JP6739137B2 - Crystal of alcohol having fluorene skeleton and method for producing the same - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention is suitable as a monomer for forming a resin (optical resin) that constitutes an optical member represented by an optical lens and an optical film, and has a novel fluorene skeleton crystal having excellent processability and productivity, and a crystal thereof. It relates to a manufacturing method.

Resin materials such as polycarbonate, polyester, polyacrylate, polyurethane, and epoxy, which use alcohol having a fluorene skeleton as a raw material monomer, are excellent in optical characteristics and heat resistance, so in recent years, new optical materials such as optical lenses and optical sheets have been developed. Has been attracting attention as. Among these, the following formula (1)

で表される構造を有する、フェニル基及びフルオレン骨格を有するアルコール及び該アルコール類から製造される樹脂は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として着目されている（例えば特許文献１〜４）。

Alcohols having a phenyl group and a fluorene skeleton having a structure represented by and resins produced from the alcohols have optical properties such as refractive index, heat resistance, water resistance, chemical resistance, electrical properties, mechanical properties, and dissolution properties. Attention has been paid to the fact that it is excellent in various properties such as properties (for example, Patent Documents 1 to 4).

As a method for producing an alcohol having a fluorene skeleton represented by the above formula (1), the following formula (2) is used in the presence of a base catalyst.

で表されるフルオレン骨格を有す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、本方法で得られる上記式（１）で表されるフルオレン骨格を有するアルコールはその純度が低く、エチレンオキサイドが３、４分子と付加した化合物が多量に副生し、上記式（１）で表されるフルオレン骨格を有するアルコールを高純度で得ることは困難である。

A method of reacting a phenol compound having a fluorene skeleton represented by and ethylene oxide is known (Patent Document 2). However, the alcohol having a fluorene skeleton represented by the above formula (1) obtained by the present method has a low purity, and a large amount of a compound obtained by adding 3 or 4 molecules of ethylene oxide to the byproduct is represented by the above formula (1). It is difficult to obtain an alcohol having a fluorene skeleton represented by

On the other hand, as a method for improving the method described in Patent Document 2, the following formula (3) is used in the presence of an acid catalyst and thiols.

で表されるアルコール類と９−フルオレノンとを反応させ上記式（１）で表されるフルオレン骨格を有するアルコールを得る方法が提案されている（特許文献３、４）。しかしながら、特許文献３記載の方法により上記式（１）で表されるフルオレン骨格を有するアルコールを製造すると、光学用途等、用途によっては特に敬遠されるような着色があり、更に該着色は精製操作を施しても除去ができないといった趣旨の記載が特許文献４に為されている。

There has been proposed a method of reacting an alcohol represented by the formula (9) with 9-fluorenone to obtain an alcohol having a fluorene skeleton represented by the formula (1) (Patent Documents 3 and 4). However, when an alcohol having a fluorene skeleton represented by the above formula (1) is produced by the method described in Patent Document 3, there is coloring that is particularly shunned depending on the application such as optical applications, and the coloring is a purification operation. Patent Document 4 describes that it cannot be removed even by applying.

Further, in Patent Document 4, for the purpose of improving the production methods described in Patent Documents 2 and 3, in the presence of an acid catalyst and 3 parts by weight or more of thiols with respect to 100 parts by weight of 9-fluorenones, the above formula ( A method has been proposed in which an alcohol represented by 3) is reacted with 9-fluorenone to obtain an alcohol having a fluorene skeleton represented by the above formula (1). However, although the alcohol having a fluorene skeleton represented by the above formula (1) obtained by this method is less colored than that obtained by the method of Patent Document 3, the improvement in coloring is not sufficient. Further, since a large amount of thiols is required during the reaction, it is difficult to completely remove the thiols from the alcohol having the fluorene skeleton represented by the above formula (1), and the alcohol is used as a resin raw material. In doing so, there is a problem that the sulfur content derived from the thiols causes further coloring of the resin.

Furthermore, when the inventors of the present application additionally tried the methods described in Patent Documents 2 to 4, the reaction did not proceed with the method described in Patent Document 3, or even if the reaction proceeded, according to the above formula (1), Only an oily substance containing the alcohol having the fluorene skeleton represented was obtained, but the crystalline alcohol having the fluorene skeleton represented by the above formula (1) was not obtained. On the other hand, in the additional tests of Patent Documents 2 and 4, although the crystalline alcohol having the fluorene skeleton represented by the above formula (1) is obtained, the solvent (the crystallization operation) used in the reaction or the extraction operation (crystallization operation) after the reaction ( It has been found that the (aromatic hydrocarbons) are clathrated with the alcohol having the fluorene skeleton represented by the above formula (1) to form a clathrate.

Japanese Patent 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 an alcohol crystal having a fluorene skeleton represented by the above formula (1), which has high purity and little coloration, and is not an inclusion body.

As a result of intensive studies to solve the above problems, the present inventors have found that a phenol compound having a fluorene skeleton represented by the above formula (2) and ethylene in the presence of a chain ketone having 4 or more carbon atoms. After reacting with a carbonate to obtain a reaction solution containing an alcohol having a fluorene skeleton represented by the above formula (1), the reaction solution contains a chain ketone having 4 or more carbon atoms and has an aroma. By preparing a crystallization solution in which the total content of group hydrocarbons and cyclic ketones is less than 10% by weight, precipitating crystals from the crystallization solution in a specific temperature range, and separating the precipitated crystals, It has been found that it is possible to provide an alcohol having a fluorene skeleton represented by the above formula (1), which is pure and low in color, and is not an inclusion body. Specifically, the following inventions are included.

で表されるフルオレン骨格を有するアルコールの結晶。 [1]
The maximum melting endothermic temperature by differential scanning calorimetry is 173 to 176° C., which is expressed by the following formula (1).

An alcohol crystal having a fluorene skeleton represented by.

[2]
In the powder X-ray diffraction pattern by Cu-Kα ray, the diffraction angles 2θ=7.7±0.2°, 17.2±0.2°, 18.3±0.2°, 19.6±0.2. A crystal of an alcohol having a fluorene skeleton represented by the above formula (1), which has peaks at 2° ± 20.8 ± 0.2° and 21.4 ± 0.2°.

[3]
A crystal of an alcohol having a fluorene skeleton represented by the above formula (1), which has a melting endothermic maximum temperature of 190 to 196° C. by differential scanning calorimetry.

[4]
In the powder X-ray diffraction pattern by Cu-Kα ray, the diffraction angles 2θ=14.9±0.2°, 17.8±0.2°, 18.9±0.2°, 19.7±0.2. A crystal of an alcohol having a fluorene skeleton represented by the above formula (1), which has peaks at 2° ± 20.0 ± 0.2° and 21.0 ± 0.2°.

[5]
A crystal of an alcohol having a fluorene skeleton represented by the above formula (1), which has a melting endothermic maximum temperature of 167 to 170° C. by differential scanning calorimetry.

