WO2002100816A1

WO2002100816A1 - Process for producing 2-alkyl-2-adamantyl (meth)acrylate

Info

Publication number: WO2002100816A1
Application number: PCT/JP2002/005541
Authority: WO
Inventors: Masao Yamaguchi; Yoshihiro HIRTOA; Hirofumi Shiigi; Eiji Ohshima
Original assignee: Tokuyama Corporation
Priority date: 2001-06-07
Filing date: 2002-06-05
Publication date: 2002-12-19
Also published as: JP2003055301A; CN1239464C; CN1527810A; KR100724672B1; TWI245757B; JP3868335B2; JP2006335766A; KR20040014548A

Abstract

A metal 2-alkyl-2-adamantyl alcoholate [wherein the alkyl has 1 to 6 carbon atoms and the metal is lithium or -MgX (X is halogeno)] is reacted with (meth)acrylic anhydride or with an ester of a C2-8 alcohol having a double bond between the α- and β-positions with (meth)acrylic acid to produce a 2-alkyl-2-adamantyl (meth)acrylate. A tertiary amine compound may be added to the reaction system during the esterification, whereby the target compound can be obtained at a higher conversion.

Description

Specification

2—Alkyl—2—Adamantly (meth) acrylate Production Method Technical Field

The present invention relates to 2-alkyl-2-adamantyl acrylate and 2-alkyl-12-adamantyl methacrylate (hereinafter referred to as 2-alkyl-2-adamantyl), which are useful as raw materials for semiconductor resists. (Abbreviated as (meta) acrylate). Background art

It is known that a resist produced from an alkyl adamantyl ester such as alkyl adamantyl (meth) acrylate has a high dry etching resistance in a semiconductor manufacturing process (for example, Japanese Patent Application Laid-Open No. No. 5,26.5,212), and its potential as a resist material for semiconductors is attracting attention.

As a method for producing an alkyl adamantyl ester, 2-alkyl adamantyl alcohol is alkylated using an alkylating reagent comprising an organometallic compound, and then the resulting metal alkyl adamantyl alcoholate is converted to an acid halogen. A method of esterification using a compound is known (JP-A-10-182552, etc.).

In the above esterification reaction using (meth) acrylic acid chloride as an acid halide, it has been confirmed that chlorinated products are by-produced by some side reaction. This chlorinated product is mixed as an impurity into the obtained resist material, and there is a problem that the performance of the resist material is deteriorated even if the amount is small. Furthermore, (meth) acrylic acid chloride has high reactivity and lacks long-term storage stability. There are difficult to use problems. Disclosure of the invention

The present invention provides a method for esterifying a metal 2-alkyl-2-adamantyl alcoholate compound (hereinafter sometimes abbreviated as a metal compound) as an esterifying agent, (meth) acrylic acid. An object of the present invention is to provide a method for producing 2-alkyl-12-adamantyl (methyl) acrylate without using an octa- gen halide such as a halide. By this method, by-products of chlorinated products in the obtained ester are essentially suppressed, and as a result, high-purity esters suitable for applications such as resist materials can be produced in high yield. .

The present inventors have made various investigations to achieve the above object, and as an esterifying agent, (meth) acrylic anhydride or a compound having 2 to 2 carbon atoms having a double bond at the α and β positions. By using an ester compound of alcohol (8) and (meth) acrylic acid, it is possible to obtain a 2-alkyl_alkyl compound suitable for applications such as resists in good yields, without essentially producing chlorinated by-products. 2 — We have found that adamantyl (meth) acrylate can be manufactured, and have completed the present invention.

Therefore, the present invention that achieves the above object is as described below. [1] A metal 2-alkyl-2-adamantyl alcohol compound represented by the following formula (1):

(0

(Where R ¹ is an alkyl group having 1 to 6 carbon atoms, M is a L i atom or —M g X (where X is a halogen atom).)

And reacting (meth) acrylic anhydride or an alcohol having 2 to 8 carbon atoms having a double bond at the / 3 position with an ester compound of (meth) acrylic acid. Indicated by (2)

(However, R ² is a hydrogen atom or a methyl group.)

