TW201710231A - Crystal of alcohol having fluorene skeleton and method for producing same - Google Patents

Abstract

Provided are: a crystal of an alcohol having a fluorene skeleton represented by formula (1) which shows a melting endothermic peak temperature of 173-176 DEG C in differential scanning calorimetry; a crystal of an alcohol having a fluorene skeleton represented by formula (1) which shows a melting endothermic peak temperature of 190-196 DEG C; a crystal of an alcohol having a fluorene skeleton represented by formula (1) which shows a melting endothermic peak temperature of 167-170 DEG C; and a method for producing the same.

Description

Crystal of alcohol having an anthracene skeleton and method for producing the same

The present invention relates to a novel olefin having an anthracene skeleton which is suitable as a monomer for forming a resin (optical resin) constituting an optical member represented by an optical lens or an optical film, and which is excellent in workability and productivity, and a method for producing the same .

A resin material such as a polycarbonate, a polyester, a polyacrylate, a polyurethane, or an epoxy resin having an anthracene skeleton as a raw material monomer is excellent in optical properties, heat resistance, etc., and has recently been used as an optical lens. Or new optical materials such as optical sheets have attracted attention. Among them, there is the following formula (1):

The alcohol having a phenyl group and an anthracene skeleton and the resin produced from the alcohol having such a structure have optical properties such as refractive index, heat resistance, water resistance, chemical resistance, electrical properties, mechanical properties, and meltability. (Japanese Patent Laid-Open No. Hei 07-149881 (Patent Document 1), Japanese Patent Laid-Open No. 2001-122828 (Patent Document 2), and Japanese Patent Laid-Open Publication No. 2001-206863 (Patent No.) Document 3), Japanese Patent Laid-Open Publication No. 2009-256342 (Patent Document 4)).

The method for producing an alcohol having an anthracene skeleton represented by the above formula (1) is known to have the following formula (2) in the presence of a basic catalyst:

The method of reacting a phenol compound having an anthracene skeleton with ethylene oxide (Patent Document 2). However, the purity of the alcohol having an anthracene skeleton represented by the above formula (1) obtained by the present method is low, and a large amount of a compound of ethylene oxide and 3 or 4 molecules is added in a by-product, which is difficult to be high. The alcohol having an anthracene skeleton represented by the above formula (1) is obtained in a pure manner.

On the other hand, as a method for improving the production method described in Patent Document 2, it is revealed that the following formula (3) is obtained in the presence of an acid catalyst and a mercaptan:

A method in which the alcohol represented by the reaction is reacted with 9-fluorenone to obtain an alcohol having an anthracene skeleton represented by the above formula (1) (Patent Documents 3 and 4). However, Patent Document 4 discloses that the alcohol having an anthracene skeleton represented by the above formula (1) is produced by the method described in Patent Document 3, and it is particularly desirable depending on the use of the optical application or the like. The coloring is avoided, and the coloring cannot be removed even if a purification operation is performed.

Further, Patent Document 4 discloses a method of improving the production methods described in Patent Documents 2 and 3 by presenting 3 parts by weight of a thiol with respect to 100 parts by weight of an acid catalyst and 9-fluorenone. Under the above conditions, the alcohol represented by the above formula (3) is reacted with 9-fluorenone to obtain an alcohol having an anthracene skeleton represented by the above formula (1). However, although the color of the alcohol having an anthracene skeleton represented by the above formula (1) obtained by the method is less than that obtained by the method of Patent Document 3, the improvement in coloring is not sufficient. Again, the reaction When a large amount of mercaptans are required, it is difficult to completely remove the mercaptans from the alcohol having an anthracene skeleton represented by the above formula (1), and when the alcohol is used as a resin raw material, there is a sulfur component derived from mercaptans. The problem of further coloration of the resin.

Furthermore, the inventors of the present invention conducted additional tests on the methods described in Patent Documents 2 to 4, and found that when the method described in Patent Document 3 is used, the reaction does not proceed, or even if the reaction proceeds, only the above formula (1) is obtained. An oil having an alcohol having an anthracene skeleton, and an alcohol having an anthracene skeleton represented by the above formula (1) in a crystalline form is not obtained. On the other hand, in the additional tests of Patent Documents 2 and 4, an alcohol having an anthracene skeleton represented by the above formula (1) in a crystalline form is obtained, but the extraction operation (crystallization operation) after the reaction or the reaction is used. The solvent (aromatic hydrocarbon) is contained in the alcohol having an anthracene skeleton represented by the above formula (1) to form an inclusion.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 07-149881

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-122828

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2001-206863

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-256342

An object of the present invention is to provide a crystal of an alcohol having an anthracene skeleton represented by the above formula (1) which is high in purity and which is less colored and which is not an inclusion body.

In order to solve the above problems, the inventors of the present invention have conducted intensive studies and found that the phenolic compound having an anthracene skeleton represented by the above formula (2) is present in the presence of a chain ketone having 4 or more carbon atoms. After reacting with ethylene carbonate to obtain a reaction liquid containing the alcohol having an anthracene skeleton represented by the above formula (1), the reaction liquid is prepared from the above reaction liquid. a crystallization solution having a carbon number of 4 or more chain ketones and a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight, and crystals are precipitated from the crystallization solution in a specific temperature range, and precipitated The crystals are separated, and it is possible to provide an alcohol having an anthracene skeleton represented by the above formula (1) which is high in purity, low in coloration, and which is not an inclusion body. Specifically, the following inventions are included.

〔1〕

A crystal of an alcohol having an anthracene skeleton, which is represented by the following formula (1) having a maximum melting endothermic temperature of 173 to 176 ° C obtained by differential scanning calorimetry analysis,

〔2〕

A crystal of an alcohol having an anthracene skeleton, which is in a powder X-ray diffraction pattern obtained by using a Cu-Kα line, at a diffraction angle of 2θ=7.7±0.2°, 17.2±0.2°, 18.3±0.2°, 19.6. The following formula (1) having a peak at ±0.2°, 20.8±0.2°, and 21.4±0.2°,

[3]

A crystal of an alcohol having an anthracene skeleton, which is represented by the following formula (1) having a maximum melting endothermic temperature of 190 to 196 ° C obtained by differential scanning calorimetry analysis,

[Chemical 6]

[4]

A crystal of an alcohol having an anthracene skeleton, which is in a powder X-ray diffraction pattern obtained by using a Cu-Kα line, at a diffraction angle of 2θ=14.9±0.2°, 17.8±0.2°, 18.9±0.2°, 19.7 The following formula (1) having a peak at ±0.2°, 20.0±0.2°, and 21.0±0.2°,

[5]

A crystal of an alcohol having an anthracene skeleton, which is represented by the following formula (1) having a maximum melting endothermic temperature of 167 to 170 ° C obtained by differential scanning calorimetry analysis,

[6]

A crystal of an alcohol having an anthracene skeleton, which is in a powder X-ray diffraction pattern obtained by using a Cu-Kα line, at a diffraction angle of 2θ=9.8±0.2°, 14.9±0.2°, 17.6±0.2°, 18.8. ±0.2°, 19.4±0.2°, 20.0±0.2, and 20.6±0.2°, which are represented by the following formula (1) having a peak,

[Chemistry 9]

[7]

a crystal of an alcohol having an anthracene skeleton, which is represented by the following formula (1) having at least one endothermic peak obtained by differential scanning calorimetry in the range of 167 to 176 ° C,

〔8〕

A crystal of an alcohol having an anthracene skeleton according to any one of [1] to [7], which is not an inclusion body.

