JP6739136B2 - 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 production 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 does not use thiols, 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 produced an alcohol having a fluorene skeleton represented by the above formula (1) under specific conditions, and identified the obtained alcohols. It was found that by crystallizing under the conditions, it is possible to produce a crystal of an alcohol having a fluorene skeleton represented by the above formula (1), which is highly clever and less colored, and is not an inclusion body. Specifically, the following inventions are included.

[1]
The maximum temperature of melting endotherm by differential scanning calorimetry is 148 to 151° C., the following formula (1)

で表されるフルオレン骨格を有するアルコールの結晶。

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=7.1±0.2°, 14.3±0.2°, 15.2±0.2°, 15.8±0.2. A crystal of an alcohol having a fluorene skeleton represented by the above formula (1), which has peaks at °, 17.1 ± 0.2 ° and 22.3 ± 0.2 °.

[3]
In the powder X-ray diffraction pattern by Cu-Kα ray, the diffraction angles 2θ=8.1±0.2°, 15.4±0.2°, 16.6±0.2°, 18.0±0.2. A crystal of an alcohol having a fluorene skeleton represented by the above formula (1), which has peaks at 2° ± 20.4 ± 0.2°, 21.1 ± 0.2° and 22.7 ± 0.2°.

[4]
A crystal of an alcohol having a fluorene skeleton according to [2] or [3], which has a maximum melting endotherm by differential scanning calorimetry of 148 to 151°C.

[5]
A crystal of an alcohol having a fluorene skeleton according to any one of [1] to [4], which is not an inclusion body.

[6]
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 the fluorene skeleton in any one of [5].

[7]
The alcohol crystal having a fluorene skeleton according to any one of [1] to [6], 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。
（ｉｉ）
反応液に芳香族炭化水素類とメタノールを添加し、芳香族炭化水素類及びメタノールを含む溶液であって、該溶液中の水の含有量が１重量％以下となる晶析溶液を調製する工程。
（ｉｉｉ）
前記晶析溶液から２５℃以上で結晶を析出させ、析出した結晶を分離する工程。
（ｉｖ）
前記結晶を６０℃以上とし、メタノールを除去する工程。 [8]
The method for producing a crystal of an alcohol having a fluorene skeleton according to any one of [1] to [7], which comprises the following steps (i) to (iv) in this order.
(I)
In the presence of symmetric glycol diether, 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).
(Ii)
A process of adding aromatic hydrocarbons and methanol to the reaction liquid to prepare a crystallization solution containing aromatic hydrocarbons and methanol and having a water content of 1% by weight or less. ..
(Iii)
A step of precipitating crystals from the crystallization solution at 25° C. or higher and separating the precipitated crystals.
(Iv)
A step of removing the methanol by bringing the crystals to 60° C. or higher.

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 usually difficult to remove by a generally practiced method such as drying the crystal at a temperature equal to or higher than the boiling point of the guest molecule. It has a fluorene skeleton represented by the above formula (1), which is not an inclusion body, because it must be carried out by a method that is difficult or industrially difficult to carry out industrially, such as removing guest molecules after heating and melting. The present invention, which has found an alcohol crystal and a method for producing the same, is of great significance in producing and using an alcohol crystal having a fluorene skeleton represented by the above formula (1) on an industrial scale. Can be said.

FIG. 3 is a diagram showing a differential scanning calorimetry (DSC) curve of the crystal (crystal of the present invention) obtained in Example 1. It is a figure which shows the differential scanning calorimetry (DSC) curve of the crystal (inclusion body) obtained in Comparative Example 1. FIG. 8 is a diagram showing a differential scanning calorimetry (DSC) curve of the crystal (inclusion body) obtained in Comparative Example 9. FIG. 3 is a view showing a powder X-ray diffraction pattern of the crystal (crystal of the present invention) obtained in Example 1. FIG. 3 is a view showing a powder X-ray diffraction pattern of a crystal (inclusion body) obtained in Comparative Example 1. FIG. 9 is a view showing a powder X-ray diffraction pattern of the crystal (inclusion body) obtained in Comparative Example 9. 7 is a TG-DTA chart diagram of the crystal (inclusion body) obtained in Comparative Example 1. FIG. 9 is a diagram showing a differential scanning calorimetry (DSC) curve of the crystal (crystal of the present invention) obtained in Example 7. FIG. 7 is a view showing a powder X-ray diffraction pattern of the crystal (crystal of the present invention) obtained in Example 7. FIG.