[6]
In the powder X-ray diffraction pattern by Cu-Kα ray, the diffraction angles 2θ=9.8±0.2°, 14.9±0.2°, 17.6±0.2°, 18.8±0.2. A crystal of an alcohol having a fluorene skeleton represented by the above formula (1), which has peaks at °, 19.4 ± 0.2°, 20.0 ± 0.2 and 20.6 ± 0.2°.

[7]
A crystal of an alcohol having a fluorene skeleton represented by the above formula (1), which has 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 a fluorene skeleton represented by the above formula (1) according to any of [1] to [7], which is not an inclusion body.

[9]
12 g of alcohol having a fluorene skeleton represented by the above formula (1) is dissolved in 30 mL of N,N-dimethylformamide having a purity of 99% by weight or more to obtain a yellowness index (YI value) of 10 or less, [1 ] The crystal|crystallization of the alcohol which has a fluorene skeleton represented by said Formula (1) in any one of [8].

[10]
A crystal of an alcohol having a fluorene skeleton represented by the above formula (1) according to any one of [1] to [9], which has an aromatic hydrocarbon content of 1% by weight or less.

で表されるフルオレン骨格を有するフェノール化合物とエチレンカーボネートとを反応させ、上記式（１）で表されるフルオレン骨格を有するアルコールを含む反応液を得る工程。
（ｂ）
前記反応液から、炭素数が４以上の鎖状ケトン類を含有し、かつ芳香族炭化水素類及び環状ケトン類の合計含有量が１０重量％未満である晶析溶液を調製する工程。
（ｃ）
前記晶析溶液から７５〜８５℃で結晶を析出させ、析出した結晶を分離する工程。 [11]
A method for producing an alcohol having a fluorene skeleton represented by the above formula (1) of [1] or [2], which includes the following steps (a) to (c) in this order.
(A)
In the presence of a chain ketone having 4 or more carbon atoms, the following formula (2)

A step of reacting a phenol compound having a fluorene skeleton represented by and ethylene carbonate to obtain a reaction liquid containing an alcohol having a fluorene 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 a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight from the reaction solution.
(C)
A step of precipitating crystals from the crystallization solution at 75 to 85° C. and separating the precipitated crystals.

[12]
A method for producing an alcohol having a fluorene skeleton represented by the above formula (1) according to [3] or [4], which includes the following steps (d) to (f) in this order.
(D)
An alcohol having a fluorene skeleton represented by the above formula (1) by reacting a phenol compound having the fluorene skeleton represented by the above formula (2) with ethylene carbonate in the presence of a chain ketone having 4 or more carbon atoms. Obtaining a reaction solution containing.
(E)
A step of preparing a crystallization solution containing a chain ketone having 4 or more carbon atoms and a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight from the reaction solution.
(F)
A step of precipitating crystals from the crystallization solution at 90 to 100° C. and separating the precipitated crystals.

[13]
A method for producing an alcohol having a fluorene skeleton represented by the above formula (1) described in [5] or [6], which comprises the following steps (g) to (i) in this order.
(G)
An alcohol having a fluorene skeleton represented by the above formula (1) by reacting a phenol compound having the fluorene skeleton represented by the above formula (2) with ethylene carbonate in the presence of a chain ketone having 4 or more carbon atoms. Obtaining a reaction solution containing.
(H)
A step of preparing a crystallization solution containing a chain ketone having 4 or more carbon atoms and a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight from the reaction solution.
(I)
A step of precipitating crystals from the crystallization solution at 70° C. or lower and separating the precipitated crystals.

According to the present invention, it is possible to provide an alcohol crystal having a fluorene skeleton represented by the above formula (1), which is not a clathrate and has high purity and little coloration.

In particular, when the alcohol crystal having a fluorene skeleton represented by the above formula (1) is an inclusion complex, when the inclusion complex is reacted with acrylic acid or the like to form another compound, the inclusion complex is included. There is a problem that existing compounds (hereinafter sometimes referred to as guest molecules) interfere with the reaction and cannot be used depending on the reaction. Also, when used as a resin raw material by melting as it is, guest molecules generated during melting In some cases, it may be necessary to remove the vapor derived from the outside of the system, and due to the effect of guest molecules, the quality of the obtained resin may not be constant. Furthermore, since a guest molecule having a low flash point (in the case of the above-mentioned reference, aromatic hydrocarbons) can be included, the alcohol having the fluorene skeleton represented by the above formula (1) is stored or transported. At the same time, there are also concerns about disaster prevention, such as fires.

However, as described above, when an alcohol having a fluorene skeleton represented by the above formula (1) is to be obtained as a crystal based on a known method, it is obtained as a clathrate in which guest molecules are clathrated, and the clathrate is included. No method for obtaining an alcohol crystal having a fluorene skeleton represented by the above formula (1) was known. On the other hand, the guest molecule contained in the clathrate is difficult to remove by a generally practiced method such as drying the crystal at a temperature not lower than the boiling point of the guest molecule. Since it has to be subjected to a method that is difficult or very costly to carry out industrially, such as removing guest molecules after melting, an alcohol having a fluorene skeleton represented by the above formula (1) which is not an inclusion body The present invention, which has found the above-mentioned crystal and a method for producing the same, is extremely significant in producing and using an alcohol crystal having a fluorene skeleton represented by the above formula (1) on an industrial scale. I can say.

FIG. 3 is a diagram showing a differential scanning calorimetry (DSC) curve of the crystal (crystal B) obtained in Example 1. 5 is a diagram showing a differential scanning calorimetry (DSC) curve of the crystal (crystal C) obtained in Example 2. FIG. FIG. 6 is a diagram showing a differential scanning calorimetry (DSC) curve of the crystal (crystal A) obtained in Comparative Example 1. FIG. 3 is a view showing a powder X-ray diffraction pattern of the crystal (crystal B) obtained in Example 1. 5 is a view showing a powder X-ray diffraction pattern of the crystal (crystal C) obtained in Example 2. FIG. FIG. 3 is a diagram showing a powder X-ray diffraction pattern of a crystal (crystal A) obtained in Comparative Example 1. 7 is a TG-DTA chart diagram of the crystal (crystal A) obtained in Comparative Example 1. FIG. 7 is a TG-DTA chart diagram of the crystal obtained in Comparative Example 2. FIG. 5 is a diagram showing a differential scanning calorimetry (DSC) curve of the crystal (crystal D) obtained in Example 4. FIG. 5 is a view showing a powder X-ray diffraction pattern of the crystal (crystal D) obtained in Example 4. FIG.

<Crystal of alcohol having fluorene skeleton represented by the above formula (1)>
The alcohol crystal having a fluorene skeleton represented by the above formula (1) of the present invention (hereinafter sometimes referred to as the crystal of the present invention) has a melting endothermic maximum temperature by differential scanning calorimetry (DSC), and a powder X-ray. It has at least one characteristic of the diffraction angle 2θ in the diffraction pattern.

