JP2002284739A - Method for producing (meth)acrylic acid ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing 2-alkyladamantan-2-yl(meth) acrylate useful as a fine chemical compound by using 2-alkylideneadamantane as a raw material, remarkably simply and also in a good yield as compared with those of conventional methods. SOLUTION: This method for producing the above compound is provided by reacting a bridged cyclic hydrocarbon having an alkylidene group with (meth)acrylic acid in the presence of an acid catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a (meth) acrylate. More specifically, a method of producing a (meth) acrylic ester by reacting a bridged cyclic hydrocarbon having an alkylidene group with (meth) acrylic acid using an acid catalyst, and a method of producing a chloride ion or an organic compound obtained by this method. The present invention relates to a (meth) acrylate having a low content of amine impurities. Tertiary alkyl esters of (meth) acrylic acid, such as 2-alkyladamantan-2-yl (meth) acrylate, obtained according to the present invention are:
It is useful as fine chemicals such as pharmaceuticals, agricultural chemicals, photoresist raw materials, and the like.

[0002]

2. Description of the Related Art As a method for producing 2-methyladamantan-2-yl (meth) acrylate, which is one of the compounds produced by the present invention, for example, (1) 2-methyladamantanol is converted to (meth) acrylic. Method of reacting acid chloride with excess triethylamine (JP
olym. Sci. Tech. , 12 (3), 433
(1999), J. Mol. Polym. Sci. Tech. ,
9 (3), 509 (1996), JP-A-10-2748.
No. 52, No. 11-212265 and No. 11-3054
No. 44), (2) magnesium salt formed by the reaction of 2-adamantanone and methylmagnesium halide or lithium salt formed by the reaction of 2-adamantanone and methyllithium, and (meth) acrylic acid chloride (JP-A-10-182552), and (3) a method of esterifying 1-adamantanol and (meth) acrylic acid in the presence of a specific sulfonic acid catalyst (JP-A-8-31095). , Etc. have been proposed so far.

[0003]

However, the method (1) uses a large amount of triethylamine, which is difficult to handle as a raw material, uses expensive (meth) acrylic acid chloride, and is difficult to separate from a target product. The method (2) is problematic as an industrial production method because it uses (meth) acrylic chloride and uses a Grignard reagent or lithium metal. Further, regarding the method (3), this method is applied to a tertiary alcohol 2-methyladamantane-2 having a substituent at the 2-position.
-When applied to all, the desired ester yield is 2
There is a problem that it is limited to 0% or less.

When such a conventional synthesis method is employed, (meth) acrylic acid chloride is used as a raw material and an organic amine is used as a reaction reagent. And usually 50 ppm or more of chloride ion species and organic amine (N standard). The chlorine ion impurity causes various inconveniences such as a corrosion problem when a material containing the chlorine ion impurity is used as an electronic material. In addition, when used as a chemically amplified resist material, the presence of organic amine impurities affects the optimal amount of the photoacid generator, so if the amine content changes for each production lot of (meth) acrylates, This is a fatal disadvantage that a resist resin cannot be manufactured in a certain process.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above circumstances, and as a result, have found that by reacting 2-methylene adamantane with (meth) acrylic acid in the presence of an acid catalyst, the objective 2 -Methyladamantan-2-yl (meth) acrylate is obtained in a high yield, and the tertiary alkyl ester of (meth) acrylic acid obtained by such a method has an impurity content of chloride ion or organic amine. It has been found that it is significantly reduced, and the present invention has been completed. In the method of the present invention, as can be easily understood from the fact that chloride ions and organic amines are not used in the production of (meth) acrylates, the obtained (meth) acrylates are free from these impurities. The content is remarkably low.

That is, a first gist of the present invention is characterized in that a bridged cyclic hydrocarbon having an alkylidene group is reacted with (meth) acrylic acid in the presence of an acid catalyst.
Method for producing tertiary alkyl ester of acrylic acid. Further, a second gist of the present invention relates to a tertiary alkyl ester of (meth) acrylic acid having an organic amine content of 20 ppm or less based on N or a chlorine ion content of 20 ppm or less. is there.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The present invention reacts a bridged cyclic hydrocarbon having an alkylidene group with (meth) acrylic acid in the presence of an acid catalyst,
This is to obtain a tertiary alkyl ester of (meth) acrylic acid. In the present invention, (meth) acrylic acid means acrylic acid or methacrylic acid, and methacrylic acid is preferable.