〔9〕

The crystal of an alcohol having an anthracene skeleton according to any one of [1] to [8], wherein 12 g of the alcohol having an anthracene skeleton represented by the above formula (1) is dissolved to a purity of 99% by weight or more of N, N-di The yellowness (YI value) of the solution of methylmethamine in 30 ml is 10 or less.

[10]

The crystal of an alcohol having an anthracene skeleton according to any one of [1] to [9], wherein the content of the aromatic hydrocarbon is 1% by weight or less.

[11]

A method for producing an alcohol having an anthracene skeleton according to [1] or [2], which comprises the following steps (a) to (c) in sequence:

(a)

In the presence of a chain ketone having a carbon number of 4 or more, the following formula (2) is caused:

a step of reacting a phenol compound having an anthracene skeleton with ethylene carbonate to obtain a reaction liquid containing an alcohol having an anthracene skeleton represented by the above formula (1);

(b)

a step of preparing a crystallization solution containing a chain ketone having 4 or more carbon atoms and having a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight;

(c)

A step of separating crystals from the above crystallization solution at 75 to 85 ° C and separating the precipitated crystals.

[12]

A method for producing an alcohol having an anthracene skeleton according to [3] or [4], which comprises the following steps (d) to (f) in sequence:

(d)

In the presence of a chain ketone having a carbon number of 4 or more, the following formula (2) is caused:

a step of reacting a phenol compound having an anthracene skeleton with ethylene carbonate to obtain a reaction liquid containing an alcohol having an anthracene skeleton represented by the above formula (1);

(e)

a step of preparing a crystallization solution containing a chain ketone having 4 or more carbon atoms and having a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight;

(f)

A step of separating crystals from the above crystallization solution at 90 to 100 ° C and separating the precipitated crystals.

[13]

A method for producing an alcohol having an anthracene skeleton according to [5] or [6], which comprises the following steps (g) to (i) in sequence:

(g)

In the presence of a chain ketone having a carbon number of 4 or more, the following formula (2) is caused:

a step of reacting a phenol compound having an anthracene skeleton with ethylene carbonate to obtain a reaction liquid containing an alcohol having an anthracene skeleton represented by the above formula (1);

(h)

a step of preparing a crystallization solution containing a chain ketone having 4 or more carbon atoms and having a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight;

(i)

The step of precipitating crystals from the above crystallization solution at 70 ° C or lower and separating the precipitated crystals.

According to the present invention, it is possible to provide a crystal of an alcohol having an anthracene skeleton represented by the above formula (1) which is high in purity and which is less colored and which is not an inclusion body.

In particular, when the crystal of the alcohol having an anthracene skeleton represented by the above formula (1) is an inclusion body, when the acrylic acid or the like is reacted with the inclusion body to form another compound, the inclusion body is contained. The compound (hereinafter, also referred to as a guest molecule) hinders the reaction, and cannot be used depending on the reaction. When it is directly used for melting or the like as a resin raw material, there is also a case where it is required to be derived from the melting process. The vapor of the generated guest molecule is removed to the outside of the system, or the effect of the guest molecule causes the quality of the obtained resin to become unfixed. Further, since it is possible to store a guest molecule having a low burning point (an aromatic hydrocarbon in the case of the above-mentioned cited example), it is also changed when the alcohol having an anthracene skeleton represented by the above formula (1) is stored or transported. It is easy to cause fire disaster prevention concerns.

However, as described above, when an alcohol having an anthracene skeleton represented by the above formula (1) is obtained as a crystal based on a known method, it is not known that an entrapped body as a guest molecule is obtained, and a non-occluded body is obtained. A method of crystals of an alcohol having an anthracene skeleton represented by the above formula (1). On the other hand, it is difficult to remove the guest molecule contained in the inclusion by a usual method of drying the crystal at a temperature higher than the boiling point of the guest molecule, and temporarily heating the crystal to a melting point or higher and melting the guest molecule. The removal is equivalent to industrially difficult to implement, or it is necessary to adopt a very costly method. Therefore, it has been found that the crystal of the alcohol having an anthracene skeleton represented by the above formula (1) which is not the inclusion body and a method for producing the same are found. The present invention is particularly useful in the production and use of a crystal of an alcohol having an anthracene skeleton represented by the above formula (1) on an industrial scale.

Fig. 1 is a graph showing a differential scanning calorimetry (DSC) curve of crystals (crystal B) obtained in Example 1.

Fig. 2 is a graph showing a differential scanning calorimetry (DSC) curve of the crystal (crystal C) obtained in Example 2.

Figure 3 is a graph showing the differential scanning calorimetry of the crystal (crystal A) obtained in Comparative Example 1. A diagram of the (DSC) curve.

Fig. 4 is a view showing a powder X-ray diffraction pattern of the crystal (crystal B) obtained in Example 1.

Fig. 5 is a view showing a powder X-ray diffraction pattern of the crystal (crystal C) obtained in Example 2.

Fig. 6 is a view showing a powder X-ray diffraction pattern of the crystal (crystal A) obtained in Comparative Example 1.

Fig. 7 is a TG-DTA chart of the crystal (crystal A) obtained in Comparative Example 1.

Fig. 8 is a TG-DTA line diagram of the crystal obtained in Comparative Example 2.

Fig. 9 is a graph showing a differential scanning calorimetry (DSC) curve of the crystal (crystal D) obtained in Example 4.

Fig. 10 is a view showing a powder X-ray diffraction pattern of the crystal (crystal D) obtained in Example 4.

<Crystal of an alcohol having an anthracene skeleton represented by the above formula (1)>

The crystal of the alcohol having an anthracene skeleton represented by the above formula (1) of the present invention (hereinafter, also referred to as the crystal of the present invention) has a melting endothermic maximum temperature obtained by differential scanning calorimetry (DSC), And at least one characteristic of a diffraction angle 2θ in the powder X-ray diffraction pattern.

The crystal of the present invention can be classified into three kinds of crystals according to the maximum temperature of melting endotherm obtained by differential scanning calorimetry. Specifically, the melting endothermic maximum temperature is 173 to 176 ° C (hereinafter referred to as crystallization B), 190 to 196 ° C (hereinafter also referred to as crystallization C), and 167 to 170 ° C (There is also a case called crystal D below). Further, it is known that the inclusion of an alcohol having an anthracene skeleton represented by the above formula (1) (an inclusion of an aromatic hydrocarbon as a guest molecule; and hereinafter referred to as a crystal A) is subjected to differential scanning. The maximum temperature of melting endothermic obtained by thermal analysis is 125~147 °C.

Further, in the case where a mixed crystal of crystals B and D is obtained, the mixed crystal has at least one endothermic peak obtained by differential scanning calorimetry in the range of 167 to 176 °C. Further, even in the case of the mixed crystals of the crystals B and D, it is possible to obtain a crystal having high purity and less coloration, and further, not the inclusion body, having the same characteristics as those of the crystal of the present invention described below.

The maximum temperature of melting endotherm obtained by differential scanning calorimetry in the present invention means the temperature of the maximum endothermic peak observed when performing differential scanning calorimetry under the following conditions. Further, the melting endothermic maximum temperature shown by the crystal of the present invention sometimes fluctuates up and down due to a number of factors. As factors related to such deviation, there are the heating rate of the sample, the amount of the sample, the calibration standard used, the calibration method of the apparatus, the relative humidity of the analysis environment, and the chemical purity of the sample. The maximum temperature of the melting endotherm obtained by observing the supplied sample may vary depending on each device, but generally, as long as the device is properly calibrated, it is within the scope defined by the present invention.

