JP2010150220A - Method for producing adamantanecarboxylate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an adamantanecarboxylate, efficiently producing an adamantanecarboxylate that has an adamantane skeleton and is excellent in optical characteristics, heat resistance, acid dissociation, or the like. <P>SOLUTION: The method of producing an adamantanecarboxylate includes mixing adamantanediol with a proton acid, subsequently adding carbon monoxide or a source of carbon monoxide to the mixture, subsequently adding an alcohol compound to cause the same to react, extracting the reaction product with an organic solvent, and subsequently separating and purifying the extract. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention has an adamantane skeleton and is excellent in optical properties, heat resistance, acid dissociation properties, etc., and optical materials such as cross-linked resins, optical fibers, optical waveguides, optical disk substrates, and photoresists, raw materials thereof, pharmaceutical and agricultural chemical intermediates The present invention relates to a method for producing novel adamantane carboxylic acid esters useful as products and other various industrial products.

  Since adamantane has a rigid structure and high symmetry, and its derivative exhibits a unique function, a highly functional resin material, a pharmaceutical intermediate, an optical material (Patent Documents 1 and 2), a photoresist (Patent Document) It is known that it is useful for 3). In particular, adamantane carboxylic acid esters are useful as polyester raw materials. An adamantane derivative is used as a raw material for a photoresist material described in Patent Document 4.

特開平６−０３０５０４４号公報 特公平１−５３６３３号公報 特開平４−３９６６５号公報 特開２００６−０１６３７９号公報 Usually, the adamantanecarboxylic acid ester represented by the formula (3) is prepared by reacting the adamantanediol represented by the formula (1) with carbon monoxide or a carbon monoxide source in a protonic acid, Is crystallized with a poor solvent such as water to isolate the adamantanecarboxylic acid represented by the formula (5), which is the precursor of the formula (3), and then the alcohol compound represented by the formula (2) The method is generally obtained by reacting with an acid catalyst.

JP-A-6-0305044 Japanese Patent Publication No. 1-53333 Japanese Patent Laid-Open No. 4-39665 JP 2006-016379 A

  However, in this production method, the crystals of adamantanecarboxylic acids represented by the formula (5), which is the precursor of the formula (3), are fine powder, and therefore filtration is not easy and takes time. In addition, although the obtained crystals contain a lot of water, water hinders the next alkyl esterification reaction, so it is necessary to dry it sufficiently. It takes more than 2 days to use the method. Therefore, the production of adamantanecarboxylic acids represented by the formula (5) is accompanied by production difficulties such as requiring at least 4 days.

  The present invention has been made in view of the above circumstances, and has an adamantane skeleton, and adamantane carboxylic acid esters that can efficiently produce adamantane carboxylic acid esters having excellent optical properties, heat resistance, acid dissociation properties, and the like. It aims at providing the manufacturing method of.

  As a result of intensive studies on the above problems, the inventors of the present invention have found that the adamantane carboxylic acids represented by the formula (5) as a precursor are not extracted from the adamantane diols represented by the formula (1). It was found that adamantane carboxylic acid esters represented by) can be efficiently produced.

That is, the present invention is characterized in that after adamantanediols represented by the formula (1) are mixed with a protonic acid, carbon monoxide or a carbon monoxide source is added to react the alcohol compound represented by the formula (2). A method for producing an adamantanecarboxylic acid ester represented by the formula (3) is provided.

  According to the present invention, an optical material such as a crosslinkable resin, an optical fiber, an optical waveguide, an optical disk substrate, and a photoresist having an adamantane skeleton and excellent in optical properties, heat resistance, acid dissociation properties, and the like, pharmaceuticals Provided is a method for producing adamantane carboxylic acid esters capable of efficiently producing adamantane carboxylic acid esters useful as agricultural chemical intermediates and other various industrial products.

  Hereinafter, embodiments of the present invention will be described in detail.

  Examples of adamantanediols represented by the formula (1) include 1,3-adamantanediol, 5-methyl-1,3-adamantanediol, 5,7-dimethyl-1,3-adamantanediol, and 5,7-diethyl. -1,3-adamantanediol, 5-methoxy-1,3-adamantanediol, 5-ethoxy-1,3-adamantanediol, 5-propoxy-1,3-adamantanediol, 5-butoxy-1,3-adamantane Examples include diols.

