JP2019172650A - (meth)acrylic acid ester and manufacturing method therefor - Google Patents

Abstract

To provide a (meth)acrylic acid ester excellent in hydrophobicity.SOLUTION: There is provided (meth)acrylic acid ester represented by the formula (1). Ris H or methyl: Ris alkyl, cycloalkyl, aryl or aralkyl; R, R, Rare each independently H, alkyl or cycloalkyl and at least 2 are not H; Zis C1 to 20 substituted/unsubstituted bivalent chain hydrocarbon, C1 to 20 substituted/unsubstituted hetero-containing or hetero-free bivalent cyclic hydrocarbon or a single bond; Zis C1 to 12 bivalent chain hydrocarbon, Zis an atom group forming C3 to 10 hetero-containing or hetero-free cyclic hydrocarbon together with C to which (RRR)C- is bound; n is an integer of 0 to 3; and m is an integer of 1 to 18.SELECTED DRAWING: None

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 variety of applications such as plastics, paints, pressure-sensitive adhesives, paper processing agents, textile oils, lubricating oil additives, architectural sealants, and inks. Further, as a resist polymer used in ArF excimer laser lithography, an acrylic polymer that is transparent to light having a wavelength of 193 nm has attracted attention. In recent years, as a resist composition that can be suitably used for shortening the wavelength of irradiation light and miniaturizing patterns, a polymer in which an acid-eliminable group is eliminated by the action of an acid and becomes alkali-soluble, and a photoacid generator A so-called chemically amplified resist composition is proposed, and its development and improvement are underway. Cycloalkyl (meth) acrylate is known as a tertiary (meth) acrylic ester useful as a monomer having an acid leaving group (Patent Documents 1 and 2).

Japanese Patent Laying-Open No. 2015-141353 JP 2006-104169 A

In recent years, pattern formation by lithography has been rapidly miniaturized, and development of a resist material that can improve various lithography characteristics such as pattern formability and line width roughness (LWR) more than ever is eagerly desired. By increasing the hydrophobicity of the resist material, it is possible to improve pattern formability and LWR at the time of forming a resist pattern by lithography. For this purpose, a monomer having higher hydrophobicity is useful.
An object of this invention is to provide the (meth) acrylic acid ester excellent in hydrophobicity, and its manufacturing method.

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

[In the 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, R ²¹ , R ²² and R ²³ are each independently And a hydrogen atom, a linear or branched alkyl group, or a cycloalkyl group, at least two are a linear or branched alkyl group or a cycloalkyl group, and Z ¹ has 1 to 20 substituted or unsubstituted divalent chain hydrocarbon groups, 1 to 20 carbon atoms, substituted or unsubstituted divalent cyclic hydrocarbon groups optionally having heteroatoms, or A bond, Z ² is a divalent chain hydrocarbon group having 1 to 12 carbon atoms, and Z ³ is a hetero atom having 3 to 10 carbon atoms together with the carbon atom to which (R ²¹ R ²² R ²³ ) C— is bonded. Cyclic charcoal which may have atoms An atomic group forming a hydrogen fluoride group, 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).
The manufacturing method of (meth) acrylic acid ester which makes the said hydroxy compound and (meth) acrylic acid chloride react, and obtains the (meth) acrylic acid ester represented by following formula (5).

In the formula (2), R ³ is a linear or branched alkyl group, cycloalkyl group, aryl group or aralkyl group, and Z ³ is a heterocycle having 3 to 10 carbon atoms together with the carbon atom to which the 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 each independently a hydrogen atom, a linear or branched alkyl group, or a cycloalkyl group, at least two of which are linear or branched An alkyl group or a cycloalkyl group, and M ¹ is Li or MgX (X is a halogen atom);
In formula (4), 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).
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). is there.
[3] An ester compound represented by the following formula (6) is reacted with a compound represented by the following formula (7) to obtain a hydroxy compound represented by the following formula (4).
The manufacturing method of (meth) acrylic acid ester which makes the said hydroxy compound and (meth) acrylic acid chloride react, and obtains the (meth) acrylic acid ester represented by following formula (5).