2 —Alkyl— 2 —A process for producing adamantyl (meth) acrylate.

[2] The metal (2-alkyl-2) -adamantyl alcoholate compound and the alkyl group of 2- (alkyl-2) -adamantyl (meth) acrylate in which the alkyl group is a methyl group or an ethyl group 2—Alkyl—2—Adamantyl (meth) acrylate described.

[3],] An ester compound of an alcohol having a double bond at the 3-position and having 2 to 8 carbon atoms and (meth) acrylic acid is converted to an ester compound of vinyl (meth) acrylate or isopropyl (meth) acrylate. The method for producing 2-alkyl-12-adamantyl (meth) acrylate according to [1], which is phenyl.

[4] A metal 2-alkyl-12-adamantyl alcoholate compound represented by the formula (1), and a (meth) acrylic anhydride or an alcohol having 2 to 8 carbon atoms having a double bond at the / 3 position. When reacting an ester compound with a (meth) acrylic acid, the tertiary amine compound is converted to a metal 2-alkyl-12-adamantyl alcoholate compound with 0%. The production method according to the above [1], wherein 0.1 to 0.5 equivalent is present.

In the present invention, a metal 2-alkyl-12-adamantyl alcoholate compound and a (meth) acrylic anhydride or an alcohol having 2 to 8 carbon atoms having a double bond at the i3 position are represented by ( Since it is reacted with an ester compound with (meth) acrylic acid, 2-alkyl-2-adamantyl (meth) acrylate can be produced with high yield. In the present production method, since a chlorine-containing esterifying agent such as acid chloride is not used, the resulting 2-alkyl-2-adamantyl (meth) acrylate is chlorinated by-product-containing. The amount is small. For this reason, the resist manufactured using this has high performance.

When tertiary amine is added to the reaction system, the conversion is improved. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

(Metal compound)

One starting metal compound used in the production method of the present invention is a metal 2-alkyl-2-adamantyl al-II lat compound represented by the following formula (1).

Here, R ¹ is an alkyl group having 1 to 6 carbon atoms. Cash register for semiconductor R ¹ is preferably an alkyl group having 1 to 3 carbon atoms, such as a methyl group, an ethyl group, a propyl group, and an isopropyl group, from the viewpoint of high usefulness as a raw material of the stock material. Although those having an alkyl group having more than 6 carbon atoms can be used, the number of carbon atoms is preferably in the above range because there is no particular advantage of availability and the advantage of having more than 6 carbon atoms. Represents a L i atom or —M g X. Here, X represents a halogen atom. Examples of the octogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As the halogen atom, a chlorine atom or a bromine atom is preferable because of availability of a metal compound. Further, from the viewpoint of reactivity, a bromine atom is most preferable.

Among the metal compounds represented by the above formula (1) that can be suitably used in the present invention, a specific example of magnesium halide 2 —alkyl-2 —adamantyl alcoholate is magnesium chloride 2-methyl-2-adaman. Tyl alcoholate compound, magnesium bromide 2-methyl-2-adamantyl alcoholate compound, magnesium chloride 2 —ethyl 2-aldamantyl alcoholate compound, magnesium bromide 2-ethyl-2-adadaman Til alcoholate compounds and the like can be mentioned.

Among these metal compounds, magnesium bromide 2-methyl-2-adamantyl alcoholate compound is particularly preferred from the viewpoint of production ease.

The magnesium halide 2-alkyl-1-2-adamantyl alcoholate compound can be easily produced from 2-adamanylnon and a Grignard reagent. The Grignard reaction itself is well known to those skilled in the art.

The raw material 2-adamanone is used as it is, or after purification by recrystallization, sublimation, etc. as it is or as necessary. The metal compound produced using the above Grignard reagent can be used as a starting material in the production method of the present invention as it is or after purification such as filtration and washing as needed.

When the metal compound represented by the formula (1) is a lithium 2-alkyl-2-adamantyl alcoholate compound, the metal compound is known using 2-adamantanone and alkyl lithium as raw materials. Those manufactured by the various methods described above can be used.

This lithium 2-alkyl-2-adamantyl alcoholate compound may be prepared by any method as described above, but the following production method is particularly preferred.