  Examples of the alcohol compound represented by the formula (2) include methanol, ethanol, n-propanol, iso-propanol, n-butanol, t-butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, and cyclohexanol. Be mentioned.

  The adamantanecarboxylic acid esters represented by the formula (3) are compounds corresponding to the above formulas (1) and (2). For example, when the adamantane represented by formula (1) is 1,3-adamantanediol and the alcohol represented by formula (2) is methanol, the adamantane represented by formula (3) is 1,3- It becomes dimethyl adamantane dicarboxylate.

  Carbon monoxide used in the carboxylation reaction may be pure carbon monoxide or may be diluted with an inert gas. Carbon monoxide may be used under normal pressure or under pressure using an autoclave.

Moreover, the method of using formic acid or the alkyl formate represented by Formula (4) etc. as a carbon monoxide source instead of carbon monoxide is mentioned. For example, it is known that formic acid decomposes in concentrated sulfuric acid to generate carbon monoxide.

  Examples of the alkyl formate include methyl formate, ethyl formate, propyl formate, butyl formate, pentyl formate, hexyl formate, heptyl formate, octyl formate, nonyl formate, decanyl formate, cyclohexyl formate and the like. Since the corresponding alcohol is by-produced from the alkyl formate used at this time, the corresponding adamantanecarboxylic acid ester is partially produced as a by-product. Therefore, when using alkyl formate, it is desirable to use a desired alkyl group, that is, an alkyl formate having the same alkyl group as the alcohol compound represented by formula (2).

  The amount of carbon monoxide used is selected from the range of 1 equivalent to the substrate (in this case, when 2 carboxyl groups are introduced, 2 mol of carbon monoxide is used per 1 mol of the substrate) to 1000 equivalents. Preferably 1 to 10 equivalents, more preferably about 1 to 3 equivalents. If the amount is less than that, the yield is naturally lowered, and if it is more, the yield does not change. The same applies when formic acid or alkyl formate is used in place of carbon monoxide as the carbon monoxide source. If the amount is less than that, the yield is naturally reduced. If the amount is more than that, water produced as a by-product from formic acid inhibits the next alkyl esterification reaction and the yield is lowered.

  When the reaction is carried out in the presence of a protonic acid, the reaction can be carried out smoothly and the target compound can be obtained with high selectivity and yield. This protonic acid may be used as a solvent. Protic acids include organic acids (organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid and tartaric acid, organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid), inorganic Acids (eg, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) are included. Among them, concentrated sulfuric acid is desirable because it is inexpensive and easy to handle.

  The concentration of concentrated sulfuric acid used is preferably 90% or more of an aqueous solution, more preferably 96% or more. When the concentration is lower than that, the hydroxyl group is not sufficiently converted to a carboxyl group, and the water contained in the concentrated sulfuric acid inhibits the progress of the next alkyl esterification reaction, resulting in a decrease in yield.

  The amount of concentrated sulfuric acid used is desirably 2 to 20 times, preferably 4 to 16 times, more preferably 8 to 12 times the weight of the adamantanediol represented by the formula (1). If it is more than that, the hydroxyl group is not sufficiently converted to a carboxyl group, and if it is more than that, a large amount of organic solvent or a large amount of organic solvent is used to separate the extracted organic solvent in the separation step after the next alkyl esterification reaction. The pot efficiency will decrease because water must be added.

  In the carboxyl group introduction reaction, an inert organic solvent may be used. Examples of the organic solvent include organic carboxylic acids such as acetic acid, nitriles such as acetonitrile and benzonitrile, amides such as formamide, acetamide, dimethylformamide and dimethylacetamide, aliphatic hydrocarbons such as hexane and octane, and halogenated carbonization. Examples thereof include hydrogen, nitro compounds, ethers such as diethyl ether, diisopropyl ether and dioxane, and mixed solvents thereof.

  The above carboxylation reaction proceeds smoothly even under relatively mild conditions. The reaction temperature is, for example, −78 to 200 ° C., preferably about −20 to 100 ° C., and the reaction is usually performed at about 0 to 80 ° C. in many cases. At temperatures lower than this, the reaction does not proceed sufficiently, and at higher temperatures, side reactions proceed and yield decreases. The reaction can be carried out at normal pressure or under pressure.

