JP2018076245A - Purification method of dihydroxy compound having fluorene skeleton - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for removing or reducing an included compound (guest molecules) from or in a crystal, which is an inclusion complex of an alcohol compound (host molecules) represented by formula (1).SOLUTION: A problem is solved by mixing a crystal of an alcohol compound represented by formula (1) and at least one organic compound selected from a group consisting of aliphatic chain, which may be branched, hydrocarbons, ketones, alcohols, ethers, nitriles, and glycol ethers without subjecting the crystal of the alcohol compound represented by formula (1) to be completely dissolved in the organic compound.SELECTED DRAWING: None

Description

  The present invention is suitable as a monomer for forming a resin (optical resin) constituting an optical member typified by an optical lens or an optical film, and is a method for purifying a dihydroxy compound having a novel fluorene skeleton excellent in processability and productivity. About.

  In recent years, resin materials such as polycarbonate, polyester, polyacrylate, polyurethane, and epoxy, which use a dihydroxy compound having a fluorene skeleton as a raw material monomer, have excellent optical properties and heat resistance. It is attracting attention as a material. Among these, following formula (1)

で表される構造を有するジヒドロキシ化合物は、該ジヒドロキシ化合物から製造される樹脂が屈折率等の光学特性、耐熱性、耐水性、耐薬品性、電気特性、機械特性、溶解性等の諸特性に優れることから、特に光学樹脂の原材料として着目されている（例えば特許文献１〜４）。

In the dihydroxy compound having the structure represented by the above, the resin produced from the dihydroxy compound has various properties such as optical properties such as refractive index, heat resistance, water resistance, chemical resistance, electrical properties, mechanical properties, and solubility. Since it is excellent, it attracts attention especially as a raw material of optical resin (for example, patent documents 1-4).

  As a method for producing the dihydroxy compound represented by the above formula (1), in the presence of a base catalyst, the following formula (2)

で表されるフェノール化合物とエチレンオキサイドとを反応させる方法が知られている（特許文献２）。しかしながら、該方法で得られる上記式（１）で表されるジヒドロキシ化合物はその純度が低く、エチレンオキサイドが３分子以上付加した化合物（以下、多量体と称することもある）が多量に副生し、目的とする上記式（１）で表されるジヒドロキシ化合物を高純度で得ることは困難である。

There is known a method of reacting a phenol compound represented by the formula (II) with ethylene oxide (Patent Document 2). However, the dihydroxy compound represented by the above formula (1) obtained by this method has low purity, and a large amount of a compound (hereinafter sometimes referred to as a multimer) in which 3 or more molecules of ethylene oxide are added is produced as a by-product. It is difficult to obtain the target dihydroxy compound represented by the above formula (1) with high purity.

  On the other hand, as an improved production method of the dihydroxy compound represented by the above formula (1), in the presence of an acid catalyst and thiols, the following formula (3)

で表されるアルコールと９−フルオレノンとを反応させ上記式（１）で表されるジヒドロキシ化合物を得る方法が提案され（特許文献３）、また、該製法による着色の問題を改善する手法として、酸触媒及び９―フルオレノン類１００重量部に対して３重量部以上のチオール類存在下、上記式（３）で表されるアルコールと９―フルオレノンとを反応させ上記式（１）で表されるジヒドロキシ化合物を得る方法が提案されている（特許文献４）。

A method of obtaining the dihydroxy compound represented by the above formula (1) by reacting the alcohol represented by the formula (9) with fluorenone is proposed (Patent Document 3), and as a technique for improving the coloring problem due to the production method, In the presence of 3 parts by weight or more of thiols with respect to 100 parts by weight of the acid catalyst and 9-fluorenone, the alcohol represented by the above formula (3) is reacted with 9-fluorenone and represented by the above formula (1). A method for obtaining a dihydroxy compound has been proposed (Patent Document 4).