In the crystal of the present invention, the crystal B is in the powder X-ray diffraction pattern obtained by the Cu-Kα line at the diffraction angles 2θ=7.7±0.2°, 17.2±0.2°, 18.3±0.2°, 19.6±0.2°. Characteristic peaks at 20.8±0.2° and 21.4±0.2°. Crystalline C has characteristic peaks at diffraction angles 2θ=14.9±0.2°, 17.8±0.2°, 18.9±0.2°, 19.7±0.2°, 20.0±0.2°, and 21.0±0.2°. Crystalline D has characteristic peaks at diffraction angles 2θ=9.8±0.2°, 14.9±0.2°, 17.6±0.2°, 18.8±0.2°, 19.4±0.2°, 20.0±0.2, and 20.6±0.2°. On the other hand, the known crystal A has a diffraction angle of 2θ=7.6±0.2°, 15.6±0.2°, 16.4±0.2°, 18.7±0.2°, 19.0±0.2°, 20.5±0.2°, and 23.6±0.2°. Characteristic peaks.

Regarding the purity of the crystal of the present invention, the HPLC (High Performance Liquid Chromatography) purity determined by the following method is usually 90% or more, preferably 95% or more, more preferably 98% or more. . Further, the bulk density of the crystal B is 0.2 to 0.5 g/cm ³ , the bulk density of the crystal C is 0.6 to 0.8 g/cm ³ , and the bulk density of the crystal D is 0.4 to 0.6 g/cm ³ . On the other hand, the known density of crystal A is 0.2 to 0.4 g/cm ³ . Thus, in the crystal of the present invention, the crystal C is improved by 1.5 to 4 times the bulk density with respect to the known crystal A. Therefore, in the crystal of the present invention, the crystal C can of course be transported during the production of the crystal. Significantly improve volumetric efficiency during storage and use. The bulk density is measured, for example, by using a powder property evaluation device called a powder tester, or can be measured by putting the crystal of the crystal of the present invention into a graduated cylinder and calculating the weight when it is placed in a specific volume.

Further, the YI value of the crystal of the present invention measured by the following method is usually 10 or less, preferably 7 or less. On the other hand, the known crystal A is usually 30 or more. Therefore, the crystal of the present invention can be suitably used in the field where coloring such as optical use is a problem.

Further, the crystal of the present invention may have characteristics that are not occluded (no guest molecules are included). Therefore, the content of the aromatic hydrocarbons in the crystal A is 3% by weight to 6% by weight, and the content of the aromatic hydrocarbons contained in the crystal of the present invention is usually 1% by weight or less. It can be set to 0.5% by weight or less, and more preferably 0.1% by weight or less. Further, since the organic compound is not contained, the content of the organic solvent having a boiling point of 150 ° C or less under the condition of 101.3 kPa can be usually 1% by weight or less, preferably 0.5% by weight or less, and more preferably It is 0.1% by weight or less. Therefore, when the alcohol having an anthracene skeleton represented by the above formula (1) is stored or transported, the fear of occurrence of fire prevention can be reduced, and therefore it is of course suitable for use as polycarbonate, polyester, polyacrylate, A resin material such as a polyurethane or an epoxy resin can be suitably used as a raw material in which a occluded guest molecule is a problem, for example, a raw material (intermediate) for pharmaceutical and agricultural chemicals.

Whether or not the inclusion body can be judged by, for example, TG-DTA (differential thermo-thermal weight simultaneous measurement) analysis, X-ray analysis, NMR analysis, or by sufficiently drying the obtained crystal to the guest molecule After the degree of no change in weight above the boiling point, the obtained crystal is dissolved in a solvent, and analyzed by gas chromatography or high-speed liquid chromatography, and judged based on the presence or absence of a peak belonging to the guest molecule. . Again, in In the method of the TG-DTA analysis described above, it is possible to measure the change in weight when the sample is heated at a constant rate, and the heat absorption and heat generation behavior accompanying the measurement, and it is also possible to simultaneously observe the weight change and the heat absorption (or heat generation). At the time, it is judged whether or not the guest molecule is released.

<Method for Producing Alcohol Having An Anthracene skeleton represented by the above formula (1)>

The crystal of the present invention is obtained by subjecting a phenol compound having an anthracene skeleton represented by the above formula (2) to ethylene carbonate in the presence of a chain ketone having 4 or more carbon atoms in the presence of a chain ketone having 4 or more carbon atoms. a step of obtaining a reaction liquid containing an alcohol having an anthracene skeleton represented by the above formula (1) (hereinafter, also referred to as a reaction step); and preparing a chain having a carbon number of 4 or more from the above reaction liquid a ketone-based step of arranging a total amount of aromatic hydrocarbons and cyclic ketones of less than 10% by weight (hereinafter, also referred to as a crystallization solution preparation step); and in a specific temperature range A step in which crystals are precipitated from the above crystallization solution and the precipitated crystals are separated (hereinafter, also referred to as a crystallization step). Hereinafter, each step will be described in detail.

<Reaction step>

The phenol compound having an anthracene skeleton represented by the above formula (2) used in the reaction step may be a commercially available product, or may be produced by reacting an anthrone with 2-phenylphenol in the presence of an acid catalyst. .

Examples of the chain ketone having 4 or more carbon atoms used in the reaction step include methyl ethyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone, and 2-octyl group. Ketone, diisobutyl ketone, and the like. By using a chain ketone having a carbon number of 4 or more, a sufficient reaction rate can be obtained, and an alcohol having an anthracene skeleton represented by the above formula (1) can be industrially advantageously obtained. Further, in the case of using a ketone having a carbon number of less than 4, the reaction does not proceed, or the reaction rate is very slow, and in the case of using a cyclic ketone, although the reaction proceeds, the cyclic ketone is carried out. Since it is occluded to form an occlusion body, it is difficult to obtain an alcohol having an anthracene skeleton represented by the above formula (1) which is not an occlusion body.

The amount of the chain ketone having a carbon number of 4 or more is represented by the formula (2) The phenolic compound of the anthracene skeleton is 1 part by weight, usually 0.1 to 5 times by weight, preferably 0.5 to 3 times by weight. These chain ketones having a carbon number of 4 or more may be used alone or in combination of two or more kinds as needed.

In the reaction step, in addition to the chain ketone having 4 or more carbon atoms, an organic solvent other than the aromatic hydrocarbon or the cyclic ketone may be used in combination. In the case where aromatic hydrocarbons and cyclic ketones are used in combination, the aromatic hydrocarbons and the cyclic ketones are removed before the crystallization step, but the alcohol having an anthracene skeleton represented by the above formula (1) Since the aromatic hydrocarbons or the cyclic ketones are easily contained, it is difficult to remove them, and as a result, the crystals obtained are likely to be crystals in which aromatic hydrocarbons or cyclic ketones are contained, and it becomes difficult to obtain the crystal of the present invention.