In formula (6), R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, a linear or branched alkyl group, or a cycloalkyl group, at least two of which are linear or branched 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, 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 each independently MgX (X is a halogen atom), and m is an integer of 1 to 18.
In formula (4), R ²¹ , R ²² and R ²³ are the same as in formula (6), R ³ and m are the same as in formula (7), and Z ³ is (R ²¹ R ²² R ²³ ). It is an atomic group that forms a cyclic hydrocarbon group that may have a heteroatom having 3 to 10 carbon atoms together with the 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 in Formula (6), R ³ and m are the same as in Formula (7), Z ³ is the same as equation (4).

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

The following definitions of terms apply throughout this specification and the claims.
In this specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid.
In this specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas.

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

In the 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 of 1-18.
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, plural R ³ bonded to Z ³ may be mutually the same or different. Two R ³ 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, and a t-butyl group. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the aryl group include a phenyl group, an alkylphenyl group such as 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 ease of synthesis, R ³ is preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group.
m is preferably 1 to 10 and more preferably 1 to 4 from the viewpoint of ease of synthesis.

R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, a linear or branched alkyl group, or a cycloalkyl group, and at least two are a linear or branched alkyl group or cycloalkyl group. It 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, and a t-butyl group.
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 remaining two are methyl groups, or all of R ²¹ , R ²² and R ²³ are methyl groups. Is preferred.

Z ¹ is a substituted or unsubstituted divalent chain hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted hetero atom having 1 to 20 carbon atoms, and optionally having a hetero atom. 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-. 1-10 are preferable and, as for carbon number, 1-6 are more preferable.
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 from the viewpoint of enhancing hydrophobicity while ensuring good solubility in an organic solvent used as a resist solvent.

Z ² is a divalent chain hydrocarbon group having 1 to 12 carbon atoms. It may be linear or branched. As the chain hydrocarbon group, an alkylene group is preferred. 1-6 are preferable and, as for carbon number, 1-3 are more preferable.
n is an integer of 0 to 3, preferably 0 to 2, and 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 the carbon atom to which (R ²¹ R ²² R ²³ ) C— is bonded. is there. The cyclic hydrocarbon group may be monocyclic or polycyclic. The cyclic hydrocarbon group is preferably a cyclic hydrocarbon group comprising a hydrocarbon (having no heteroatoms).
The carbon number of the cyclic hydrocarbon group includes a carbon atom to which (R ²¹ R ²² R ²³ ) C— is bonded.
Examples of the cyclic hydrocarbon group comprising a monocyclic hydrocarbon having 3 to 10 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclopentenyl Group, cyclohexenyl group, 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 comprising a polycyclic hydrocarbon having 3 to 10 carbon atoms include bicyclo [4.3.0] nonanyl group, naphthalenyl group, decahydronaphthalenyl group, bornyl group, isobornyl group, norbornyl. Group, adamantyl group, noradamantyl group and the like. Among these, a norbornyl group and an adamantyl group are preferable from the viewpoint of availability.

The following is mentioned as a preferable aspect of a compound (1).
R ¹ is a hydrogen atom or a methyl group, and Z ³ is an atomic group that forms a cyclopentyl group, a cyclohexyl group, a norbornyl group or an adamantyl group together with the carbon atom to which (R ²¹ R ²² R ²³ ) C— is bonded. 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 one 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.

<Method for producing (meth) acrylic acid ester>
[First embodiment]
The ketone compound (2) represented by the following formula (2) is reacted with an alkyl metal compound (3) represented by the following formula (3) to obtain a hydroxy compound (4) represented by the following formula (4). (Meth) acrylic acid ester obtained by reacting hydroxy compound (4) with (meth) acrylic acid chloride to obtain (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 , m include R ¹ , R ³ , R ²¹ , The 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 bonded to (R ²¹ R ²² R ²³ ) C— 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 which Z ¹ is a single bond and n = 0 in Formula (1).