<Method for producing crystal of alcohol having fluorene skeleton represented by the above formula (1)>
Crystals of an alcohol having a fluorene skeleton represented by the above formula (1) of the present invention having the above-mentioned characteristics are produced by the following steps (i) to (iv).
(I) Reaction in which a phenol compound having a fluorene skeleton represented by the above formula (2) and ethylene carbonate are reacted in the presence of a symmetric glycol diether, and an alcohol having a fluorene skeleton represented by the above formula (1) is included. A step of obtaining a liquid (hereinafter sometimes referred to as a reaction step).
(Ii)
A process of adding aromatic hydrocarbons and methanol to the reaction liquid to prepare a crystallization solution containing aromatic hydrocarbons and methanol and having a water content of 1% by weight or less. (Hereinafter, it may be referred to as a crystallization solution preparation step).
(Iii)
A step of precipitating crystals from the crystallization solution at 25° C. or higher and separating the precipitated crystals (hereinafter, also referred to as crystallization step).
(Iv)
A step of removing the methanol by setting the temperature of the crystal to 60° C. or higher (hereinafter, also referred to as a drying step).
Hereinafter, the steps (i) to (iv) will be described in detail.

<Reaction process>
The alcohol having a fluorene skeleton represented by the above formula (1) of the present invention is produced by reacting a phenol compound having a fluorene skeleton represented by the above formula (2) with ethylene carbonate in the presence of a symmetric glycol diether. Needs to be done. The methods of the above-mentioned Patent Documents 2 to 4 are known as a method for producing an alcohol having a fluorene skeleton represented by the above formula (1), but when produced by these production methods, impurities derived from these production methods are known. Probably due to the influence of the above, it is not possible to produce a crystal of an alcohol having the fluorene skeleton represented by the above formula (1) (hereinafter, the crystal may be referred to as the crystal of the present invention) having the characteristics described below. ..

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

The symmetrical glycol diether used in the present invention is represented by the following formula (4).
_{R-O (CH 2 CH 2} O) n -R (4)
(In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4.)
It has a structure represented by. Specific examples of such symmetrical glycol diethers include methyl tetraglyme, butyl diglyme, methyl triglyme, ethyl diglyme, methyl glyme, ethyl monoglyme, and methyl monoglyme.

The symmetrical glycol diether used in the present invention is usually 0.05 to 3 times by weight, preferably 0.08 to 1 times by weight, relative to 1 time by weight of the phenol compound having the fluorene skeleton represented by the above formula (2). use. By using more than 0.05 times by weight, it is possible to achieve higher purity, and in particular, it is possible to suppress the production of impurities in which 3 or more molecules of ethylene carbonate are added, and the amount used should be less than 3 times by weight. As a result, the amount of expensive symmetric glycol diether used can be reduced, so that an alcohol having a fluorene skeleton represented by the above formula (1) can be produced more economically.

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.

When carrying out the reaction step, an organic solvent may be used in combination with the symmetric glycol diether, if necessary. As the organic solvent that can be used in combination, any solvent that is inert to the phenol compound having a fluorene skeleton represented by the above formula (2) and ethylene carbonate may be used, and ketones, aromatic hydrocarbons, halogenated aromas, and the like. Examples thereof include group hydrocarbons, aliphatic hydrocarbons, halogenated aliphatic hydrocarbons, ethers, esters, aliphatic nitriles, amides, sulfoxides and the like. More specifically, as the ketones, acetone, methyl ethyl ketone, butyl methyl ketone, diisobutyl ketone, methyl isobutyl ketone, methyl isoamyl ketone, 2-heptanone, 2-octanone, cyclohexanone and the like, and aromatic hydrocarbons such as toluene, xylene and mesitylene. And the like, chlorobenzene, dichlorobenzene and the like as halogenated aromatic hydrocarbons, pentane, hexane, heptane and the like as aliphatic hydrocarbons, dichloromethane and 1,2-dichloroethane and the like as halogenated aliphatic hydrocarbons, ethers As diethyl ether, di-iso-propyl ether, methyl-tert-butyl ether, cyclopentyl methyl ether, diphenyl ether and the like, as the esters ethyl acetate, butyl acetate and the like, as aliphatic nitriles acetonitrile and the like, amides as dimethyl Formamide, dimethylacetamide and the like are exemplified, and examples of the sulfoxides include dimethylsulfoxide and the like. Among these organic solvents which can be used in combination, aromatic hydrocarbons, ketones or ethers having a boiling point of 110° C. or higher at 101.3 kPa are preferably used because of their availability and easy handling. These organic solvents may be used alone or, if necessary, as a mixture of two or more kinds. The amount used when these organic solvents are used in combination is usually 0.1 to 5 times by weight, preferably 0.5 to 3 times by weight, based on 1 time by weight of the phenol compound having the fluorene skeleton represented by the above formula (2). Double.