The solvent other than the aromatic carbonized water and the cyclic ketone which can be used in combination in the present invention may be inactive to the phenol compound having an anthracene skeleton represented by the above formula (2) and ethylene carbonate. Examples of the organic solvent include aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, glycol diethers, esters, aliphatic nitriles, guanamines, and anthraquinones. More specifically, examples of the aliphatic hydrocarbons include pentane, hexane, and heptane. Examples of the halogenated aliphatic hydrocarbons include dichloromethane and 1,2-dichloroethane. Examples of the ethers include ethers. Diisopropyl ether, methyl tert-butyl ether, cyclopentyl methyl ether, diphenyl ether, etc., as glycol diethers, diethylene glycol dimethyl ether, triethylene glycol diethylene glycol Examples of the esters include ethyl acetate and butyl acetate. Examples of the esters include acetonitrile and the like. Examples of the guanamines include dimethylformamide. And dimethylacetamide, etc., as an anthraquinone, a dimethyl hydrazine, etc. are illustrated. Among these organic solvents which can be used in combination, an ether or a glycol diether having a boiling point of 80 ° C or higher under the conditions of 101.3 kPa is preferably used in terms of availability, workability, and reactivity. These organic solvents may be used alone or in combination of two or more kinds as needed. The amount of the organic solvent to be used is usually 0.1 to 5 times by weight, preferably 0.5 to 3 times by weight, based on 1 part by weight of the phenol compound having an anthracene skeleton represented by the above formula (2).

The ethylene carbonate used in the present invention has an antimony expressed in relation to the above formula (2). The skeleton phenolic compound 1 mole is usually used in an amount of 2 to 10 moles, preferably 2 to 4 moles. By using 2 mol or more, a sufficient reaction rate can be obtained, and by using the amount of 10 mol or less, the alcohol having an anthracene skeleton represented by the above formula (2) can be produced more economically.

When the phenol compound having an anthracene skeleton represented by the above formula (2) is reacted with ethylene carbonate, the reaction is carried out in the presence of a basic compound as necessary. The basic compound used in the reaction step may, for example, be a carbonate, a hydrogencarbonate, a hydroxide or an organic base. More specifically, examples of the carbonates include potassium carbonate, sodium carbonate, lithium carbonate, and cesium carbonate. Examples of the hydrogencarbonate include potassium hydrogencarbonate, sodium hydrogencarbonate, lithium hydrogencarbonate, and cesium hydrogencarbonate. Examples of the hydroxides include sodium hydroxide, potassium hydroxide, and lithium hydroxide. Examples of the organic bases include triethylamine, dimethylaminopyridine, triphenylphosphine, and tetramethylammonium bromide. Tetramethylammonium chloride and the like. Among these basic compounds, potassium carbonate, sodium carbonate, and triphenylphosphine are preferably used in terms of workability. The amount of the phenol compound having an anthracene skeleton represented by the above formula (2) is usually from 0.01 to 1.0 mol, preferably from 0.03 to 0.2 mol, based on the amount of the phenol compound represented by the above formula (2).

The reaction of the phenol compound having an anthracene skeleton represented by the above formula (2) with ethylene carbonate is a phenol compound having an anthracene skeleton represented by the above formula (2), ethylene carbonate, and a chain having a carbon number of 4 or more. The ketones and the optional basic compound and the organic solvent which can be used in combination are added to the reaction container, and are usually carried out at 30 to 150 ° C, preferably 100 to 130 ° C.

The reaction liquid containing the alcohol having an anthracene skeleton represented by the above formula (1) thus obtained can be directly concentrated, dried, and used for the crystallization solution preparation step, or can be post-treated by water washing, adsorption treatment, or the like. The crystallization solution preparation step is carried out by a conventional method such as precipitation or column purification, but after the water washing step described below, the crystallization solution preparation step can be used to improve the ruthenium skeleton represented by the above formula (1). The purity of the alcohol is preferred. Hereinafter, the washing step will be described in detail.

The water washing step is carried out in the obtained reaction liquid, relative to the above used in the reaction The phenol compound having an anthracene skeleton represented by the formula (2) is added in an amount of 0.1 to 10 times by weight, preferably 0.5 to 5 times by weight, based on 1 part by weight of the phenolic compound, and is carried out at 60 to 95 ° C, preferably 70 to 90 ° C. Stirring was carried out by standing and separating the aqueous layer. By using 0.1 times by weight or more of water, the effect of the water washing step is further exhibited, and by using the amount of use to 10 times or less, the volumetric efficiency can be improved. In addition, the water-washing temperature is 60° C. or higher, and the liquid separation speed at the time of standing is increased. When the temperature is 95° C. or lower, it is possible to suppress the ruthenium skeleton represented by the above formula (1) at the time of water washing. The decomposition of alcohol.

The washing step can also be carried out as many times as needed. Further, when the water washing step is carried out, the by-product or the like may be decomposed by adding a base or an acid together with water, or may be extracted into the aqueous layer.

<Cleavage solution preparation step>

When the reaction liquid produced by the above method contains aromatic hydrocarbons and/or cyclic ketones, it is necessary to remove aromatic hydrocarbons and/or cyclic ketones by distillation, concentration, or the like. The total content of the aromatic hydrocarbons and the cyclic ketones contained in the crystallization solution is less than 10% by weight, preferably 5% by weight or less. When the crystallization solution contains 10% by weight or more of aromatic hydrocarbons and/or cyclic ketones, the alcohol having an anthracene skeleton represented by the above formula (1) contains aromatic hydrocarbons and/or a cyclic group. The ketones do not provide the crystal of the present invention. Further, even if it is 5% by weight or less, a part of the obtained crystal is in the form of an inclusion body. Therefore, in order to surely contain the crystal A, it is preferred to use an aromatic hydrocarbon and a cyclic ketone in the crystallization solution. The total content of the classes was set to be less than 1% by weight.

The chain ketone having 4 or more carbon atoms contained in the crystallization solution can be the same as the chain ketone which can be used in the above reaction step. These chain ketones may be used alone or in combination of two or more kinds as needed. The chain ketone having 4 or more carbon atoms contained in the crystallization solution is 1 to 10 times by weight based on the alcohol having an anthracene skeleton represented by the above formula (1), and 0.5 to 10 times by weight in the case of obtaining the crystal B. It is preferably 1 to 5 times by weight, and is 0.1 to 5 times by weight, preferably 0.5 to 4 times by weight in the case of obtaining crystal C, and 1 to 15 times by weight, preferably 2, in the case of obtaining crystal D. ~10 times the weight. By setting the above usage range, Yu Jing In the precipitation step, it is easy to precipitate crystals in a desired temperature range, which is preferable.

In the crystallization solution, in addition to the chain ketone having a carbon number of 4 or more, in terms of increasing the amount of the obtained crystal B, C or D, it is preferred to use an aliphatic hydrocarbon (for example, hexane). , heptane, octane, etc.). In the case of using an aliphatic hydrocarbon in combination, the amount used is usually 0.3 to 5 times by weight, preferably 0.5 to 3 times by weight, based on 1 part by weight of the alcohol having an anthracene skeleton represented by the above formula (1). Further, a solvent other than the aliphatic hydrocarbons in which the alcohol having an anthracene skeleton represented by the above formula (1) is inactive (excluding aromatic hydrocarbons and cyclic ketones) may be used in combination, but in order to obtain more surely The crystal of the present invention is preferably a solvent other than an aliphatic hydrocarbon.

<Cleavage step>

When the crystallization solution obtained as described above contains crystals in the crystallization solution, the crystals are completely dissolved and then cooled, and when the crystal B is obtained, the crystals are precipitated at 75 to 85 ° C to obtain In the case of the crystal C, the crystal is precipitated at 90 to 100 ° C, and when the crystal D is obtained, the crystal is precipitated at 70 ° C or lower. Hereinafter, a method of depositing crystals in this temperature range will be described in detail.

