TW201400448A - Method for producing adamantyl (meth)acrylate - Google Patents

Abstract

Provided is a method for producing, efficiently and at high purity, an adamantyl (meth)acrylate which is suitable as a monomer for a photoresist resin. A method for producing an adamantyl (meth)acrylate represented by general formula (i) that reacts a metal alkoxide and a (meth)acrylic anhydride.

Description

Method for producing gold steel alkyl (meth) acrylate

The present invention relates to a method for producing adamantyl (meth) acrylate, and more particularly to a method for efficiently producing an adamantyl (meth) acrylate useful as a photoresist material.

Adamantane has a structure in which four cyclohexane rings are condensed into a cage shape, and a compound having high symmetry and stability, and a derivative thereof exhibits a specific function, and thus is known as a raw material for pharmaceutical materials or a material for high-performance industrial materials. . For example, adamantyl (meth) acrylate has been attracting attention as a monomer for a resist resin by utilizing its acid sensitivity, dry etching resistance, ultraviolet ray permeability, and the like.

The method for producing adamantyl (meth) acrylate is, for example, a tertiary alcohol such as 1-(1-adamantyl)-1-methylethanol, an adamantyl carboxylate or adamantanecarboxylic acid. The halide is reacted with an organometallic compound and a (meth)acrylic acid halide to carry out esterification (for example, refer to Patent Documents 1 and 2).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2002-161070

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-173466

In the conventional production method, there is a problem that the yield of the target adamantyl (meth) acrylate is low, and it is desired to develop an efficient production method.

The present invention has been made in an effort to provide a method for producing adamantyl (meth) acrylate which is suitable as a monomer for a resist resin in high purity and efficiently.

As a result of repeated efforts by the inventors of the present invention, it has been found that the above problem can be solved by reacting an organometallic compound with a specific adamantane carboxylate and then reacting with (meth)acrylic anhydride. The present invention has been completed based on such findings.

That is, the present invention provides a method for producing adamantyl (meth) acrylate represented by the following general formula (i), which is characterized in that a metal alkoxide is reacted with (meth)acrylic anhydride.

(In the formula, R ^{1 is} each independently and represents an alkyl group having 1 to 3 carbon atoms, and R ³ is a hydrogen atom or a methyl group).

According to the present invention, there is provided a method of producing adamantyl (meth) acrylate which is suitable as a monomer for a resist resin in a high purity.

[Best form for carrying out the invention]

The method for producing adamantyl (meth) acrylate according to the present invention is a method for producing an adamantyl (meth) acrylate represented by the following general formula (i).

In the above general formula (i), R ¹ is an alkyl group having 1 to 3 carbon atoms. R ³ is a hydrogen atom or a methyl group.

The alkyl group having 1 to 3 carbon atoms may be any of a linear chain and a branched chain, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

The gold steel alkyl (meth) acrylate represented by the above general formula (i) may, for example, be 1-(1-gold steel alkyl)-1-methylethyl (meth) acrylate, 1-( 1-gold steel alkyl)-1-ethylpropyl (meth) acrylate, 1-(1-gold steel alkyl)-1-propylbutyl (meth) acrylate, 1-(1- Gold alkyl alkyl)-1-isopropyl-2-methylpropyl (meth) acrylate, etc., among these, preferably 1-(1-gold steel alkyl)-1-methyl b Base (meth) acrylate, 1-(1-gold steel alkyl)-1-ethylpropyl (meth) acrylate.

The reaction formula in the method for producing a gold steel alkyl (meth) acrylate of the present invention is specifically represented by the following formula.

In the formula, R ¹ and R ³ are the same as described above. R ² is an alkyl group having 1 to 3 carbon atoms, and X ¹ is a halogen atom. The metal alkoxide of the above general formula (5) is a reaction intermediate formed in the reaction of a 1-gold alkanecarboxylate with an organometallic compound. The 1-gold steel alkylalkanol represented by the above general formula (6) is a by-product (unreacted product) in the reaction of the aforementioned metal alkoxide (reaction intermediate) with (meth)acrylic anhydride.