The crystal of the present invention can be classified into three kinds of crystals by the melting endothermic maximum temperature by differential scanning calorimetry. Specifically, the melting endothermic maximum temperature is 173 to 176° C. (hereinafter, may be referred to as crystal B), and the melting endothermic maximum temperature is 190 to 196° C. (hereinafter, may be referred to as crystal C). And 167 to 170° C. (hereinafter sometimes referred to as crystal D). Incidentally, a well-known clathrate of an alcohol having a fluorene skeleton represented by the above formula (1) (a clathrate in which an aromatic hydrocarbon is clathrated as a guest molecule; hereinafter, also referred to as a crystal A) The maximum temperature of melting endotherm by differential scanning calorimetry is 125 to 147°C.

In some cases, a mixed crystal of crystals B and D may be obtained, and the mixed crystal has at least one endothermic peak obtained by differential scanning calorimetry in the range of 167 to 176°C. It should be noted that even a mixed crystal of the crystals B and D is a crystal having the same characteristics as those of the crystal of the present invention described below, such as high purity and little coloration, and further that it is not an inclusion body.

The melting endothermic maximum temperature by differential scanning calorimetry in the present invention means the temperature at which the maximum endothermic peak is observed when the differential scanning calorimetric analysis is carried out under the conditions described later. The maximum temperature of melting endotherm exhibited by the crystal of the present invention may fluctuate up and down due to several factors. Factors responsible for such deviations include the heating rate of the sample when performing the analysis, the sample volume, the calibration standard used, the instrument calibration method, the relative humidity of the analytical environment and the chemical purity of the sample. The maximum melting endothermic temperature observed for a given sample may vary from device to device, but is generally within the range defined in this application if the device is properly calibrated.

Among the crystals of the present invention, crystal B has a diffraction angle 2θ of 7.7±0.2°, 17.2±0.2°, 18.3±0 in a powder X-ray diffraction pattern by Cu-Kα ray. It has characteristic peaks at .2°, 19.6±0.2°, 20.8±0.2° and 21.4±0.2°. Crystal C has diffraction angles 2θ=14.9±0.2°, 17.8±0.2°, 18.9±0.2°, 19.7±0.2°, 20.0±0. It has characteristic peaks at 2° and 21.0±0.2°. Crystal D has diffraction angles 2θ=9.8±0.2°, 14.9±0.2°, 17.6±0.2°, 18.8±0.2°, 19.4±0. It has characteristic peaks at 2°, 20.0±0.2 and 20.6±0.2°. On the other hand, in the known crystal A, the diffraction angles 2θ=7.6±0.2°, 15.6±0.2°, 16.4±0.2°, 18.7±0.2°, 19. It has characteristic peaks at 0±0.2°, 20.5±0.2° and 23.6±0.2°.

The purity of the crystal of the present invention is usually 90% or higher, preferably 95% or higher, more preferably 98% or higher, as determined by the method described below. The bulk density of the crystal B is 0.2-0.5 g / cm ^3, the bulk density of the crystal C is 0.6~0.8g / cm ^3, the bulk density of the crystal D is 0.4 to 0.6 g / It is cm ³ . On the other hand, the known crystal A has a bulk density of 0.2 to 0.4 g/cm ³ . As described above, among the crystals of the present invention, since the crystal C has an improvement in bulk density of 1.5 to 4 times that of the known crystal A, the crystal C among the crystals of the present invention is Not only during manufacturing, but also during transportation, storage, and use, it is possible to significantly improve volumetric efficiency. The bulk density is measured, for example, by using a powder property evaluation device called a powder tester, or by inserting the crystal of the crystal of the present invention into a graduated cylinder and calculating it from the weight when a predetermined volume is put. You can

The YI value of the crystal of the present invention measured by the method described later 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 preferably used in a field where coloring may be a problem, particularly in optical applications.

Further, the crystal of the present invention can have a characteristic that it is not an inclusion body (does not include a guest molecule). Therefore, the known content of aromatic hydrocarbons in the crystal A is 3 to 6% by weight, whereas the content of aromatic hydrocarbons contained in the crystals of the present invention is usually 1% by weight or less, preferably Can be 0.5% by weight or less, more preferably 0.1% by weight or less. Moreover, since it does not include other organic compounds, the content of the organic solvent having a boiling point of 150° C. at 101.3 kPa is usually 1% by weight or less, preferably 0.5% by weight or less, and more preferably 0.1% by weight or less. It is also possible to set the content to be less than or equal to weight %. Therefore, when storing or transporting the alcohol having the fluorene skeleton represented by the above formula (1), it is possible to reduce the risk of disasters such that a fire is likely to occur. It is not only preferably used as a resin material such as polyacrylate, polyurethane, and epoxy, but is also suitably used as a raw material (intermediate) for medical and agricultural chemicals, for example, in the field where the guest molecules included are a problem. be able to.

Whether it is an inclusion body is determined by, for example, a method such as TG-DTA (differential thermogravimetric simultaneous measurement) analysis, X-ray analysis, and NMR analysis, as well as a condition that the obtained crystal has a boiling point of a guest molecule or more. After drying sufficiently so that there is no change in weight with, the obtained crystals are dissolved in a solvent and analyzed by gas chromatography or high performance liquid chromatography to determine whether there is a peak corresponding to the guest molecule. You can judge. Further, in the method using the TG-DTA analysis, the weight change when the measurement sample is heated at a constant rate and the endothermic/exothermic behavior accompanying it can be measured, and the weight change and the endothermic (or exothermic) are observed simultaneously It is also possible to determine that the guest molecule has been released at the time of the release.

<Method for producing alcohol having fluorene skeleton represented by the above formula (1)>
The crystal of the present invention is represented by the above formula (1) by reacting a phenol compound having a fluorene skeleton represented by the above formula (2) with ethylene carbonate in the presence of a chain ketone having 4 or more carbon atoms. A step of obtaining a reaction solution containing an alcohol having a fluorene skeleton (hereinafter, also referred to as a reaction step), containing a chain ketone having 4 or more carbon atoms from the reaction solution, and aromatic hydrocarbons And a step of preparing a crystallization solution in which the total content of cyclic ketones is less than 10% by weight (hereinafter, also referred to as a crystallization solution preparation step), and a crystal is precipitated from the crystallization solution within a specific temperature range. It is obtained by going through a step of separating the precipitated crystals (hereinafter sometimes referred to as a crystallization step). Hereinafter, each step will be described in detail.

<Reaction process>
The phenol compound having a fluorene skeleton represented by the above formula (2) used in the reaction step may be a commercially available product, and is also produced by reacting fluorenone with 2-phenylphenol in the presence of an acid catalyst. You can also

Examples of chain ketones having 4 or more carbon atoms used in the reaction step include methyl ethyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone, 2-octanone, diisobutyl ketone and the like. By using a chain ketone having 4 or more carbon atoms, a sufficient reaction rate can be obtained, and an alcohol having a fluorene skeleton represented by the above formula (1) can be industrially advantageously obtained. It should be noted that when a ketone having less than 4 carbon atoms is used, the reaction does not proceed or the reaction rate becomes very slow even if it proceeds, and when a cyclic ketone is used, the reaction proceeds but the cyclic ketone Since the clathrates are included in the clathrate, it is difficult to obtain an alcohol having a fluorene skeleton represented by the above formula (1) that is not the clathrate.