The bridged hydrocarbon having an alkylidene group used in the present invention is not particularly limited, but usually has 1 to 5 carbon atoms such as a methylene group, an ethylidene group and an isopropylidene group, preferably It is preferably an alkylidene group of the formulas 1 to 3. As a specific example,
For example, 2-methylene norbornane, 4-methylenetetracyclo [6.2.1 ^1,9 . ^13-6 . 0 ^{2, 7]} alkylidene norbornane such as dodecane; 2-methylene adamantane, 2-ethylidene adamantane, 2-isopropylidene-alkylidene adamantane such as adamantane; and the like, this in 4-methylene-tetracyclo [6.
2.1 ^1,9 . ^13-6 . 0 ^{2, 7]} dodecane or 2-methylene adamantane are preferred, particularly preferably 2-methylene adamantane. In particular, 2-alkylidene adamantane can be usually produced by a dehydration reaction of 2-alkyl adamantane-2-ol. When the dehydration reaction is performed in the presence of a small amount of a carboxylic acid compound and an acid catalyst, 2-alkylidene adamantane can be obtained in a high yield.

The acid catalyst used in the present invention is not particularly limited, but specific examples thereof include, for example, 1)
Inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic sulfonic acids such as benzenesulfonic acid, toluenesulfonic acid, cresolsulfonic acid and methanesulfonic acid; Blensted acid catalyst such as sulfonic acid type ion exchange resin; 2) trifluorination Boron and its complex (hereinafter sometimes abbreviated as boron trifluoride (complex)), anhydrous zinc halide, anhydrous aluminum halide, anhydrous iron halide, tin halide,
Commonly used Lewis acids such as metal salts of trifluoromethanesulfonic acid such as ytterbium triflate; anhydrous halides or alkoxides of Group 4 metals such as titanium, zirconium, and hafnium; and the like; It is preferable that the pKa of the aqueous solution is 6 or less. These acid catalysts may be used alone or in combination.

[0010] Among them, the use of a Lewis acid catalyst is preferable because the reaction rate is drastically improved. Note that among the Lewis acids, boron trifluoride is preferable. The amount of these acid catalysts used varies depending on the type of catalyst,
Generally, it is 0.01 to 50 mol%, preferably 0.1 to 0.1 mol%, based on the bridged cyclic hydrocarbon having an alkylidene group as a raw material.
~ 20 mol%.

For the esterification reaction, for example, a bridged cyclic hydrocarbon having an alkylidene group as a raw material, (meth) acrylic acid, an acid catalyst, and a solvent, if desired, are charged into a reactor, and a predetermined solvent is preferably added while stirring. It is performed at temperature and time. In the method of the present invention, a solvent that is stable in the reaction system can be used without a solvent. When a Bronsted acid is used as a catalyst, aliphatic saturated hydrocarbons such as hexane, heptane, octane and decane; aromatic hydrocarbons such as benzene, toluene and xylene; diethyl ether, dipropyl ether, dibutyl ether, Ethers such as tetrahydrofuran and dioxane;
lactones such as γ-butyrolactone and δ-valerolactone; dichloromethane, dichloroethane, chloroform,
Aprotic solvents such as halogenated hydrocarbons such as chlorobenzene can be used. Further, as a protic solvent,
(Meth) acrylic acid, which is also a reaction substrate, can be used as a solvent.