The manufacturing method of the present invention is based on the above general formula (1) The metal alkoxide (reaction intermediate) represented by the above general formula (5) is formed by reacting the 1-adamantane carboxylate with a metal organic compound represented by the general formula (2) or (3) described later. In the case, it is preferred to carry out the reaction by reacting the (meth) acrylate. These reactions are usually carried out in an organic solvent.

Further, the present invention may be an organometallic compound such as 1-gold steel alkylalkanol or alkyllithium represented by the above general formula (6), an alkali metal such as metallic sodium or metallic lithium, or a Grignard reagent (Grignard test) The reaction is carried out to form a metal alkoxide (reaction intermediate) represented by the general formula (5), and it is preferred to carry out the reaction by reacting (meth)acrylic anhydride. Further, when sodium metal is used, M in the above general formula (5) is MgX ¹ , Li or Na.

(Meth)acrylic anhydride is used as an esterifying agent in the present invention. As the (meth)acrylic anhydride, acrylic anhydride, methacrylic anhydride, or a mixed acid anhydride thereof can be used.

The amount of (meth)acrylic anhydride used is preferably 1 to 6 moles, preferably 1 to 5 moles, more preferably 1 to 4 moles, per mole of the metal alkoxide.

Further, from the viewpoint of efficiently producing a target, the amount of (meth)acrylic anhydride used is usually 1 to 6 m for the carboxylate 1 mol represented by the above general formula (1). It is better, 1~5 moles is better, and 1~4 moles is better.

The 1-gold steel alkanecarboxylate used in the present invention is represented by the following general formula (1).

In the above general formula (1), R ² is an alkyl group having 1 to 3 carbon atoms, and is an alkyl group having a carbon number of 1 to 3, which is linear or branched, and specifically, a methyl group can be exemplified. Ethyl, n-propyl, isopropyl.

Examples of the 1-adamantanecarboxylate represented by the above general formula (1) include methyl 1-adamantanecarboxylate, ethyl 1-adamantanecarboxylate, 1-adamantanecarboxyl-propyl ester, and 1-gold. The isopropyl methacrylate or the like is preferably a methyl 1-adamantanecarboxylate from the viewpoint of reactivity.

The 1-adamantanecarboxylate represented by the above general formula (1) can be obtained by a usual esterification reaction of an adamantylcarboxylic acid with an alcohol in the presence of an acid catalyst.

The organometallic compound used in the present invention is represented by the following general formula (2) or (3).

R ¹ MgX ¹ (2)

R ¹ Li (3)

In the above general formulas (2) and (3), X ¹ is a halogen atom. The halogen atom may, for example, be a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom.

Representative examples of the organometallic compound represented by the above general formulas (2) and (3) include organomagnesium compounds such as methyl magnesium chloride, ethyl magnesium chloride, and isopropyl magnesium chloride (Grenner test) Medicine, etc.); an organic lithium compound such as methyl lithium, ethyl lithium or isopropyl lithium. Organomagnesium The material can also be used in combination with a copper halide. Among them, preferred are methyl magnesium chloride, ethyl magnesium chloride, methyl lithium, and ethyl lithium.

The amount of the organometallic compound used is usually 2 to 6 moles, preferably 2 to 4 moles, more preferably 2 to 3 moles, per mole of the carboxylic acid vinegar represented by the above general formula (1). .

The organic solvent which can be used in the present invention may, for example, be a hydrocarbon solvent such as n-hexane or n-heptane; an ether solvent such as diethyl ether or tetrahydrofuran. Among them, toluene and tetrahydrofuran are preferred. When tetrahydrofuran is used, the effect of stabilizing the reaction intermediate is high, so that the target can be obtained in a high yield. These solvents may be used alone or in combination of two or more. Further, in the metal alkoxide represented by the above general formula (5), it is preferred to carry out the present invention by mixing the solvent and continuing the reaction once.

The reaction temperature can be appropriately selected depending on the kind of the reaction component, and it is usually in the range of -20 to 100 °C. From the viewpoint of not lowering the reaction rate and suppressing polymerization of a (meth)acrylic group, a range of from 0 to 50 ° C is preferred. The reaction pressure is usually in the range of 0.01 to 0.1 MPa in terms of absolute pressure. If it is used for this range, no special pressure-resistant device is required, which is economical.