The amount of the chain ketone having 4 or more carbon atoms is usually 0.1 to 5 times by weight, preferably 0.5 to 1 times by weight the phenol compound having the fluorene skeleton represented by the above formula (2). ~3 times the weight. These chain ketones having 4 or more carbon atoms may be used alone or in combination of two or more, if necessary.

When carrying out the reaction step, an organic solvent other than aromatic hydrocarbons and cyclic ketones may be used together with the chain ketones having 4 or more carbon atoms. When aromatic hydrocarbons and cyclic ketones are used in combination, it is necessary to remove the aromatic hydrocarbons and cyclic ketones before carrying out the crystallization step, but it has a fluorene skeleton represented by the above formula (1). Since aromatic hydrocarbons or cyclic ketones are easily included in alcohol, it is difficult to remove them, and as a result, the obtained crystals are likely to be crystals in which aromatic hydrocarbons or cyclic ketones are included. It becomes difficult to obtain the crystals of the invention.

As the solvent other than the aromatic hydrocarbons and cyclic ketones that can be used in the present invention, any solvent that is inert to the phenol compound having the fluorene skeleton represented by the above formula (2) and ethylene carbonate may be used. Examples of such organic solvents include aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, glycol diethers, esters, aliphatic nitriles, amides, sulfoxides and the like. More specifically, pentane, hexane, heptane and the like as aliphatic hydrocarbons, dichloromethane and 1,2-dichloroethane and the like as halogenated aliphatic hydrocarbons, di-iso-propyl ether, methyl-tertiary ether as ethers. Li-butyl ether, cyclopentyl methyl ether, diphenyl ether and the like, diglyme as glycol diethers, triglyme, triethylene glycol dibutyl ether and the like, ethyl acetate as esters, butyl acetate and the like, acetonitrile and the like as aliphatic nitriles, Examples of amides include dimethylformamide and dimethylacetamide, and examples of sulfoxides include dimethylsulfoxide. Among these organic solvents that can be used in combination, ethers or glycol diethers having a boiling point of 80° C. or higher at 101.3 kPa are preferably used because of their availability, handleability, and reactivity. These organic solvents may be used alone or, if necessary, as a mixture of two or more kinds. The amount of these organic solvents used is usually 0.1 to 5 times by weight, preferably 0.5 to 3 times by weight, with respect to 1 time by weight of the phenol compound having the fluorene skeleton represented by the above formula (2).

The ethylene carbonate used in the present invention is usually used in an amount of 2 to 10 mol, preferably 2 to 4 mol, per 1 mol of the phenol compound having a fluorene skeleton represented by the above formula (2). A sufficient reaction rate can be obtained by using 2 moles or more, and an alcohol having a fluorene skeleton represented by the above formula (2) can be more economically produced by using the amount of 10 moles or less. You can

When the phenol compound having a fluorene skeleton represented by the above formula (2) is reacted with ethylene carbonate, the reaction is carried out in the presence of a basic compound, if necessary. Examples of the basic compound used in the reaction step include carbonates, hydrogen carbonates, hydroxides, organic bases and the like. More specifically, the carbonates include potassium carbonate, sodium carbonate, lithium carbonate, cesium carbonate, etc., the hydrogencarbonates include potassium hydrogencarbonate, sodium hydrogencarbonate, lithium hydrogencarbonate, cesium hydrogencarbonate, etc., and the hydroxides include water. Examples of the organic bases include sodium oxide, potassium hydroxide and lithium hydroxide, and triethylamine, dimethylaminopyridine, triphenylphosphine, tetramethylammonium bromide, tetramethylammonium chloride and the like. Among these basic compounds, potassium carbonate, sodium carbonate and triphenylphosphine are preferably used from the viewpoint of easy handling. The amount of the basic compound used is usually 0.01 to 1.0 mol, preferably 0.03 to 0 mol, per 1 mol of the phenol compound having the fluorene skeleton represented by the above formula (2). 0.2 mol.

The reaction between the phenol compound having the fluorene skeleton represented by the above formula (2) and ethylene carbonate is performed by the phenol compound having the fluorene skeleton represented by the above formula (2), ethylene carbonate, and a chain having 4 or more carbon atoms. Ketones and, if necessary, a basic compound, and an organic solvent that can be used in combination are added to a reaction vessel, and the reaction is usually carried out at 30 to 150°C, preferably 100 to 130°C.

The thus obtained reaction liquid containing the alcohol having the fluorene skeleton represented by the above formula (1) may be directly concentrated and dried, and then used in the crystallization solution preparation step, or after-treatment such as washing with water or adsorption treatment. Alternatively, it may be used in the crystallization solution preparation step after purification by a conventional method such as crystallization/column purification, but after performing the water washing step described below, by using it in the crystallization solution preparation step, the above formula is obtained. It is preferable because the purity of the alcohol having a fluorene skeleton represented by (1) can be further improved. Hereinafter, the washing step will be described in detail.

In the water washing step, the obtained reaction liquid is 0.1 to 10 times by weight, preferably 0.5 to 5 times by weight, based on 1 time by weight of the phenol compound having the fluorene skeleton represented by the above formula (2) used in the reaction. It is carried out by adding water by weight and stirring at 60 to 95° C., preferably 70 to 90° C., and then allowing to stand and separating the aqueous layer. By using water in an amount of 0.1 times by weight or more, the effect of the water washing step can be more exerted, and by using the amount in an amount of 10 times by weight or less, it becomes possible to improve volume efficiency. Further, when the washing temperature is 60° C. or higher, the liquid separation speed during standing is higher, and when it is 95° C. or lower, the alcohol having the fluorene skeleton represented by the above formula (1) at the time of washing with water is used. It is possible to suppress the decomposition of.

The water washing step may be carried out multiple times if necessary. Further, at the time of carrying out the water washing step, a base and an acid may be added together with water to decompose by-products and remove them into an aqueous layer.

<Crystallization solution preparation step>
When the reaction liquid produced by the above method contains aromatic hydrocarbons and/or cyclic ketones, the aromatic hydrocarbons and/or cyclic ketones are removed by an operation such as distillation/concentration, The total content of aromatic hydrocarbons and cyclic ketones contained in the crystallization solution must be 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 a fluorene skeleton represented by the above formula (1) is aromatic hydrocarbons and/or The crystals of the present invention cannot be obtained because they enclose the cyclic ketones. Even if the amount is 5% by weight or less, a part of the obtained crystal may become an inclusion body. Therefore, in order to ensure that the crystal A is not contained, the aromatic carbonization in the crystallization solution is performed. The total content of hydrogens and cyclic ketones is preferably less than 1% by weight.

As the chain ketones having 4 or more carbon atoms contained in the crystallization solution, the same chain ketones that can be used in the above-mentioned reaction step can be used. These chain ketones may be used alone or in combination of two or more if necessary. The chain ketone having a carbon number of 4 or more contained in the crystallization solution is 0.5 to 10 parts by weight in order to obtain the crystal B with respect to 1 part by weight of the alcohol having the fluorene skeleton represented by the formula (1). 1 to 5 times, preferably 1 to 5 times by weight, 0.1 to 5 times by weight, preferably 0.5 to 4 times by weight to obtain the crystal C, and 1 to 15 times by weight, preferably 1 to 15 times by weight, to obtain the crystal D. 2 to 10 times by weight. The use amount range described above is preferable because it facilitates precipitation of crystals in a desired temperature range in each crystallization step.