That is, by mixing a solution or suspension (hereinafter also referred to as an organic raw material solution) containing 2-adamanone nonone and an alkyl halide compound with lithium metal, the lithium 2 —Alkyl-2—Adamantyl alcoholate compound is obtained.

According to the above-mentioned production method, the target product can be obtained in a higher yield than when the Grignard reagent is used. Moreover, since no separately synthesized alkyllithium is used, there is no need to worry about the price and storage stability of expensive and chemically unstable alkyllithium. The alkyl halide compound is represented by the following formula (3)

R 1-X (3)

(In the formula, Ri is an alkyl group having 1 to 6 carbon atoms, and X is a halogen atom.)

The halogenated alkyl compound is not particularly limited, and alkyl bromide, alkyl iodide, alkyl chloride, and the like can be used. Alkyl groups with 1 to 6 carbon atoms because of easy availability of raw materials Alkyl chloride rides or alkyl chlorides having the following are preferred. From the viewpoint of high reactivity, an alkyl amide or an alkyl iodide is preferred. Specific examples thereof include butyl chloride, pentyl chloride, hexyl chloride, methyl bromide, butyl bromide, butyl bromide, methyl iodide, and acetyl chloride.

The amount of the alkyl halide to be used is, in consideration of the high conversion rate of 2-adamanone nonone, a molar ratio of 2-adamanone nonone: alkyl halide compound = 1: 1: 1 to 1: 1. 2 is preferred.

As a solvent or a dispersing medium for dissolving or dispersing the 2-adamantanone and the alkyl halide compound, an organic solvent stable to lithium metal, alkyl lithium, and lithium alkoxide can be used. Examples of such organic solvents include ether solvents such as getyl ether, tetrahydrofuran, and dioxane; hydrocarbon solvents such as hexane, benzene, and toluene; and mixed solvents thereof.

The amount of the organic solvent used is not particularly limited, but from the viewpoint of the yield of the kettle, the solubility and the reaction rate, the concentration of 2-Adamanthin is 0.01 to 10 mo 1/1, especially 0.1 to 1 mol. It is preferable to make it 5 mo 1/1. '

2—A method for mixing and reacting a solution or suspension (organic raw material liquid) containing adaman-nonone and an alkyl halide compound with lithium metal involves reacting the organic raw material liquid with lithium metal suspension. A method in which the solution is gradually added to the solution and mixed is preferable. According to this method, the calorific value can be easily controlled, and the surface of the metallic lithium is activated first, so that the reaction can be rapidly progressed.

In this case, the metal lithium used is preferably one having a large surface area, such as granules, flakes, or fine particles, and such a shape is used. This increases the reaction rate.

The rate at which the above-mentioned organic raw material liquid is added to metallic lithium differs depending on the type of the alkyl halide compound used, and cannot be specified unconditionally, but the reaction temperature depends on the boiling point of the alkyl halide compound or the organic solvent used. It is desirable to adjust the rate of addition of the organic raw material liquid so that the temperature does not exceed the lower one of the boiling points.

In particular, when the alkyl halide compound is an alkyl iodide, it is desirable to add the organic raw material liquid while maintaining the reaction temperature at 0 ° C or lower. Thereby, a side reaction can be suppressed.

When the alkyl halide compound is a bromide, the above conditions are satisfied, and the reaction temperature is 20 or higher (that is, 20 to the boiling point of the alkyl bromide compound or the boiling point of the organic solvent used, whichever is lower). It is desirable to add the organic raw material liquid while adjusting so that This can prevent the deactivation of lithium metal. It is preferable to stir the solvent when dropping the organic raw material liquid.

The total amount of metallic lithium added is not particularly limited. However, from the viewpoint of yield and prevention of excessive use of lithium metal, 1.6 to 2.4 g atom of metal lithium, especially 1.8 to 2.2 g atom, is added to 1 mole of 2-adamanone nonone. It is preferred to add atoms.

In addition, when the esterification reaction described later is continuously performed, it is preferable that almost no metallic lithium remains in the reaction solution after the completion of the reaction. For this reason, the addition amount of metallic lithium is preferably 2 g atoms or less, and more preferably 1.8 to 2.0 g atoms, per 1 mol of 2-adamannonone.