The reaction step is carried out at 30 to 150° C., preferably 100 to 130° C., by adding a symmetric glycol diether and, if necessary, a basic compound and an organic solvent which can be used together, to the reaction vessel.

The thus obtained reaction liquid containing the alcohol having the fluorene skeleton represented by the above formula (1) may be concentrated and dried as it is, and then used in the crystallization solution preparation step. Although it may be purified by a conventional method such as treatment or crystallization/column purification, it can be used in the crystallization solution preparation step of the present invention after carrying out the following water washing step and/or concentration step. It is preferable because the purity of the alcohol having a fluorene skeleton represented by 1) can be further improved. Hereinafter, the washing process and the concentration process will be described in detail.

In the water washing step, the obtained reaction solution is used in the reaction in an amount of 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). It is carried out by adding a weight amount of water, stirring at 60 to 95° C., preferably 75 to 90° C., 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.

Next, the concentration step will be described in detail. Concentration step, after completion of the washing step, or under normal pressure or under reduced pressure the reaction solution not subjected to the washing step, the symmetric glycol diether used in the reaction step or part or all of the organic solvent that can be used in combination Is removed from the system.

<Crystallization solution preparation step and crystallization step>
In the method for producing a crystal of the present invention, a reaction liquid containing an alcohol having a fluorene skeleton represented by the above formula (1), a crystal of an alcohol having a fluorene skeleton represented by the above formula (1), or the like is aromatized. A crystallization solution is prepared by adding group hydrocarbons and methanol. When the crystallization solution contains 1% by weight or more of water, the content of water needs to be 1% by weight or less. After the crystallization solution is adjusted, when the crystal is not completely dissolved in the solution, the crystal is completely dissolved and then cooled to precipitate an alcohol crystal having a fluorene skeleton represented by the above formula (1). , Need to be separated.

Examples of aromatic hydrocarbons usable in the present invention include toluene, xylene, mesitylene and the like. Further, when the crystallization step is carried out using only aromatic hydrocarbons, it becomes a clathrate in which the aromatic hydrocarbons are clathrated, so that it is necessary to use methanol together. Incidentally, when an alcohol other than methanol is used, as in the case of carrying out the crystallization step with the aromatic hydrocarbons alone, it becomes a clathrate in which the aromatic hydrocarbons are clathrated, and the crystals of the present invention are I can't get it.

The ratio of aromatic hydrocarbons to methanol in the crystallization solution is, for example, by weight, aromatic hydrocarbons:methanol=1:0.3 to 1:5, preferably 1:0.5 to 1:1. It is 4. By setting the ratio of methanol to 0.3 times or more the weight of aromatic hydrocarbons, it is possible to suppress the formation of clathrates containing aromatic hydrocarbons, and to set the weight to 5 times or less. This makes it easier to dissolve the alcohol having the fluorene skeleton represented by the above formula (1), which facilitates the crystallization operation, and the purity of the alcohol having the fluorene skeleton represented by the above formula (1) and It is preferable because the color tone is easily improved. These ratios are prepared, for example, by quantifying the content of aromatic hydrocarbons and methanol contained in the reaction liquid or the like by gas chromatography and then adding the aromatic hydrocarbons and methanol so that the desired ratios are obtained. be able to.

