JP2000309558A - Method for producing 2-adamantyl (meth) acrylates - Google Patents

Abstract

(57) [Summary] [PROBLEMS] A method that can be easily implemented on an industrial scale.
-Manufacture purified products of adamantyl (meth) acrylates. SOLUTION: According to the following reaction formula, 2-adamantyl (meth) acrylates (I) are produced from (meth) acrylic halide (II) and 2-adamantanols (III), and the organic solvent of the product After treating the solution with activated carbon and then removing the activated carbon, high quality 2-adamantyl (meth) acrylates (I) are removed from the solution. In the formula, R ¹ represents hydrogen or methyl, R ² represents hydrogen or lower alkyl, X represents halogen, and Y represents hydrogen, alkali metal or magnesium halide. The activated carbon treatment can be performed while containing the polar solvent used in the reaction,
After removing the reaction solvent, the reaction may be performed in a state of being dissolved in another non-polar solvent. For removing activated carbon after treatment, it is advantageous to use a filter precoated with silica gel.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a compound of the formula (I)

[0002]

Wherein R ¹ represents hydrogen or methyl;
² represents hydrogen or lower alkyl), and relates to a method for producing 2-adamantyl (meth) acrylates represented by the formula:

[0004]

^2. Description of the Related Art It has been found that 2-adamantyl (meth) acrylates represented by the above formula (I), particularly compounds in which R ² is alkyl, are useful as raw materials for chemically amplified resists. It is described in the gazette. As a method for producing such 2-adamantyl (meth) acrylates, it is common to react a corresponding (meth) acrylic acid halide with a corresponding 2-adamantanol. The product obtained by such a reaction has many impurities, and the crude product is often colored. Therefore, usually, a purification treatment is performed thereafter. For example, a method in which the above reaction is performed in an organic solvent, the resulting reaction mixture is subjected to post-treatment such as washing with water, the solvent is distilled off, and then column purification or distillation is considered.

For example, JP-A-10-182552 discloses a method of reacting 2-adamantanols obtained from 2-adamantanone and an alkyl Grignard compound or an alkyl alkali metal compound with (meth) acrylic halide. Since this product contains many impurities, the crude product obtained by performing the reaction in an organic solvent and then concentrating in the example of the above publication is subjected to column purification. I have.

[0006]

However, in column purification, for example, when a silica gel column is used, it is said that a large amount of silica gel (filler) is required, which is about 30 times by weight of the substrate to be purified. It takes time to pass the solution to be processed and is not efficient in terms of processing capacity. Further, if it is intended to purify by distillation, the thermal stability of the 2-adamantyl (meth) acrylate to be purified is not sufficient, so that special conditions such as addition of a stabilizer and high vacuum are required. Therefore, it is difficult to apply column purification or distillation to the purification of the above 2-adamantyl (meth) acrylates on an industrial scale.

The present inventors have conducted intensive studies to produce a purified product of the 2-adamantyl (meth) acrylate represented by the formula (I) by a method which can be easily carried out even on an industrial scale. It has been found that high-quality 2-adamantyl (meth) acrylates can be produced extremely efficiently by adsorbing and removing impurities produced as a result of the reaction between (meth) acrylic halide and 2-adamantanol with activated carbon, The present invention has been completed.

[0008]

That is, the present invention provides a compound of the formula (II)

[0009]

Wherein R ¹ is as defined above and X represents halogen, and a (meth) acrylic acid halide represented by the formula (III)

[0011]