  In the reaction of the compound (2) and the compound (3), the amount of the compound (3) used is not particularly limited. 5 mol or more is preferable, 0.8 mol or more is more preferable, and 1.0 mol or more is more preferable. Moreover, 2 mol or less per 1 mol of compound (2) is preferable, 1.8 mol or less is more preferable, and 1.5 mol or less is further more preferable from the point which suppresses the load to the processing process after a side reaction or reaction. .

In the reaction of the compound (2) and the compound (3), an inorganic compound may be added from the viewpoint of obtaining the compound (4) with good yield. 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 mol of the ketone compound (2) from the viewpoint of reaction yield. Moreover, from the point which suppresses the load to the process process after reaction, 2.0 mol or less is preferable and 1.5 mol or less is more preferable.

In the reaction of compound (2) and compound (3), it is preferable to use a solvent. The solvent is not particularly limited as long as it does not react with the compound (3). For example, 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 . These solvents may be used alone or in combination of two or more. The usage-amount of a solvent can be set suitably.
The reaction temperature between 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. 65 degreeC or less is preferable from the point which suppresses problems, such as a side reaction, and 45 degrees C or less is more preferable.
Since the reaction time varies depending on the reaction temperature and the like, it may be determined appropriately. For example, about 0.5 to 20 hours is preferable.

  You may refine | purify the compound (4) obtained by reaction of a compound (2) and a compound (3). The purification method of the compound (4) takes into account the physical properties of the product, the raw materials, the type and amount of the alkyl metal compound (3) and inorganic compound, the type of solvent, etc., washing with alkaline water, washing with water, distillation, crystallization, filtration The known purification methods such as can be combined as appropriate.

Compound (5) is obtained by reacting compound (4) with (meth) acrylic acid chloride.
The (meth) acrylic acid chloride may be a commercially available product or a separately synthesized product. Although the usage-amount of (meth) acrylic acid chloride is not specifically limited, From the point which obtains a compound (5) with a sufficient yield, 0.5 mol or more per 1 mol of compound (4) is preferable, and 0.7 mol or more Is more preferable, and 0.9 mol or more is more preferable. Further, in terms of preventing polymerization derived from (meth) acrylic acid chloride, it is preferably 3 mol or less, more preferably 2.5 mol or less, further preferably 2 mol or less, per mol of the compound (4).

In the reaction between the compound (4) and (meth) acrylic acid chloride, a base may be added from the viewpoint of obtaining the compound (5) with good yield. 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-undecene and the like.
As the usage-amount of a base, 0.1 mol or more is preferable with respect to 1 mol of compounds (4) from the point of reaction yield, and 0.5 mol or more is more preferable. Moreover, from the point which suppresses the load to the process process after reaction, 3 mol or less is preferable with respect to 1 mol of compound (4), and 2 mol or less is more preferable.

  In the reaction between the compound (4) and (meth) acrylic acid chloride, a solvent may be used. The solvent is not particularly limited as long as it does not react with (meth) acrylic acid chloride. For example, 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. . These solvents may be used alone or in combination of two or more. The usage-amount of a solvent can be set suitably.

  In order to suppress polymerization in the reaction between the compound (4) and (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, -tetramethylpiperidine-N-oxyl, phenothiazine, and a copper salt. These may be used alone or in combination of two or more.

The reaction temperature in the step of reacting compound (4) with (meth) acrylic acid chloride may be any temperature used in ordinary esterification. In terms of shortening the reaction time, −100 ° C. or higher is preferable, and −80 ° C. or higher is more preferable. Moreover, 65 degreeC or less is preferable and 45 degrees C or less is more preferable at the point which suppresses problems, such as a side reaction and superposition | polymerization.
Since the reaction time varies depending on the reaction temperature and the like, it may be determined appropriately. For example, about 0.5 to 20 hours is preferable.

