JP4463622B2 - Process for producing 1,3-adamantanediols - Google Patents

Description

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

  Since adamantane derivatives are characterized by excellent heat resistance and high transparency, they 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-adamantanediols are important as raw materials for synthesizing various adamantane derivatives including functional polymers, and are also useful as various coating materials.

  As a method for producing 1,3-adamantanediols, a method of oxidizing adamantane and a method of reacting 1,3-dihalogenated adamantane with water are known. As a method of oxidizing adamantane, (i) a method of oxidizing adamantane with oxygen in the presence of an imide compound and a vanadium compound (see Patent Document 1) and (ii) oxidizing adamantane with hypochlorous acid in the presence of a ruthenium compound. A method (see Patent Document 2) is known. As a method of reacting 1,3-dihalogenated adamantane with water, (iii) a method of reacting with water in the presence of pyridine (see Patent Documents 3 and 4) is known.

  However, when the methods (i) and (ii) are used, other oxides such as adamantanone, adamantanol, and triadamantanol are by-produced, and the yield of the target product is as low as 60% or less. In addition, there is a problem that it is difficult to separate the target product from the reaction solution containing these by-products. Further, in the method (i), the reaction needs to be performed under pressure while blowing air, and a pressurizing facility is required to carry out the method. On the other hand, according to the method (iii), 1,3-adamantanediol can be obtained with a high yield of, for example, 85% or more. However, in the method (iii), it is necessary to carry out the reaction at a high temperature of about 150 ° C. and under a pressure of about 0.5 MPa, and there are restrictions on the production equipment as in the method (i).

JP 2000-38360 A JP 2000-219646 A JP 2000-327604 A JP 2003-192619 A

  As described above, the methods (i) to (iii) are not necessarily industrially advantageous methods in terms of reaction yield, purification of the target product, or reaction equipment. Therefore, a production method capable of obtaining 3-adamantanediols has been desired.

  Accordingly, an object of the present invention is to provide a method for efficiently producing 1,3-adamantanediols from 1,3-dihalogenated adamantanes by a reaction under normal pressure.

  The present inventors have intensively studied to solve the above problems. As a result, 1,3-dihalogenated adamantanes were reacted with formic acid in the presence of formate or metal oxide to synthesize a precursor, and then water was added to the reaction solution containing the precursor and reacted. In some cases, it was found that 1,3-adamantanediols can be efficiently obtained by a reaction under normal pressure, and the present invention has been completed.

（式中、Ｒ ^１ 及びＲ ^２ は、各々独立に、水素原子または炭素数１〜５のアルキル基であり、Ｘは、フッ素原子、塩素原子、臭素原子又はヨウ素原子である。）

（式中、Ｒ ^１ 及びＲ ^２ は、各々前記式（１）におけるものと同義である。）
That is, the present invention relates to 1,3-adamantanediols by mixing and reacting 1,3-dihalogenated adamantanes represented by the following formula (1) with formic acid and formate or metal oxide. A precursor synthesis step for obtaining a reaction solution containing a precursor, and a diolation step for mixing and reacting the reaction solution obtained in this step with water to convert the precursor into 1,3-adamantanediols. This is a method for producing 1,3-adamantanediols represented by the following formula (5) .

(In the formula, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)

(In the formula, R ¹ and R ² have the same meanings as those in the formula (1)).

  According to the present invention, 1,3-adamantanediols can be obtained from 1,3-dihalogenated adamantanes at a low cost and in a high yield by a reaction under normal pressure. Although chlorinated products are generally cheaper than brominated or iodinated products, they are known to have low reactivity. However, in the present invention, even when 1,3-dichloroadamantane is used as a raw material, the target product is obtained in a high yield. It is possible to obtain Therefore, the production method of the present invention is important as a raw material for synthesizing various adamantane derivatives including functional polymers, and as an industrial production method for 1,3-adamantanediols useful as various coating materials. Very useful.

  In the production method of the present invention, first, a reaction liquid containing a precursor of 1,3-adamantanediol is prepared by mixing 1,3-dihalogenated adamantane, formic acid, formate, or metal oxide and reacting them. (Precursor synthesis step), then, the obtained reaction solution and water are mixed and reacted to convert the precursor into 1,3-adamantanediols (diolation step).