The reaction between the 1-adamantane carboxylate and the metal organic compound and the reaction intermediate obtained by the above reaction with (meth)acrylic anhydride is usually from 1 minute to 24 hours, preferably 30 minutes. 5 hours range.

After the reaction is completed, the salt is removed by washing with water, followed by alkaline Wash the aqueous solution. By this operation, unreacted acid anhydride is removed. Examples of the alkaline aqueous solution include inorganic alkali compounds such as sodium hydrogencarbonate, potassium hydrogencarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and ammonia; and organic alkali compounds such as ethylenediamine, aniline, triethylamine, and pyridine. Wait.

The purification and separation of the target compound may be distillation, crystallization, column separation, etc., depending on the nature of the product and the type of the impurity, but particularly if recrystallization or crystallization of water and a water-soluble solvent is used, it may be high. The desired adamantyl (meth)acrylate is produced in purity and in high yield. Specifically, the solvent is distilled off from the reaction liquid after the post-treatment, and then water and a water-soluble solvent are added, and if necessary, it is cooled, and the high-purity adamantyl (meth)acrylate is precipitated. The precipitate can be separated by filtration, centrifugation or the like. Examples of the water-soluble solvent include alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, and glycerin; ether solvents such as tetrahydrofuran and dioxane; and acetonitrile and N,N-dimethyl Formamide, dimethyl hydrazine, acetone, and the like. Among them, it is preferred to use methanol. The obtained compound can be identified by gas chromatography (GC), liquid chromatography (LC), gas chromatography mass spectrometry (GC-MS), nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR). The melting point measuring device or the like is carried out.

[Examples]

Next, the present invention will be described in more detail by way of examples, but the invention is not limited by the examples.

(GC purity)

The purity of the product and the progress of the reaction were measured by gas chromatography (GC). The GC analysis was performed using the Agilent model "6850" and the analysis conditions were as follows.

Capillary column [DB-1 manufactured by J&W Co., Ltd.: coating agent (dimethyl polysiloxane); film thickness: 0.25 μm] inner diameter: 0.25 mm, length: 30 m

Heating conditions: 10 ° C per minute, from 100 ° C to 250 ° C

Injection temperature: 250 ° C

Detector: FID

Detector temperature: 250 ° C

Carrier gas: 氦

<Manufacturing Example 1:1 - Production of methyl adamantyl carboxylate>

Methanol, toluene, and sulfuric acid were added to 50 g (277 mmol) of 1-adamantanecarboxylic acid, and the reaction was carried out at 66 ° C for 3 hours. At the time of the reaction for 3 hours, the residual raw material was 1.5% by mass. After cooling the reaction liquid, it was washed with an aqueous sodium hydrogencarbonate solution and concentrated to give 50 g of the desired 1-adamantanic acid methyl ester.

[Example 1]

(synthesis step)

To 40 g (206 mmol) of methyl 1-adamantanecarboxylate obtained in Production Example 1, 40 g of toluene was added, and nitrogen substitution was carried out, followed by cooling with a refrigerant. The toluene solution was dropped into methyl magnesium for 4.5 hours while being kept at 10 ° C or lower. Chloride THF solution (2M) 247 g (494 mmol), then warmed naturally, and reacted at room temperature (25 ° C) for 3 hours. The reaction solution was again cooled with a refrigerant, and 82.3 g (534 mmol) of methacrylic anhydride was added dropwise over 3.3 hours while maintaining the temperature at 10 ° C or lower. After that, the temperature was naturally raised, and the reaction was carried out at room temperature (25 ° C) for 3 hours. The GC measurement result by this crude reaction liquid is as follows.

Residual raw material = 1 - Adamantanecarboxylic acid methyl ester: 1.5%

Parabiotic = 1 - (1-adamantyl)-1-methylethanol: 7.3%

Target = 1-(1-adamantyl)-1-methylethyl methacrylate: 91.2%

(purification step)

The crude reaction liquid was decomposed with an aqueous hydrochloric acid solution while maintaining the temperature at 25 ° C or lower, and the aqueous layer was separated. Then, it was washed with a 10% aqueous sodium hydroxide solution and a saturated saline solution, and then concentrated. The concentrate was subjected to crystallization from methanol to obtain 1-(1-adamantyl)-1-methylethyl methacrylate (37 g). The isolated yield was 68.5%, and the purity by GC was 98.3% by mass.