When a Lewis acid is used as a catalyst, among the solvents that can be used when the above Bronsted acids are used, solvents other than Bronsted acids, such as ethers and lactones, which exhibit strong coordination to the catalyst, are used. It is possible to use the same solvents as when using acids. The amount of these solvents to be used is not limited and is arbitrary, but is generally 0.01 to 1000 times, preferably 0.1 to 5 times by weight the bridged cyclic hydrocarbon compound having an alkylidene group as a raw material.
The range is 00 times. The addition reaction of the present invention is an exothermic reaction, and as is clear from the equilibrium constant, the lower the temperature, the more advantageous the product yield. In fact, when the Lewis acid catalyst is used, the target reaction proceeds very smoothly even at a reaction temperature of room temperature or lower, and as a result, the tertiary alkyl of (meth) acrylic acid, which is the target product in a short time and with high yield, is obtained. Esters can be produced.

The reaction temperature ranges from -80 to 200 ° C, preferably from -50 to 100 ° C. Although the optimum reaction time varies depending on the reaction temperature, it is generally 0.01
５０50 hours, preferably 0.1 to 20 hours. If necessary, other additives such as (meth)
An additive or the like for suppressing the polymerization of acrylic acid can also be present. In this reaction, for example, a 2-alkyladamantane-2-
After obtaining 2-alkylidene adamantane by dehydration reaction of all, a predetermined amount of (meth) acrylic acid is added to the reaction solution as it is, and left at low temperature, for example, room temperature, to give 2-alkyl adamantane-2-yl (meta). ) It is also possible to produce an acrylate, or a predetermined amount of (meth) acrylic acid and a Lewis acid such as boron trifluoride are added to the reaction solution in which the 2-alkylidene adamantane has been formed, and the mixture is left to stand or stirred to further increase. A 2-alkyladamantan-2-yl (meth) acrylate can be produced with high efficiency. This reaction can be performed in a batch operation, but can also be performed in a continuous operation by using an appropriate reaction apparatus.

The production method of the present invention comprises the steps of:
Since it is not necessary to use (meth) acrylic acid chloride or organic amines, the amount of chloride ion or organic amine contained in the obtained tertiary alkyl ester of (meth) acrylic acid is significantly reduced, or Tertiary alkyl esters of (meth) acrylic acid that do not contain any of the above impurities can be produced. Specifically, according to the present invention, chloride ion is usually 20 ppm or less, preferably 1 ppm or less.
0 ppm or less, more preferably 5 ppm or less.
pm or less, preferably 10 ppm or less, more preferably 5 ppm or less. It is also possible to reduce both the chloride ion and the organic amine (N standard) within the above-mentioned range. Here, the organic amine which is an impurity includes triethylamine, tripropylamine, triisopropylamine, tributylamine, pyridine,
Examples thereof include 2-methylpyridine and 2,6-dimethylpyridine. Among them, it is preferable to control the amount of trialkylamine, particularly triethylamine, to be reduced. Such (meth) acrylates having a significantly reduced amount of impurities cannot be synthesized by conventional methods, and are particularly suitable as electronic materials and chemically amplified resist materials.

[0015]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist of the invention. Example 1 A 10 ml eggplant-shaped flask was charged with 88.9 mg (0.6 mmol) of 2-methylene adamantane, 533.7 mg (6.2 mmol) of methacrylic acid, and 1.8 mg (0.01 mmol) of cresolsulfonic acid.
The gas in the system was replaced with nitrogen. The reaction was carried out at 120 ° C. for 1 hour on an oil bath while stirring the contents. The temperature of the contents of the flask was set to room temperature, and a saturated aqueous solution of sodium hydrogen carbonate 10
After addition of 10 ml, extraction with 10 ml of dichloromethane,
The product in the organic layer was qualitatively and quantitatively analyzed using gas chromatography. As a result, 2-methyladamantan-2-yl methacrylate was formed in a yield of 28% (based on the raw material 2-methylene adamantane).

Example 2 Example 1 was repeated except that the reaction temperature was room temperature and the reaction time was 43 hours.
The same operation and analysis as described above were performed. As a result, 2-methyladamantan-2-yl methacrylate was produced in a yield of 73% (based on the raw material 2-methylene adamantane).