The crystallization solution may contain other solvent in addition to aromatic hydrocarbons and methanol. As the solvent which may be contained, for example, in addition to the symmetric glycol diether used in the above reaction, aliphatic hydrocarbons (eg pentane, hexane, heptane, etc.), chain ketones (eg acetone, methyl ethyl ketone, methyl isobutyl ketone) Etc.) and the like. When other solvent is contained, the amount of the solvent is usually 0.5 times or less by weight, preferably 0.3 times or less by weight, with respect to the total amount of aromatic hydrocarbons and methanol in the crystallization solution. By adjusting the amount to be 0.5 times by weight or less, the crystal of the present invention can be obtained economically and more stably.

The total amount of the solvent contained in the crystallization solution is usually 0.5 to 20 times, preferably 1 to 10 times the weight of the alcohol having the fluorene skeleton represented by the above formula (1) contained in the crystallization solution. It is twice the weight. When it is used in an amount of 0.5 times by weight or more, the purification effect by the crystallization operation is more exhibited, and when it is 20 times by weight or less, an alcohol having a fluorene skeleton represented by the above formula (1) can be obtained in good yield.

When the crystallization solution contains more than 1% by weight of water, the crystalline alcohol having the fluorene skeleton represented by the above formula (1) may not be obtained. Further, even when a crystalline alcohol having a fluorene skeleton represented by the above formula (1) is obtained, the crystals of the present invention having the characteristics described below are not obtained, and the purity and the color tone are not sufficiently improved. .. As a method of reducing the water content in the crystallization solution to 1% by weight or less, for example, before adding methanol, an aromatic hydrocarbon solvent is first added, and water is removed by azeotropic dehydration under normal pressure or reduced pressure. A method of adding methanol containing no water can be mentioned.

Next, the crystallization process will be described in detail. The crystallization solution prepared by the above method is usually heated to a temperature of 40° C. or higher and the boiling point of the crystallization solution or lower to completely dissolve the crystals, and then cooled, 25° C. or higher, preferably 25 to 60° C. Crystals are preferably precipitated at 40 to 50°C. When crystals are precipitated at a temperature lower than 25° C., the crystals of the present invention may not be obtained, and a clathrate in which aromatic hydrocarbons are clathrated may be obtained. Further, when crystals are deposited at a temperature higher than 60° C., the operability may be a problem because it is close to the boiling point of the solvent. Examples of the method for precipitating crystals in the above temperature range include a method of maintaining the temperature of the crystallization solution in the above temperature range until the crystals are precipitated, a method of inoculating a seed crystal in the above temperature range, and the like. Note that 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 crystal precipitation, further cooling is performed as necessary to separate the precipitated crystal. The crystals thus separated contain the solvent (aromatic hydrocarbon, methanol, etc.) used in the crystallization process, but unlike the crystals in which the aromatic hydrocarbons are included, the temperature is above the melting point (melting point) of the crystals. Even if it is not, since the solvent used in the crystallization step can be removed by setting the temperature to 60° C. or higher, the crystal of the present invention which is not an inclusion body can be produced.

<Drying process>
By carrying out the drying step, the solvent used in the crystallization step containing methanol can be removed. The drying step is carried out by controlling the temperature of the obtained crystal to 60°C or higher and the melting point of the crystal or lower, preferably 60°C to 110°C. When the temperature is lower than 60° C., methanol cannot be removed even in the solvent used in the crystallization step, or even if it is completed, it takes a long time and is not efficient from an industrial viewpoint. The drying step may be carried out under normal pressure or under reduced pressure, but under industrial conditions, it is preferable under reduced pressure because the solvent used in the crystallization step containing methanol can be removed more efficiently.

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 the guest molecule is not included in the crystal, it is not only preferably used as a resin material such as polycarbonate, polyester, polyacrylate, polyurethane, and epoxy, but also in a field where the guest molecule is a problem, for example, medical and agricultural chemicals. It can also be suitably used as a raw material (intermediate) for.

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

Specifically, the crystal of the present invention has a melting endothermic maximum temperature of 148 to 151° C. by differential scanning calorimetry. 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.