  It is preferable to purify the compound (5) obtained by the reaction between the compound (4) and (meth) acrylic acid chloride. The purification method of the compound (5) is a known purification method such as alkaline water washing, water washing, distillation, crystallization, filtration, etc. in consideration of the physical properties of the product, the raw material, the type and amount of base, the type of solvent, etc. They can be combined as appropriate.

[Second embodiment]
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 above formula (4). Then, the hydroxy compound (4) and (meth) acrylic acid chloride are reacted to obtain the (meth) acrylic acid ester (5) represented by the formula (5). Method.

Equation (6), in ^{(7), R 3, R} 21, R 22, R 23, m is, ^R 3 a preferred embodiment be included in the formula ^(1), the same as ^{R 21, R 22, R 23} , m It is.
In the formula (6), R ¹¹ is a linear or branched alkyl group or a cycloalkyl group. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, 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 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 each independently MgX (X is a halogen atom). .
Examples of the alkylene group for 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. Among these, a butylene group and a pentylene group are preferable from the viewpoint of availability.

  In the reaction of the compound (6) and the compound (7), the amount of the compound (7) used is not particularly limited. 5 mol or more is preferable, 0.8 mol or more is more preferable, and 1.0 mol or more is more preferable. Moreover, 5 mol or less per 1 mol of compound (6) is preferable, 4 mol or less is more preferable, and 3 mol or less is further more preferable from the point which suppresses the load to the side reaction or the processing process after reaction.

  In the reaction between the compound (6) and the compound (7), a solvent may be used. A solvent will not be specifically limited if it is a solvent which does not react with a compound (7). For example, 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. . These solvents may be used alone or in combination of two or more. The usage-amount of a solvent can be set suitably.

The reaction temperature between the compound (6) and the compound (7) may be a 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. Moreover, 100 degrees C or less is preferable and 80 degrees C or less is more preferable at the point which suppresses problems, such as a side reaction.
Since the reaction time varies depending on the reaction temperature and the like, it may be determined appropriately. For example, about 0.5 to 30 hours is preferable.

You may refine | purify the compound (4) obtained by reaction of a compound (6) and a compound (7).
The purification method can be appropriately combined with known purification methods such as alkaline water washing, water washing, distillation, crystallization, and filtration in consideration of the physical properties of the product, the kind and amount of raw materials, the kind of solvent, and the like.
The step of reacting compound (4) and (meth) acrylic acid chloride to obtain compound (5) can be carried out in the same manner as in the first embodiment.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. The reaction was traced by gas chromatography.

<Synthesis Example 1: Synthesis of Compound (4)>
In this example, t-butylmagnesium chloride was used as compound (3) and reacted with compound (2) to synthesize compound (4).
To a glass flask were added 5.4684 g (22 mmol) of cerium chloride and 12.2 mL of tetrahydrofuran, 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., and 2.1815 g (22 mmol) of 2-methylcyclopentanone was added dropwise, stirred for 2.5 hours, and then stirred at −25 ° C. for 21 hours. The reaction yield was 48%. Saturated aqueous ammonium chloride solution (20 mL) and ethyl acetate (20 mL) were added for liquid separation, and the aqueous layer was extracted twice with ethyl acetate (20 mL). The organic layer was washed by adding 20 mL of a saturated aqueous sodium hydrogen carbonate solution and then 10 mL of saturated brine. 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 compound (3) and reacted with compound (2) to synthesize compound (4).
To a glass flask, 8.0 mL of t-butyllithium (18 mass% pentane solution, 15 mmol) and 5 mL of tetrahydrofuran were added and 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 stirred for 1 hour. The yield of 2-methyl-t-butylcyclopentanol was 30%.

<Synthesis Example 3: Synthesis of Compound (4)>
In this example, compound (4) was synthesized by reacting compound (6) with compound (7).
To a glass flask, 6.090 g (248 mmol) of shaved 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 over 1.2 hours. did. Thereafter, the mixture was stirred for 2.8 hours. After cooling to −5 ° C., 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., 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)>
The synthesis was performed in the same manner as in Synthesis Example 1 except that 3-methylcyclopentanone was used instead of 2-methylcyclopentanone to obtain 3-methyl-t-butylcyclopentanol.