When the crystal is precipitated at 75 to 85 ° C, the crystallization solution is heated to 75 ° C or higher and below the boiling point of the crystallization solution, preferably after heating to 100 to 110 ° C, at 0.3 ° C to 1.0 ° C / min, It is preferably cooled at a rate of 0.5 to 0.9 ° C / minute, and then crystallized at 75 to 85 ° C. Examples of the method for precipitating crystals at 75 to 85 ° C include a method of continuing stirring at the same temperature until crystallization is precipitated, a method of inoculating seed crystals in the above temperature range, and the like. In the case of adding a seed crystal, it may be crystal B, crystal C, crystal D or known crystal A, but in order to obtain crystal B more reliably, it is preferred to use crystal B as a seed crystal. Further, it is preferred that the crystal of the present invention can be obtained more reliably by maintaining the crystal at a constant temperature for a certain period of time after crystal precipitation.

When the crystal is precipitated at 90 to 100 ° C, the crystallization solution is heated to 90 ° C or higher, below the boiling point of the crystallization solution, preferably after heating to 100 to 110 ° C, and 0.05 ° C. The temperature is 0.5 ° C / min, preferably at a rate of 0.08 - 0.3 ° C / min, and then the crystal is precipitated at 90 - 100 ° C. Examples of the method for precipitating crystals at 90 to 100 ° C include a method of continuing stirring at the same temperature until precipitation of crystals, a method of inoculating seed crystals in the above temperature range, and the like. In the case of adding a seed crystal, it may be crystal B, crystal C, crystal D or a known crystal A, but in order to obtain crystal C more reliably, it is preferred to use crystal C as a seed crystal. Further, it is more preferable to obtain the crystal of the present invention more reliably by maintaining the crystal at a same temperature for a certain period of time after crystal precipitation.

When the crystal is precipitated at 70 ° C or lower, the crystallization solution is heated to 70 ° C or higher and the boiling point of the crystallization solution or lower, preferably after heating to 100 to 110 ° C, preferably 0.5 ° C to 2.0 ° C / min. The cooling was carried out at a rate of 1.0 to 1.5 ° C /min, and thereafter, the crystal was precipitated at 70 ° C or lower. Examples of the method for precipitating crystals at 70 ° C or lower include a method of continuing stirring at the same temperature until crystal precipitation, a method of inoculating seed crystals in the above temperature range, and the like. In the case of adding a seed crystal, it may be crystal B, crystal C, crystal D or a known crystal A, but in order to obtain crystal D more reliably, it is preferred to use crystal D as a seed crystal. Further, it is preferred that the crystal of the present invention can be obtained more reliably by maintaining the crystal at a constant temperature for a certain period of time after crystal precipitation.

Further, after the crystals are precipitated in the specific temperature range as described above, the crystals precipitated at the same temperature as the crystallization temperature may be separated, but in order to obtain crystals at a higher yield, it is preferred to cool to 30 ° C or lower. The precipitated crystals are separated. The separated crystals may be dried as needed to remove chain ketones having a carbon number of 4 or more attached to the crystal. In addition, since the crystal of the present invention is not an inclusion body, the carbon number can be removed by drying at a temperature equal to or higher than the boiling point of a chain ketone having a carbon number of 4 or more used in the reaction or crystallization step. Since the chain ketones and the like of 4 or more are in a crystalline state, chain ketones having a carbon number of 4 or more can be removed. Further, in the case of the known crystal A, since the temperature at which the encapsulated aromatic hydrocarbon is released is substantially the same as the melting point of the crystal, if the aromatic hydrocarbon is removed from the crystal A by heating, the crystal is crystallized. Will melt temporarily, so Yu Fang When the aromatic hydrocarbon is released, if it is cooled, it is no longer crystallized and becomes an amorphous body.

The crystal of the present invention thus obtained may be subjected to a usual purification operation such as adsorption, steam distillation, recrystallization, etc., if necessary, but it is sufficiently high in purity without performing such an operation, and since it is not an inclusion body, Of course, it is suitably used as a resin material such as polycarbonate, polyester, polyacrylate, polyurethane, epoxy resin, etc., and can also be suitably used in the field where the guest molecule becomes a problem, for example, a raw material for pharmaceutical pesticides ( Intermediate).

[Examples]

Hereinafter, the present invention will be specifically described by way of examples and test examples, but the present invention is not limited thereto. Further, various measurements in the examples were carried out by the following methods. In addition, the production rate (residual ratio) and purity of each component described in the following examples, comparative examples, and reference examples are the area percentages of HPLC measured under the following conditions.

(1) HPLC purity

Device: LC-2010A manufactured by Shimadzu Corporation, column: SMMIPAX ODS A-211 (5μm, 4.6mm ×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 the amount of residual solvent and the amount of occluded solvent

The content of the residual amount of the solvent or the guest molecule (aromatic hydrocarbon or the like) contained in the alcohol having an anthracene skeleton represented by the above formula (1) is quantified by gas chromatography based on the following conditions. .

Device: GC-2014 manufactured by Shimadzu Corporation, column: DB-1 (0.25 μm, 0.25 mm ID × 30 m), temperature rise: 40 ° C (for 5 minutes) → 20 ° C / min → 250 ° C (for 10 minutes), Inj Temperature: 250 ° C, Det temperature: 300 ° C, split ratio 1:10, carrier: nitrogen 54.4 kPa (fixed), Sample preparation method: 100 mg of the crystal of the alcohol having an anthracene skeleton represented by the above formula (1), which was sufficiently dried, was placed in a 10 ml volumetric flask, and a previously prepared 1,2-dimethoxygen was added thereto by using a full pipette. 5 ml of an ethyl acetonitrile solution (formed by dissolving 400 mg of 1,2-dimethoxyethane in 200 ml of acetonitrile), and the solution was adjusted to a volume of acetonitrile and dissolved to obtain a sample solution.

On the other hand, 10 mg of the compound to be measured for the residual amount (occlusion amount) is weighed into a 10 ml volumetric flask, and the same amount of the above-mentioned 1,2-dimethoxyethane in acetonitrile is added to make a constant volume using acetonitrile. The resulting product was dissolved as a standard solution.

The sample solution and the standard solution were analyzed under the above conditions, and the peak area of each component obtained was determined by a data processing apparatus, and the content (% by weight) of each component was calculated (internal standard method).

(3) Analysis to confirm the inclusion

5 mg of the crystal of the alcohol having an anthracene skeleton represented by the above formula (1) was accurately weighed and placed in an aluminum pan, and the measurement was carried out under the following operating conditions using a differential thermal scale TG-DTA8121 manufactured by Rigaku Co., Ltd.

(Operating conditions)

Heating rate: 10 ° C / min, measuring range: 30-250 ° C, environment: open, nitrogen 250 ml / min.

(4) Differential Scanning Calorimetry (DSC)

5 mg of the crystal of the alcohol having an anthracene skeleton represented by the above formula (1) was accurately weighed and placed in an aluminum pan, and oxidized using a differential scanning calorimeter (SII NanoTechnology Co., Ltd.: DSC7020) under the following operating conditions. Aluminum was measured for the control.

(Operating conditions)

Heating rate: 10 ° C / min, measuring range: 30-250 ° C, Environment: Open, nitrogen 40 ml/min.

(5) Powder X-ray diffraction

150 mg of the crystal of the alcohol having an anthracene skeleton represented by the above formula (1) was filled in a sample filling portion of a glass test plate, and a powder X-ray diffraction apparatus (manufactured by Spectris: X'PertPRO) was used under the following conditions. The measurement was carried out.

X-ray source: CuKα, output: 1.8kW (45kV-40mA), measurement range: 2θ=5°~70°, scanning speed: 2θ=2°/min, slit: DS=1°, mask=15mm, RS = 変 (0.1mm~).