The crystal of the present invention has a diffraction angle 2θ=7.1±0.2°, 14.3±0.2° in the powder X-ray diffraction pattern by Cu-Kα ray due to the difference in the drying temperature in the above-mentioned drying step. , 15.2±0.2°, 15.8±0.2°, 17.1±0.2° and 22.3±0.2°, or 8.1±0. .2°, 15.4±0.2°, 16.6±0.2°, 18.0±0.2°, 20.4±0.2°, 21.1±0.2° and 22. It becomes a crystal having a characteristic peak at 0.7±0.2°. On the other hand, a crystal (inclusion body) of an alcohol having a fluorene skeleton represented by the above formula (1), which includes an aromatic hydrocarbon as a known guest molecule, has a diffraction angle 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. It has a characteristic peak at 0.6±0.2°. It can be obtained by confirming whether or not the characteristic peaks of these clathrates have a peak of 7.6±0.2° that can be clearly distinguished from other peaks of the crystal of the present invention. It is also possible to distinguish whether or not the crystals are clathrates.

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. Further, the crystal of the present invention has a YI value of usually 10 or less, preferably 7 or less, which is measured by the method described below, and thus can be suitably 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, for example, the content of the aromatic hydrocarbons in the crystal of the alcohol having the fluorene skeleton represented by the above formula (1) which includes the aromatic hydrocarbons as the guest molecule, which is obtained by the method described in the above-mentioned document. Is 3 to 6% by weight, the content of aromatic hydrocarbons contained in the crystal of the present invention is usually 1% by weight or less, preferably 0.5% by weight or less, more preferably 0.1% by weight. It can be: Further, according to the above-mentioned method for drying crystals of the present invention, the content of the organic solvent having a boiling point of 150° C. or less at 101.3 kPa is usually 1% by weight or less, preferably 0.5% by weight or less, more preferably 0% by weight or less. It is also possible to make it 1% by weight or less. 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.

Hereinafter, the present invention will be specifically described with reference to Examples and the like, 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 area percentage values of HPLC measured under the following conditions (excluding the peaks of the solvent and guest molecules in the reaction solution). (Corrected area percentage value), and "multimers" in Examples and Comparative Examples refer to compounds in which one or more ethylene carbonate molecules are added to an alcohol having a fluorene skeleton represented by the above formula (1). ..

(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-mentioned conditions, the peak area of each obtained component was determined by a data processor, and the content (%) 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) Water content The water content in the crystallization solution was measured by the method (Karl Fischer volumetric titration method) according to JIS-K0068.

<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) 150 g (0.298 mol), potassium carbonate 3.4 g (0.025 mol), ethylene carbonate 60.1 g (0.682 mol), toluene 225 g, and methyl triglyme 15 g were charged, and the temperature was raised to 115°C. After stirring at the temperature for 8 hours, it was confirmed by HPLC that the raw materials had disappeared. The production rate of the multimer at the end of the reaction was about 1%.
The obtained reaction solution was cooled to 90° C., 225 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 three times, the solvent was removed by concentrating the obtained organic solvent layer to obtain a concentrate. To the obtained concentrate, 49 g of toluene and 188 g of methanol were added to obtain a crystallization solution. The water content in the obtained crystallization solution was 0.1%.
The obtained crystallization solution was heated to 65° C., stirred at the same temperature for 1 hour to completely dissolve the crystals, and then cooled at 0.1° C./minute to precipitate crystals at 45° C. After that, the mixture was stirred at the same temperature for 2 hours. After stirring, the mixture was further cooled to 22° C. and then filtered to obtain crystals.
The obtained crystals were dried at an internal temperature of 55 to 59° C. for 3 hours under a reduced pressure of 1.3 kPa, and a part of the crystals was analyzed by gas chromatography. As a result, it was found that methanol was 4% among the solvents used in the crystallization step. It was confirmed that the content was wt%. Further, when the drying was continued for 3 hours under the same condition and analyzed, the content of methanol did not change to 4% by weight. Therefore, the internal temperature was raised to 68°C to 73°C under the reduced pressure of 1.3 kPa. After further drying for 3 hours, the content of methanol was 0.2% by weight, so the drying was completed.

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: 139 g (yield: 79%)
HPLC purity: 98.5% (multimer content: 1.1%)
Toluene content: 0.03% by weight
Content of organic solvent having a boiling point of 150° C. or lower at 101.3 kPa: 0.25% by weight
YI value: 0.7
DSC melting endothermic maximum temperature: 150°C

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 3. As shown in Table 3, the alcohol having a fluorene skeleton represented by the above formula (1) obtained in this example has diffraction angles 2θ=7.1±0.2°, 14.3±0.2°. , 15.2±0.2°, 15.8±0.2°, 17.1±0.2° and 22.3±0.2°. Further, no peak was found at 7.6±0.2°, which is a typical peak of the clathrate. (Hereinafter, a pattern having the same X-ray peak as this pattern may be referred to as "pattern A".)