  However, even with this method, the color improvement is not sufficient, and since a large amount of thiols is required during the reaction, it is difficult to completely remove thiols from the product, and the resin is removed from the dihydroxy compound. During production, there is a problem that sulfur derived from thiols causes further coloring of the resin.

  Further, when the inventors of the present application made additional trials on the methods described in Patent Documents 2 and 4, the resulting crystal of the dihydroxy compound represented by the above formula (1) was subjected to a reaction or a removal operation after the reaction (crystallization). It was found that the solvent (aromatic hydrocarbons) used in the operation) was taken in and became an inclusion body.

Japanese Patent Application Laid-Open No. 07-149881 JP 2001-122828 A JP 2001-206863 A JP 2009-256342 A

  An object of the present invention is to provide a method for removing or reducing an inclusion compound (guest molecule) from an inclusion body crystal containing the dihydroxy compound represented by the above formula (1) as a host molecule. .

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that a clathrate crystal containing a dihydroxy compound represented by the above formula (1) as a host molecule and a specific organic compound, By mixing the crystals without completely dissolving them, it is possible to remove or reduce the guest molecules from the clathrate crystals containing the dihydroxy compound represented by the above formula (1) as the host molecules. I found it. Specifically, the following invention is included.

[1]
A clathrate crystal having a dihydroxy compound represented by the following formula (1) as a host molecule and an aliphatic chain which may have a branch, hydrocarbons, ketones, alcohols, ethers, A crystal of an inclusion body having at least one organic compound selected from the group consisting of nitriles and glycol ethers as a host molecule and a dihydroxy compound represented by the following formula (1) is completely dissolved in the organic compound. The purification method of the dihydroxy compound represented by following formula (1) including the process made to mix, without performing.

[2]
The method for purifying a dihydroxy compound according to [1], wherein the mixing temperature is 65 ° C or higher.

[3]
Further, after mixing, the crystal of the dihydroxy compound represented by the above formula (1) and the organic compound are separated.
The method for purifying a dihydroxy compound according to [1] or [2], comprising a step of separating.

[4]
The method further comprises the step of drying the separated crystal, and the step of purifying the dihydroxy compound according to [3].
Manufacturing method.

  According to the present invention, it is possible to remove or reduce the guest molecules from the clathrate crystals having the dihydroxy compound represented by the above formula (1) as the host molecule. When a clathrate crystal having a guest molecule and containing a dihydroxy compound represented by the above formula (1) as a host molecule is used as a resin raw material, the guest molecule included during melting of the crystal is released. Therefore, it may be necessary to safely remove the released guest molecules out of the system, or the quality of the resulting resin may not be constant due to the influence of the guest molecules included. Furthermore, when storing and transporting the crystals of the clathrate containing the dihydroxy compound represented by the above formula (1) as a host molecule, it is necessary to consider the possibility of flammability caused by the guest molecule, and more strictly Disaster prevention measures are also required.

  The present invention is carried out by mixing a clathrate crystal containing the dihydroxy compound represented by the above formula (1) as a host molecule and a specific organic compound described later without completely dissolving them. The clathrate crystals using the dihydroxy compound represented by the above formula (1) as a host molecule for purification in the present invention are produced, for example, by the production method described in the aforementioned patent document. Can be used.

  Whether or not it is an inclusion body can be determined by, for example, TG-DTA (differential thermogravimetric simultaneous measurement) analysis, X-ray diffraction, NMR analysis, etc. After the sample is sufficiently dried so that there is no change in weight, the obtained crystals are dissolved in a solvent and analyzed using gas chromatography or high-performance liquid chromatography to determine whether there is a peak corresponding to the guest molecule. Judgment can be made. In the method using TG-DTA analysis, the change in weight when the sample is heated at a constant rate and the associated endothermic / exothermic behavior can be measured, and the change in weight and endothermic (or exothermic) are observed simultaneously. At this point, it can also be determined that the guest molecule has been released.