  Here, the precursor means a compound that reacts with water and converts to 1,3-adamantanediols. It is well known that an ester compound is hydrolyzed and converted to an alcohol. A compound in which one or two halogen atoms of 1,3-dihalogenated adamantanes are substituted with a formyloxy group, that is, 1, 3-diformyloxydamantanes and 3-halogenated-1-formyloxyadamantanes correspond to the precursors described above. In addition, in the reaction of the precursor synthesis step, in addition to these two compounds, other products (identified as 7-methylenebicyclo [3.3.1] nonan-3-ones from the analysis results) are also available. However, the amount of 1,3-adamantanediols obtained in the diolization step depends only on the conversion rate of 1,3-dihalogenated adamantanes regardless of the composition (product ratio) of these reaction solutions. Therefore, it is considered that the above other products also correspond to the precursors.

  Thus, in the production method of the present invention, a plurality of compounds produced by the reaction in the precursor synthesis step are precursors, and the reaction solution is used as it is as a raw material for the next step without isolating a specific compound. It has a feature in that it can be done, and this feature is a very significant industrial advantage.

Hereinafter, reactants (reactant: reaction raw materials, catalysts, etc.), reaction conditions, reaction procedures, products and the like used in the production method of the present invention will be described in detail.
1,3-dihalogenated adamantane used as a raw material in the production process of the present invention, the 1- and 3-positions of the hydrogen atoms of adamantane, chlorine, bromine, lower following formula is substituted by halogen, iodine (1 )

{Wherein, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. It is a compound represented by}.

  Specific examples of suitable compounds among the 1,3-dihalogenated adamantanes represented by the formula (1) include 1,3-dichloroadamantane, 1,3-dibromoadamantane, and 1,3-diiodo. Adamantane, 5-methyl-1,3-dichloroadamantane, 5-ethyl-1,3-dichloroadamantane, 5-methyl-1,3-dibromoadamantane, 5-ethyl-1,3-dibromoadamantane, 5-methyl- 1,3-diiodoadamantane, 5-ethyl-1,3-diiodoadamantane, 5,7-dimethyl-1,3-dichloroadamantane, 5,7-diethyl-1,3-dichloroadamantane, 5,7- Dimethyl-1,3-dibromoadamantane, 5,7-diethyl-1,3-dibromoadamantane, 5,7-dimethyl-1,3-diiodo Kalimantan, mention may be made of 5,7-diethyl-1,3-diiodo adamantane.

  As formic acid which is another raw material compound in the production method of the present invention, those industrially available as a reagent can be suitably used. The amount of formic acid used in the precursor synthesis step is not particularly limited as long as it is not less than the amount corresponding to the stoichiometric number, that is, not less than 2 mol with respect to 1 mol of 1,3-dihalogenated adamantane. Formic acid is used in an amount of 2 to 100 moles, particularly 2 to 1 mole of 1,3-dihalogenated adamantanes, due to the balance between the effect of increasing the reaction rate as a reaction solvent and the ease of post-treatment after completion of the reaction. It is suitable that it is ˜50 mol. Although there is no particular advantage, it is of course possible to carry out the reaction using less than 2 moles per mole of 1,3-dihalogenated adamantanes. In addition, when the reaction is performed in the presence of formate, there is a reaction system in which an ester bond is introduced by replacing the formyloxy group of the formate with a halogen atom. In this case, the chemical including the amount of formate is also included. The amount may be equal to or greater than the amount corresponding to the stoichiometric number. However, even if 1,3-dihalogenated adamantane is mixed with formate without using formic acid, the reaction hardly proceeds. Therefore, in order to carry out the reaction efficiently, at least 1,3-dihalogenated adamantane is used. It is necessary to use 1 mol, in particular 2 mol, of formic acid per mol.

  The formate used in the precursor synthesis step is not particularly limited as long as it is a salt of formic acid used in the reaction, but sodium formate, potassium formate, magnesium formate, calcium formate, formic acid are more easily available and highly reactive. Copper (I), silver formate (I), zinc formate (II), ammonium formate and the like are preferably used, and sodium formate, potassium formate, zinc formate (II) and ammonium formate are particularly preferred. The formate may be used by mixing different kinds of cationic species.

  The amount of formate used in the production method of the present invention depends on the amount of formic acid used, but due to its high reactivity and good operability after reaction, 1 mol of 1,3-dihalogenated adamantanes, It is suitable that it is 0.5 mol to 10 mol, especially 1 mol to 5 mol. When using formic acid and formate, 1 to 100 mol of formic acid, 0.5 to 10 mol of formate, and particularly 2 to 50 mol of formic acid are used with respect to 1 mol of 1,3-dihalogenated adamantane. It is preferable to use 1 to 5 moles of formate.