  The reaction time is usually 1 to 100 hours, preferably 1 to 10 hours. If it is shorter than that, the carboxylation reaction does not proceed sufficiently, and even if it is longer than that, the yield does not change.

  Among the above methods, the method using 1,3-adamantanediol as the adamantanediol, concentrated sulfuric acid as the protonic acid, and formic acid as the carbon monoxide source is preferably handled in a simple and mild liquid phase reaction. The desired 1,3-adamantanecarboxylic acid ester can be obtained with high selectivity and high yield.

  The added amount of the alcohol compound represented by the formula (2) is 2 to 6 times by weight, preferably 3 to 5 times by weight, with respect to the adamantanediol represented by the formula (1). If it is less, alkyl esterification will not proceed sufficiently. If it is more than that, the separation between the organic solvent and the concentrated sulfuric acid layer will worsen in the subsequent separation step, and the extraction efficiency will also decrease.

  The reaction temperature is 0 to 120 ° C, preferably 20 to 80 ° C. The reaction temperature depends on the alcohol compound represented by the formula (2), but if it is lower than that, the alkyl esterification reaction does not proceed sufficiently, and if it is higher than that, the side reaction proceeds and the yield decreases.

  The reaction time is usually 1 to 100 hours, preferably 1 to 10 hours. Although the reaction time depends on the alcohol compound, if it is shorter than that, the alkyl esterification reaction does not proceed sufficiently, and even if it is longer than that, the yield does not change.

  After completion of the alkyl esterification reaction, an organic solvent is added to the reaction solution to extract and extract the adamantane dicarboxylic acid ester represented by the formula (3).

  The reaction solution depends on the amount of concentrated sulfuric acid and carbon monoxide used, the adamantanediol represented by the formula (1), particularly the amount of the alcohol compound represented by the formula (2), but an organic solvent is added. But separation may be bad. Therefore, in order to improve separation, the reaction solution may be concentrated to remove unreacted alcohol compounds and moisture before adding the organic solvent. Further, water may be added to improve separation. When adding water, it is added 0.1 to 3 times by weight, preferably 0.2 to 1.5 times by weight, based on the concentrated sulfuric acid used. If it is less than that, the separation is not good, and if it is more than that, only the pot efficiency is lowered.

  As an organic solvent to be added, aromatic compounds such as benzene, toluene, xylene, mesitylene, cumene, ethylbenzene, pseudocumene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, methyl formate, ethyl formate, Esters such as propyl formate, butyl formate, pentyl formate, hexyl formate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, pentyl propionate, hexyl propionate, butanol, pentanol, hexanol, heptanol, octanol And alcohol compounds.

  The above organic solvents may be used alone or in combination of two or more. In particular, some organic solvents have good extraction efficiency of adamantanecarboxylic acid esters represented by the formula (3), but are poorly separated from concentrated sulfuric acid (sulfuric acid aqueous solution, sulfuric acid aqueous solution containing alcohol). . On the other hand, separation from concentrated sulfuric acid (sulfuric acid aqueous solution, sulfuric acid aqueous solution containing alcohol) is good, but there are some which have poor extraction efficiency of adamantanecarboxylic acid esters represented by the formula (3). In such a case, it is desirable to use two or more organic solvents.

  The amount of the extracted organic solvent to be used is usually 1 to 100 times, preferably 1 to 20 times, more preferably 2 to 20 times the weight of the raw material. Since it depends on the amount of concentrated sulfuric acid and carbon monoxide used, adamantanediols represented by the formula (1), particularly the alcohol compound represented by the formula (2), there is no particular limitation. Moreover, there is no restriction | limiting in particular in the frequency | count of extraction.

  When adding the extraction organic solvent, it is desirable to cool the temperature of the reaction solution to 40 ° C. or lower in order to suppress side reactions between the extraction organic solvent and concentrated sulfuric acid.

  After completion of extraction, it is desirable to wash the extraction solution with water. Thereby, impurities such as unreacted adamantanecarboxylic acids are removed. At this time, the washing water may contain an appropriate inorganic salt such as sodium chloride or sodium bicarbonate. Moreover, you may wash with alkali. Examples of the alkali cleaning include an aqueous sodium hydroxide solution, a potassium hydroxide solution, and aqueous ammonia, but there are no particular restrictions on the alkaline component used. In addition, acid cleaning may be performed to remove metal impurities. Examples of acid cleaning include inorganic acids such as aqueous hydrochloric acid, aqueous sulfuric acid, and aqueous phosphoric acid, and organic acids such as aqueous oxalic acid.