<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)) Fluorene) 150 g (0.298 mol), potassium carbonate 3.4 g (0.025 mol), ethylene carbonate 60.1 g (0.682 mol), toluene 225 g, and methyl diglyme 150 g were charged, and the temperature was raised to 115°C. After stirring at temperature for 13 hours, it was confirmed by HPLC that the raw materials had disappeared. The production rate of the multimer at the end of the reaction was about 0.5%.
The obtained reaction liquid was cooled to 85° C., 225 g of water was added, 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 three times, the obtained organic solvent layer was partially concentrated to obtain a solution containing an alcohol having a fluorene skeleton represented by the above formula (1), toluene, and methyldiglyme.
54 g of toluene and 84 g of methanol were added to the solution to obtain a crystallization solution. The water content in the obtained crystallization solution was 0.1%, and the solution contained 173 g of toluene, 84 g of methanol and 61 g of methyldiglyme.
The obtained crystallization solution was heated to 65° C., stirred at the same temperature for 1 hour to completely dissolve the crystals, and then cooled at 0.1° C./min to 50° C., and in Example 1, When 0.01 g of the obtained crystal was added as a seed crystal, a crystal was precipitated. Then, it stirred at the same temperature for 1 hour. After stirring, the mixture was further cooled to 25°C and then filtered to obtain crystals.
The obtained crystals were dried at an internal temperature of 68° C. to 73° C. for 3 hours under a reduced pressure of 1.1 kPa, and the content of methanol 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: 123 g (yield: 70%)
HPLC purity: 98.0% (multimer content: 0.10%)
Toluene content: 0.05% by weight
Content of organic solvent having a boiling point of 150° C. or lower at 101.3 kPa: 0.26% by weight
YI value: 0.7
DSC melting endothermic maximum temperature: 150°C
X-ray diffraction pattern: Pattern A

<Example 3-6>
Reaction and post-treatment were carried out in the same manner as in Example 1 to obtain a concentrate. The obtained concentrate was divided into four equal parts, toluene and methanol were added so that the ratios shown in Table 1 below were obtained, and crystallization and drying operations were performed in the same manner as in Example 1, to obtain the above formula (1). A crystal of alcohol having a fluorene skeleton represented by The analytical values of each crystal are shown in Table 1 below. The addition amount of toluene/methanol in Table 1 is the ratio (weight ratio) to the alcohol having the fluorene skeleton represented by the above formula (1) contained in each concentrate.

<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. In addition, it was confirmed that about 3% of multimers were by-produced in the reaction solution.
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 The water content in the crystallization solution was 0.1%.
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% (multimer content: 2.6%)
Toluene content: 4.1% by weight
DSC melting endotherm maximum temperature: 151°C

The DSC analysis chart is shown in FIG. 2, the powder X-ray pattern is shown in FIG. 5, the main peaks of the powder X-ray (having a relative intensity exceeding 5%) are shown in Table 4, and the TG-DTA analysis chart is shown in FIG. Enumerate in. As shown in Table 4, the alcohol having a fluorene skeleton represented by the above formula (1) obtained in Comparative Example 1 had diffraction angles 2θ of 7.6±0.2° and 15.6±0.2. Characteristic of °, 16.4 ± 0.2 °, 18.7 ± 0.2 °, 19.0 ± 0.2 °, 20.5 ± 0.2 ° and 23.6 ± 0.2 °. A diffraction peak was shown. (Hereinafter, a pattern having an X-ray pattern similar to this pattern may be referred to as an “inclusion body pattern”.)
Also, since the residual amount of toluene 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 or not, and it was found that the temperature was above the boiling point of toluene. Since the weight started to decrease at 139° C. and then an endothermic peak at about 150° C. was observed, the alcohol having the fluorene skeleton represented by the above formula (1) obtained in Comparative Example 1 was included in the clathrate. Is supported.