The reaction time of the above-mentioned alkylation reaction varies depending on the rate of addition of metal lithium, the efficiency of removing the reaction heat, and the like, but is usually preferably 0.5 to 48 hours. In order to prevent the deactivation of metallic lithium, argon It is desirable to carry out the reaction under an inert atmosphere.

By the above reaction, a lithium 2-alkyl-2-adamantyl alcoholate compound can be obtained.

In the present invention, the lithium 2-alkyl-2-adamantyl alcoholate can be isolated and purified if necessary.

(Esterifying agent)

The esterification agent, which is the other starting material used in the present invention, is a (meth) acrylic anhydride represented by the following formula (4) or a double bond at the, position represented by the following formula (5). It is an ester compound of an alcohol having 2 to 8 carbon atoms and (meth) acrylic acid.

Here, in the formulas (4) and (5), R ² represents a hydrogen atom or a methyl group. R ³ , R ⁴ and R ⁵ represent a hydrogen atom or an alkyl group or an aryl group which may have a substituent, and R ³ and R ⁴ or R ⁴ and R ⁵ may be connected to each other to form a ring. The total number of carbon atoms of R ³ , R ⁴ and R ⁵ is 0 to 6.

As the (meth) acrylic anhydride represented by the formula (4), acrylic anhydride and methacrylic anhydride are preferable. Also, a mixture of these Acid anhydrides can also be used.

As an ester compound of an alcohol having 2 to 8 carbon atoms having a double bond at the 3-position represented by the formula (5) and (meth) acrylic acid, (meth) vinyl acrylate , (Meth) isoprobenyl acrylate, (meth) acrylic acid 1-cyclohexenyl, (meth) acrylic acid 2,6 -dimethyl-1 -cyclohexenyl, (meth) acrylic acid Examples include 1-phenylenyl, phenyl (meth) acrylate, 4-nitrophenyl (meth) acrylate, and the like. Particularly, from the viewpoint of availability, vinyl (meth) acrylate, isoprobenyl (meth) acrylate, and phenyl (meth) acrylate are preferred.

As these esterifying agents, those synthesized by a known method can be used without limitation. For example, as a method of synthesizing an acid anhydride, a method using thionyl chloride in methylene chloride as reported in Tetra Hedron Letters, Vol. 27, No. 41, No. 49, pp. 196, U.S. Pat. A method by reacting with diketene in the presence of copper acetate as shown in JP-A-246768 is exemplified. Also, a method for synthesizing an ester compound using (meth) acrylic acid and an alcohol having 2 to 8 carbon atoms having a double bond at the α, 0 position is described in British Chemical Society C, 1968, 2010. 6 pages, Journalof Polymer Science, A_1, Vol. 4, 1966, pp. 1191, Zh. Prik 1.K him. (Leningrad), 24, 1 951, 851 (eng 1 .A υsg.S. 967, 969), Zh.Obshch.Khim., 24, 1954, 450 ( eng 1. A usg. S. 459), Journal of the American Chemical Society, Vol. 83, 196 1, 851, page 1, Bu 11. A cad. S ci. USSRD iv. Chem. S Ci. (Engl. Trans 1.) 1967, page 243. These esterifying agents can be used as they are or dissolved in a solvent for the esterification reaction described later.

(Esterification reaction)

In the present invention, the metal compound represented by the above formula (1) is reacted with the esterifying agent represented by the formula (4) or the formula (5) to obtain a compound represented by the formula (2) ) To produce 2-alkyl-1 2-adamantyl (meth) acrylates.

This reaction is performed by mixing the above compounds with each other. The use of a reaction solvent improves the workability and facilitates the control of the reaction temperature. Any solvent that does not react with the metal compound and the esterifying agent can be used for the reaction. Available. Specific examples include ether solvents such as ethyl ether, tetrahydrofuran (THF), and dioxane; hydrocarbon solvents such as hexane, benzene, toluene, and xylene; and halogen solvents such as dichloromethane.