(6) YI value

12 g of the alcohol having an anthracene skeleton represented by the above formula (1) was dissolved in 30 ml of N,N-dimethylformamide having a purity of 99% by weight or more, and N, N obtained under the following conditions was measured. - YI value (yellowness) of dimethylformamide solution.

Device: Color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., SE6000), using components: quartz element with an optical path length of 33 mm.

Further, in order to make the color of the N,N-dimethylformamide itself used for the measurement does not affect the measured value, the hue of N,N-dimethylformamide is measured in advance and corrected ( Blank determination). Based on the implementation of the blank measurement, the value obtained by measuring the sample is taken as the YI value in the present invention.

(7) bulk density

The crystals obtained in the examples and the comparative examples were placed in a 10 ml measuring cylinder until 5 ml was reached, and the bulk density was calculated from the weight of the crystals entering the measuring cylinder.

<Example 1>

Into a glass reactor equipped with a stirrer, a heating cooler, and a thermometer, a phenol compound having an anthracene skeleton represented by the above formula (2) (9,9'-bis(4-hydroxy-3-phenyl group) was charged. benzene 120 g (0.239 mol), potassium carbonate 2.8 g (0.020 mol), ethylene carbonate 48 g (0.545 mol), methyl isobutyl ketone (hereinafter also referred to as MIBK) 180 g, and the temperature was raised to After stirring at 120 ° C for 6 hours at the same temperature, the disappearance of the starting material was confirmed by HPLC.

After cooling the obtained reaction liquid to 80 ° C, 180 g of MIBK and 180 g of water were added, and the mixture was stirred at 80 to 85 ° C for 1 hour, and after standing, the aqueous layer was separated. After the same operation was repeated 3 times, MIBK 130 g and heptane 210 g were added to obtain a crystallization solution.

The obtained crystallization solution was heated to 100 ° C, stirred for 30 minutes to completely dissolve the crystal, and then the crystallization solution was cooled at a rate of 0.8 ° C / minute to precipitate crystals at 80 ° C at the same temperature. Stir under 2 hours. After stirring, it was further cooled to 25 ° C to obtain crystals.

The obtained crystals were dried under an internal pressure of 0.4 kPa under reduced pressure at an internal temperature of 85 to 90 ° C for 9 hours. As a result, the total content of MIBK and heptane was 0.2% by weight, and the drying was completed.

The respective analysis values of the obtained crystal of the alcohol having an anthracene skeleton represented by the above formula (1) are as follows.

Weight of crystal obtained: 125 g (yield: 82%), HPLC purity: 98.6%, content of organic solvent having a boiling point of 150 ° C or less at 101.3 kPa (including the content of MIBK and heptane): 0.24% by weight, YI value: 5.2, DSC melting endothermic maximum temperature: 175 ° C, bulk density: 0.5 g / cm ³ .

The DSC analysis is shown in Figure 1, the powder X-ray pattern is shown in Figure 4, and the main peaks of the powder X-ray (with a relative strength of more than 5%) are listed in Table 1. As shown in Table 1, the alcohol having an anthracene skeleton represented by the above formula (1) obtained in the present example has a diffraction angle of 2θ=7.7±0.2°, 17.2±0.2°, 18.3±0.2°, and 19.6±0.2. °, 20.8 ± 0.2 ° and 21.4 ± 0.2 ° A characteristic diffraction peak is shown (hereinafter, a case where the X-ray peak having the same spectrum as the map is referred to as "Map B") is also shown.

<Example 2>

A phenol compound having an anthracene skeleton represented by the above formula (2) (9,9'-bis(4-hydroxy-3-phenylbenzene) is charged into a glass reactor equipped with a stirrer, a heating cooler, and a thermometer. 138g (0.275mol), potassium carbonate 3.1g (0.022mol), ethylene carbonate 50.8g (0.577mol), MIBK 138g, heated to 120 ° C, stirred at the same temperature for 9 hours, using HPLC Confirm that the raw materials disappear.

After cooling the obtained reaction liquid to 80 ° C, 276 g of MIBK and 207 g of water were added, and the mixture was stirred at 70 to 75 ° C for 2 hours, and after standing, the aqueous layer was separated. After repeating the same operation three times, MIBK 55 g and heptane 198 g were added to obtain a crystallization solution.

The obtained crystallization solution was heated to 105 ° C, stirred for 30 minutes to completely dissolve the crystal, and then the crystallization solution was cooled at a rate of 0.1 ° C / minute to precipitate crystals at 95 ° C at the same temperature. Stir under 2 hours. Thereafter, it was cooled to 25 ° C and filtered to obtain crystals.

The obtained crystals were dried at an internal temperature of 80 to 90 ° C for 3 hours under reduced pressure of an internal pressure of 1.3 kPa. As a result, the content of MIBK was 0.06% by weight, and the drying was completed.

The respective analysis values of the obtained crystal of the alcohol having an anthracene skeleton represented by the above formula (1) are as follows.

Weight of crystal obtained: 127 g (yield: 78%), HPLC purity: 98.7%, content of organic solvent having a boiling point of 150 ° C or less at 101.3 kPa (including the content of MIBK and heptane): 0.07 wt%, YI value: 7.0, DSC melting endothermic maximum temperature: 195 ° C, bulk density: 0.6 g / cm ³ .

The DSC analysis is shown in Figure 2, the powder X-ray pattern is shown in Figure 5, and the main peaks of the powder X-ray (with a relative strength of more than 5%) are listed in Table 2. As shown in Table 2, the alcohol having an anthracene skeleton represented by the above formula (1) obtained in the present example has a diffraction angle of 2θ=14.9±0.2°, 17.8±0.2°, 18.9±0.2°, and 19.7±0.2°. Characteristic diffraction peaks are exhibited at 20.0±0.2° and 21.0±0.2° (hereinafter, the case where the X-ray peak having the same spectrum as the map is also referred to as “Map C”).

<Example 3>

A phenol compound having an anthracene skeleton represented by the above formula (2) (9,9'-bis(4-hydroxy-3-phenylbenzene) is charged into a glass reactor equipped with a stirrer, a heating cooler, and a thermometer. 150 g (0.298 mol), potassium carbonate 3.4 g (0.025 mol), ethylene carbonate 65.7 g (0.747 mol), methyl isoamyl ketone (hereinafter, also referred to as MIAK) 150 g, heating After stirring at the same temperature for 7 hours at 120 ° C, the disappearance of the starting material was confirmed by HPLC.

After cooling the obtained reaction liquid to 90 ° C, 150 g of water was added thereto, and the mixture was stirred at 85 to 90 ° C for 30 minutes, and after standing, the aqueous layer was separated. After repeating the same operation three times, 250 g of MIAK was added to obtain a crystallization solution.

The obtained crystallization solution was heated to 110 ° C, stirred for 30 minutes to completely dissolve the crystal, and then the crystallization solution was cooled to 98 ° C at a rate of 0.3 ° C / min. At the same temperature, in Example 2 20 mg of the obtained crystal was inoculated as a seed crystal, and the mixture was stirred for 10 minutes. As a result, precipitation of crystals began, and the mixture was stirred at the same temperature for 1 hour. After stirring, the mixture was further cooled to 22 ° C, and then filtered to obtain crystals.

The obtained crystal was stirred at an internal temperature of 80 to 90 ° C under an internal pressure of 1.3 kPa, and stirred for 3 hours. As a result, the content of MIAK was 0.07% by weight, and the drying was completed.