<Comparative example 2>
In the crystallization step, ethanol is used instead of methanol, and the same operation as in Example 1 is performed except that the final drying temperature is 90° C. to obtain a crystal of an alcohol having a fluorene skeleton represented by the above formula (1). Obtained. The analytical values of the obtained crystals are as follows.
Weight of crystals obtained: 127 g
HPLC purity: 98.0% (multimer content: 0.8%)
Toluene content: 4.1% by weight
DSC melting endothermic maximum temperature: 150°C
X-ray diffraction pattern: clathrate pattern

<Comparative Examples 3 to 6>
Reaction and post-treatment were carried out in the same manner as in Example 1 to obtain a concentrate. The obtained concentrate was divided into 4 equal parts, each solvent was added so that the ratio was as shown in Table 2 below, and the final drying temperature was 90°C. The operation was performed to obtain an alcohol crystal having a fluorene skeleton represented by the above formula (1). The analytical values of each crystal are shown in Table 2 below. The addition amount of each solvent in Table 2 is the ratio (weight ratio) to the alcohol having the fluorene skeleton represented by the above formula (1) contained in each concentrate.

As shown in Table 2, the alcohol having a fluorene skeleton represented by the above formula (1) forms an inclusion complex with aromatic hydrocarbons, and when xylene is used alone or a solvent other than methanol is mixed. It was found that even after crystallization, an inclusion body in which aromatic hydrocarbons are included is formed.

<Comparative Example 7>
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 production rate of the polymer at the end of the reaction was about 1.2%.
The obtained reaction liquid was cooled to 90° C., 23 g of cyclohexanone and 27 g of normal heptane were added, and the organic solvent layer was washed 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. The water content in the crystallization solution was 0.1%.
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 at an internal temperature of 90° C. for 3 hours under a reduced pressure of 1.1 kPa, and contained 14% by weight of cyclohexanone.

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% (multimer content: 0.8%)
Cyclohexanone content: 14% by weight
DSC melting endothermic maximum temperature: 114°C

<Comparative Example 8>
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 9>
When the amount of 9-fluorenone used was 18 g and the method described in Example 1 of JP-A-2009-256342 was supplemented, 34.2 g of an alcohol having a fluorene skeleton represented by the above formula (1) (purity 85.1%) was used. ) 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: 4.8% by weight
YI value: 51
DSC melting endotherm maximum temperature: 141°C

The DSC analysis chart is listed in FIG. 3, the powder X-ray pattern is listed in FIG. 6, and the main peaks of the powder X-ray (having a relative intensity of more than 5%) are listed in Table 5. As shown in Table 5, the alcohol having a fluorene skeleton represented by the above formula (1) which clathrates xylene obtained in Comparative Example 9 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 °.

<Comparative Example 10>
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

The major peaks of the powder X-rays (those with a relative intensity of more than 5%) are shown in Table 6. As shown in Table 6, the alcohol having a fluorene skeleton represented by the above formula (1) that clathrates toluene obtained in Comparative Example 10 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 °.

<Comparative Example 11>
When the method described in Example 3 of JP-A-2009-256342 was supplemented by using 9-fluorenone in an amount of 18 g, an alcohol having a fluorene skeleton represented by the above formula (1) was 23.6 g (purity: 91.2%). ) 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: 5.0% by weight
YI value: 18
DSC melting endothermic maximum temperature: 147°C

The major peaks of the powder X-rays (those with a relative intensity above 5%) are shown in Table 7. As shown in Table 7, the alcohol having the fluorene skeleton represented by the above formula (1) which clathrates xylene, obtained in Comparative Example 11, 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 12>
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

The major peaks of the powder X-rays (those with a relative intensity above 5%) are shown in Table 8. As shown in Table 8, the alcohol having the fluorene skeleton represented by the above formula (1) which clathrates xylene, obtained in Comparative Example 12, 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 °.