  The metal oxide used in the precursor synthesis step is not particularly limited as long as it is a metal oxide, but magnesium oxide, calcium oxide, silver oxide (I), copper oxide ( It is preferable to use I), zinc oxide (II) or the like, and zinc (II) oxide is particularly preferable. These metal oxides may be used in combination of two or more. The amount of metal oxide used in the precursor synthesis step is 0.5 to 10 mol with respect to 1 mol of 1,3-dihalogenated adamantane because of the high reaction rate and the ease of post-treatment at the end of the reaction. It is particularly preferable to use 1 to 5 mol.

  In the precursor synthesis step, a formyloxy group of formic acid or formate is substituted with a halogen atom of 1,3-dihalogenated adamantane in the reaction process to introduce an ester bond, and 3-halogenated-1-formyloxyadamantane , 1,3-diformyloxyadamantanes, 7-methylenebicyclo [3.3.1] nonan-3-ones, and other reaction compounds containing precursor compounds are obtained.

  The 3-halogenated-1-formyloxyadamantanes are compounds in which the 1st and 3rd hydrogen atoms of adamantane are substituted with a formyloxy group and a halogen such as chlorine, bromine, iodine, etc. When the compound represented by the formula (1) is used as the 3-dihalogenated adamantane, the compound is represented by the following formula (2).

{Wherein R ¹ and R ² have the same meanings as those in the formula (1), and X represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. }
Specific examples of the 3-halogenated-1-formyloxyadamantanes represented by the formula (2) include 3-chloro-1-formyloxyadamantane and 3-bromo-1-formyl. Oxyadamantane, 3-iodo-1-formyloxyadamantane, 3-chloro-5-methyl-1-formyloxyadamantane, 3-bromo-5-methyl-1-formyloxyadamantane, 3-iodo-5-methyl-1 -Formyloxyadamantane, 3-chloro-5-ethyl-1-formyloxyadamantane, 3-bromo-5-ethyl-1-formyloxyadamantane, 3-iodo-5-ethyl-1-formyloxyadamantane, 3-chloro -5,7-dimethyl-1-formyloxyadamantane, 3-bromo-5,7-dimethyl -1-formyloxyadamantane, 3-iodo-5,7-dimethyl-1-formyloxyadamantane, 3-chloro-5,7-diethyl-1-formyloxyadamantane, 3-bromo-5,7-diethyl-1 -Formyloxyadamantane, 3-iodo-5,7-diethyl-1-formyloxyadamantane, etc. can be mentioned.

  The 1,3-diformyloxyadamantane means a compound in which the 1-position and 3-position hydrogen atoms of adamantane are substituted by a formyloxy group, respectively. When the compound represented by (1) is used, the compound is represented by the following formula (3).

{Wherein R ¹ and R ² have the same meanings as those in the formula (1). }
Of the 1,3-diformyloxyadamantanes represented by the formula (3), specific examples of suitable compounds include 1,3-diformyloxyadamantane and 5-methyl-1,3-diformyl. Oxyadamantane, 5-ethyl-1,3-diformyloxyadamantane, 5,7-dimethyl-1,3-diformyloxyadamantane, 5,7-diethyl-1,3-diformyloxyadamantane, etc. it can.

  In addition, 7-methylenebicyclo [3.3.1] nonane-3-one is a hydrogen atom at the 1-position and 5-position of 7-methylenebicyclo [3.3.1] nonane-3-one, respectively. When the compound represented by the above formula (1) is used as the 1,3-dihalogenated adamantane, it is a compound represented by the following formula (4).

{Wherein R ¹ and R ² have the same meanings as those in the formula (1). }
Of the 7-methylenebicyclo [3.3.1] nonan-3-ones represented by the formula (4), specific examples of suitable compounds include 7-methylenebicyclo [3.3.1]. Nonan-3-one, 1-methyl-7-methylenebicyclo [3.3.1] nonane-3-one, 1-ethyl-7-methylenebicyclo [3.3.1] nonane-3-one, 1, 5-dimethyl-7-methylenebicyclo [3.3.1] nonane-3-one, 1,5-diethyl-7-methylenebicyclo [3.3.1] nonane-3-one, and the like can be given.

  The reaction solution obtained in the precursor synthesis step can be used as a raw material for the next step (diolation step) if any one of the compounds shown above is included, but from the viewpoint of reaction efficiency of the diolation step, the precursor is Preferably, at least 3-halogenated-1-formyloxyadamantanes are included. Further, it is preferable that the amount of the precursor contained in the reaction solution is large, and it is preferably 80% or more, particularly 90% or more when expressed by the conversion rate of the raw material 1,3-dihalogenated adamantanes. .