The concentration of the metal compound in the solvent is preferably from 0.01 to 10 mol 1 Z 1, and more preferably from 0.1 l to 5 mol 1 no 1 in terms of handling.

The amount of the esterifying agent used in the reaction is preferably 0.9 to 1.3 mol per 1 mol of the metal compound.

The mixing method of the metal compound and the esterifying agent is not particularly limited, and the method of adding the esterifying agent or the solution thereof to the metal compound solution or the method of mixing the metal compound (or the solution) and the esterifying agent (or the ) May be separately and simultaneously added. Among them, a method of adding a metal compound solution to the esterifying agent or a solution thereof is preferable because polymerization of the obtained target compound can be suppressed. If the metal compound solution is added to the esterifying agent or its solution, the reaction temperature is controlled and the reaction is continued over a relatively long period of time in small portions. Preferably, the metal compound solution is dropped intermittently. Therefore, depending on the size of the production scale, the usual dropping time is often about 1 to 24 hours.

Although the reaction time varies depending on the length of the dropping time, it is usually preferably 0.5 to 6 hours after the completion of the dropping.

The esterification reaction temperature is preferably from −20 to 100 ° C., and particularly preferably from 0 to 40 in view of a balance between the reaction rate and polymerization prevention.

From the viewpoint of preventing the deactivation of the esterifying agent and the metal compound, the reaction is desirably performed in an inert atmosphere such as nitrogen or argon.

Furthermore, by adding a tertiary amine compound to the reaction system during the esterification reaction, an ester compound can be obtained at a higher conversion. When primary and secondary amines are added to the reaction system, they are reacted with an esterifying agent (meth) acrylic anhydride or an ester compound of alcohol and (meth) acrylic acid to form an amine. The effect of the addition of amine is not recognized because of the formation of metal chloride.

The tertiary amine compound is not particularly limited, but includes triaderamine, tributylamine, Ν-methylbeveridine, Ν-methylmorpholine, 1,4-diazabicyclo [2.2.2] octane, 7 — diazabicyclo [4.3.0] nona 6-ene, 1, 8 — diazabicyclo [5.4.0] pendant force 7 — cyclic or acyclic aliphatic tertiary ami such as diene And aromatic tertiary amines such as dimethylaniline, pyridine and 4-dimethylaminopyridine.

It is not necessary to add an equivalent amount of the tertiary amine compound to the metal 2-alkyl-12-adamantyl alcoholate compound, and usually 0.01 to 0.5 equivalent is sufficient. If the amount is less than 0.01 equivalent, the effect of adding the tertiary amine compound is low, and even if 0.5 equivalent or more is added, no further improvement in the conversion is observed. The method and timing of addition of the tertiary amine compound are optional, without being affected by the method of addition of the esterifying agent, the reaction temperature, and the like. For example, a metal 2-alkyl-2-adamantyl alcoholate compound and a tertiary amine compound may be mixed and then reacted with an esterifying agent. Further, after reacting the metal 2-alkyl-2-adamantyl alcoholate compound with the esterifying agent, a tertiary amine compound may be added to the reaction solution to further react.

A polymerization inhibitor that does not react with the metal compound may be added to the reaction system. Examples of such a polymerization inhibitor include inhibitors having no phenolic hydroxyl group, such as phenothiazine.

After the completion of the esterification reaction, various known purification means can be used for recovering the target substance from the reaction solution. Specifically, purification means such as washing with water, solvent extraction, column chromatography, distillation, and recrystallization can be exemplified. Example

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

The conversion at the time of esterification was calculated by the following method. First, the reaction mixture was poured into water and extracted with getyl ether, and the obtained extract was analyzed by gas chromatography. The peak area of 2-alkyl-2-adamantyl (derived from metal 2-alkyl-2-adamantyl alcoholate) of the obtained gas chromatogram and the 2-alkyl-12-adamantyl (product) The conversion calculated was the percentage of the total peak area of the (meth) acrylate and divided by the peak area of the 2-alkyl-2-adamantyl (meth) acrylate.

