JP2005082563A - Process for producing 1,3-adamantanediol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide 1,3-adamantanediol, which is important as a raw material for electronic materials such as highly functional materials such as heat resistant polymers and resists for semiconductors, with a relatively low value of 0.4 MPa or less, preferably 0.3 MPa or less. To provide a method for manufacturing inexpensively under pressure.
For example, 1,3-dihalogenated adamantane such as 1,3-dichloroadamantane obtained by halogenating adamantane with chlorosulfonic acid is used as a raw material, and the 1,3-dihalogenated adamantane is N, N Reaction with water in the presence of a water-soluble organic solvent such as dimethylformamide and an alkali metal salt or alkaline earth metal salt of a carboxylic acid such as sodium acetate to produce 1,3-adamantanediol.
[Selection figure] None

Description

  The present invention relates to a method for producing 1,3-adamantanediol useful as a raw material for functional materials and electronic materials.

  Since adamantane derivatives have excellent heat resistance and high transparency, they are compounds that are expected to be applied to highly functional materials such as heat resistant polymers and electronic materials such as semiconductor resists. Among these, 1,3-adamantanediol is important as a raw material for synthesizing various adamantane derivatives including functional polymers.

  As a method of directly synthesizing 1,3-adamantanediol from adamantane, a method in which adamantane is oxidized with oxygen in the presence of an imide compound and a cobalt compound (see, for example, Patent Document 1), or adamantane in the presence of a ruthenium compound is hypochlorous. A method of oxidizing with chloric acids (for example, see Patent Document 2) has been reported. However, when these methods are used, the target product is usually obtained as a mixture with adamantanol, adamantanone, etc., and the yield is 58% in the case of the reaction using the imide compound, and the ruthenium catalyst is used. In the case of the reaction, it was 55% and neither was satisfactory.

  As another method, a method of obtaining 1,3-adamantanediol from 1,3-dibromoadamantane has been proposed (see, for example, Patent Documents 3 and 4). In this method, 1,3-dibromoadamantane is reacted with water in the presence of pyridine or a tertiary amine compound to obtain 1,3-adamantanediol in a high yield of 85% or more.

JP-A-9-327626 JP 2000-219646 A Japanese Patent Laid-Open No. 3-118342 JP 2000-327604 A

  However, in the above method using 1,3-dibromoadamantane as a raw material, it is necessary to carry out under a high temperature of 150 ° C. under a pressure of 0.5 to 1 MPa. Furthermore, the pyridine and tertiary amine compounds used in the reaction are added for the purpose of absorbing the hydrogen halide gas generated during the reaction, but there is a problem that it is somewhat expensive to use as such an absorbent. there were. Therefore, an object of the present invention is to provide a method for efficiently producing 1,3-adamantanediol under mild conditions.

  The present inventors have intensively studied to solve the above problems. As a result, when the 1,3-dihalogenated adamantane is reacted with water in the presence of a water-soluble organic solvent, the above problem is solved by adding an alkali metal salt or alkaline earth metal salt of carboxylic acid. The present inventors have found that the present invention can be accomplished and have completed the present invention.

  That is, the present invention is characterized by reacting 1,3-dihalogenated adamantane with water in the presence of a water-soluble organic solvent and an alkali metal salt of a carboxylic acid or an alkaline earth metal salt of a carboxylic acid. This is a method for producing 3-adamantanediol.

  When the reaction is carried out without the presence of the above specific salt, not only the inside of the system needs to be pressurized because of the high temperature, but also the pressure rises due to the generation of hydrogen halide. When an amine compound is used as the hydrogen halide trapping agent, the increase in pressure due to the generation of hydrogen halide can be suppressed, but the reaction must still be performed under a relatively high pressure. On the other hand, in the production method of the present invention, the specific carboxylate that probably coexists chemically absorbs the hydrogen halide gas generated during the reaction and increases the boiling point of the reaction solution by adding the salt. This seems to be due to the combined effect that the water vapor pressure decreases, but it is possible to reduce the pressure during the reaction. In addition, when other salts are used instead of the specific carboxylate, the reaction is inhibited, whereas when the specific carboxylate is used, such reaction inhibition does not occur. Absent.