The respective analysis values of the obtained crystal of the alcohol having an anthracene skeleton represented by the above formula (1) are as follows.

Weight of crystal obtained: 112 g (yield: 64%), HPLC purity: 98.1%, content of organic solvent having a boiling point of 150 ° C or less at 101.3 kPa (including MIAK): 0.08 wt%, YI value: 1.7, DSC melting endothermic maximum temperature: 195 ° C, bulk density: 0.8 g / cm ³ , X-ray diffraction pattern: map C.

<Example 4>

After the reaction step and the water washing step were carried out in the same manner as in Example 1, the MIBK 240 g and the heptane (240 g) were added to the reaction liquid after the obtained water washing step to obtain a crystallization solution.

The obtained crystallization solution was heated to 100 ° C, stirred for 30 minutes to completely dissolve the crystal, and then the crystallization solution was cooled at a rate of 1.5 ° C / minute to precipitate crystals at 69 ° C at the same temperature. Stir under 2 hours. After stirring, the mixture was further cooled to 20 ° C, and then filtered to obtain crystals.

The obtained crystals were dried under reduced pressure of an internal pressure of 1.3 kPa at an internal temperature of 80 to 85 ° C for 3 hours. As a result, the total content of MIBK and heptane was 0.8% by weight, and the drying was completed.

The respective analysis values of the obtained crystal of the alcohol having an anthracene skeleton represented by the above formula (1) are as follows.

Weight of crystal obtained: 107 g (yield: 76%), HPLC purity: 98.3%, content of organic solvent having a boiling point of 150 ° C or less at 101.3 kPa (including the content of MIBK and heptane): 0.8% by weight, YI value: 4.5, DSC melting endothermic maximum temperature: 169 ° C, bulk density: 1.5 g / cm ³ .

The DSC analysis is shown in Figure 9, the powder X-ray pattern is shown in Figure 10, and the main peaks of the powder X-ray (with a relative strength of more than 5%) are listed in Table 6. As shown in Table 6, the alcohol having an anthracene skeleton represented by the above formula (1) obtained in the present example has a diffraction angle of 2θ=9.8±0.2°, 14.9±0.2°, 17.6±0.2°, and 18.8±0.2°. Characteristic diffraction peaks are exhibited at 19.4±0.2°, 20.0±0.2, and 20.6±0.2° (hereinafter, the case where the X-ray peak having the same spectrum as the spectrum is also referred to as “Map D”).

<Comparative Example 1>

A phenol compound having an anthracene skeleton represented by the above formula (2) (9,9'-bis(4-hydroxy-3-phenylbenzene) is charged into a glass reactor equipped with a stirrer, a heating cooler, and a thermometer. 40.0 g (0.080 mol), ethylene carbonate (16.1 g (0.183 mol), potassium carbonate 0.8 g (0.006 mol), and toluene 40.0 g, and the mixture was stirred at 110 ° C for 11 hours, and the peak of the raw material was confirmed by HPLC. 1% or less.

After cooling the obtained reaction liquid to 85 ° C, 68 g of water was added, and the mixture was stirred at 80 to 85 ° C for 30 minutes, and after standing, the aqueous layer was separated. After the same operation was repeated 3 times, the obtained organic solvent layer was dehydrated under reflux using a Dean-Stark apparatus to obtain a crystallization solution in which the alcohol having an anthracene skeleton represented by the above formula (1) was dissolved. .

After the obtained crystallization solution was cooled at a rate of 0.3 ° C /min, crystals were precipitated at 65 ° C and stirred at the same temperature for 2 hours. After stirring, the mixture was further cooled to 26 ° C, and then filtered to obtain crystals.

The obtained crystal was dried under reduced pressure of internal pressure of 1.1 kPa at an internal temperature of 68 ° C to 73 ° C for 3 hours. However, since the content of toluene was 4% by weight, the internal temperature was raised to 110 ° C and dried at the same temperature. 3 hours, but the toluene content was still 4% by weight.

The respective analysis values of the obtained crystal of the alcohol having an anthracene skeleton represented by the above formula (1) are as follows.

The weight of the obtained crystal: 39.3 g, HPLC purity: 97.5%, toluene content: 4.1% by weight, DSC melting endothermic maximum temperature: 151 ° C, bulk density: 0.3 g/cm ³ .

The DSC analysis is shown in Figure 3, the powder X-ray pattern is shown in Figure 6, and the main peaks of the powder X-ray (with a relative intensity of more than 5%) are listed in Table 3, and the TG-DTA analysis icon is shown. In Figure 7. As shown in Table 3, the alcohol having an anthracene skeleton represented by the above formula (1) obtained in the comparative example was at a diffraction angle of 2θ=7.6±0.2°, 15.6±0.2°, 16.4±0.2°, 18.7±0.2. Characteristic diffraction peaks are shown at °, 19.0 ± 0.2 °, 20.5 ± 0.2 °, and 23.6 ± 0.2 °.

In addition, since the residual amount of toluene was not reduced even at a high temperature and under reduced pressure, TG-DTA analysis was performed to confirm whether or not it was an inclusion body. As a result, as shown in Fig. 7, the temperature above the boiling point of toluene was about At 139 ° C, the weight began to decrease, and then an endothermic peak was observed at about 150 ° C. Therefore, the case where the alcohol having an anthracene skeleton represented by the above formula (1) obtained in the above Comparative Example was supported as an inclusion body was supported.

<Comparative Example 2>

A phenol compound having an anthracene skeleton represented by the above formula (2) (9,9'-bis(4-hydroxy-3-phenylbenzene) is charged into a glass reactor equipped with a stirrer, a heating cooler, and a thermometer. 30.0 g (0.060 mol), 12.0 g (0.136 mol) of ethylene carbonate, 0.7 g (0.005 mol) of potassium carbonate, and 30.0 g of cyclohexanone, and stirred at 140 ° C for 7 hours, and confirmed by HPLC. The peak of the raw material is 1% or less.

After cooling the obtained reaction liquid to 90 ° C, 23 g of cyclohexanone and 27 g of 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 obtained organic solvent layer was dehydrated under reflux using a Dean-Stark apparatus to obtain a crystallization solution in which the alcohol having an anthracene skeleton represented by the above formula (1) was dissolved.

Thereafter, the crystals were precipitated by cooling to 70 ° C and holding at 70 ° C for 1 hour. After that, it was stirred 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 crystal was dried under an internal pressure of 1.1 kPa under reduced pressure at an internal temperature of 90 ° C for 3 hours. However, since 14% by weight of cyclohexanone was contained, the internal temperature was raised to 110 ° C and dried at the same temperature. Hour, but the cyclohexanone content was still 14% by weight.

The respective analysis values of the obtained crystal of the alcohol having an anthracene skeleton represented by the above formula (1) are as follows.

The weight of the obtained crystal: 33.0 g, HPLC purity: 97.8%, cyclohexanone content: 14% by weight, DSC melting endothermic maximum temperature: 114 ° C, bulk density: 0.4 g/cm ³ .

Further, since the residual amount of cyclohexanone was not reduced even when dried at a high temperature and under reduced pressure, TG-DTA analysis was performed to confirm whether or not it was an inclusion. The analysis of TG-DTA is shown in Figure 8. As shown in the figure, since the weight starts to decrease at about 114 ° C and the endothermic peak is observed at the same temperature, the alcohol having the anthracene skeleton represented by the above formula (1) obtained in Comparative Example 2 is supported. The case of the inclusion.