(Wherein R ² is as defined above, and Y represents hydrogen, an alkali metal or a magnesium halide), and is reacted with a 2-adamantanol represented by the formula (I). A method of producing 2-adamantyl (meth) acrylates shown in the following, treating an organic solvent solution of the product with activated carbon, removing the activated carbon, and taking out purified 2-adamantyl (meth) acrylates. To provide.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the formula (II) representing a raw material (meth) acrylic halide, a halogen represented by X is
For example, it can be chlorine or bromine, and specific (meth) acrylic halides include acryloyl chloride, methacryloyl chloride, acryloyl bromide, and methacryloyl bromide. Also,
Formula representing the other raw material, 2-adamantanols
In (III), the lower alkyl represented by R ² may have, for example, about 1 to 4 carbon atoms. The alkali metal represented by Y can be, for example, lithium, sodium and the like, and the magnesium halide can be magnesium chloride, magnesium bromide and the like. Y is preferably hydrogen. Specific examples of 2-adamantanol include 2-adamantanol, 2-methyl-2-adamantanol, 2-ethyl-2-adamantanol, lithium 2-adamantoxide, sodium 2-adamantoxide, and 2-adamantoxide. Magnesium halide, lithium 2-methyl-2-adamantoxide, sodium 2-methyl-2-adamantoxide, 2-methyl-2-adamantoxide magnesium halide, lithium 2-ethyl-2-adamantoxide,
Sodium 2-ethyl-2-adamantoxide, 2-ethyl-2-adamantoxide magnesium halide and the like can be mentioned. Here, 2-adamantanols in which Y is an alkali metal or magnesium halide can be produced, for example, by reacting a corresponding ketone with an alkyl Grignard compound or an alkyl alkali metal compound (for example, JP-A-10-182552) ).

The method of the present invention is basically based on the above formula (I
(M) acrylic acid halide represented by the formula (I) and the above-mentioned formula (II)
2-adamantanol represented by the formula (I) is condensed to give 2-adamantyl (meth) represented by the formula (I).
This is for producing acrylates, and the condensation reaction itself can be carried out according to a known method. For example,
(Meth) acrylic halide of formula (II) and 2 of formula (III)
-A method of reacting adamantanols in a suitable solvent may be employed. As the reaction solvent used here, a polar organic solvent is advantageous, and specific examples thereof include acetone, methyl ethyl ketone, ketones such as methyl isobutyl ketone, and ethers such as tetrahydrofuran and tert-butyl methyl ether. Can be The solvent has the formula (I
(I) a (meth) acrylic halide and 2- (formula (III))
It is preferably used in the range of about 1 to 10 times by weight based on the total amount of adamantanols, and more preferably about 1 to 5 times by weight in consideration of volumetric efficiency and the like.

In the 2-adamantanols of the formula (III), when Y is hydrogen, hydrogen halide is formed by condensation, so that the reaction is advantageously carried out in the presence of a dehydrohalogenating agent. It is. As the dehydrohalogenating agent in this case, an organic amine such as triethylamine or pyridine, an inorganic base such as sodium carbonate or potassium carbonate, or the like can be used, and it is particularly preferable to use an organic amine. When a dehydrohalogenating agent is used, the 2-adamantanol of the formula (III) and the dehydrohalogenating agent are present in a suitable solvent, and the (meth) acrylic halide of the formula (II) is added thereto. The formula (I
A method of dissolving the (meth) acrylic halide of I) and the 2-adamantanols of the formula (III) in an appropriate solvent and adding a dehydrohalogenating agent thereto can be employed. When a dehydrohalogenating agent is used, its amount is determined by the formula (III)
-It is usually about 1 to 5 mol times, preferably about 1 to 3 mol times, relative to adamantanols.

In the reaction of the present invention, the molar ratio of the (meth) acrylic halide of the formula (II) to the 2-adamantanols of the formula (III) is an important factor for the smooth progress of the reaction. Generally, it is preferable to use the (meth) acrylic halide of the formula (II) in a ratio of about 1 to 3 mol per 1 mol of the 2-adamantanol of the formula (III). The more preferable molar ratio varies depending on the type of the dehydrohalogenating agent or the like. (Meth) acrylic halide is 1.1
When the inorganic base is used as the dehydrohalogenating agent, the amount of (meth) acrylic halide is about 2 to 3 times the molar amount of 2-adamantanol.

This reaction proceeds at any temperature from a low temperature of about −10 ° C. to a high temperature of about the boiling point of the reaction solvent, but the reaction is carried out at a temperature ranging from about 40 ° C. to the boiling point of the reaction solvent. Economical in terms of progress. Usually, the reaction can be carried out under normal pressure, and the reaction time is 2-3.
It is about 0 hours.