(Example 3) In Example 1, 148.5 mg (1.00 mmol) of 2-methylene adamantane was used.
l), 95.9 mg (1.11 mmol) of methacrylic acid
Then, 5.5 mg (0.04 mmol) of boron trifluoride diethyl ether complex was used in place of cresol sulfonic acid, and 0.5 ml of dichloromethane was further charged as a solvent. The reaction temperature was set to 0 ° C., and after stirring for 30 minutes,
The same reaction stop operation and analysis as in were performed. As a result, the conversion of the raw material 2-methylene adamantane was 75%,
2-methyladamantan-2-yl methacrylate was formed in a yield of 71% (based on the raw material 2-methyleneadamantane) (selectivity based on the converted 2-methyleneadamantane was 95%).

Example 4 In Example 3, 148.9 mg (1.00 mmol) of 2-methylene adamantane was used.
l), 424.5 mg (4.93 mmol) of methacrylic acid
l) and the same operation and analysis as in Example 3 were carried out except that the reaction time was changed to 2 hours. As a result, the conversion of the starting material 2-methylene adamantane was 88%, and the yield of the starting material was 86% (the starting material was 86%). 2-methyladamantan-2-yl methacrylate was formed (based on 2-methyleneadamantane) (selectivity based on the converted 2-methyleneadamantane was 98%).

Example 5 In Example 4, 148.8 mg (1.00 mmol) of 2-methylene adamantane was used.
l), 216.2 mg (2.51 mmol) of methacrylic acid
1) Boron trifluoride diethyl ether complex was added to 18.5
mg (0.13 mmol) and the same operation and analysis as in Example 4 except that the reaction time was -20 ° C. As a result, the conversion of the starting material 2-methylene adamantane was 91
% And 2-methyladamantan-2-yl methacrylate was produced in a yield of 90% (based on the starting material 2-methyleneadamantane) (selectivity based on the converted 2-methyleneadamantane was 99%).

[0020]

[Table 1]

Example 6 2-Methyladamantane-2
-One-pot production from oar A 500 ml round bottom flask was equipped with a Dean-Stark water drop separator equipped with a reflux condenser, and 30.003 g (18) of 2-methyladamantan-2-ol was added thereto.
0.46 mmol) and 1.607 g (1
8.67 mmol), 0.17 cresol sulfonic acid
2 g (0.95 mmol) and 300 ml of toluene were charged, and the gas in the system was replaced with nitrogen. When the mixture was heated to the reflux condition of toluene on an oil bath and stirred for 2 hours, about 2 ml of produced water was separated in the Dean-Stark water drop separator. Then, after a total of 270 ml of toluene was distilled off through a water drop separator, the reactor was cooled to room temperature. 2-Methylene adamantane is produced in the reaction product liquid obtained here. 37.35 g of methacrylic acid was added to the reaction product solution.
(433.86 mmol) and 2.718 g (19.15 mmol) of boron trifluoride diethyl ether complex were added, and the contents were stirred at 0 ° C. for 1 hour. Saturated aqueous sodium carbonate solution was slowly added until the aqueous layer reached pH 8, and the contents were transferred to a separatory funnel.
The mixture was extracted with 0 ml of toluene, and this was combined with the above oil layer. The oil layer was washed three times with 50 ml of ion-exchanged water each time, and anhydrous sodium sulfate was added thereto and stirred for 30 minutes to remove residual water. About the obtained product liquid,
As a result of performing the same analysis as in Example 1, the conversion of the raw material 2-methyladamantan-2-ol was 99% or more,
2-methyladamantan-2-yl methacrylate was produced in a yield of 85%, and 2-methyleneadamantane was produced in a yield of 12% (starting material 2-methyladamantan-
2-ol standard).

The resulting solution was treated by the following method to isolate the desired 2-methyladamantan-2-yl methacrylate. (1) The product liquid was treated at 60 ° C. for 2 hours under a reduced pressure of 1.6 × 10 ³ Pa, and toluene as a solvent was distilled off. (2) 100 ml of ion-exchanged water was added to the residue, and 132
The treatment was performed under reduced pressure of Pa at 60 ° C. until the distillation of water was completed (about 2 hours). (3) The residue was subjected to thin-film distillation at 60 ° C. under a reduced pressure of 1.6 × 10 ³ Pa to obtain 29.4 g as an evaporating fraction. As a result of analysis by gas chromatography, the purity of 2-methyladamantan-2-yl methacrylate was 97.8.
%Met. (4) A part of this fraction was analyzed by a conventional method for total nitrogen analysis (N standard) and chlorine analysis by the following analysis method. As a result, all values were below the detection limit (1 ppm).