<Comparative Example 3>

In addition to the above, the method described in Example 6 of JP-A-2001-206863 was used to carry out the reaction, and the mixture was stirred at 65 ° C for 1 hour to utilize a high-speed liquid. The reaction solution was analyzed by a chromatography method, but the alcohol having an anthracene skeleton represented by the above formula (2) was not substantially formed, and the 9-fluorenone of the starting material remained 98%. Therefore, the stirring was further continued at the same temperature for 7 hours, and the reaction liquid was analyzed by high-speed liquid chromatography. However, the reaction was not substantially carried out in the same manner, and the 9-fluorenone of the starting material remained 97%.

Therefore, based on the description of Japanese Patent Laid-Open No. 2001-206863 [0019], the reaction temperature is changed from 65 ° C to 100 ° C, and stirring is continued at the same temperature, and the result is as the original. It takes 73 hours to stir until the 9-fluorenone disappears.

In order to carry out the treatment based on the document, the obtained reaction liquid was divided into two, 10 g of methanol was added to one, and 10 g of isopropanol was added to the other, and the mixture was heated to 60 ° C, and stirring was continued for 1 hour, respectively. 30 g of pure water was added and the mixture was cooled to 30 ° C, but no crystals were precipitated in either of them, and a tar-like liquid separated from water was obtained.

<Comparative Example 4>

The amount of 9-fluorenone used was set to 18 g, and the method described in Example 4 of JP-A-2009-256342 was added to obtain 20.7 g of an alcohol having an anthracene skeleton represented by the above formula (1) (purity). 88.6%). The respective analysis values of the obtained crystal of the alcohol having an anthracene skeleton represented by the above formula (1) are as follows.

Xylene content: 5.2% by weight, YI value: 46, DSC melting endothermic maximum temperature: 146 ° C, bulk density: 0.3 g / cm ³ .

The main peaks of the powder X-rays (having a relative strength of more than 5%) are shown in Table 4. As shown in Table 4, the alcohol having an anthracene skeleton represented by the above formula (1) obtained in Comparative Example 4 was at a diffraction angle of 2θ=7.6±0.2°, 15.6±0.2°, 16.4±0.2. Characteristic diffraction peaks are shown at °, 18.7 ± 0.2 °, 19.0 ± 0.2 °, 20.5 ± 0.2 °, and 23.6 ± 0.2 °.

<Comparative Example 5>

The amount of 9-fluorenone used was set to 9 g, and the method described in Example 2 of JP-A-2009-256342 was added to obtain 13.5 g of an alcohol having an anthracene skeleton represented by the above formula (1). 74.7%). The respective analysis values of the obtained crystal of the alcohol having an anthracene skeleton represented by the above formula (1) are as follows.

Toluene content: 3.0% by weight, YI value: 83, DSC melting endothermic maximum temperature: 126 ° C, bulk density: 0.2 g/cm ³ .

The main peaks of the powder X-rays (having a relative strength of more than 5%) are shown in Table 5. As shown in Table 5, the alcohol having an anthracene skeleton represented by the above formula (1), which was obtained by the present invention, was obtained at the diffraction angles 2θ=7.6±0.2°, 15.6±0.2°, 16.4±0.2°. Characteristic diffraction peaks are shown at 18.7±0.2°, 19.0±0.2°, 20.5±0.2°, and 23.6±0.2°.

Claims (13)

A crystal of an alcohol having an anthracene skeleton, which is represented by the following formula (1) having a maximum melting endothermic temperature of 173 to 176 ° C obtained by differential scanning calorimetry analysis, A crystal of an alcohol having an anthracene skeleton, which is in a powder X-ray diffraction pattern obtained by using a Cu-Kα line, at a diffraction angle of 2θ=7.7±0.2°, 17.2±0.2°, 18.3±0.2°, 19.6. The following formula (1) having a peak at ±0.2°, 20.8±0.2°, and 21.4±0.2°, A crystal of an alcohol having an anthracene skeleton, which is represented by the following formula (1) having a maximum melting endothermic temperature of 190 to 196 ° C obtained by differential scanning calorimetry analysis, A crystal of an alcohol having an anthracene skeleton, which is in a powder X-ray diffraction pattern obtained by using a Cu-Kα line, at a diffraction angle of 2θ=14.9±0.2°, 17.8±0.2°, 18.9±0.2°, 19.7 The following formula (1) having a peak at ±0.2°, 20.0±0.2°, and 21.0±0.2°, A crystal of an alcohol having an anthracene skeleton, which is represented by the following formula (1) having a maximum melting endothermic temperature of 167 to 170 ° C obtained by differential scanning calorimetry analysis, A crystal of an alcohol having an anthracene skeleton, which is in a powder X-ray diffraction pattern obtained by using a Cu-Kα line, at a diffraction angle of 2θ=9.8±0.2°, 14.9±0.2°, 17.6±0.2°, 18.8. The following formula (1) having a peak at ±0.2°, 19.4±0.2°, 20.0±0.2, and 20.6±0.2°, A crystal of an alcohol having an anthracene skeleton, which is represented by the following formula (1) having at least one endothermic peak obtained by differential scanning calorimetry in the range of 167 to 176 ° C, [Chem. 7] A crystal of an alcohol having an anthracene skeleton according to any one of claims 1 to 7, which is not an inclusion body. The crystal of an alcohol having an anthracene skeleton according to any one of claims 1 to 7, wherein 12 g of the alcohol having an anthracene skeleton represented by the above formula (1) is dissolved to an N,N-dimethyl group having a purity of 99% by weight or more. The yellowness (YI value) of the solution obtained in 30 ml of carbamide is 10 or less. The crystal of an alcohol having an anthracene skeleton according to any one of claims 1 to 7, wherein the content of the aromatic hydrocarbon is 1% by weight or less. A method for producing an alcohol having an anthracene skeleton according to claim 1 or 2, which comprises the following steps (a) to (c): (a) in the presence of a chain ketone having a carbon number of 4 or more Let the following formula (2): a step of reacting a phenol compound having an anthracene skeleton with ethylene carbonate to obtain a reaction liquid containing an alcohol having an anthracene skeleton represented by the above formula (1); (b) preparing a carbon-containing material from the above reaction liquid a step of crystallization of a chain ketone of 4 or more and a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight; (c) crystallization from the crystallization solution at 75 to 85 ° C The step of separating and separating the precipitated crystals. A method for producing an alcohol having an anthracene skeleton according to claim 3 or 4, which comprises the following steps (d) to (f): (d) in the presence of a chain ketone having a carbon number of 4 or more Let the following formula (2): a step of reacting a phenol compound having an anthracene skeleton with ethylene carbonate to obtain a reaction liquid containing an alcohol having an anthracene skeleton represented by the above formula (1); (e) preparing a carbon-containing material from the above reaction liquid a step of crystallization of a chain ketone of 4 or more and a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight; (f) crystallization from the above crystallization solution at 90 to 100 ° C The step of separating and separating the precipitated crystals. A method for producing an alcohol having an anthracene skeleton according to claim 5 or 6, which comprises the following steps (g) to (i): (g) in the presence of a chain ketone having a carbon number of 4 or more Let the following formula (2): a step of reacting a phenol compound having an anthracene skeleton with ethylene carbonate to obtain a reaction liquid containing an alcohol having an anthracene skeleton represented by the above formula (1); (h) preparing a carbon-containing material from the above reaction liquid a step of crystallization of a chain ketone of 4 or more and a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight; (i) precipitation of crystals from the crystallization solution at 70 ° C or lower; And the step of separating the precipitated crystals.