<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 JP2011-111399A.
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 solution was concentrated and then purified by distillation under reduced pressure to obtain 83.6 g of methyl succinic anhydride.
To a glass flask, 26.3 g (705 mmol) of lithium aluminum hydride and 800 mL of tetrahydrofuran were added, 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 resulting 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, 5.568 g (53.5 mmol) of 2-methyl-1,4-butanediol and 72.18 g (428 mmol) of 48% hydrobromic acid were added and stirred at 90 ° C. for 5 hours. After adding toluene 100mL and liquid-separating, the aqueous layer was extracted once with 100mL toluene. The organic layer was washed by adding 50 mL of a saturated aqueous sodium hydrogen carbonate solution and then 25 mL of saturated brine. 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)>
The synthesis was performed in the same manner as in Synthesis Example 3 except that 1,4-dibromo-2-methylbutane was used in place of 1,4-dibromopentane to obtain 3-methyl-t-butylcyclopentanol. .

<Synthesis Example 7: Synthesis of Compound (4)>
The synthesis was performed in the same manner as in Synthesis Example 3 except that methyl isobutyrate was used instead of methyl pivalate in Synthesis Example 3 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 cooled to −40 ° C. under a nitrogen flow. n-Butyllithium 1.12mL (15 mass% hexane solution, 1.8mmol) was dripped, and it stirred at 0 degreeC for 1 hour. The mixture was again cooled to −40 ° C., 225 μL (2.3 mmol) of methacrylic acid chloride was added dropwise, and the mixture was stirred at 0 ° C. for 2 hours. After adding 1.1 g of 10 mass% lithium hydroxide aqueous solution and stirring at 50 degreeC for 1 hour, it liquid-separated. The aqueous layer was extracted twice with 5 mL of ethyl acetate, and the organic layer was washed with 5 mL of saturated aqueous sodium hydrogen carbonate solution and then 5 mL of saturated brine. After drying with magnesium sulfate, the solvent was distilled off. The resulting crude product was purified by silica gel column chromatography to obtain 234.0 mg of the target compound.
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 H NMR (270 MHz, CDCl ₃ ) (cis + trans): δ 6.05 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)>
The same procedure as in Example 1 was performed except that 3-methyl-t-butylcyclopentanol obtained in Synthesis Example 4 was used instead of 2-methyl-t-butylcyclopentanol in Example 1. To give a compound.
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 H NMR (270 MHz, CDCl ₃ ) (cis + trans): δ 6.02 ppm (m, 1H), 5.47 ppm (m, 1H), 1.92 ppm (s, 3H), 2.78-1.41 ppm (m, 7H), 0.99 ppm (s, 9H), 1.06, 0.98 ppm (d, 3H).

<Example 3: Production of compound (5)>
Example 1 Example 1 was carried out 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.
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 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), 1.03 ppm (d, 3H), 0.98 (d, 3H), 0.95 ppm (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 JP-A-2015-141353.
Cyclopentanone (8.4 g) and tetrahydrofuran (200 mL) were added to a three-necked flask and 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. Next, 100 mL of t-butylmagnesium bromide (1.0 mol / L tetrahydrofuran solution) was added dropwise at 0 ° C. and stirred for 2 hours. Subsequently, 100 mL of a saturated aqueous ammonium chloride solution 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 bicarbonate solution and 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. Normal butyl lithium (1.6 mol / L hexane solution) 55mL was dripped at -40 degreeC, and it stirred at 0 degreeC for 1 hour. After the reaction solution was cooled again to −40 ° C., 8.4 g of methacrylic acid chloride was added dropwise, and the temperature was raised to room temperature. After stirring for 1 hour, it 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 then 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, the same procedure as in Comparative Example 1 was performed except that isopropyl magnesium bromide was used instead of t-butylmagnesium bromide to obtain isopropylcyclopentyl methacrylate (shown by the structural formula in Table 1).