(Chlorine Analysis Method) A 0.2-0.5 g sample was weighed on a quartz boat and inserted into a combustion furnace. Combustion: room temperature → 900 ° C / gradually heating over 20 minutes (Ar
/ O ₂ ), and then kept at 900 ° C under O ₂ for 10 minutes. Absorption: An absorption tube containing 10 ml of water was installed at the furnace outlet, and the outlet gas for 30 minutes of combustion was ventilated to collect Cl. IC detection: Ion chromatography, model DX-120 manufactured by DIONEX was used. Measurement conditions: column used; AS-12A, eluent; 2.7
mM-Na ₂ CO ₃ /0.3 mM-NaHCO ₃ aqueous solution A NaCl aqueous solution is used as a standard solution. 0, 0.25,
A calibration curve was prepared at 0.5 and 1 ppm, and when the measurement solution was strong, it was appropriately diluted and measured.

(Total Nitrogen Analysis Method) Apparatus: 10-100 mg of TN-10 type sample manufactured by Dia Instruments was placed in a quartz boat, and after combustion, the generated NOx was reacted with O ₃ and the intensity was measured by chemiluminescence detection. As a standard sample, a solution in which pyridine was dissolved in toluene was used, and 0, 500, 1000, 1500
A calibration curve was prepared with ngN.

[0025]

According to the present invention, a 2-alkyladamantan-2-yl (meth) acrylate, which is useful as a fine chemical such as a drug, a pesticide, a photoresist, or the like, using 2-alkylidene adamantane as a starting material, can be obtained by a conventional method. It can be produced significantly easier and with a higher yield as compared to.

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Claims (10)

[Claims] 1. A method for producing a tertiary alkyl ester of (meth) acrylic acid, comprising reacting a bridged cyclic hydrocarbon having an alkylidene group with (meth) acrylic acid in the presence of an acid catalyst. 2. The pKa of an acid of an acid catalyst or an aqueous solution thereof is 6
The manufacturing method according to claim 1, wherein: 3. The acid catalyst is selected from boron trifluoride (complex), metal salts of trifluoromethanesulfonic acid, alkoxides of Group 4 metals, and halides of Group 4 metals, aluminum, iron or tin. The production method according to claim 1, wherein the production method is at least one Lewis acid. 4. The method according to claim 1, wherein the acid catalyst is a Bronsted acid selected from inorganic acids and organic sulfonic acids. 5. The bridged cyclic hydrocarbon having an alkylidene group is 2-alkylidene norbornane, 4-alkylidenetetracyclo [6.2.1 ^1,9 . ^13-6 . [ ^2,7 ] dodecane or 2-alkylidene adamantane. 6. The bridged cyclic hydrocarbon having an alkylidene group is obtained by subjecting a tertiary alcohol corresponding to the bridged cyclic hydrocarbon to a dehydration reaction in the presence of an acid catalyst. 5. The production method according to any one of 5. 7. A tertiary alcohol corresponding to a bridged cyclic hydrocarbon is 2-alkylnorbornan-2-ol, 4-alkyltetracyclo [6.2.1 ^1,9 . ^13-6 . 0 ^2,7 ]
Dodecane-4-ol or 2-alkyladamantane-
The production method according to claim 6, wherein the production method is 2-ol. 8. An organic amine content of 20 pp on an N basis.
a tertiary alkyl ester of (meth) acrylic acid having a molecular weight of m or less. 9. A tertiary alkyl ester of (meth) acrylic acid having a chlorine ion content of 20 ppm or less. 10. The organic amine content is 20 p
pm or less and the chlorine ion content is 20 pp
a tertiary alkyl ester of (meth) acrylic acid having a molecular weight of m or less.