After the completion of the condensation reaction, if necessary, an excess amount of unreacted (meth) acrylic acid halide is converted into an ester by adding an alcohol, an aqueous solution of sodium bicarbonate or the like to deactivate the ester. After washing with saline, a treatment with activated carbon is performed according to the invention. This activated carbon treatment can be performed in a state where the product is dissolved in the reaction solvent. Depending on the conditions during the condensation reaction, a considerable amount of polymerization components may be produced as a by-product.In this case, when the product is dissolved in the reaction solvent which is a polar solvent, impurities of the polymerization system may be generated. May not be sufficiently removed.

Therefore, if the impurities in the polymerization system cannot be completely removed in the state where the product is dissolved in the reaction solvent, the polar reaction solvent is once removed from the reaction mixture by, for example, a method of concentration and distillation. After that, the obtained crude product is dissolved in a non-polar solvent, and activated carbon treatment is performed in this state, whereby impurities are efficiently removed, and 2-adamantyl (meth) acrylates of the formula (I) can be converted to high quality. Can be obtained at The non-polar solvent used in this case may be a non-polar hydrocarbon solvent, and specific examples thereof include aliphatic hydrocarbon solvents such as hexane and heptane. The non-polar solvent in this case is 2
0.5 with respect to adamantyl (meth) acrylates
It is used in an amount of about 10 to 10 times by weight, preferably about 1 to 5 times by weight.

It is also effective to perform the activated carbon treatment in two stages, for example, by performing an activated carbon treatment in a state of being dissolved in a polar solvent which is a reaction solvent, and then performing an activated carbon treatment again in a state of being dissolved in a non-polar solvent. It is. For example, a reaction mixture in which the target substance is dissolved in a reaction solvent is treated with activated carbon,
Next, the activated carbon was removed, the reaction solvent was removed from the resulting solution by concentration and distillation, etc., and then the crude product was dissolved in a non-polar solvent and treated again with activated carbon,
Such two-stage activated carbon treatment can be performed.

Activated carbon treatment is usually the object of acquisition, 2-
Activated carbon may be added to a solution in which adamantyl (meth) acrylates are dissolved in a reaction solvent or a non-polar solvent, and the mixture may be stirred so that the solution and the activated carbon come into good contact with each other. It is about one minute to one hour. There are various types of activated carbon, but the type is not particularly limited as long as it has an adsorption ability. In this treatment, the activated carbon is preferably used in an amount of about 0.05 to 1 times by weight, more preferably 0.1 to 1 times by weight, of the 2-adamantyl (meth) acrylates to be obtained.
It is about 0.7 times the weight.

After the treatment with activated carbon, the activated carbon used for the treatment remains as a solid, which must be removed. Activated carbon can be removed by passing the solution in a suspended state through a conventional filter. In addition,
Depending on the conditions at the time of the condensation reaction, monomeric impurities such as unreacted 2-adamantanol represented by the formula (III) may be present in a non-negligible amount. After that, simply performing ordinary filtration may not sufficiently remove such monomeric impurities.

Therefore, when a large amount of such monomeric impurities are contained, it is effective to precoat the filter with silica gel at the time of filtration. For the pre-coating, for example, a method in which silica gel powder is spread over a filter, and a suitable solvent, for example, hexane or heptane, is passed through the solvent constituting the solution to be treated, and the silica gel is adhered, and the silica gel is dispersed in a suitable solvent. Let
The solution can be flowed through a filter and a method of attaching silica gel can be used. When such silica gel pre-coating is performed, 0.05 parts of the 2-adamantyl (meth) acrylate, which is the object of purification, is used.
Silica gel may be used in a range of about 1 to about 1 times by weight, and a more preferable pre-coat amount is 2-adamantyl (meth).
It is about 0.1 to 0.7 times the weight of acrylates.

As described above, silica gel is often used for column purification. In this case, the silica gel is 30 times by weight based on the substrate to be purified (2-adamantyl (meth) acrylates in the case of the present invention). It is said that a certain amount of silica gel is required. However, when the solution treated with activated carbon is treated as in the present invention, the amount of silica gel may be significantly smaller than that in the case of column purification.