  In the present invention, “the inclusion crystal containing the dihydroxy compound represented by the above formula (1) as a host molecule does not completely dissolve in the organic compound described later” means that at least the purification method of the present invention is carried out. In the meantime, it means that at least a part of the dihydroxy compound represented by the above formula (1) exists as crystals. When the purification method of the present invention is carried out, if the crystals are completely dissolved in the organic compound described later, the content of the guest molecule is reduced even if the crystals of the alcohol compound represented by the above formula (1) are subsequently precipitated by cooling or the like. May not be.

  In the present invention, “a mixture of a clathrate crystal having a dihydroxy compound represented by the above formula (1) as a host molecule and an organic compound to be described later” refers to an organic compound to be described later and the above formula (1). A state in which the crystal of the clathrate having the dihydroxy compound represented by the host molecule as a host molecule can be brought into contact, specifically, for example, an inclusion having the dihydroxy compound represented by the above formula (1) as the host molecule. An operation may be mentioned in which a mixture of the crystals of the inclusion body and an organic compound described later is placed in a container to such an extent that the mixture can be stirred and stirred for a certain period of time until the guest molecules are reduced to a desired content. The guest molecule content is determined by separating a portion of the dihydroxy compound crystal represented by the above formula (1) in the mixture and analyzing the separated crystal using gas chromatography under the conditions described below. It can be confirmed. In addition, the crystal to be mixed may contain a substance other than the crystal. For example, a slurry of the solvent used for producing the crystal and the crystal can be used in the present invention.

  The organic compound used in the present invention is at least selected from the group consisting of hydrocarbons, ketones, alcohols, ethers, nitriles, and glycol ethers, which may have a branched aliphatic chain. One organic compound is mentioned. Examples of aliphatic hydrocarbons that may have a branched chain include liquid hydrocarbons having 6 or more carbon atoms such as hexane, heptane, octane, nonane, decane, dichloromethane, trichloroethylene, dibromoethane, and the like. And halogen-containing hydrocarbons. Examples of the aliphatic chain-like ketones that may have a branch include acetone, methyl ethyl ketone, dibutyl ketone, diisobutyl ketone, and methyl isobutyl ketone. Examples of the alcohol having an aliphatic chain which may have a branch include methanol, ethanol, propanol, isopropanol, butanol, and octanol. Examples of aliphatic ethers that may be branched include dibutyl ether and methyl tertiary butyl ether. Examples of the nitriles which are aliphatic chain which may have a branch include acetonitrile and butyronitrile. Examples of the aliphatic ether which may have a branched chain include ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, and triethylene glycol dibutyl ether. Among these organic compounds, hexane, heptane, dichloromethane, trichloromethane, methanol, ethanol, propanol, isopropanol, butanol, octanol, acetone, methyl ethyl ketone, acetonitrile, and dibutyl ether are preferably used because they are inexpensive. These organic compounds may be used singly or in combination of two or more as required, or may contain other organic compounds in addition to these organic compounds. The amount of the organic compound used in the present invention is such that a clathrate crystal containing the dihydroxy compound represented by the above formula (1) as a host molecule and an organic compound described later can be mixed, and the above formula (1) The amount of the dihydroxy compound crystal represented may be an amount that does not completely dissolve during the purification method of the present invention. For example, the lower limit amount is the dihydroxy compound represented by the above formula (1) as the host molecule. 0.1 parts by weight or more, preferably 0.5 parts by weight or more, and more preferably 1 part by weight or more with respect to 1 part by weight of crystals of the clathrate, and the upper limit is dihydroxy represented by the above formula (1) Although it varies depending on the solubility of the compound in the organic compound, it is usually 30 parts by weight or less, preferably 20 parts by weight or less, more preferably 10 parts by weight or less.