[Examples 2 to 6]

The reaction was carried out in the same manner as in Example 1 except that the reaction conditions were changed to those shown in Table 1, and 1-(1-adamantyl)-1-methylethyl methacrylate was obtained. The conditions of each reaction and the analysis results by GC are shown in Table 1.

[Example 7]

To 126 g (650 mmol) of methyl 1-adamantanecarboxylate obtained in Production Example 1, 1.5 L of THF was added and dissolved to carry out nitrogen substitution, and then, by adding 26 g (3770 mol) of lithium, it was cooled by a refrigerant and kept at 10 Under the conditions of ° C or less, 146 mL (1960 mmol) of ethyl bromide was added dropwise over 2 hours to form ethyl lithium. After that, the temperature was naturally raised while reacting for 15 hours. The mixture was cooled again with a refrigerant, and 101 g (660 mmol) of methacrylic anhydride was added dropwise thereto over 10 minutes while maintaining the temperature at 10 ° C or lower. After that, the temperature was naturally raised while reacting for 3 hours.

After the lithium remaining in the crude reaction liquid was removed by decantation, 300 mL of water was added while maintaining the temperature at 25 ° C or lower, and the reaction was stopped. The aqueous layer was separated, extracted with hexane, washed with brine and dried over magnesium sulfate. This solution was filtered and concentrated to obtain 140 g of 1-(1-adamantyl)-1-ethylpropyl methacrylate (isolation yield: 74%, GC purity: 98.7%).

Further, the substrate of the raw material 1 in Table 1 is "methyl 1-adamantanecarboxylate", and the solvent of the raw material 1 is "toluene (Example 1)" or "THF (tetrahydrofuran) (Examples 2 to 7)".

Further, the matrix of the raw material 2 indicates "methyl magnesium chloride (Examples 1 to 6)" or "ethyl lithium (Example 7)", and the temperature 2 indicates the temperature of the reaction after the completion of the dropwise addition of the raw material 2. (°C)", time 2 means "reaction time (h) at the end of the dropwise addition of the raw material 2".

In addition, the raw material 3 indicates "methacrylic anhydride" and the temperature 3 series The "temperature (°C) of the reaction solution after the completion of the dropwise addition of the raw material 3" is shown, and the time 3 indicates "the reaction time (h) at the end of the dropwise addition of the raw material 3".

In addition, the "residual raw material" in Table 1 means the compound represented by the above general formula (5), and the alcohol which is decomposed by water (the compound represented by the above general formula (6)).

<Production Example 2: Production of 1-(1-adamantyl)-1-methylethanol>

To 40 g (206 mmol) of methyl 1-adamantanecarboxylate obtained in Production Example 1, 40 g of toluene was added, and nitrogen substitution was carried out, followed by cooling with a refrigerant. The toluene solution was poured into a THF solution (2M) of 247 g (494 mmol) of methyl magnesium chloride for 4.5 hours while maintaining the temperature in the toluene solution, and then the mixture was naturally heated while reacting for 15 hours, and the reaction was stopped by adding water.

The crude reaction liquid was decomposed with an aqueous hydrochloric acid solution while maintaining the temperature at 25 ° C or lower, and the aqueous layer was separated. Then, it was washed with a 10% aqueous sodium hydroxide solution and a saturated saline solution, and then concentrated. The concentrate was crystallized from methanol to give the desired 1-(1-adamantyl)-1-methylethyl ester (37 g). The isolated yield was 92% by mass, and the purity by GC was 99.1% by mass.

[Comparative Example 1]

To 194 mg (1.0 mmol) of 1-(1-adamantyl)-1-methylethanol synthesized in Production Example 2, 20 mL of THF was added to dissolve, and then triethylamine 0.21 mL (1.5 mmol) and methacrylic acid were sequentially added. 0.12 mL (1.2 mmol) of chloride was started and the reaction was started at room temperature.