As described above, the solution after the activated carbon treatment and then the removal of the activated carbon is subjected to an appropriate post-treatment such as concentration to obtain a high-quality compound represented by the formula (I) 2 Adamantyl (meth) acrylates can be taken out;

[0026]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the examples,% representing the concentration is based on weight unless otherwise specified. In the following examples, the reaction was controlled by gas chromatography, and the production of the final product was confirmed by proton nuclear magnetic resonance (NMR), gas chromatography, and gel permeation chromatography (GPC). confirmed.

Example 1 2.1 liters of methyl isobutyl ketone, 2-methyl-
665.2 g (4.0 mol) of 2-adamantanol and 607.29 g (6.0 mol) of triethylamine were charged into a reaction vessel and heated to 60 ° C. with stirring. A solution of 434.55 g (4.8 mol) of acryloyl chloride dissolved in 0.4 liter of methyl isobutyl ketone was added dropwise thereto. At the end of the dropwise addition, the temperature of the reaction was raised to nearly 80 ° C. by the heat of reaction. Subsequently, the mixture was stirred at 80 ° C. for 2 hours to complete the reaction. After cooling, the temperature was kept at 40 ° C. or lower, and 64.02 g (2.0 mol) of methanol was added dropwise to deactivate unreacted acryloyl chloride. Next, 3.3 liters of water was added for washing and liquid separation, and then 2.8 liters of saturated saline was added to the organic layer, followed by washing again and liquid separation. After 204 g of activated carbon “carboraffin” manufactured by Takeda Pharmaceutical Co., Ltd. was charged into the organic layer after the liquid separation and stirred for 1 hour, the mixture was filtered and washed with 2 liters of methyl isobutyl ketone. The filtrate and the washings are combined, concentrated at a bath temperature of 45 ° C, and crude 2-
886.17 g of methyl-2-adamantyl acrylate
I got

To 886.17 g of the crude 2-methyl-2-adamantyl acrylate, 1,635 g of hexane and 204 g of activated carbon (carboraffin) were added, and the mixture was stirred for 1 hour. Then, the mixture was filtered through a filter precoated with 204 g of silica gel to give hexane. Washed with 3 liters. The combined filtrate and washings were concentrated at a bath temperature of 45 ° C. to give pure 2-methyl-2-adamantyl acrylate 83 as a slightly yellow transparent liquid.
2.37 g were obtained. The yield based on the charged 2-methyl-2-adamantanol was 94%. NM of this compound
The R pattern was consistent with the purified column product. The purity of this compound determined by gas chromatography internal standard method was 9%.
The GPC area percentage purity by 9%, ultraviolet (UV) detection was 96%, and the GPC area percentage purity by differential refractive index (RI) detection was 97%.

Example 2 A reaction vessel was charged with 33.26 g of methyl ethyl ketone, 16.63 g (0.1 mol) of 2-methyl-2-adamantanol and 30.36 g (0.3 mol) of triethylamine, and stirred at 60 ° C. Temperature. A solution of 13.58 g (0.15 mol) of acryloyl chloride dissolved in 16.63 g of methyl ethyl ketone was added dropwise thereto. At the end of the dropping, the temperature was raised to 77 ° C. by the heat of reaction and the mixture was boiling.
Subsequently, stirring was continued for 3 hours while maintaining the boiling state to complete the reaction. After cooling, the temperature was kept at 40 ° C. or lower, and 3.20 g (0.1 mol) of methanol was added dropwise to inactivate unreacted acryloyl chloride. Next, 103 g of water was added for washing and liquid separation, and then 10 g of activated carbon (carboraffin) was added to the brown organic layer, followed by stirring, followed by filtration and washing with methyl ethyl ketone. The filtrate and the washing were combined, and concentrated at a bath temperature of 45 ° C. to obtain 21.68 g of crude red-orange 2-methyl-2-adamantyl acrylate.