  The temperature at which the clathrate crystal containing the dihydroxy compound represented by the above formula (1) as a host molecule is mixed with the organic compound described above is not particularly limited. Above, preferably above 80 ° C., and below the boiling point of the organic compound described above.

  After carrying out the above-described purification method of the present invention, it is preferable to separate the dihydroxy compound crystal represented by the above formula (1) from the organic compound used in the present invention. Examples of the separation method include a solid-liquid separation operation such as filtration, and the above mixture from the crystal of the dihydroxy compound represented by the above formula (1) by setting the mixture to a temperature equal to or higher than the boiling point of the organic compound used in the present invention. Examples include a method of removing the organic compound used in the invention.

  In order to remove the organic compound adhering to the dihydroxy compound crystal represented by the formula (1) after separating the dihydroxy compound crystal represented by the formula (1) and the organic compound used in the present invention, The obtained crystals may be dried. Specifically, for example, a method of drying the crystal of the dihydroxy compound represented by the above formula (1) obtained by separation or drying the crystal for a certain period of time at a temperature equal to or higher than the boiling point of the organic compound used in the present invention. Is mentioned.

  The crystals of the present invention thus obtained may be subjected to ordinary purification operations such as adsorption, steam distillation and recrystallization as necessary. In addition, since guest molecules such as aromatic hydrocarbons are not included in the crystal, it is of course suitable for use as a resin material such as polycarbonate, polyester, polyacrylate, polyurethane, and epoxy. It can also be suitably used as a raw material (intermediate) for fields in which molecules are a problem, for example, medical and agricultural chemicals.

  In addition, the purification method of the present invention is a clathrate containing the dihydroxy compound represented by the above formula (1) as a host molecule, which incorporates the aromatic hydrocarbon produced by the above-mentioned known method as a guest compound. As well as the above-mentioned crystals, as shown in the examples and the like to be described later, it can be applied to clathrate in which specific compounds other than aromatic hydrocarbons (for example, cyclic ketones and esters) are incorporated as guest compounds. is there.

  EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited to these. In the examples, various measurements were performed by the following methods.

(1) HPLC purity The HPLC purity of the dihydroxy compound represented by the above formula (1) contained in the clathrate crystals containing the dihydroxy compound represented by the above formula (1) as a host molecule is a liquid based on the following conditions. It is the area percentage of chromatography (however, the peak derived from the guest molecule is based on the corrected surface percentage excluding the peak).
Apparatus: Shimadzu LC-2010A,
Column: SUMPAX ODS A-211 (5 μm, 4.6 mmφ × 250 mm),
Mobile phase: pure water / acetonitrile (acetonitrile 30% → 100%),
Flow rate: 1.0 ml / min, column temperature: 40 ° C., detection wavelength: UV 254 nm.

(2) Analysis of guest molecule content and organic compound content used in purification The guest molecule content and the organic compound content used in the purification were quantified by gas chromatography based on the following conditions.
Apparatus: GC-2014 manufactured by Shimadzu Corporation
Column: DB-1 (0.25 μm, 0.25 mm ID × 30 m),
Temperature rise: 40 ° C. (10 minutes hold) → 20 ° C./min→300° C. (20 minutes hold),
Inj temperature: 200 ° C., Det temperature: 300 ° C., split ratio 1:10,
Carrier: nitrogen 55.0 kPa (constant),
Sample preparation method: 100 mg of the crystal of the dihydroxy compound represented by the above formula (1), which has been sufficiently dried, is weighed into a 10 ml volumetric flask, and a previously prepared acetonitrile solution of 1,2-dimethoxyethane (1,1, 5 ml of 2-dimethoxyethane (400 mg dissolved in 200 ml of acetonitrile) was added with a whole pipette, and the sample solution was dissolved in acetonitrile to prepare a sample solution.
On the other hand, 10 mg of the compound whose content is to be measured was weighed into a 10 ml volumetric flask, an acetonitrile solution of 1,2-dimethoxyethane in the same amount as described above was added, and the volume was dissolved in acetonitrile to obtain a standard solution.
The sample solution and the standard solution were analyzed under the above-mentioned conditions, the peak areas of the obtained components were obtained with a data processor, and the content (% by weight) of each component was calculated (internal standard method).
When acetonitrile was used as the organic compound during the purification, triethylene glycol dimethyl ether was used in place of acetonitrile when preparing the sample solution and the standard solution.