<Test example: Evaluation of hydrophobicity>
Using the methacrylic acid ester obtained in the above Examples and Comparative Examples as a sample, silica gel surface-treated with a hydrocarbon group having 18 carbon atoms was used as a column filler, and reverse phase liquid chromatography measurement was performed under the following conditions. .
[Measurement condition]
Apparatus: Liquid chromatography system ACQUITY UPLC H-Class (product name) manufactured by Waters.
Column: manufactured by Waters, ACQUITY UPLC BEH C18 (product name), 1.7 μm (particle size).
Moving bed: 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 a packing material, the sample moves. Moves on hydrocarbon silica gel (stationary phase) by phase solvent. The sample is held on the stationary phase by the partition coefficient between the stationary phase (hydrocarbon group) and the mobile phase (water). Therefore, the hydrophilic compound elutes earlier and the hydrophobic compound elutes later. That is, it can be determined that a sample having a longer holding time is superior in hydrophobicity.
Table 2 shows the measurement results of the retention time.

As shown in Table 2, in liquid chromatography using 2-methyl-t-butylcyclopentyl methacrylate obtained in Example 1 as a sample, two isomers (denoted as (i) (ii) in the table) Separated and the retention times were 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 and excellent hydrophobicity than the t-butylcyclopentyl methacrylate obtained in Comparative Example 1. It was recognized that
Similarly, it was confirmed that 2-methyl-isopropylcyclopentyl methacrylate obtained in Example 3 has a longer retention time than isopropylcyclopentyl methacrylate obtained in Comparative Example 2 and is excellent in hydrophobicity.

  The (meth) acrylic acid ester provided in the present invention is excellent in hydrophobicity and is useful for a wide variety of uses such as plastics and paints. Moreover, it is useful for improving lithography properties as a raw material for semiconductor resist.

Claims (3)

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

[Wherein 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, R ²¹ , R ²² and R ²³ are each independently hydrogen An atom, a linear or branched alkyl group, or a cycloalkyl group, at least two of which are a linear or branched alkyl group or a cycloalkyl group, and Z ¹ has 1 to 20 carbon atoms, A substituted or unsubstituted divalent chain hydrocarbon group, a C1-C20 substituted or 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 has a heteroatom having 3 to 10 carbon atoms together with the carbon atom to which (R ²¹ R ²² R ²³ ) C— is bonded. Optional cyclic hydrocarbons An atomic group forming a group, n is an integer of 0 to 3, and m is an integer of 1 to 18. ] 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),
The manufacturing method of (meth) acrylic acid ester which makes the said hydroxy compound and (meth) acrylic acid chloride react, and obtains the (meth) acrylic acid ester represented by following formula (5).

[Wherein R ³ represents a linear or branched alkyl group, cycloalkyl group, aryl group or aralkyl group, and Z ³ represents a heteroatom having 3 to 10 carbon atoms together with the carbon atom to which the oxygen atom is bonded. The atomic group which forms the cyclic hydrocarbon group which may have, m is an integer of 1-18. ]

[Wherein, R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, a linear or branched alkyl group, or a cycloalkyl group, and at least two are linear or branched alkyl groups. Or a cycloalkyl group, and M ¹ is Li or MgX (X is a halogen atom). ]

[Wherein 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). ]

[Wherein, 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).
The manufacturing method of (meth) acrylic acid ester which makes the said hydroxy compound and (meth) acrylic acid chloride react, and obtains the (meth) acrylic acid ester represented by following formula (5).

[Wherein, R ²¹ , R ²² and R ²³ are each independently a hydrogen atom, a linear or branched alkyl group, or a cycloalkyl group, and at least two are linear or branched alkyl groups. Or a cycloalkyl group, and R ¹¹ is a linear or branched alkyl group or a cycloalkyl group. ]

[Wherein R ³ is a linear or branched alkyl group, cycloalkyl group, aryl group or aralkyl group, 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 each independently MgX (X is a halogen atom), and m is an integer of 1 to 18. ]

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

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