  The reaction in the precursor synthesis step is performed by mixing a predetermined amount of a reactant. (A) a predetermined amount of 1,3-dihalogenated adamantane, formic acid and formate, respectively, or (b) a predetermined amount of 1,3-dihalogenated adamantane, formic acid and formate or metal oxide, respectively. May be mixed and reacted by appropriately introducing and stirring. Although the reaction can be carried out in the presence of a solvent other than formic acid, it is preferred to carry out the reaction without solvent (in the absence of a solvent) from the viewpoint of reaction rate and yield.

  The reaction conditions in the precursor synthesis step may be appropriately determined according to the type of reactant used, but the reaction temperature is preferably 10 to 150 ° C., particularly 40 to 130 ° C., because of high reactivity. In particular, the reaction is preferably performed near the boiling point of the formic acid used. Usually, a sufficient conversion can be obtained by reacting for 1 to 60 hours.

Next, a diol-ized process is demonstrated. In the diolization step, the reaction solution obtained in the precursor synthesis step and water are mixed and reacted to convert the precursor into 1,3-adamantanediols. As described above, the precursor synthesis is performed. The reaction solution obtained in the step can be used as it is in the diol formation step. When a compound represented by the above formula (1) is used as a 1,3-dihalogenated adamantane as a raw material compound in the precursor synthesis step, the following formula (5)

{ Wherein R ¹ and R ² have the same meanings as those in the formula (1). }
1,3-adamantanediols represented by the following formula are obtained.

  Specific examples of suitable compounds among the 1,3-adamantanediols represented by the formula (5) include 1,3-adamantanediol, 5-methyl-1,3-adamantanediol, and 5-ethyl. -1,3-adamantanediol, 5,7-dimethyl-1,3-adamantanediol, 5,7-diethyl-1,3-adamantanediol, and the like.

  Precursors such as 3-halogenated-1-formyloxyadamantanes are converted to 1,3-adamantanediols upon contact with water under acidic conditions. The reaction mechanism at this time is considered as follows. That is, for 3-halogenated-1-formyloxyadamantanes, 7-methylenebicyclo [3.3.1] nonane, which is hydrolyzed when the compound comes into contact with water under acidic conditions, is also another precursor. Converts to 3-ones. The 7-methylenebicyclo [3.3.1] nonan-3-ones (those produced by the above reaction and those present in the reaction liquid from the beginning of the diolization step) were dissolved under acidic conditions. It is considered that 1,3-adamantanediols are produced by reacting with. Further, 1,3-diformyloxyadamantanes, which are other precursor compounds, are considered to be hydrolyzed under acidic conditions to produce 1,3-adamantanediols.

  Thus, in order for the precursor compound to be converted to 1,3-adamantanediols, it is important that the contact between the precursor and water is carried out under acidic conditions, preferably at a pH of 2 or less. Usually, formic acid as a raw material and in some cases a by-product acid (hydrogen halide) are present in the reaction solution obtained in the precursor synthesis step, so the water mixed with the reaction solution is an acidic aqueous solution. . Therefore, the water mixed with the reaction liquid does not need to be acidified in advance. In other words, the water used in the diolization step is not particularly limited as long as it becomes acidic (preferably acidic at pH 2 or less) after mixing with the reaction solution, and any of acidic, basic, and neutral can be used. (However, water is most preferable because it is inexpensive).

  The timing of mixing the reaction solution obtained in the precursor synthesis step and water may be appropriately determined according to the progress of the reaction in the precursor synthesis step, but when the reaction is performed under the conditions as described above Since the 1,3-dihalogenated adamantanes of the raw material almost disappear after a lapse of a predetermined time, water may be added when the 1,3-dihalogenated adamantanes become less than the target abundance.

  The amount of water used in the diolization step is 0.2 to 20 parts by mass with respect to 1 part by mass of 1,3-dihalogenated adamantanes because of the high reaction rate and the ease of post-treatment at the end of the reaction. The amount is particularly preferably 1 to 10 parts by mass. The reaction conditions in the diolization step may be appropriately determined according to the type of reactant used, but the reaction temperature is 10 to 100 ° C., particularly 40 to 100, considering the high reactivity and the boiling point of water. Preferably it is carried out at ° C. Usually, sufficient conversion can be obtained by reacting for 0.5 to 10 hours.