<Comparative Example 1>
In a glass reactor equipped with a stirrer, a heating / cooling device, and a thermometer, 9,9′-bis (4-hydroxy-3-phenylphenyl) fluorene 120.0 g (0.240 mol), ethylene carbonate 48.3 g (0.549 mol), 2.4 g (0.018 mol) of potassium carbonate, and 120.0 g of toluene were charged and stirred at 110 ° C. for 11 hours to obtain a reaction solution.
After cooling the obtained reaction liquid to 85 degreeC, 204g of water was added, it stirred at 80-85 degreeC for 30 minutes, and after standing still, the water layer was isolate | separated. After repeating the same operation three times, the resulting organic solvent layer was dehydrated under reflux using a Dean-Stark apparatus to obtain a crystallization solution.
When the obtained crystallization solution was cooled, crystals were precipitated at 65 ° C. After the crystals were precipitated, the mixture was stirred at the same temperature for 2 hours. After further cooling to 26 ° C., filtration was performed to obtain crystals. The obtained crystal was dried at 110 ° C. to 112 ° C. for 12 hours under reduced pressure with an internal pressure of 1.1 kPa.

When the obtained crystal was analyzed by the method described above, it was confirmed to be an inclusion body having the dihydroxy compound represented by the formula (1) as a host molecule and toluene as a guest molecule. The analysis results are shown below.
Weight of the obtained crystal: 118.2 g
HPLC purity: 97.2%
Toluene (guest molecule) content: 4.83% by weight

<Comparative example 2>
In a glass reactor equipped with a stirrer, a heating / cooling device, and a thermometer, 90.0 g (0.180 mol) of 9,9′-bis (4-hydroxy-3-phenylphenyl) fluorene and 36.0 g of ethylene carbonate were added. (0.408 mol), 2.1 g (0.015 mol) of potassium carbonate, and 90.0 g of cyclohexanone were charged and stirred at 140 ° C. for 7 hours to obtain a reaction solution.
After cooling the obtained reaction liquid to 90 ° C., 69 g of cyclohexanone and 81 g of normal heptane were added, and the organic solvent layer was kept at 90 ° C. and washed with water until the washing water became neutral. After washing with water, the resulting organic solvent layer was dehydrated under reflux using a Dean-Stark apparatus to obtain a crystallization solution.
Thereafter, the obtained crystallization solution was cooled to 70 ° C. and kept at 70 ° C. for 1 hour to precipitate crystals, followed by stirring at the same temperature for 2 hours. After stirring, the mixture was further cooled to 19 ° C. and then filtered to obtain crystals. The obtained crystals were dried at 90 ° C. for 3 hours under reduced pressure with an internal pressure of 1.1 kPa.

When the obtained crystal was analyzed by the method described above, it was confirmed to be an inclusion body having the dihydroxy compound represented by the formula (1) as a host molecule and cyclohexanone as a guest molecule. The analysis results are shown below.
Weight of the obtained crystal: 99.6 g
HPLC purity: 97.5%
Cyclohexanone (guest molecule) content: 15.3% by weight

<Example 1>
Inclusion in which a dihydroxy compound represented by the above formula (1) obtained in Comparative Example 1 is a host molecule and toluene is a guest molecule in a glass reactor equipped with a stirrer, a heating / cooling device, and a thermometer After charging 10 g of the body and 70 g of methanol, the mixture was stirred at 25 ° C. for 3 hours. During the stirring, the crystals of the dihydroxy compound represented by the above formula (1) were not completely dissolved.
After stirring, the mixture was filtered at 25 ° C. to obtain crystals. The obtained crystal was dried at 90 ° C. for 3 hours under a reduced pressure of an internal pressure of 0.13 kPa to obtain a crystal of the dihydroxy compound represented by the above formula (1).