To 10 g of the crude 2-methyl-2-adamantyl acrylate, 10 g of hexane and 5 g of activated carbon (carboraffin) were added, and the mixture was stirred for 1 hour and filtered.
Further washing with hexane. The filtrate and the washing were combined and concentrated at a bath temperature of 45 ° C. to obtain 9.25 g of pure 2-methyl-2-adamantyl acrylate as a pale yellow transparent liquid. The yield based on the charged 2-methyl-2-adamantanol was 98%. The NMR pattern of this compound was almost the same as that of the purified column product. The purity of this compound by gas chromatography internal standard method is 100
%, GPC area percentage purity by UV detection is 89%, R
The GPC area percentage purity by I detection was 93%.

Example 3 To 10 g of the crude 2-methyl-2-adamantyl acrylate obtained in the first half of Example 2, 10 g of hexane and 5 g of activated carbon (carborafine) were added, and the mixture was stirred for 1 hour.
The mixture was filtered through a filter precoated with 5 g of silica gel to obtain 8.75 g of pure 2-methyl-2-adamantyl acrylate acrylate as a nearly colorless transparent liquid. Preparation 2
The yield based on -methyl-2-adamantanol was 93%. The NMR pattern of this compound was consistent with the purified column product. The purity of this compound was 100% according to the gas chromatography internal standard method, and GP was determined by UV detection.
The C area percentage purity was 98%, and the GPC area percentage purity by RI detection was 95%.

Comparing the results of Example 3 with the results of Example 2, it was found that by pre-coating the filter with silica gel, trace impurities were removed and the hue was also improved.

EXAMPLE 4 598.54 g of methyl isobutyl ketone and 74.82 g (0.45 mol) of 2-methyl-2-adamantanol were charged into a reaction vessel, and 72.75 g (0.675 g) of methacryloyl chloride was stirred at room temperature under stirring. Mol) was added. Thereto, 82.79 g (0.81 mol) of triethylamine was added dropwise, and after aging for 15 minutes, the temperature was raised to 80 ° C., and further kept at that temperature for 24 hours to continue the reaction. After cooling, keep at 10.degree. C. or less and 14.42 g of methanol (0.4%).
5 mol) was added dropwise to inactivate unreacted methacryloyl chloride. Next, 223 g of water was added for washing and liquid separation. 112 g of a saturated saline solution was added to the organic layer, and the mixture was neutralized with a 5% aqueous sulfuric acid solution to pH 7 to 8, and then separated.
The separated organic layer was concentrated at a bath temperature of 40 ° C. to give a brown crude 2
-Methyl-2-adamantyl methacrylate 109.9
3 g were obtained.

This crude product was dissolved in 316 g of hexane, 21 g of activated carbon (carboraffin) was added, and the mixture was stirred for 1 hour. The mixture was filtered with a filter precoated with 21 g of silica gel and washed with hexane. The combined filtrate and washings were concentrated at a bath temperature of 45 ° C. to give 99.36 g of pure 2-methyl-2-adamantyl methacrylate as a colorless transparent liquid. The yield based on the charged 2-methyl-2-adamantanol was 94%. The NMR pattern of this compound was almost the same as that of the purified column product. The purity of this compound determined by gas chromatography internal standard method was 93.
%, GPC area percentage purity by UV detection is 86%, R
The GPC area percentage purity by I detection was 94%.

Example 5 116.41 g of tetrahydrofuran and 2-methyl-
16.63 g (0.1 mol) of 2-adamantanol was charged into a reaction vessel, and 21.56 g (0.2 mol) of methacryloyl chloride was added thereto while stirring at -10 ° C. Then, 25.56 g (0.25 mol) of triethylamine was added dropwise,
After aging for 15 minutes, the temperature was raised to the reflux temperature of 69 ° C., and the stirring was continued for 11 hours while maintaining the reflux state to cause a reaction. After cooling, at −10 ° C., 6.41 g of methanol (0.2 g).
Mol) was added dropwise to inactivate unreacted methacryloyl chloride. Next, methyl isobutyl ketone 116.41
After dilution with g, 68.87 g of water was added to wash and separate. 112 g of saturated saline was further added to this organic layer,
The mixture was neutralized with a 5% aqueous sulfuric acid solution under ice-cooling so that the pH became 7 to 8, and then separated. The organic layer after liquid separation was concentrated at a bath temperature of 40 ° C. to obtain 23.62 g of brown crude 2-methyl-2-adamantyl methacrylate.

