min.
UV detection wavelength: 220 nm.

According to OECD Guidelines for the Testing of Chemicals, Section 1 (Test No. 117), in reverse phase liquid chromatography using silica gel surface treated with long chain hydrocarbon groups (eg C8, C18) as filler, the sample moves. It moves on silica gel (stationary phase) hydrocarbons depending on the solvent of the phase. The sample is held on the stationary phase by the partition coefficient between the stationary phase (hydrocarbon group) and the mobile phase (water). Therefore, hydrophilic compounds elute faster, and hydrophobic compounds elute later. That is, it can be determined that the sample having a longer holding time is superior in hydrophobicity.
Table 2 shows the measurement results of the holding time.

As shown in Table 2, in the liquid chromatography using the 2-methyl-t-butylcyclopentyl methacrylate obtained in Example 1 as a sample, two isomers (indicated as (i) and (ii) in the table). Separated, and the retention time was 1.79 minutes and 1.93 minutes, respectively.
The 2-methyl-t-butylcyclopentyl methacrylate and 3-methyl-t-butylcyclopentyl methacrylate obtained in Examples 1 and 2 have a longer retention time than the t-butyl cyclopentyl methacrylate obtained in Comparative Example 1 and are excellent in hydrophobicity. Was recognized.
Similarly, it was found that the 2-methyl-isopropylcyclopentyl methacrylate obtained in Example 3 had a longer retention time than the isopropylcyclopentyl methacrylate obtained in Comparative Example 2 and was excellent in hydrophobicity.

The (meth) acrylic acid ester provided in the present invention has excellent hydrophobicity and is useful for a wide range of applications such as plastics and paints. It is also useful as a raw material for semiconductor resists to improve lithography characteristics.

Claims (3)

A (meth) acrylic acid ester represented by the following formula (1).

[In the formula, R ¹ is a hydrogen atom or a methyl group, R ³ is a linear or branched alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and R ²¹ , R ²² and R ²³ are independent and direct. It is a chain or branched alkyl group or cycloalkyl group, and Z ¹ is a substituted or unsubstituted divalent chain hydrocarbon group having 1 to 20 carbon atoms, substituted with 1 to 20 carbon atoms. Alternatively, an unsubstituted, divalent cyclic hydrocarbon group which may have a hetero atom, or a single bond, Z ² is a divalent chain hydrocarbon group having 1 to 12 carbon atoms, and Z ³ is a divalent chain hydrocarbon group. (R ²¹ R ²² R ²³ ) N is an atomic group forming a monocyclic cyclic hydrocarbon group having 3 to 10 carbon atoms and optionally having a hetero atom together with the carbon atom to which C- is bonded. An integer of 0 to 3 and m is an integer of 1 to 18. ] The ketone compound represented by the following formula (2) is reacted with the alkyl metal compound represented by the following formula (3) to obtain a hydroxy compound represented by the following formula (4).
A method for producing a (meth) acrylic acid ester, which comprises reacting the hydroxy compound with a (meth) acrylic acid chloride to obtain a (meth) acrylic acid ester represented by the following formula (5).

[In the formula, R ³ is a linear or branched alkyl group, cycloalkyl group, aryl group or aralkyl group, and Z ³ is a hetero atom having 3 to 10 carbon atoms together with a carbon atom to which an oxygen atom is bonded. An atomic group forming a monocyclic cyclic hydrocarbon group, m is an integer of 1 to 18. ]

[In the formula, R ²¹ , R ²² , and R ²³ are independently linear or branched alkyl groups or cycloalkyl groups, and M ¹ is Li or Mg X (X is a halogen atom). ]

[In the formula, R ³ , Z ³ , and m are the same as the formula (2), and R ²¹ , R ²² , and R ²³ are the same as the formula (3). ]

[In the formula, R ¹ is a hydrogen atom or a methyl group, R ³ , Z ³ , and m are the same as in formula (2), and R ²¹ , R ²² , and R ²³ are the same as in formula (3). ] The ester compound represented by the following formula (6) is reacted with the compound represented by the following formula (7) to obtain a hydroxy compound represented by the following formula (4).
A method for producing a (meth) acrylic acid ester, which comprises reacting the hydroxy compound with a (meth) acrylic acid chloride to obtain a (meth) acrylic acid ester represented by the following formula (5).

[In the formula, R ²¹ , R ²² , and R ²³ are independently linear or branched alkyl groups or cycloalkyl groups, and R ¹¹ is a linear or branched alkyl group or cyclo. It is an alkyl group. ]

[In the formula, R ³ is a linear or branched alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and Y ¹ is a linear or branched alkylene group having 2 to 9 carbon atoms or a cycloalkylene group. , M ² and M ³ are independently MgX (X is a halogen atom), and m is an integer of 1 to 18. ]

[In the formula, R ²¹ , R ²² and R ²³ are the same as the formula (6), R ³ and m are the same as the formula (7), and Z ³ is (R ²¹ R ²² R ²³ ) C-. It is an atomic group that forms a monocyclic cyclic hydrocarbon group having 3 to 10 carbon atoms and may have a heteroatom together with the carbon atom to which the atom is bonded. ]

[In the formula, R ¹ is a hydrogen atom or a methyl group, R ²¹ , R ²² and R ²³ are the same as the formula (6), R ³ and m are the same as the formula (7), and Z ³ is the same. It is the same as the equation (4). ]