Each analytical value of the crystal | crystallization of the obtained dihydroxy compound represented by the said Formula (1) is as follows.
Weight of crystal obtained: 9.2 g (recovery rate 92%)
Toluene (guest molecule) content: 0.01% by weight
Methanol (organic compound used in purification) content: 0.10% by weight

<Example 2>
A crystal of the dihydroxy compound represented by the above formula (1) was obtained in the same manner as in Example 1 except that the stirring temperature was 68 ° C. (under methanol reflux) and the amount of methanol used was 50 g. Each analytical value of the crystal | crystallization of the obtained dihydroxy compound represented by the said Formula (1) is as follows.
Weight of the obtained crystal: 8.6 g (recovery rate 86%)
Toluene (guest molecule) content: 0.01% by weight
Methanol (organic compound used in purification) content: 0.08% by weight

<Example 3>
The dihydroxy compound crystal represented by the above formula (1) was obtained in the same manner as in Example 2 except that methanol was changed to octanol, the amount of octanol used was 20 g, and the stirring temperature was 100 ° C. Each analytical value of the crystal | crystallization of the obtained dihydroxy compound represented by the said Formula (1) is as follows.
Weight of crystals obtained: 6.3 g (63% recovery rate)
Toluene (guest molecule) content: 0.01% by weight
Octanol (organic compound used in purification) content: 0.07% by weight

<Example 4>
After charging 1 g of clathrate containing dihydroxy compound represented by the above formula (1) obtained in Comparative Example 1 as a host molecule and toluene as a guest molecule and 5 g of diisobutyl ketone in a test tube containing a stir bar The mixture was stirred at 27 ° C. for 48 hours. During the stirring, the crystals of the dihydroxy compound represented by the above formula (1) were not completely dissolved.
Thereafter, the crystals were filtered and the obtained crystals were sufficiently dried in the form of filter paper, and then the obtained crystals were analyzed by gas chromatography. The analytical values are shown in Table 1.

<Examples 5 to 21>
The dihydroxy compound represented by the above formula (1) was obtained by carrying out in the same manner as in Example 4 except that the organic compound used, the amount used, the stirring temperature, and the stirring time were changed to those shown in Tables 1 to 3. The compound crystals were analyzed by gas chromatography. The analysis values are shown in Tables 1-3. In all Examples, the crystals of the dihydroxy compound represented by the above formula (1) were not completely dissolved during stirring.

<Comparative Examples 3-6>
The dihydroxy compound represented by the above formula (1) was obtained by carrying out in the same manner as in Example 4 except that the organic compound used, the amount used, the stirring temperature, and the stirring time were changed to those shown in Table 4. The crystals were analyzed by gas chromatography. The analytical values are shown in Table 4. In all comparative examples, the crystals of the dihydroxy compound represented by the above formula (1) were not completely dissolved during stirring.

  As is apparent from the above results, at least one selected from the group consisting of hydrocarbons, ketones, alcohols, ethers, nitriles and glycol ethers, which may be branched, is an aliphatic chain. When a clathrate containing a dihydroxy compound represented by the above formula (1) as a host molecule and toluene as a guest molecule is purified using an organic compound, until the clathrated toluene is reduced or hardly detected. It was found to be removable.

  On the other hand, the organic compound other than at least one organic compound selected from the group consisting of hydrocarbons, ketones, alcohols, ethers, nitriles and glycol ethers, which may have a branched aliphatic chain In the case of using the compound, it was found that the organic compound used was replaced by the included toluene and became a new inclusion body.