The yield is 2 -alkyl- 1-2-adamantyl (meth) ac The weight of the relay was divided by the stoichiometric amount of the 2-alkyl-12-adamantyl (meth) acrylate calculated using the weight of the 2-adamanone used and expressed as a percentage. Example 1

Under a nitrogen atmosphere, a 500 ml flask was charged with 30 g (0.2 mO 1) of 2-adamanone, and 90 g of tetrahydrofuran (THF) was added to dissolve the mixture. Here, a commercially available solution of methylmagnesium bromide in THF (1. Omol / 1) (220 ml, 0.22 mo1) is transferred so that the reaction solution temperature does not exceed 40 ° C. It was dripped. After the completion of the dropping, the mixture was stirred for 1 hour to obtain a THF solution of magnesium bromide 2-methyl-2-adamantyl alcoholate. To this, 37 g (0.24 mol) of methacrylic anhydride was slowly added dropwise so that the reaction solution temperature did not exceed 40. After completion of the dropwise addition, the mixture was stirred at room temperature for 4 hours (conversion rate: 90%). Thereafter, while maintaining the liquid temperature at 10 or lower, methanol 108 and 10% sodium hydroxide aqueous solution 16 g were added, and the mixture was stirred for 1 hour, and then the organic layer was separated. After the organic layer was further washed with a 10% aqueous sodium hydroxide solution, the solvent was distilled off under reduced pressure. The obtained residue was distilled from 85 to 9013 under a reduced pressure of 0.3 mmHg to obtain 23.0 g of 2-methyl-2-adamantyl methyl acrylate (yield 49%). . Analysis with a gas chromatograph mass spectrometer (GC-MS) revealed no chlorine-containing impurities. Comparative Example 1

2-Methyl-12-adamantyl methyl acrylate was synthesized according to Example 1 using methacrylic acid chloride in place of methyl methacrylate anhydride. The conversion was 95% and the isolation yield was 54.9%. When the obtained compound was analyzed by gas chromatography mass spectrometry, 0.5% of impurities considered to be 2-chloro-2-methyladamantane were detected, and two types of chlorine-containing impurities of unknown structure were detected. However, 0.2% and 0.1% were detected respectively, and 0.1% of bromine-containing impurities of unknown structure were also detected. Example 2

Under a nitrogen atmosphere, 30 g of THF and 2.78 g (0.4 mol) of metal lithium were added to a 500 ml flask. To this suspension was previously dissolved a solution prepared by dissolving 30 g (0.2 mol) of 2-adamanthin and 26.2 g (0.24 mo1) of bromide chill in 90 g. Under a nitrogen atmosphere, the mixture was added dropwise while controlling so that the reaction temperature was about 40 ° C. After the completion of the dropwise addition, the reaction solution was heated to 45, and the reaction was aged for 1 hour. After visually confirming that the metallic lithium had disappeared, the mixture was further stirred at 45 ° C. for 1 hour to obtain a solution of lithium 2._ethyl_2-adamantyl alcohol. To this solution, 22.0 g (0.21 mol) of acrylic acid anhydride was added dropwise over 2 hours while maintaining the reaction temperature at 40 or lower. After completion of the dropwise addition, the mixture was stirred at 40 for 4 hours to mature the reaction (conversion rate: 97%).

After the reaction aging, 10 g of methanol and 16 g of a 10% aqueous sodium hydroxide solution were added while maintaining the reaction solution at 10 or less, and the mixture was stirred for 1 hour, and then the organic layer was separated. After the organic layer was washed with a 10% aqueous sodium hydroxide solution, the solvent was distilled off under reduced pressure. The residue was distilled from 80 to 85 under a reduced pressure of 0.3 mmHg to obtain 24.6 g of 2- (ethyl-2) -adamantyl acrylate (yield: 53%). When this was analyzed using a gas chromatograph mass spectrometer, no impurities containing chlorine were detected. Examples 3 to 7

According to Example 1, 2_methyl-2-adamantyl (meth) acrylate was synthesized according to Example 1 using the compounds shown in Table 1 instead of methacrylic anhydride. Table 1 shows the conversion, yield, and analysis results of the obtained compound by gas chromatography mass spectrometry. table 1

Example 8

According to Example 1, a THF solution of magnesium bromide 2-methyl_2-adamantyl alcoholate was prepared.