  Thus, by the method of the present invention, 1,3-adamantanediol, which can be suitably used as a raw material for functional materials such as heat-resistant polymers and electronic materials such as resists, is converted into an expensive tertiary amine. In addition, it can be efficiently produced under mild reaction conditions, specifically under a slight pressure of 0.4 MPa or less, preferably 0.3 MPa.

  In the production method of the present invention, 1,3-adamantanediol is obtained by reacting 1,3-dihalogenated adamantane with water in the presence of a water-soluble organic solvent and an alkali metal salt or alkaline earth metal salt of a carboxylic acid. To manufacture.

  The 1,3-dihalogenated adamantane used as a raw material in the present invention is one in which the 1-position and 3-position hydrogen atoms of adamantane are substituted by halogens such as chlorine and bromine. Examples include 1,3-dichloroadamantane, 1,3-dibromoadamantane, 1,3-diiodoadamantane, and the like.

  As the 1,3-dihalogenated adamantane, any reagent or industrially available one can be used without particular limitation. Of course, it is also possible to use 1,3-dihalogenated adamantane synthesized from adamantane, which is industrially easily available and inexpensive, as a starting material. In this case, as a method for producing 1,3-dihalogenated adamantane, a method in which boron halide and aluminum halide are used as described in Non-Patent Document 1 or Non-Patent Document 2 described above, or Non-Patent Document 3. A method using halosulfonic acid as described in 3 or a method in which general direct halogenation using halogen as described in Non-Patent Document 4 is applied to adamantane, although the yield is poor. be able to. Among these methods, it is preferable to employ a method in which adamantane is reacted with halosulfonic acid because the target product is easily separated with a high yield. Hereinafter, a method for producing 1,3-dihalogenated adamantane by reacting adamantane with halosulfonic acid will be described.

  The above reaction can be suitably carried out by mixing adamantane and halosulfonic acid in a solvent or in the absence of a solvent. From the standpoint that both can be efficiently contacted and the reaction temperature is easily controlled, a solvent is used, or an excess amount of halosulfonic acid is used to give the halosulfonic acid a function as a solvent. Is preferred. Any solvent can be used without limitation as long as it has no reactivity with halosulfonic acid. Specifically, a chlorine-based solvent such as dichloromethane or 1,2-dichloroethane can be preferably used as the organic solvent, and concentrated sulfuric acid or the like can be preferably used as the inorganic solvent.

As adamantane and halosulfonic acid used in the above reaction, those which are available as reagents or industrially can be used without particular limitation. Here, the halosulfonic acid means a compound represented by XSO ₃ H (wherein X represents a halogen). Examples of the halosulfone that can be suitably used include chlorosulfonic acid, bromosulfonic acid, iodosulfonic acid and the like, and it is particularly preferable to use chlorosulfonic acid because of its availability.

  In the above reaction, the amount ratio (charge ratio) of adamantane and halosulfonic acid to be used is not particularly limited, but if the amount of halosulfonic acid is too small, the reaction will not proceed sufficiently, so halosulfonic acid is 1 mole of adamantane. The amount is preferably 4 mol or more. In order to further improve the yield or to function as a reaction medium, the amount ratio of halosulfonic acid is particularly preferably 6 to 12 mol per 1 mol of adamantane.

  Mixing of adamantane and halosulfonic acid may be performed by any method, but it is usually preferable to add halosulfonic acid dropwise to adamantane or a solution thereof. The reaction can be carried out at normal pressure, and is usually carried out in the range of −5 ° C. to 35 ° C. for 6 to 48 hours.

  The 1,3-dihalogenated adamantane may be separated from the reaction solution obtained by such a reaction by any known method. For example, by pouring the reaction solution after completion of the reaction into ice, After decomposing the halosulfonic acid remaining in the solution, a reactive product deposited by adding a solvent is extracted, then the extract is washed with an alkali, washed with water, and then the solvent is removed and dried to obtain 1,3-dihalogen. A solid containing 85 to 95% by mass of adamantane can be obtained. In this case, an organic solvent that can be used as a reaction solvent can be used as the solvent. The 1,3-dihalogenated adamantane thus obtained is used as a raw material in the production method of the present invention as it is or after purification as necessary.