After 1 hour and 2 hours later, samples were taken, heated to 60 ° C, and samples were taken after 1 hour, and analyzed by GC for each sample. In all the samples, only the peak of the starting material 1-(1-adamantyl)-1-methylethanol was observed, and no target 1-(1-adamantyl)-1-methacrylate was observed. The peak of methyl ethyl ester showed that the reaction did not proceed at all.

[Comparative Example 2]

To 194 mg (1.0 mmol) of 1-(1-adamantyl)-1-methylethanol synthesized in Preparation Example 2, N,N-dimethylamino-4-pyridine 12 mg (0.1 mmol) was added as THF 20 mL After dissolving, 0.21 mL (1.5 mmol) of triethylamine and 0.18 mL (1.2 mmol) of methacrylic anhydride were sequentially added, and the reaction was started at room temperature.

After 1 hour and 2 hours later, samples were taken, heated to 60 ° C, and samples were taken after 1 hour, and analyzed by GC for each sample. In all the samples, only the peak of the starting material 1-(1-adamantyl)-1-methylethanol was observed, and no target 1-(1-adamantyl)-1-acrylate was observed. The peak of methyl ethyl ester showed that the reaction did not proceed at all.

[Comparative Example 3]

In Comparative Example 1, except that 0.12 mL (1.5 mmol) of pyridine was used instead of 0.21 mL (1.5 mmol) of triethylamine, the same reaction as in Comparative Example 1 and sampling were carried out, and only all the samples were observed. The peak of 1-(1-adamantyl)-1-methylethanol, the peak of 1-(1-adamantyl)-1-methylethyl methacrylate was not observed. The reaction did not proceed at all.

[Comparative Example 4]

In Comparative Example 2, the same procedure as in Comparative Example 2 was carried out except that 0.22 mL (1.5 mmol) of pyridine was used instead of 0.21 mL (1.5 mmol) of triethylamine. When the reaction was carried out and sampling was carried out, only the peak of the starting material 1-(1-adamantyl)-1-methylethanol was observed in all the samples, and no target methacrylic acid 1-(1-) was observed. The peak of adamantyl)-1-methylethyl ester showed that the reaction did not proceed at all.

[Comparative Example 5]

To 984 mg (5.1 mmol) of 1-(1-adamantyl)-1-methylethanol synthesized in Production Example 2, 20 mL of toluene was added to dissolve, and 0.86 mL (10.1 mmol) of methacrylic acid was added and heated. At the beginning of the reflux, 1 drop of concentrated sulfuric acid was added. After 30 minutes, 1 hour later, after 2 hours, sampling was carried out. When performing GC analysis, the starting material 1-(1-adamantyl)-1-methylethanol was all converted to 2-propenyl-1-adamantane. The peak of the target 1-(1-adamantyl)-1-methylethyl methacrylate was observed, and it was found that only a side reaction was carried out.

From the above results, when Examples 1 to 7 were compared with Comparative Examples 1 to 5, it was found that the method for producing adamantyl (meth) acrylate of the present invention can obtain a target with high purity and high yield. Therefore, adamantyl (meth) acrylate which is suitable as a monomer for the resist resin can be efficiently produced.

Claims (4)

A method for producing adamantyl (meth) acrylate represented by the following general formula (i), characterized in that a metal alkoxide is reacted with (meth)acrylic anhydride, (In the formula, R ^{1 is} each independently and represents an alkyl group having 1 to 3 carbon atoms, and R ³ is a hydrogen atom or a methyl group). The method for producing adamantyl (meth) acrylate according to claim 1, which is characterized by the following general formula (1) (In the formula, R ² is an alkyl group having 1 to 3 carbon atoms), a 1-adamantane carboxylate represented by the following general formula (2) or (3) R ¹ MgX ¹ (2) R ¹ Li (3) The metal alkoxide formed by the reaction of the organometallic compound represented by the formula (wherein X ¹ is a halogen atom and R ¹ is an alkyl group having 1 to 3 carbon atoms) is reacted with (meth)acrylic anhydride. The method for producing adamantyl (meth) acrylate according to claim 2, wherein, for the 1-adamantane carboxylate 1 mol, the addition is (Meth)acrylic anhydride 1~6 moles. The method for producing adamantyl (meth) acrylate according to claim 2 or 3, wherein the 1-adamantane carboxylate is methyl 1-adamantanecarboxylate.