In the crystallization solution, in addition to chain ketones having 4 or more carbon atoms, aliphatic hydrocarbons (eg, hexane, heptane, octane, etc.) from the viewpoint of improving the yield of the obtained crystals B, C or D. Is preferably used in combination. When the aliphatic hydrocarbons are used 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 time by weight of the alcohol having the fluorene skeleton represented by the formula (1). Double. It is also possible to use a solvent other than the aliphatic hydrocarbons inert to the alcohol having the fluorene skeleton represented by the above formula (1) (however, excluding aromatic hydrocarbons and cyclic ketones) in combination. However, in order to more reliably obtain the crystal of the present invention, it is preferable not to use any other solvent other than the aliphatic hydrocarbons in combination.

<Crystallization process>
The crystallization solution obtained as described above, when the crystallization solution contains crystals, the crystals are completely dissolved and then cooled, and when crystals B are obtained, the crystals are precipitated at 75 to 85° C., To obtain the crystal C, the crystal is deposited at 90 to 100° C., and to obtain the crystal D, the crystal is deposited at 70° C. or lower. Hereinafter, the method of precipitating crystals within the temperature range will be described in detail.

When precipitating crystals at 75 to 85°C, the crystallization solution is heated to 75°C or higher and lower than the boiling point of the crystallization solution, preferably 100 to 110°C, and then 0.3°C to 1.0°C/minute, preferably Is cooled at 0.5 to 0.9° C./minute, and then crystals are precipitated at 75 to 85° C.
Examples of the method for precipitating crystals at 75 to 85° C. include a method in which stirring is continued at the same temperature until crystals are precipitated, and a method in which seed crystals are inoculated in the above temperature range. When a seed crystal is added, crystal B, crystal C, crystal D or a known crystal A may be used, but crystal B is preferably used as a seed crystal in order to obtain crystal B more reliably. Further, it is preferable to hold the same temperature for a certain period of time after crystal precipitation to grow the crystal, because the crystal of the present invention can be obtained more reliably.

When precipitating crystals at 90 to 100°C, the crystallization solution is heated to 90°C or higher and lower than the boiling point of the crystallization solution, preferably 100 to 110°C, and then 0.05°C to 0.5°C/minute, preferably Is cooled at 0.08 to 0.3° C./minute, and then crystals are precipitated at 90 to 100° C. Examples of the method for precipitating crystals at 90 to 100° C. include a method in which stirring is continued at the same temperature until crystals are precipitated, and a method in which seed crystals are inoculated in the above temperature range. When a seed crystal is added, it may be crystal B, crystal C, crystal D or a known crystal A, but crystal C is preferably used as a seed crystal in order to obtain crystal C more reliably. Further, it is preferable to hold the same temperature for a certain period of time after crystal precipitation to grow the crystal, because the crystal of the present invention can be obtained more reliably.

When precipitating a crystal at 70° C. or lower, the crystallization solution is heated to 70° C. or higher and lower than the boiling point of the crystallization solution, preferably 100 to 110° C., and then 0.5° C. to 2.0° C./min, preferably It is cooled at 1.0 to 1.5° C./minute, and then crystals are precipitated at 70° C. or less. Examples of the method of precipitating crystals at 70° C. or lower include a method of continuing stirring at the same temperature until the precipitation of crystals, a method of inoculating a seed crystal in the above temperature range, and the like. When a seed crystal is added, it may be crystal B, crystal C, crystal D or a known crystal A, but crystal D is preferably used as a seed crystal in order to obtain crystal D more reliably. Further, it is preferable to hold the same temperature for a certain period of time after crystal precipitation to grow the crystal, because the crystal of the present invention can be obtained more reliably.

After precipitating the crystal in the predetermined temperature range as described above, the crystal precipitated at the same temperature as the crystal precipitation temperature may be separated, but in order to obtain a crystal with a higher yield, it was cooled to 30° C. or lower. After that, it is preferable to separate the precipitated crystal. The separated crystals may be dried if necessary to remove chain ketones having 4 or more carbon atoms attached to the crystals.

Since the crystal of the present invention is not an inclusion complex, it is dried at a temperature not lower than the boiling point of the chain ketone having a carbon number of 4 or more used in the reaction/crystallization step, and thus the carbon number of 4 or more is obtained. Since it is possible to remove chain ketones and the like, it is possible to remove chain ketones and the like having 4 or more carbon atoms while maintaining the crystalline state. In the case of the known crystal A, the temperature at which the aromatic hydrocarbons included therein are released and the melting point of the crystal are substantially the same, so if the aromatic hydrocarbons are removed from the crystal A by heating, the crystal However, once it is melted, when it is cooled after releasing the aromatic hydrocarbons, it becomes an amorphous body instead of a crystal.

The crystals of the present invention thus obtained, if necessary, adsorption, steam distillation, it is also possible to repeat normal purification operations such as recrystallization, but sufficiently high purity without performing such operations, Further, since it is not an inclusion body, it is not only suitably used as a resin material such as polycarbonate, polyester, polyacrylate, polyurethane, and epoxy, but also in a field where guest molecules are a problem, for example, raw materials (intermediates for medical and agricultural chemicals). ) Can also be preferably used.

The present invention will be specifically described below with reference to examples and test examples, but the present invention is not limited thereto. In the examples, various measurements were carried out by the following methods. The production rate (residual rate) 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: Shimadzu LC-2010A,
Column: SUMPIPAX 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 amount of residual solvent, amount of clathrate solvent The amount of residual solvent, or of the guest molecules (aromatic hydrocarbons, etc.) clathrated by the alcohol having the fluorene skeleton represented by the above formula (1) The content was quantified by gas chromatography under the following conditions.
Device: Shimadzu Corporation GC-2014,
Column: DB-1 (0.25 μm, 0.25 mm ID×30 m),
Temperature rise: 40°C (hold for 5 minutes) → 20°C/min → 250°C (hold for 10 minutes),
Inj temperature: 250° C., Det temperature: 300° C., split ratio 1:10,
Carrier: Nitrogen 54.4 kPa (constant),
Sample preparation method: 100 mg of fully dried alcohol crystals having a fluorene skeleton represented by the above formula (1) was weighed into a 10 ml volumetric flask, and 1,2-dimethoxyethane acetonitrile solution prepared in advance was placed therein. 5 ml of (400 mg of 1,2-dimethoxyethane dissolved in 200 ml of acetonitrile) was added with a whole pipette, and the solution was dissolved in acetonitrile to make a sample solution.
On the other hand, 10 mg of the compound whose residual amount (inclusion amount) is to be measured is weighed into a 10 ml measuring flask, the same amount of an acetonitrile solution of 1,2-dimethoxyethane as described above is added, and the solution dissolved in acetonitrile to make a standard solution is added. And
The sample solution and the standard solution were analyzed under the above conditions, the peak area of each obtained component was determined by a data processor, and the content (% by weight) of each component was calculated. (Internal standard method)

(3) Analysis for confirmation of inclusion body 5 mg of alcohol crystals having a fluorene skeleton represented by the above formula (1) was accurately weighed in an aluminum pan, and the differential heat manufactured by Rigaku Corporation was used. The balance TG-DTA8121 was used and it measured on the following operating conditions.
(Operating conditions)
Temperature rising rate: 10°C/min,
Measuring range: 30-250°C,
Atmosphere: Open, nitrogen 250 ml/min.