  The 1,3-adamantanediols thus obtained can be obtained by, for example, cooling the reaction solution as it is to 5 ° C. or less, and depositing a solid of 1,3-adamantanediols, followed by filtration and washing with water. By doing so, it can be obtained as a crude product of 1,3-adamantanediol (usually containing 90 mol% or more of 1,3-adamantanediol).

  In the diolization step, an organic solvent may be added when the crude product of 1,3-adamantanediols is obtained by cooling to remove impurities that are insoluble in water. As a solvent to be added at this time, halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, and aliphatic hydrocarbons such as hexane, heptane and octane from the viewpoint of easy concentration and easy extraction operation. , Halogenated aromatic hydrocarbons such as chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, ethers such as diethyl ether, diisopropyl ether, di-t-butyl ether, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate In addition, esters such as isobutyl acetate can be preferably used.

The method for purifying the crude 1,3-adamantanediols thus separated is not particularly limited, but can be suitably performed by, for example, the following method. Impurities (by - products, unreacted precursors in the reaction of the diolation step, other substances other than the target substance included in the reaction) dissolve, but 1,3-adamantanediols do not dissolve or are difficult to dissolve, that is, The organic solvent (hereinafter also referred to as a reslurry solvent) that selectively dissolves impurities contained in the crude product of 1,3-adamantanediols is added to form a reslurry, and then the slurry is filtered and dried. 1,3-adamantane diols having a high molecular weight (usually containing 95 mol% or more of 1,3-adamantane diols) (hereinafter, such treatment is also referred to as reslurry treatment). As the organic solvent used in the reslurry treatment, since the effect of removing impurities is high, halogenated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, and aliphatic hydrocarbons such as hexane, heptane and octane. , Halogenated aromatic hydrocarbons such as chlorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, ethers such as diethyl ether, diisopropyl ether, di-t-butyl ether, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate It is preferable to use esters such as isobutyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and cyano compounds such as acetonitrile. In the reslurry process, a method of heating the organic solvent once and then heating it, cooling to room temperature or lower, and filtering is preferable from the viewpoint of a large amount of acquisition.

  In combination with the reslurry treatment, adsorption treatment such as activated carbon treatment, silica treatment, alumina treatment, etc. is performed to remove various impurities and to further improve the purity, and to achieve the effect of decolorization (removal of coloring derived from impurities). It can also be obtained. In addition to such treatment, a high-purity target product can be obtained by performing purification by a known method such as recrystallization or sublimation purification. In addition, the purity of the target product can be confirmed by measurement by gas chromatography (GC).

  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.

Example 1
(Precursor synthesis process)
In a 300 ml four-necked flask, 10.3 g (0.05 mol) of 1,3-dichloroadamantane, 4.1 g (0.05 mol) of zinc oxide (II) in an equimolar amount with 1,3-dichloroadamantane, and formic acid were added. 15.3 g (0.33 mol) of 1.5 times the weight of 1,3-dichloroadamantane was added, and the mixture was heated and stirred at 110 ° C. for 1 hour. At the beginning of the reaction, zinc oxide (II) and 1,3-dichloroadamantane were not completely dissolved but were in a suspended state. However, as the reaction progressed, it dissolved, and after 1 hour from the start of the reaction, It became a homogeneous solution. After the reaction, a part of the reaction solution was sampled and analyzed by GC. As a result, 30 mol% of 1,3-dichloroadamantane was 3-chloro-1-formyloxyadamantane, and 68 mol% of 1,3-dichloroadamantane was 1. , 3-diformyloxyadamantane, converted to a compound identified as 7-methylenebicyclo [3.3.1] nonan-3-one (conversion based on raw material 1,3-dichloroadamantane) Rate 98%).

(Diolization process)
The temperature of the reaction solution obtained in the precursor synthesis step was lowered to 80 ° C., 20.4 g of ion-exchanged water, 2 times the weight of 1,3-dichloroadamantane as a raw material, was added, and the mixture was heated and stirred at 80 ° C. for 1 hour. The pH of the reaction solution was about 1, and kept uniform at any time. After the reaction, a part of the reaction solution was sampled and analyzed by GC. As a result, it was confirmed that 93 mol% of 1,3-dichloroadamantane was converted to 1,3-adamantanediol (raw material 1,3-dichloromethane). Reaction yield 93% based on adamantane). After the reaction, the reaction solution was cooled to 5 ° C., stirred for 3 hours and aged, then the solid was filtered and washed with ion exchanged water to obtain 8.0 g of 1,3-adamantanediol crude.