  In the production method of the present invention, 1,3-dihalogenated adamantane is hydrolyzed to produce 1,3-adamantanediol. Hydrolysis is carried out using a water-soluble organic solvent and an alkali metal salt of carboxylic acid or alkaline earth of carboxylic acid. It is necessary to carry out in the presence of a metal salt (hereinafter also referred to as a specific carboxylate). When the reaction is carried out in the absence of the specific carboxylate, the effect of reducing the reaction pressure cannot be obtained. In addition, when the reaction is carried out in the absence of an aqueous organic solvent, the reaction rate becomes extremely slow and virtually no reaction occurs.

  The specific carboxylate used in the present invention is not particularly limited as long as it is an alkali metal salt or alkaline earth metal salt of carboxylic acid, and a known compound can be used. Specific carboxylates that can be suitably used in the present invention include salts of carboxylic acids such as formic acid, acetic acid and propionic acid and alkali metals such as lithium, sodium and potassium, or alkaline earth metals such as magnesium and calcium. Examples of salts that can be used particularly preferably include sodium formate, potassium formate, lithium acetate, sodium acetate, potassium acetate, magnesium acetate, calcium acetate, sodium propionate and the like. These specific carboxylate salts are industrially cheaper than pyridine and tertiary amine compounds, but lithium acetate, sodium acetate or potassium acetate is used among them because it is cheaper to obtain. Most preferred. In the production method of the present invention, these specific carboxylates have an action of absorbing the hydrogen halide formed as a by-product during the reaction, but when other hydrogen halide absorbents are used, the target product is efficiently obtained at normal pressure. Is difficult. For example, when an alkali such as sodium hydroxide or tetramethylammonium hydroxide is used as the hydrogen halide absorbent, the reactivity of the hydrolysis reaction is significantly impaired, and amines other than tertiary amine compounds are used. When a compound is used, a side reaction is induced. In the present invention, the specific carboxylate is used in an amount of 1 mol of 1,3-dihalogenated adamantane when the specific carboxylate is an alkali metal salt for the purpose of absorbing by-produced hydrogen halide. 2 mol or more, when the specific carboxylate is an alkaline earth metal salt, it is not particularly limited as long as it is 1 mol or more per 1 mol of 1,3-dihalogenated adamantane, but it surely absorbs all the hydrogen halide. Therefore, in the former case, the amount is preferably 2 to 2.4 mol, particularly 2 to 2.2 mol, based on 1 mol of 1,3-dihalogenated adamantane, and in the latter case, 1,3-dihalogenated adamantane is preferably 1 to 1.2 mol, more preferably 1 to 1.1 mol, per 1 mol.

  The water-soluble organic solvent used in the present invention means an organic solvent that can be arbitrarily mixed with water at room temperature. As the aqueous solvent, a known organic solvent can be used without any limitation as long as the above conditions are satisfied. However, the relative dielectric constant at 25 ° C. is 10 because the reaction proceeds relatively quickly. In particular, those of 30 or more are preferably used. Specific examples of such water-soluble organic solvents include methanol (relative permittivity 33.1), ethanol (relative permittivity 23.8), 2-propanol (relative permittivity 18.3), 2-methoxyethanol. (Relative permittivity 16.9), 2-ethoxyethanol (relative permittivity 29.6), acetone (relative permittivity 20.7), nitromethane (relative permittivity 35.9), acetonitrile (relative permittivity 37.5) ), N, N-dimethylformamide (relative permittivity 36.7), N, N-dimethylacetamide (relative permittivity 37.8), N-methylformamide (relative permittivity 182), formamide (relative permittivity 111) In particular, N, N-dimethylformamide is used because the reaction proceeds very easily and there are few side reactions, the vapor pressure during the reaction is relatively low, and the treatment after the reaction is easy. And N, N-dimethylacetamide are preferred. In the production method of the present invention, pyridine (relative dielectric constant: 12.3) can be used as an aqueous organic solvent depending on the reaction conditions. In the present invention, the use amount of the water-soluble organic solvent is not particularly limited, but considering the reactivity, it is used in an amount of 1 mol or more, particularly 2 to 20 mol, per 1 mol of 1,3-dihalogenated adamantane. It is preferable to do this. The amount of water used for the hydrolysis is not particularly limited as long as it is 2 mol or more with respect to 1 mol of 1,3-dihalogenated adamantane, but considering the reactivity and solubility of the product, The amount is preferably 5 mol or more, particularly 20 to 500 mol per mol of 1,3-dihalogenated adamantane.