(4) Differential scanning calorimetry (DSC)
Precisely weighing 5 mg of an alcohol crystal having a fluorene skeleton represented by the above formula (1) in an aluminum pan, and using a differential scanning calorimeter (SII Nanotechnology Inc.: DSC7020), aluminum oxide was used as a control. It measured on the following operating conditions.
(Operating conditions)
Temperature rising rate: 10°C/min,
Measuring range: 30-250°C,
Atmosphere: Open, nitrogen 40 ml/min.

(5) Powder X-ray Diffraction 150 mg of an alcohol crystal having a fluorene skeleton represented by the above formula (1) was filled in a sample filling part of a glass test plate, and a powder X-ray diffractometer (Specttris: X'Pert PRO) was used. Was measured under the following conditions.
X-ray source: CuKα,
Output: 1.8 kW (45 kV-40 mA),
Measuring range: 2θ=5° to 70°,
Scan speed: 2θ=2°/min,
Slit: DS=1°, mask=15 mm, RS=variable (0.1 mm-).

(6) YI value 12 g of an alcohol crystal having a fluorene 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 to obtain N, The YI value (yellowness) of the N-dimethylformamide solution was measured.
Device: Color difference meter (Nippon Denshoku Industries Co., Ltd., SE6000),
Cell used: Optical path length 33 mm Quartz cell.
The hue of N,N-dimethylformamide used in the measurement was measured and corrected in advance so that the coloring of N,N-dimethylformamide itself did not affect the measured value. (Blank measurement).
A value obtained by measuring the sample after performing the above blank measurement is set as the YI value in the present invention.

(7) Bulk density
The crystals obtained in Examples and Comparative Examples were placed in a 10 ml graduated cylinder up to 5 ml, and the bulk density was calculated from the weight of the crystals in the graduated cylinder.

<Example 1>
In a glass reactor equipped with a stirrer, a heating/cooling device, and a thermometer, a phenol compound having a fluorene skeleton represented by the above formula (2) (9,9'-bis(4-hydroxy-3-phenylphenyl)) Fluorene) 120 g (0.239 mol), potassium carbonate 2.8 g (0.020 mol), ethylene carbonate 48 g (0.545 mol), methyl isobutyl ketone (hereinafter sometimes referred to as MIBK) 180 g were charged, and the temperature was raised to 120°C. After warming and stirring at the same temperature for 6 hours, it was confirmed by HPLC that the raw materials had disappeared.
After cooling the obtained reaction liquid to 80 degreeC, MIBK180g and the water 180g were added, and it stirred at 80-85 degreeC for 1 hour, and left still, and isolate|separated the water layer. After repeating the same operation 3 times, 130 g of MIBK and 210 g of heptane were added to obtain a crystallization solution.
The obtained crystallization solution was heated to 100° C., stirred for 30 minutes to completely dissolve the crystals, and then the crystallization solution was cooled at 0.8° C./minute to precipitate crystals at 80° C. The mixture was stirred at the same temperature for 2 hours. After stirring, the mixture was further cooled to 25° C. to obtain crystals.
The obtained crystals were dried at an internal temperature of 85 to 90° C. for 9 hours under a reduced pressure of 0.4 kPa, and the total content of MIBK and heptane was 0.2% by weight.

The respective analytical values of the obtained crystals of alcohol having a fluorene skeleton represented by the above formula (1) are as follows.
Weight of crystals obtained: 125 g (yield: 82%)
HPLC purity: 98.6%
Content of organic solvent having a boiling point of 150° C. or lower at 101.3 kPa (including 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 chart is listed in FIG. 1, the pattern of powder X-rays is shown in FIG. 4, and the main peaks of powder X-rays (having a relative intensity of more than 5%) are listed in Table 1. As shown in Table 1, the alcohol having a fluorene skeleton represented by the above formula (1) obtained in this example has diffraction angles 2θ=7.7±0.2° and 17.2±0.2°. , 18.3±0.2°, 19.6±0.2°, 20.8±0.2° and 21.4±0.2°. (Hereinafter, a pattern having the same X-ray peak as this pattern may be referred to as "pattern B".)

<Example 2>
In a glass reactor equipped with a stirrer, a heating/cooling device, and a thermometer, a phenol compound having a fluorene skeleton represented by the above formula (2) (9,9'-bis(4-hydroxy-3-phenylphenyl)) 138 g (0.275 mol) of fluorene), 3.1 g (0.022 mol) of potassium carbonate, 50.8 g (0.577 mol) of ethylene carbonate and 138 g of MIBK were charged, the temperature was raised to 120° C., and after stirring at the same temperature for 9 hours, It was confirmed by HPLC that the raw materials had disappeared.
After cooling the obtained reaction liquid to 80 degreeC, MIBK276g and the water 207g were added, it stirred at 70-75 degreeC for 2 hours, and after leaving still, the water layer was isolate|separated. After repeating the same operation 3 times, 55 g of MIBK and 198 g of heptane were added to obtain a crystallization solution.
The obtained crystallization solution was heated to 105° C., stirred for 30 minutes to completely dissolve the crystals, and then the crystallization solution was cooled at 0.1° C./minute to precipitate crystals at 95° C. The mixture was stirred at the same temperature for 2 hours. Then, it cooled to 25 degreeC and filtered, and the crystal|crystallization was obtained.
The obtained crystals were dried at an internal temperature of 80 to 90° C. for 3 hours under a reduced pressure of 1.3 kPa, and the MIBK content was 0.06% by weight.

The respective analytical values of the obtained crystals of alcohol having a fluorene skeleton represented by the above formula (1) are as follows.
Weight of crystals obtained: 127 g (yield: 78%)
HPLC purity: 98.7%
Content of organic solvent having a boiling point of 150° C. or lower at 101.3 kPa (including content of MIBK and heptane): 0.07% by weight
YI value: 7.0
DSC melting endotherm maximum temperature: 195°C
Bulk density: 0.6 g/cm ³

The DSC analysis chart is listed in FIG. 2, the powder X-ray pattern is listed in FIG. 5, and the main peaks of powder X-ray (having a relative intensity of more than 5%) are listed in Table 2. As shown in Table 2, the alcohol having a fluorene skeleton represented by the above formula (1) obtained in this example has diffraction angles 2θ=14.9±0.2° and 17.8±0.2°. , 18.9±0.2°, 19.7±0.2°, 20.0±0.2°, and 21.0±0.2°.
(Hereinafter, a pattern having the same X-ray peak as this pattern may be referred to as "pattern C".)