<Example 22>
Inclusion with a dihydroxy compound represented by the above formula (1) obtained in Comparative Example 2 as a host molecule and cyclohexanone as a guest molecule in a glass reactor equipped with a stirrer, a heating / cooling device, and a thermometer After charging 10 g of the product and 50 g of methanol, the mixture was stirred at 25 ° C. for 3 hours. During the stirring, the crystals of the dihydroxy compound represented by the above formula (1) were not completely dissolved.
After stirring, the mixture was filtered at 25 ° C. to obtain crystals. The obtained crystal was dried at 90 ° C. for 3 hours under a reduced pressure of an internal pressure of 0.13 kPa to obtain a crystal of the dihydroxy compound represented by the above formula (1).

Each analytical value of the crystal | crystallization of the obtained dihydroxy compound represented by the said Formula (1) is as follows.
Weight of crystal obtained: 8.1 g (recovery rate 81%)
Cyclohexanone (guest molecule) content: 1.56% by weight
Methanol (organic compound used in purification) content: 0.10% by weight

<Example 23>
The same procedure as in Example 22 was conducted except that the stirring temperature was 68 ° C. (under methanol reflux) to obtain crystals of the dihydroxy compound represented by the above formula (1). Each analytical value of the crystal | crystallization of the obtained dihydroxy compound represented by the said Formula (1) is as follows.
Weight of crystals obtained: 5.1 g (51% recovery rate)
Cyclohexanone (guest molecule) content: 0.53% by weight
Methanol (organic compound used in purification) content: 0.10% by weight

<Example 24>
After charging 1 g of clathrate containing dihydroxy compound represented by the above formula (1) obtained in Comparative Example 2 as a host molecule and cyclohexanone as a guest molecule and 5 g of diisobutyl ketone in a test tube containing a stir bar And stirring at 27 ° C. for 72 hours. During the stirring, the crystals of the dihydroxy compound represented by the above formula (1) were not completely dissolved.
Thereafter, filtration was performed, and the obtained crystal was sufficiently dried in the form of filter paper, and then the obtained crystal was analyzed by gas chromatography. The analytical values are shown in Table 5.

<Examples 25-29>
The dihydroxy compound represented by the above formula (1) was obtained in the same manner as in Example 24 except that the organic compound used, the amount used, the stirring temperature, and the stirring time were changed to those shown in Table 5. The crystals were analyzed by gas chromatography. The analysis values are shown in Tables 1-3. In all Examples, the crystals of the dihydroxy compound represented by the above formula (1) were not completely dissolved during stirring.

  As with the clathrate containing the dihydroxy compound represented by the above formula (1) as a host molecule, which is clathrated with toluene, it may be a crystal containing cyclohexanone or an aliphatic chain which may have a branch. When at least one organic compound selected from the group consisting of hydrocarbons, ketones, alcohols, ethers, nitriles and glycol ethers is used, the inclusion of cyclohexanone is reduced or almost detected. It turns out that it can be removed until it runs out.

Claims (4)

A clathrate crystal having a dihydroxy compound represented by the following formula (1) as a host molecule and an aliphatic chain which may have a branch, hydrocarbons, ketones, alcohols, ethers, A crystal of an inclusion body having at least one organic compound selected from the group consisting of nitriles and glycol ethers as a host molecule and a dihydroxy compound represented by the following formula (1) is completely dissolved in the organic compound. The purification method of the dihydroxy compound represented by following formula (1) including the process made to mix, without performing.

The method for purifying a dihydroxy compound according to claim 1, wherein the mixing temperature is 65 ° C or higher. Further, after mixing, the crystal of the dihydroxy compound represented by the above formula (1) and the organic compound are separated.
The method for purifying a dihydroxy compound according to claim 1, comprising a step of separating. Furthermore, the refinement | purification of the dihydroxy compound of Claim 3 including the process of drying the isolate | separated crystal | crystallization.
Manufacturing method.