<Example 7>
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 1.2 g (0.009 mol), ethylene carbonate 65.6 g (0.745 mol), toluene 150 g, and methyl triglyme 90 g were charged, and the temperature was raised to 115°C. After stirring at the temperature for 5 hours, it was confirmed by HPLC that the raw materials had disappeared. The production rate of the multimer at the end of the reaction was about 0.7%.
The obtained reaction solution was cooled to 90° C., 225 g of water and 225 g of toluene were added, 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 three times, the obtained organic solvent layer was partially concentrated to obtain a solution containing an alcohol having a fluorene skeleton represented by the above formula (1), toluene, and methyl triglyme.
To the solution was added 18 g of toluene and 225 g of methanol to obtain a crystallization solution. The water content in the obtained crystallization solution was 0.1%, the amount of toluene contained in the solution was 150 g, the amount of methanol was 225 g, and the amount of methyltriglyme was 76 g.
The obtained crystallization solution was heated to 65° C., stirred at the same temperature for 1 hour to completely dissolve the crystals, and then cooled at 0.1° C./min to precipitate crystals at 48° C. After that, 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 100 to 105° C. for 12 hours under a reduced pressure of 1.3 kPa, and the content of methanol was 0.1% 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: 145 g (yield: 82%)
HPLC purity: 98.2% (multimer content: 0.7%)
Toluene content: 0.02% by weight
Content of organic solvent having a boiling point of 150° C. or lower at 101.3 kPa: 0.1% by weight
YI value: 0.8
DSC melting endothermic maximum temperature: 150°C

The DSC analysis chart is listed in FIG. 8, the powder X-ray pattern is listed in FIG. 9, and the main peaks of powder X-ray (having a relative intensity of more than 5%) are listed in Table 9. As shown in Table 9, the alcohol having a fluorene skeleton represented by the above formula (1) obtained in this example has diffraction angles 2θ of 8.1±0.2° and 15.4±0.2°. , 16.6 ± 0.2°, 18.0 ± 0.2°, 20.4 ± 0.2°, 21.1 ± 0.2° and 22.7 ± 0.2° Showed a peak. Further, no peak was found at 7.6±0.2°, which is a typical peak of the clathrate.

<Comparative Example 13>
The reaction and post-treatment were carried out in the same manner as in Example 2, and then the solvent was removed to obtain 171 g of a concentrate. After adding 228 g of toluene and 114 g of methanol to the obtained concentrate, the temperature was raised to 65° C., and the crystals were completely dissolved by stirring at the same temperature for 1 hour. Then, the crystals were precipitated at 21° C. by cooling at 1.5° C./min, and after the precipitation, the crystals were stirred at the same temperature for 2 hours. After stirring, filtration was performed 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.

Claims (7)

In the powder X-ray diffraction pattern by Cu-Kα ray, there is no peak at the diffraction angle 2θ=7.6±0.2°, and the maximum melting endothermic temperature by differential scanning calorimetry is 148 to 151° C. (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=7.1±0.2°, 14.3±0.2°, 15.2±0.2°, 15.8±0.2. °, with a peak at 17.1 ± 0.2 ° and 22.3 ± 0.2 °, the alcohol having a fluorene skeleton represented by the following formula (1) crystal.

In the powder X-ray diffraction pattern by Cu-Kα ray, there is no peak at the diffraction angle 2θ=7.6±0.2°, and the diffraction angle 2θ=8.1±0.2°, 15.4±0. Peaks at 2°, 16.6±0.2°, 18.0±0.2°, 20.4±0.2°, 21.1±0.2° and 22.7±0.2° with crystals of alcohols having a fluorene skeleton represented by the following formula (1).

The crystal of an alcohol having a fluorene skeleton according to claim 2 or 3, wherein the maximum melting endotherm by differential scanning calorimetry is 148 to 151°C. 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. An alcohol crystal having a fluorene skeleton according to any one of claims 1 to 4 . The content of aromatic hydrocarbons is below 1% by weight, crystals of alcohols having Claim 1-5 fluorene skeleton according to any one claim. The following (i) ~ including steps in this order of (iv), the production method of the alcohol crystals having Claim 1-6 fluorene skeleton according to any one claim.
(I)
The following formula (4)
_{R-O (CH 2 CH 2} O) n -R (4)
(In the formula, R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 1 to 4.)
Having a structure represented by the following formula (2) in the presence of a symmetric glycol diether.

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).
(Ii)
A process of adding aromatic hydrocarbons and methanol to the reaction liquid to prepare a crystallization solution containing aromatic hydrocarbons and methanol and having a water content of 1% by weight or less. ..
(Iii)
A step of precipitating crystals from the crystallization solution at 25° C. or higher and separating the precipitated crystals.
(Iv)
A step of removing the methanol by bringing the crystals to 60° C. or higher.

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