<Example 3>
In a glass reactor equipped with a stirrer, a heating/cooling device, and a thermometer, a phenol compound having a fluorene skeleton represented by the above formula (2) (9,9'-bis(4-hydroxy-3-phenylphenyl)) Fluorene) 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 sometimes referred to as MIAK) 150 g were charged, and 120° C. The temperature was raised to, and after stirring at the same temperature for 7 hours, it was confirmed by HPLC that the raw materials had disappeared.
The obtained reaction solution was cooled to 90° C., 150 g of water was added, the mixture was stirred at 85 to 90° C. for 30 minutes, and allowed to stand, and then the aqueous layer was separated. After repeating the same operation 3 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 crystals, and then the crystallization solution was cooled to 98° C. at 0.3° C./minute and carried out at the same temperature. 20 mg of the crystal obtained in Example 2 was inoculated as a seed crystal, and after stirring for 10 minutes, crystals started to precipitate, so 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 crystals were dried under an internal pressure of 1.3 kPa under reduced pressure at an internal temperature of 80 to 90° C. for 3 hours. The content of MIAK was 0.07% by weight.

The respective analytical values of the obtained crystals of alcohol having a fluorene skeleton represented by the above formula (1) are as follows.
Weight of crystals obtained: 112 g (yield: 64%)
HPLC purity: 98.1%
Content of organic solvent having a boiling point of 150° C. or lower at 101.3 kPa (including MIAK): 0.08% by weight
YI value: 1.7
DSC melting endotherm maximum temperature: 195°C
Bulk density: 0.8 g/cm ³
X-ray diffraction pattern: Pattern C

<Example 4>
After performing the reaction step and the water washing step in the same scale and the same method as in Example 1, 240 g of MIBK and 240 g of heptane were added to the obtained reaction solution after the 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 crystals, and then the crystallization solution was cooled at 1.5° C./minute to precipitate crystals at 69° C. The mixture was stirred at the same temperature for 2 hours. After stirring, the mixture was further cooled to 20° C. and then filtered to obtain crystals.
The obtained crystals were dried at an internal temperature of 80 to 85° C. for 3 hours under a reduced pressure of 1.3 kPa, and the total content of MIBK and heptane was 0.8% by weight.
The respective analytical values of the obtained crystals of alcohol having a fluorene skeleton represented by the above formula (1) are as follows.
Weight of crystals obtained: 107 g (yield: 76%)
HPLC purity: 98.3%
Content of organic solvent having a boiling point of 150° C. or lower at 101.3 kPa (including content of MIBK and heptane): 0.8% by weight
YI value: 4.5
DSC melting endotherm maximum temperature: 169℃
Bulk density: 1.5 g/cm ³

The DSC analysis chart is listed in FIG. 9, the powder X-ray pattern is listed in FIG. 10, and the main peaks of the powder X-ray (having a relative intensity of more than 5%) are listed in Table 6. As shown in Table 6, the alcohol having a fluorene skeleton represented by the above formula (1) obtained in this example has diffraction angles 2θ=9.8±0.2° and 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° showed that. (Hereinafter, a pattern having an X-ray peak similar to this pattern may be referred to as "pattern D".)

<Comparative Example 1>
In a glass reactor equipped with a stirrer, a heating/cooling device, and a thermometer, a phenol compound having a fluorene skeleton represented by the above formula (2) (9,9'-bis(4-hydroxy-3-phenylphenyl)) Fluorene) 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 were charged, and the mixture was stirred at 110° C. for 11 hours and then subjected to HPLC. It was confirmed that the raw material peak was 1% or less.
The obtained reaction liquid was cooled to 85° C., 68 g of water was added, and the mixture was stirred at 80 to 85° C. for 30 minutes and allowed to stand, and then the aqueous layer was separated. After repeating the same operation 3 times, the obtained organic solvent layer was dehydrated under reflux using a Dean-Stark apparatus to obtain a crystallization solution in which an alcohol having a fluorene skeleton represented by the above formula (1) was dissolved. It was
When the obtained crystallization solution was cooled at 0.3° C./minute, 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 crystals were dried under an internal pressure of 1.1 kPa under reduced pressure at 68° C. to 73° C. for 3 hours. However, since 4 wt% of toluene was contained, the internal temperature was raised to 110° C. After further drying at temperature for 3 hours, the content of toluene remained 4% by weight.

The respective analytical values of the obtained crystals of alcohol having a fluorene skeleton represented by the above formula (1) are as follows.
Weight of crystals obtained: 39.3 g
HPLC purity: 97.5%
Toluene content: 4.1% by weight
DSC melting endotherm maximum temperature: 151°C
Bulk density: 0.3 g/cm ³

The DSC analysis chart is shown in FIG. 3, the powder X-ray pattern is shown in FIG. 6, the main peaks of the powder X-ray (having a relative intensity exceeding 5%) are shown in Table 3, and the TG-DTA analysis chart is shown in FIG. Enumerate in. As shown in Table 3, the alcohol having a fluorene skeleton represented by the above formula (1) obtained in this comparative example has diffraction angles 2θ=7.6±0.2° and 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° Showed a peak.
Also, since the residual amount of toluene did not decrease even after drying under high temperature and reduced pressure, TG-DTA analysis was performed to confirm whether it was an inclusion complex. As shown in FIG. 7, the boiling point of toluene was At the above temperature of about 139° C., the weight started to decrease, and then an endothermic peak was observed at about 150° C. Therefore, it has the fluorene skeleton represented by the above formula (1) obtained in this comparative example. Alcohol is supported to be an inclusion body.

<Comparative example 2>
In a glass reactor equipped with a stirrer, a heating/cooling device, and a thermometer, a phenol compound having a fluorene skeleton represented by the above formula (2) (9,9'-bis(4-hydroxy-3-phenylphenyl)) 30.0 g (0.060 mol) of fluorene), 12.0 g (0.136 mol) of ethylene carbonate, 0.7 g (0.005 mol) of potassium carbonate, and 30.0 g of cyclohexanone were charged, and the mixture was stirred at 140° C. for 7 hours and then subjected to HPLC. It was confirmed that the raw material peak was 1% or less.
The obtained reaction liquid was cooled to 90° C., 23 g of cyclohexanone and 27 g of heptane were added, and the organic solvent layer was washed with water while keeping the organic solvent layer at 90° C. 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 an alcohol having a fluorene skeleton represented by the above formula (1) was dissolved.
Then, the mixture was cooled to 70° C. and kept at 70° C. for 1 hour to precipitate crystals, and then 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 crystals were dried under reduced pressure of 1.1 kPa at an internal temperature of 90° C. for 3 hours. However, since cyclohexanone was contained at 14% by weight, the internal temperature was raised to 110° C. and further at the same temperature. After drying for 3 hours, the cyclohexanone content remained 14% by weight.

The respective analytical values of the obtained crystals of alcohol having a fluorene skeleton represented by the above formula (1) are as follows.
Weight of crystals obtained: 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

In addition, since the residual amount of cyclohexanone did not decrease even after drying at high temperature and reduced pressure, TG-DTA analysis was performed to confirm whether it was an inclusion complex. The analysis chart of TG-DTA is shown in FIG. As shown in the chart, the weight started to decrease at about 114° C. and the endothermic peak was also observed at the same temperature. Therefore, the fluorene skeleton represented by the above formula (1) obtained in Comparative Example 2 was obtained. Alcohols with are supported to be clathrates.