This crude product was dissolved in 70.32 g of hexane, 11.72 g of activated carbon (carboraffin) was added, and the mixture was stirred for 1 hour. The mixture was filtered through a filter precoated with 11.72 g of silica gel, and washed with hexane. . The filtrate and the washing were combined and concentrated at a bath temperature of 40 ° C. to obtain 19.77 g of pure 2-methyl-2-adamantyl methacrylate as a slightly yellow transparent liquid. The yield based on the charged 2-methyl-2-adamantanol was 84%. The NMR pattern of this compound was almost the same as that of the purified column product.
In addition, the purity of this compound by gas chromatography internal standard method was 98%, the purity of GPC area percentage by UV detection was 96%, and the purity of GPC area percentage by RI detection was 99%.

Example 6 In Example 1, 2-ethyl-2-adamantanol was used instead of 2-methyl-2-adamantanol.
Using 3 g (4.0 mol), the temperature was raised to 80 ° C. with stirring, and a solution of acryloyl chloride dissolved in methyl isobutyl ketone was added dropwise thereto.
The procedure was carried out in the same manner as in Example 1 except that the stirring was continued for a period of time to complete the reaction, whereby 960.91 g of crude 2-ethyl-2-adamantyl acrylate was obtained.

Except for using 960.91 g of the crude 2-ethyl-2-adamantyl acrylate, 9 liters of hexane and 612 g of silica gel, treatment with activated carbon was carried out in accordance with Example 1 to obtain a fine yellow transparent liquid.
672.07 g of ethyl-2-adamantyl acrylate
I got The NMR pattern of this compound was consistent with the purified column product. The purity of this compound by gas chromatography internal standard method was 99%, the GPC area percentage purity by ultraviolet (UV) detection was 96%, and the differential refractive index (R
I) GPC area percentage purity by detection was 97%.

It was confirmed that the 2-adamantyl (meth) acrylates obtained in each of the examples had no significant difference from the purified column products obtained by the conventional method when used as a resin material for a chemically amplified resist.

[0040]

According to the present invention, compared to the conventional methods such as column purification and distillation, the equipment and method are extremely general,
It is possible to efficiently produce high-quality 2-adamantyl (meth) acrylates.

Claims (7)

[Claims] (1) Formula (II) (Wherein, R ¹ represents hydrogen or methyl, and X represents a halogen).
(III) (Wherein R ² represents hydrogen or lower alkyl, Y represents hydrogen, an alkali metal or magnesium halide), and reacted with a 2-adamantanol represented by the formula (I) Wherein R ¹ and R ² are as previously defined, to produce a 2-adamantyl (meth) acrylate, treating the organic solvent solution of the product with activated carbon, A method for producing 2-adamantyl (meth) acrylates represented by the formula (I), wherein the product is taken out after the removal. 2. The method according to claim 1, wherein the reaction between the (meth) acrylic halide and the 2-adamantanol is carried out in a polar organic solvent, and the mixture is treated with activated carbon while containing the polar organic solvent. 3. The reaction between a (meth) acrylic halide and 2-adamantanol is carried out in a polar organic solvent. After the reaction is completed, the polar organic solvent is removed, and the product is treated with another non-polar organic solvent. The method according to claim 1, wherein the solution is dissolved in a solvent, and the nonpolar organic solvent solution is treated with activated carbon. 4. After completion of the reaction, the mixture is treated with activated carbon while containing a polar organic solvent, then the activated carbon is removed and the polar organic solvent is removed, and then the product is dissolved in another non-polar organic solvent. 4. The method according to claim 3, wherein the activated carbon is treated again with activated carbon. 5. The method according to claim 3, wherein the non-polar organic solvent is an aliphatic hydrocarbon. 6. The method according to claim 1, wherein the activated carbon after the treatment is removed by filtration. 7. The method according to claim 6, wherein the filtration is performed using a filter precoated with silica gel.