  Then, 20 g of ethyl acetate was added as a reslurry solvent, twice the weight of 1,3-dichloroadamantane charged, and stirred at 55 ° C. for 1 hour. At this time, 1,3-adamantanediol was not completely dissolved and was in a suspended state. Thereafter, the mixture was cooled to 5 ° C., stirred for 2 hours and aged, and then the solid was filtered to obtain 7.5 g (yield 89%) of a white solid. As a result of analyzing this solid by GC, the content of 1,3-adamantanediol was GC purity 98%.

Examples 2-4
The same procedure was performed except that the reslurry solvent used in Example 1 was changed to that shown in Table 1. The results are shown in Table 1.

Example 5
(Precursor synthesis process)
In a 300 ml four-necked flask, 10.3 g (0.05 mol) of 1,3-dichloroadamantane, 6.8 g (0.10 mol) of sodium formate, 2 mol times the amount of 1,3-dichloroadamantane, 30.6 g (0.67 mol) of 3 times the weight of 3-dichloroadamantane was added, and the mixture was heated and stirred at 110 ° C. for 30 hours. At the beginning of the reaction, 1,3-dichloroadamantane was not completely dissolved and was in a suspended state. However, as the reaction progressed, a tendency to dissolve was observed. After the reaction, a part of the reaction solution was sampled and analyzed by GC. As a result, 20 mol% of 1,3-dichloroadamantane was 3-chloro-1-formyloxyadamantane, and 78 mol% of 1,3-dichloroadamantane was 1. , 3-diformyloxyadamantane, converted to a compound identified as 7-methylenebicyclo [3.3.1] nonan-3-one (conversion based on raw material 1,3-dichloroadamantane) Rate 98%).

(Diolization process)
The temperature of the reaction solution obtained in the precursor synthesis step was lowered to 80 ° C., 20.4 g of ion-exchanged water, 2 times the weight of 1,3-dichloroadamantane as a raw material, was added, and the mixture was heated and stirred at 80 ° C. for 1 hour. The reaction solution was in a suspended state. After the reaction, a part of the reaction solution was sampled and analyzed by GC. As a result, it was confirmed that 92 mol% of 1,3-dichloroadamantane was converted to 1,3-adamantanediol (raw material 1,3-dichloromethane). 92% reaction yield based on adamantane). After the reaction, the reaction solution was cooled to 5 ° C., stirred for 3 hours and aged, then the solid was filtered and washed with ion-exchanged water to obtain 8.2 g of 1,3-adamantanediol crude.

  Then, 20 g of ethyl acetate was added as a reslurry solvent, twice the weight of 1,3-dichloroadamantane charged, and stirred at 55 ° C. for 1 hour. At this time, 1,3-adamantanediol was not completely dissolved and was in a suspended state. Thereafter, the mixture was cooled to 5 ° C., stirred for 2 hours and aged, and then the solid was filtered to obtain 7.6 g (yield 90%) of a white solid. As a result of analyzing this solid by GC, the content of 1,3-adamantanediol was GC purity 98%.

Examples 6-8
In Example 5, the same procedure was performed except that the sodium formate used in the precursor synthesis step was changed to that shown in Table 2 and the amount used was changed as shown in Table 2. The results are shown in Table 2.

Example 9
(Precursor synthesis process)
In a 300 ml four-necked flask, 14.7 g (0.05 mol) of 1,3-dibromoadamantane, 4.1 g (0.05 mol) of zinc (II) in an equimolar amount with 1,3-dibromoadamantane, and formic acid were added. 15.3 g (0.33 mol) of 1.5 times the weight of 1,3-dibromoadamantane was added, and the mixture was heated and stirred at 110 ° C. for 1 hour. At the beginning of the reaction, zinc oxide (II) and 1,3-dibromoadamantane were not completely dissolved but were in a suspended state. It became a homogeneous solution. After the reaction, a part of the reaction solution was sampled and analyzed by GC. As a result, 20 mol% of 1,3-dibromoadamantane was 3-bromo-1-formyloxyadamantane, and 78 mol% of 1,3-dibromoadamantane was 1. , 3-diformyloxyadamantane, 7-methylenebicyclo [3.3.1] nonan-3-one was confirmed to be converted to a compound identified (conversion based on raw material 1,3-dibromoadamantane) Rate 98%).