  The hydrolysis reaction in the production method of the present invention is suitably performed by, for example, charging 1,3-dihalogenated adamantane, a water-soluble organic solvent, water, and a carboxylate salt in an autoclave, and sealing and heating to 150 ° C with stirring. It can be carried out. At this time, it is desirable to sufficiently substitute the inside of the reaction system with an inert gas such as nitrogen in order to prevent the side reaction from proceeding.

  Although reaction conditions are not specifically limited, It is preferable to implement reaction temperature at 120-200 degreeC, especially 140-180 degreeC. The reaction time varies depending on the concentration of 1,3-dihalogenated adamantane in the reaction solution, but is preferably 3 to 48 hours in order to complete the reaction. In order to prevent evaporation of the solvent and achieve an appropriate reaction temperature, the reaction is usually carried out in a closed system, and the pressure in that case is about 0.2 to 0.5 MPa (the reaction pressure is equal to the reaction temperature). Dependent). This pressure is about 0.1 to 0.3 MPa lower than the pressure during the reaction at the same temperature when no specific carboxylate is added. In the conventional reaction using 1,3-dibromoadamantane, the target product could not be obtained in a high yield at a reaction pressure of 0.4 MPa or less. However, in the production method of the present invention, 0.4 MPa or less, preferably 0 Even when the reaction is carried out under a pressure of 3 MPa or less, the target product can be obtained in a high yield.

  In the hydrolysis reaction in the production method of the present invention, since the produced 1,3-adamantanediol is soluble in a solvent containing water, the reaction solution changes from a suspended state to a transparent solution as the reaction proceeds. The method for isolating 1,3-adamantanediol dissolved in the reaction solution after completion of the reaction is not particularly limited, but the following method is preferably employed from the viewpoint of easy operation. That is, after filtering the reaction solution, an alkali or an aqueous solution thereof is added to the solution, and the generated hydrogen halide (absorbed by the specific carboxylate and present in the form of a halide salt) is treated. As the alkali, sodium carbonate, potassium carbonate, sodium hydroxide, sodium hydrogen carbonate and the like can be used. Thereafter, an inorganic salt such as sodium chloride is added to the solution so as to be saturated, an organic solvent such as tetrahydrofuran is added to extract the target product, the solvent is removed, and drying is further performed, followed by acetone, ethyl acetate, etc. The method of washing with a polar solvent having a low solubility of 1,3-adamantanediol can be suitably employed. By such a method, a white solid of 1,3-adamantanediol can be obtained.

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

Production Example 1
100 g (0.74 mol) of adamantane was placed in a 1 (l) four-necked flask and dried through nitrogen gas. Next, while flowing nitrogen, the temperature was cooled to 0 ° C., and 514 g (4.4 mol) of chlorosulfonic acid was added dropwise. When the temperature of the suspended reaction solution was raised to 10 ° C., foaming started from the reaction solution. When the temperature was maintained until foaming subsided, the solution became a transparent homogeneous solution after 2 hours. Next, when the temperature was raised to 25 ° C., foaming gently resumed and the reaction was continued for 6 hours. The suspended reaction solution was poured into a large amount of ice water in small portions, extracted by adding 300 g of chloroform, washed with alkali, washed with water, then the solvent was removed, and dried to give 148 g (yield 98%). A yellow solid was obtained. The content of 1,3-dichloroadamantane in the solid was 92% by mass.

Example 1
30.0 g (0.15 mol) of 1,3-dichloroadamantane obtained in Production Example 1 was placed in a pressure resistant reactor, 21.4 g (0.29 mol) of N, N-dimethylformamide, and 24.0 g of sodium acetate (0. 29 mol) and 90.0 g (5.0 mol) of ion-exchanged water were added, and after purging with nitrogen, sealed and reacted at 150 ° C. for 18 hours. The solution which was initially in a suspended state became a transparent homogeneous solution at the end of the reaction. The maximum pressure during the reaction was 0.29 MPa. Thereafter, 15.5 g (0.15 mol) of sodium carbonate is added to the reaction solution, about 5 g of sodium chloride and 400 ml of tetrahydrofuran are added to separate the solution, 200 ml of tetrahydrofuran is further added to the aqueous phase, and the organic phases are combined. After removing the solvent, acetone was added and heated to 40 ° C. and stirred for 1 hour, then cooled to 0 ° C., filtered and dried to obtain 21.8 g (based on the pure content of 1,3-dichloroadamantane). Thus, a white solid having a substantial yield of 96% was obtained.