  Further, when washing, an organic solvent may be added to the reaction solution according to the physical properties of the adamantanecarboxylic acid esters represented by the formula (3). The organic solvent to be added may be the same as that used in the reaction or extraction, or may be different, but it is usually desirable to use an organic solvent with a low polarity that is easily separated from water. .

  After washing the extraction solution, the desired formula (3) is obtained by a conventional method, for example, separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination of these. The adamantanecarboxylic acid esters represented can be easily separated and purified.

  Hereinafter, the contents of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Example 1
A flask equipped with a stirrer, a thermometer, a dropping funnel, and a Dim funnel was charged with 100.7 g of 1,3-adamantanediol (purity 96%), and 801.3 g of concentrated sulfuric acid was added. After stirring at room temperature and confirming that the raw material was dissolved, 76.4 g of formic acid was added dropwise over 2.3 hours. The temperature in the meantime was 25-38 degreeC. After completion of dropping, the mixture was aged for 1 hour at room temperature, and then 500 mL of toluene and 300.8 g of methanol were added and heated to 57 ° C. and stirred for 3 hours. Thereafter, the flask was ice-cooled, and 800 mL of ion-exchanged water was added over a period of time so as to remain in the liquid temperature range of 10 to 20 ° C. Thereafter, 500 mL of ethyl acetate was added, and the mixture was sufficiently stirred and separated. After separation, 500 mL of toluene and 500 mL of ethyl acetate were again added to the aqueous sulfuric acid solution, and the mixture was sufficiently stirred and separated. When the toluene / ethyl acetate solution was mixed and analyzed by GC, the reaction yield of dimethyl 1,3-adamantanedicarboxylate was 82%.

  The toluene / ethyl acetate solution was washed successively with 100 mL of ion exchange water, 100 mL of 5% aqueous sodium hydroxide, 50 mL of ion exchange water, and 50 mL of ion exchange water, then concentrated to 122 g, and 24 g of hexane was added. Crystals precipitated and were filtered off to obtain 81.4 g of dimethyl 1,3-adamantanedicarboxylate (removal yield 56%). The number of days required for removal was two days.

(Comparative Example 1)
A flask equipped with a stirrer, a thermometer, a dropping funnel and a Dimroth condenser was charged with 168 g of 1,3-adamantanediol (purity 96%), 670 mL of 1,2-dichloroethane, 2012 g of 96% sulfuric acid, and 503 g of formic acid over 3 hours. And then reacted at room temperature for 25 hours. Crystals deposited by adding 1000 mL of ion-exchanged water were filtered off and washed with water to obtain 328 g of 1,3-adamantane dicarboxylic acid (removal yield 94%, containing a large amount of water). Filtration took 2 hours. Subsequently, vacuum drying was performed for 2 days to obtain 200 g of 1,3-adamantanedicarboxylic acid.

  Next, 200 g of the above 1,3-adamantane dicarboxylic acid, 59 g of 96% sulfuric acid, and 682 g of methanol were added to a flask equipped with a stirrer, a thermometer, and a Dimroth condenser, and reacted at 65 to 70 ° C. for 6 hours. After the reaction, the reaction mixture was cooled to room temperature, and 100 mL of ion exchange water and 500 mL of 1,2-dichloroethane were added for liquid separation. The water / methanol layer was further extracted twice with 500 mL of 1,2-dichloroethane. The organic layer was concentrated to 288 g and 100 mL of hexane was added. Crystals were precipitated and separated by filtration to obtain 149 g of dimethyl 1,3-adamantanedicarboxylate (total extraction yield: 59%). Compared with the Examples, the yield of extraction was approximately the same, but it took 6 days to extract.

Claims (3)

After mixing adamantanediols represented by the formula (1) with a proton acid, carbon monoxide or a carbon monoxide source is added, and then an alcohol compound represented by the formula (2) is added and reacted. A method for producing an adamantanecarboxylic acid ester represented by the formula (3), which is extracted and separated and purified.

The production method according to claim 1, wherein the carbon monoxide source is formic acid or an alkyl formate represented by the formula (4).

  The production method according to claim 1, wherein the protic acid is sulfuric acid.