Then, in a 500 ml flask previously charged with 37 g (0.24 m 01) of methacrylic anhydride and 100 ml of THF, keeping the temperature not exceeding 40 ° C. The THF solution was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 4 hours (conversion rate: 91%). Next, 10 g of methanol and 16 g of a 10% aqueous sodium hydroxide solution were added to the reaction solution while maintaining the reaction solution at 10 ° C or lower, and the mixture was stirred for 1 hour, and then the organic layer was separated. . After the organic layer was washed with a 10% aqueous sodium hydroxide solution, the solvent was distilled off under reduced pressure. The residue was distilled at 85-90 ° C under a reduced pressure of 0.3 mmHg to obtain 26.3 g of 2-methyl_2-adamantyl methacrylate (yield 56%). ). This is called Gas Chroma Todara When analyzed by mass spectrometry, no impurities containing chlorine were detected. Example 9

According to Example 8, 2-methyl-2-adamantyl ester was synthesized according to Example 8 using vinyl methacrylate instead of methacrylic anhydride. At that time, the conversion was 70.0%, and the yield was 34.0%. When this was analyzed with a gas chromatograph mass spectrometer, no impurities containing chlorine were detected. Example 10

According to the same manner as that of Example 1, magnesium 2-bromo-2-adamantyl alcoholate was reacted with methacrylic anhydride. At this time, the conversion was the same as that of Example 1 (90%). When 2 g (0.02 mol, 0.1 equivalent) of triethylamine was added to the reaction solution at room temperature and the mixture was stirred for 2 hours, the conversion was improved to 98%. The subsequent treatment was carried out according to Example 1 to obtain 26.2 g of 2-methyl-2-adamantyl methacrylate (yield 56%). When this was analyzed with a gas chromatograph mass spectrometer, no chlorine-containing impurities were detected. Example 1 1

A THF solution of magnesium bromide 2-methyl-2-adamantyl alcohol was prepared in the same manner as in Example 1. At room temperature, 1.2 g (0.01 mol, 0.05 equivalents) of dimethylaminopyridine is added at room temperature, and then the acrylic anhydride is added while keeping the temperature not exceeding 40 :. It was dropped. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. The roll at this time The conversion was 99%. The subsequent treatment was carried out in the same manner as in Example 1 to obtain 27.7 g (yield: 63%) of 2-methyl-2-adamantyl acrylate. When this was analyzed with a gas chromatograph-mass spectrometer, no impurities containing chlorine were detected.

Claims

The scope of the claims

1. A metal dialkyl-2-adamantyl alcoholate compound represented by the following formula (1):

And reacting an ester compound of (meth) acrylic anhydride or an alcohol having 2 to 8 carbon atoms having a double bond at the / 3 position with an ester compound of (meth) acrylic acid. 2)

(However, R ² is a hydrogen atom or a methyl group.)

2-Monoalkyl-2-A adamantyl (meth) acrylate production method. 2. The metal 2 _alkyl-2 -adamantyl alcoholate compound and the alkyl group of 2 -alkyl-2 -adamantyl (meth) acrylate in which the alkyl group is a methyl group or an ethyl group. 2. A method for producing a 2-alkyl-2-adamantyl (meth) acrylate according to item 1.

3. With an alcohol having 2 to 8 carbon atoms having a double bond at the i3 position 2. The 2-alkyl-2-adamantyl (2) according to claim 1, wherein the ester compound with (meth) acrylic acid is vinyl (meth) acrylate or isopropenyl (meth) acrylate. Meta) Manufacturing method of acrylic rate.

4. Metal 2-alkyl-2-adamantyl alcoholate compound represented by formula (1) and (meth) acrylic anhydride or alcohol having 2 to 8 carbon atoms having a double bond at the / 3 position. When reacting an ester compound with (meth) acrylic acid, the tertiary amine compound is added to the metal 2-alkyl-2-adamantyl alcoholate in an amount of 0.01 to 0.5. 2. The method for producing a 2_alkyl-2-adamantyl (meth) acrylate according to claim 1, wherein an equivalent amount is present.