  When this white solid was analyzed by gas chromatography, the content of 1,3-adamantanediol was 99% by weight.

Example 2
In Example 1, in place of sodium acetate, 19.1 g (0.29 mol) of lithium acetate was used and the same results were obtained. As a result, 21.8 g (substantial yield based on the pure content of 1,3-dichloroadamantane) 96%) of a white solid. The maximum pressure during the reaction was 0.29 MPa. As a result of analyzing the obtained white solid, the content of 1,3-adamantanediol was 99% by weight.

Example 3
In Example 1, 19.7 g (0.29 mol) of sodium formate was used instead of sodium acetate, and the same results were obtained. As a result, 21.6 g (substantial yield based on the pure content of 1,3-dichloroadamantane) 95%) of a white solid. The maximum pressure during the reaction was 0.29 MPa. As a result of analyzing the obtained white solid, the content of 1,3-adamantanediol was 99% by weight.

Example 4
In Example 1, 25.2 g (0.29 mol) of N, N-dimethylacetamide was used in place of N, N-dimethylformamide, and the same procedure was performed. As a result, 21.8 g (pure content of 1,3-dichloroadamantane was obtained. The white solid was obtained in an actual yield of 96%. The maximum pressure during the reaction was 0.29 MPa. As a result of analyzing the obtained white solid, the content of 1,3-adamantanediol was 99% by weight.

Example 5
In Example 1, 17.4 g (0.29 mol) of 2-propanol was used instead of N, N-dimethylformamide, and the same results were obtained. As a result, 20.7 g (based on the pure content of 1,3-dichloroadamantane) A white solid having a substantial yield of 92%) was obtained. The maximum pressure during the reaction was 0.29 MPa. As a result of analysis of the obtained white solid, the content of 1,3-adamantanediol was 98% by weight.

Comparative Example 1
In Example 1, 17.0 g (0.29 mol) of sodium chloride was used in place of sodium acetate, and the same results were obtained. As a result, 2.7 g (substantial yield based on the pure content of 1,3-dichloroadamantane) 12%) of a white solid was obtained. The maximum pressure during the reaction was 0.30 MPa. As a result of analysis of the obtained white solid, the content of 1,3-adamantanediol was 86% by weight.

Comparative Example 2
In Example 1, 21.3 g (0.15 mol) of hydrogen disodium phosphate was used instead of sodium acetate, and the same results were obtained. As a result, 13.3 g (based on the pure content of 1,3-dichloroadamantane, A white solid having a substantial yield of 59% was obtained. The maximum pressure during the reaction was 0.29 MPa. As a result of analysis of the obtained white solid, the content of 1,3-adamantanediol was 89% by weight.

Comparative Example 3
In Example 1, it carried out similarly without adding sodium acetate. As a result, 21.1 g (substantial yield of 93% based on the pure content of 1,3-dichloroadamantane) was obtained as a white solid. The maximum pressure during the reaction was 0.82 MPa. As a result of analysis of the obtained white solid, the content of 1,3-adamantanediol was 98% by weight.

Comparative Example 4
In Example 1, 22.9 g (0.29 mol) of pyridine was used instead of N, N-dimethylformamide, and the same operation was carried out without adding sodium acetate. As a result, 20.1 g (of 1,3-dichloroadamantane) was obtained. A white solid having an actual yield of 89% based on the pure content was obtained. The maximum pressure during the reaction was 0.46 MPa. As a result of analysis of the obtained white solid, the content of 1,3-adamantanediol was 98% by weight.

Claims (3)

Production of 1,3-adamantanediol characterized by reacting 1,3-dihalogenated adamantane with water in the presence of a water-soluble organic solvent and an alkali metal salt of a carboxylic acid or an alkaline earth metal salt of a carboxylic acid Method. The method for producing 1,3-adamantanediol according to claim 1, wherein at least one selected from the group consisting of sodium acetate, potassium acetate and lithium acetate is used as the alkali metal salt of carboxylic acid or the alkaline earth metal salt of carboxylic acid. . The method according to claim 1 or 2, further comprising a step of halogenating adamantane using halosulfonic acid as a step of producing 1,3-dihalogenated adamantane used as a raw material.