<Comparative example 3>
Charge and reaction were carried out by the method described in Example 6 of JP 2001-206863 A except that the scale was reduced to 1/10, and the reaction solution was subjected to high performance liquid chromatography at the stage of stirring at 65° C. for 1 hour. As a result of analysis, almost no alcohol having a fluorene skeleton represented by the above formula (2) was produced, and 98% of 9-fluorenone as a raw material remained. Then, stirring was further continued at the same temperature for 7 hours, and the reaction solution was analyzed by high performance liquid chromatography. Similarly, the reaction hardly proceeded and 97% of 9-fluorenone as a raw material remained.
Then, based on the description of JP 2001-206863 [0019], the reaction temperature was changed from 65° C. to 100° C. and stirring was continued at the same temperature, and it took 73 hours until the raw material 9-fluorenone disappeared. there were.
In order to carry out a post-treatment based on the description of the literature, the obtained reaction solution was divided into two, 10 g of methanol was added to one side and 10 g of isopropyl alcohol was added to the other side, the mixture was heated to 60° C., and the mixture was stirred for 1 hour. 30 g of pure water was added to each, and the mixture was cooled to 30° C. However, crystals did not precipitate in both of them, and a tar-like liquid separated from water was obtained.

<Comparative example 4>
When the amount of 9-fluorenone used was 18 g and the method described in Example 4 of JP-A-2009-256342 was additionally tested, 20.7 g of an alcohol having a fluorene skeleton represented by the above formula (1) (purity: 88.6%) ) Got. The respective analytical values of the obtained crystals of alcohol having a fluorene skeleton represented by the above formula (1) are as follows.

Xylene content: 5.2% by weight
YI value: 46
DSC melting endotherm maximum temperature: 146°C
Bulk density: 0.3 g/cm ³

The major peaks of the powder X-rays (those with a relative intensity above 5%) are shown in Table 4. As shown in Table 4, the alcohol having a fluorene skeleton represented by the above formula (1) which clathrates xylene, obtained in Comparative Example 4, had diffraction angles 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 It showed a characteristic diffraction peak at °.

<Comparative Example 5>
When the method described in Example 2 of JP-A-2009-256342 was additionally tested with 9 g of 9-fluorenone used, 13.5 g of an alcohol having a fluorene skeleton represented by the above formula (1) (purity: 74.7%) ) Got. The respective analytical values of the obtained crystals of alcohol having a fluorene 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 major peaks of the powder X-rays (those with a relative intensity above 5%) are shown in Table 5. As shown in Table 5, the alcohol having a fluorene skeleton represented by the above formula (1) that clathrates toluene obtained in Comparative Example 5 has diffraction angles 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 It showed a characteristic diffraction peak at °.

Claims (12)

The maximum melting endothermic temperature by differential scanning calorimetry is 173 to 176° C., which is expressed by the following formula (1).

An alcohol crystal having a fluorene skeleton represented by. In the powder X-ray diffraction pattern by Cu-Kα ray, the diffraction angles 2θ=7.7±0.2°, 17.2±0.2°, 18.3±0.2°, 19.6±0.2. °, with a peak at 20.8 ± 0.2 ° and 21.4 ± 0.2 °, the alcohol having a fluorene skeleton represented by the following following formula (1) crystal.

Is a differential scanning calorimetry melting endotherm maximum temperature of 190-196 ° C. by crystals of alcohols having a fluorene skeleton represented by the following following formula (1).

In the powder X-ray diffraction pattern by Cu-Kα ray, the diffraction angles 2θ=14.9±0.2°, 17.8±0.2°, 18.9±0.2°, 19.7±0.2. °, with a peak at 20.0 ± 0.2 ° and 21.0 ± 0.2 °, the alcohol having a fluorene skeleton represented by the following following formula (1) crystal.

It is a differential scanning calorimetry melting endotherm maximum temperature of 167-170 ° C. due to crystals of an alcohol having a fluorene skeleton represented by the following following formula (1).

In the powder X-ray diffraction pattern by Cu-Kα ray, the diffraction angles 2θ=9.8±0.2°, 14.9±0.2°, 17.6±0.2°, 18.8±0.2. °, 19.4 ± 0.2 °, with a peak at 20.0 ± 0.2 and 20.6 ± 0.2 °, crystal alcohols having a fluorene skeleton represented by the following following formula (1).

Not a clathrate crystals of alcohols having a fluorene skeleton represented by the claims 1-6 to any one claim of the formula (1). A yellowness (YI value) of a solution obtained by dissolving 12 g of an alcohol having a fluorene skeleton represented by the formula (1) in 30 mL of N,N-dimethylformamide having a purity of 99% by weight or more is 10 or less. A crystal of an alcohol having a fluorene skeleton represented by the above formula (1) according to any one of 1 to 7 . The alcohol crystal having a fluorene skeleton represented by the above formula (1) according to any one of claims 1 to 9 , wherein the content of aromatic hydrocarbons is 1% by weight or less. The method for producing an alcohol having a fluorene skeleton represented by the above formula (1) according to claim 1 or 2, which comprises the following steps (a) to (c) in this order.
(A)
In the presence of a chain ketone having 4 or more carbon atoms, the following formula (2)

A step of reacting a phenol compound having a fluorene skeleton represented by and ethylene carbonate to obtain a reaction liquid containing an alcohol having a fluorene 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 a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight from the reaction solution.
(C)
A step of precipitating crystals from the crystallization solution at 75 to 85° C. and separating the precipitated crystals. The method for producing an alcohol having a fluorene skeleton represented by the above formula (1) according to claim 3 or 4, which comprises the following steps (d) to (f) in this order.
(D)
Presence chain ketones number of 4 or more carbon atoms, by reacting a phenol compound with ethylene carbonate having a fluorene skeleton represented by the following following formula (2), having a fluorene skeleton represented by the above formula (1) A step of obtaining a reaction solution containing alcohol.

(E)
A step of preparing a crystallization solution containing a chain ketone having 4 or more carbon atoms and a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight from the reaction solution.
(F)
A step of precipitating crystals from the crystallization solution at 90 to 100° C. and separating the precipitated crystals. The method for producing an alcohol having a fluorene skeleton represented by the above formula (1) according to claim 5 or 6, which comprises the following steps (g) to (i) in this order.
(G)
Presence chain ketones number of 4 or more carbon atoms, by reacting a phenol compound with ethylene carbonate having a fluorene skeleton represented by the following following formula (2), having a fluorene skeleton represented by the above formula (1) A step of obtaining a reaction solution containing alcohol.

(H)
A step of preparing a crystallization solution containing a chain ketone having 4 or more carbon atoms and a total content of aromatic hydrocarbons and cyclic ketones of less than 10% by weight from the reaction solution.
(I)
A step of precipitating crystals from the crystallization solution at 70° C. or lower and separating the precipitated crystals.

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