(Diolization process)
The temperature of the reaction solution obtained in the precursor synthesis step was lowered to 80 ° C., 29.4 g of ion-exchanged water, twice the weight of 1,3-dibromoadamantane as a raw material, was added, and the mixture was heated and stirred at 80 ° C. for 1 hour. The reaction solution was kept in a uniform state at any time. After the reaction, a part of the reaction solution was sampled and analyzed by GC. As a result, it was confirmed that 94 mol% of 1,3-dibromoadamantane was converted to 1,3-adamantanediol (raw material 1,3-dibromo). 94% reaction yield based on adamantane). After the reaction, the reaction solution was cooled to 5 ° C., stirred for 3 hours and aged, then the solid was filtered and washed with ion-exchanged water to obtain 8.2 g of 1,3-adamantanediol crude.

  Thereafter, 29 g of ethyl acetate as a reslurry solvent, 29 g, twice the amount of 1,3-dibromoadamantane charged, was added and stirred at 55 ° C. for 1 hour. At this time, 1,3-adamantanediol was not completely dissolved and was in a suspended state. Thereafter, the mixture was cooled to 5 ° C., stirred for 2 hours and aged, and then the solid was filtered to obtain 7.7 g (yield 92%) of a white solid. As a result of analyzing this solid by GC, the content of 1,3-adamantanediol was GC purity 98%.

Examples 10-12
In Example 9, it carried out similarly except having changed the reslurry solvent used by the diol-ized process into what is shown in Table 3. The results are shown in Table 3.

Example 13
(Precursor synthesis process)
In a 300 ml four-necked flask, 14.7 g (0.05 mol) of 1,3-dibromoadamantane, 6.8 g (0.10 mol) of sodium formate, 2 mol times the amount of 1,3-dibromoadamantane, 30.6 g (0.67 mol) of 3 times the weight of 3-dibromoadamantane was added, and the mixture was heated and stirred at 110 ° C. for 20 hours. At the beginning of the reaction, 1,3-dibromoadamantane was not completely dissolved and was in a suspended state, but as the reaction proceeded, a tendency to dissolve was observed. After the reaction, a part of the reaction solution was sampled and analyzed by GC. As a result, 20 mol% of 1,3-dibromoadamantane was 3-bromo-1-formyloxyadamantane, and 78 mol% of 1,3-dibromoadamantane was 1. , 3-diformyloxyadamantane, 7-methylenebicyclo [3.3.1] nonan-3-one was confirmed to be converted to a compound identified (conversion based on raw material 1,3-dibromoadamantane) Rate 98%).

(Diolization process)
The temperature of the reaction solution obtained in the precursor synthesis step was lowered to 80 ° C., 29.4 g of ion-exchanged water was added 2 times as much as the raw material 1,3-dichloroadamantane, and the mixture was stirred at 80 ° C. for 1 hour. The reaction solution was in a suspended state. After the reaction, a part of the reaction solution was sampled and analyzed by GC. As a result, it was confirmed that 92 mol% of 1,3-dibromoadamantane was converted to 1,3-adamantanediol (raw material 1,3-dichloromethane). 92% reaction yield based on adamantane). After the reaction, the reaction solution was cooled to 5 ° C., stirred for 3 hours and aged, then the solid was filtered and washed with ion-exchanged water to obtain 8.2 g of 1,3-adamantanediol crude.

  Thereafter, 29 g of ethyl acetate was added in an amount of 2 times the amount of 1,3-dibromoadamantane charged, and the mixture was stirred at 55 ° C. for 1 hour. At this time, 1,3-adamantanediol was not completely dissolved and was in a suspended state. Thereafter, the mixture was cooled to 5 ° C., stirred for 2 hours and aged, and then the solid was filtered to obtain 7.6 g (yield 90%) of a white solid. As a result of analyzing this solid by GC, the content of 1,3-adamantanediol was GC purity 98%.

Examples 14-16
In Example 13, the same procedure was performed except that the sodium formate used in the precursor synthesis step was changed to that shown in Table 4 and the amount used was changed as shown in Table 4. The results are shown in Table 4.

Example 17
A precursor synthesis step was performed in the same manner as in Example 1. The resulting reaction solution was cooled to 80 ° C., 20.4 g of ion-exchanged water, 2 times the weight of 1,3-dichloroadamantane as a raw material, was added, and the mixture was heated and stirred at 80 ° C. for 1 hour. The pH of the reaction solution was about 1, and kept uniform at any time. After the reaction, a part of the reaction solution was sampled and analyzed by GC. As a result, it was confirmed that 93 mol% of 1,3-dichloroadamantane was converted to 1,3-adamantanediol (raw material 1,3-dichloromethane). Reaction yield 93% based on adamantane). Thereafter, 10.2 g of toluene, which is 1 times the weight of 1,3-dihalogenated adamantane, is added to the reaction solution, cooled to 5 ° C., stirred for 3 hours, aged, filtered, washed with ion-exchanged water, A crude product of 3-adamantanediol 7.8 g was obtained.

  Thereafter, 20 g of ethyl acetate was added in an amount of 2 times the amount of 1,3-dichloroadamantane charged, and the mixture was stirred at 55 ° C. for 1 hour. At this time, 1,3-adamantanediol was not completely dissolved and was in a suspended state. Thereafter, the mixture was cooled to 5 ° C., stirred for 2 hours and aged, followed by solid filtration to obtain 7.0 g (yield 83%) of a white solid. As a result of analyzing this solid by GC, the content of 1,3-adamantanediol was GC purity 99%.

Example 18
A precursor synthesis step was performed in the same manner as in Example 1. The obtained reaction liquid was cooled to 80 ° C., 20.4 g of a 10% aqueous sodium hydroxide solution, twice the weight of 1,3-dichloroadamantane as a raw material, was added, and the mixture was heated and stirred at 80 ° C. for 1 hour. The pH of the reaction solution was about 1, and kept uniform at any time. After the reaction, a part of the reaction solution was sampled and analyzed by GC. As a result, it was confirmed that 90 mol% of 1,3-dichloroadamantane was converted to 1,3-adamantanediol (raw material 1,3-dichloromethane). 90% reaction yield based on adamantane). After the reaction, the reaction solution was cooled to 5 ° C., stirred for 3 hours and aged, then the solid was filtered and washed with ion-exchanged water to obtain 7.7 g of a crude 1,3-adamantanediol. Thereafter, 20 g of ethyl acetate was added in an amount of 2 times the amount of 1,3-dichloroadamantane charged, and the mixture was stirred at 55 ° C. for 1 hour. At this time, 1,3-adamantanediol was not completely dissolved and was in a suspended state. Thereafter, the mixture was cooled to 5 ° C., stirred for 2 hours and aged, and then the solid was filtered to obtain 7.0 g (yield 83%) of a white solid. As a result of analyzing this solid by GC, the content of 1,3-adamantanediol was GC purity 98%.

Comparative Example 1
In a 300 ml four-necked flask, 10.3 g (0.05 mol) of 1,3-dichloroadamantane, 6.8 g (0.10 mol) of sodium formate, 2 mol times the amount of 1,3-dichloroadamantane, and 1 of dimethylformamide , 3-Dichloroadamantane, 30.6 g (0.42 mol), 3 times by weight, was added and stirred at 150 ° C. for 5 hours. After 5 hours from the start of the reaction, the solution was homogeneous, but 1,3-dichloroadamantane remained in the reaction solution with a GC purity of 98%, and isolation was not achieved.

Comparative Example 2
To a 200 ml four-necked flask, 10.2 g (0.05 mol) of 1,3-dichloroadamantane, 10 ml (0.12 mol) of pyridine and 4 ml (0.22 mol) of water were added and stirred at 100 ° C. for 30 hours. In the liquid, 1,3-adamantanediol was not confirmed and could not be isolated.

Claims (3)

A reaction liquid containing a precursor of 1,3-adamantanediol by mixing and reacting 1,3-dihalogenated adamantane represented by the following formula (1) , formic acid and formate or metal oxide following the precursor synthesis step and a reaction solution and water obtained in about該工is mixed and reacted, characterized in that it comprises the precursor 1,3-adamantane diol diol step of converting the get A process for producing 1,3-adamantanediols represented by the formula (5) .

(In the formula, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.)

(In the formula, R ¹ and R ² have the same meanings as those in the formula (1)). The method according to claim 1, further comprising a precipitation step of precipitating 1,3-adamantanediols from the reaction solution containing 1,3-adamantanediols obtained in the diolization step. Separating the solid 1,3-adamantanediols precipitated in the precipitation step, the separated 1,3-adamantanediols, halogenated aliphatic hydrocarbons, aliphatic hydrocarbons, The mixture was reslurried by mixing with an organic solvent selected from the group consisting of halogenated aromatic hydrocarbons, ethers, esters, ketones, and cyano compounds , and then purified by filtering the slurry. The method according to claim 2, further comprising a purification step for obtaining 1,3-adamantanediols.