JP2000026349A - 9,9-bis(alkyl substituted-4-hydroxyphenyl)fluorene and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound useful as a raw material of a highly heat resistant and highly transparent polyester resin, polyether resin, polyimide resin and epoxy resin and as a raw material of an optical material having a large refractive index and transparency, or the like. SOLUTION: This 9, 9 bis(an alkyl-substituted-4-hydroxyphenyl)fluorene is a compound of formula I [R1 is H or methyl; R2 is a 2-4C alkyl, 5C or 6C cycloalkyl or the like; (n) is 1, 2], e.g. 9,9-bis(4-hydroxy-3-isopropylphenyl) fluorene. The compound of formula I is obtained by reacting 1 pt.mol 9- fluorenone with preferably 4-8 pts.mol alkylphenols of formula II (e.g.; o- isopropylphnol) in the presence of an acid catalyst (e.g.; hydrogen chloride gas or a conc. hydrogen chloride), by preferably simultaneously using an alkylmercaptane, and preferably using a reaction solvent (e.g.; methanol) at 20-80 deg.C. The alkylmercaptane is used 3-20 mol.% based on the 9-fluorenone.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is useful as a raw material for highly heat-resistant and highly transparent polyester resins, polyether resins, polyimide resins, epoxy resins and the like.
The present invention relates to novel 9,9-bis (alkyl-substituted-4-hydroxyphenyl) fluorenes which are useful as raw materials for optical materials having high refractive index and transparency, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, various resins made of bisphenols as raw materials have higher heat resistance, solubility in various organic solvents, flexibility, and a higher refractive index as an optical material. In addition, there is a strong demand for new materials with impact resistance.

In such a technical environment, conventionally, 9,9-bis (4) having no alkyl substituent on the phenol skeleton is used.
-Hydroxyphenyl) various resins obtained from fluorene as raw materials have characteristics of high thermal stability and high refractive index, and are useful as high heat resistant resins and sealing materials,
It is known that it is also useful as an optical material for spectacle lenses and optical disks.

[0004] With respect to such a resin, for example, EP-A-539778 describes the use as an electronic-related resist material.
No. 68 discloses a copolymerized thermoplastic resin and its use as a plastic lens using the same as a raw material,
U.S. Pat. No. 4,707,534 describes its use as glycidyl ethers. Further, application to a high heat resistant polyester resin is disclosed in US Pat. No. 3,546,165.
And its application to a high heat-resistant polycarbonate resin is described in European Patent No. 36629 and JP-A-2-304741.

Further, European Patent No. 25058, JP-A-2-73823, JP-A-3-1481
Japanese Patent Application Laid-Open No. 5 (1993) -2005 and the like describe the use thereof as a raw material of an epoxy resin, and European Patent No. 249262 and European Patent No. 440147 describe other uses for a thermoplastic resin.

Thus, 9,9-bis (4-hydroxyphenyl) having no alkyl substituent on the phenol skeleton.
Conventionally, various uses of fluorene in resins are known. However, as 9,9-bis (alkyl-substituted-4-hydroxyphenyl) fluorenes having an alkyl substituent on a phenol skeleton, for example, , O-
9,9-bis (4) from cresol and 9-fluorenone
An example of the synthesis of -hydroxy-3-methylphenyl) fluorene is described in U.S. Pat. No. 4,707,534, and 9,9-bis (4-hydroxy-3) from 2,6-xylenol and 9-fluorenone. An example of the synthesis of (5,5-dimethylphenyl) fluorene is described in U.S. Pat. No. 4,612,350.
No. 9,9-, which has, as a substituent, an alkyl group higher than a methyl group in a phenol skeleton.
Bis (alkyl-substituted-4-hydroxyphenyl) fluorenes have hitherto not been known.

Conventionally, bisphenol structures having a methyl group at the meta position of the hydroxyl group and an alkyl group at the ortho position can be synthesized by using ordinary ketones and phenols. Difficult and not previously known.

[0008]

DISCLOSURE OF THE INVENTION The present invention relates to various resins made from bisphenols having higher heat resistance, solubility, and flexibility. Therefore, in response to the demand for new materials having impact resistance, the phenol skeleton has a higher alkyl group than a methyl group as a substituent, and is useful as a raw material for such resins and optical materials. , 9-Bis (alkyl-substituted-4
-Hydroxyphenyl) fluorenes, and furthermore, by the conventional reaction of ketones and phenols,
Disclosed are novel 9,9-bis (alkyl-4-hydroxyphenyl) fluorenes having a bisphenol structure having an alkyl group at the meta-position of a hydroxyl group, which has been difficult to synthesize, and a method for producing such fluorenes. With the goal.

[0009]

According to the present invention, the compound represented by the general formula (I)

[0010]

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(Wherein R ₁ represents a hydrogen atom or a methyl group, and when R ₁ is a hydrogen atom, R ₂ represents an alkyl group having 2 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms) , N is 1 or 2, and when R ₁ is a methyl group, R ₂ represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms, and n is 1 or 2. 9,9-bis (alkyl-4-hydroxyphenyl) fluorenes represented by the formula:

According to the present invention, such 9,9-bis (alkyl-4-hydroxyphenyl) fluorenes are
In the presence of an acid catalyst, 9-fluorenone has the general formula (II)

[0013]

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(Wherein R ₁ represents a hydrogen atom or a methyl group, and when R ₁ is a hydrogen atom, R ₂ represents an alkyl group having 2 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms) , N is 1 or 2, and when R ₁ is a methyl group, R ₂ represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms, and n is 1 or 2. ) Can be obtained by reacting an alkylphenol represented by the formula (1).

[0015]

9,9-bis (alkyl-substituted-4-hydroxyphenyl) fluorenes according to the invention DETAILED DESCRIPTION OF THE INVENTION is represented by formula (I), when R ₁ is hydrogen atom, R ₂ Represents an alkyl group having 2 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms, and specifically, the alkyl group having 2 to 4 carbon atoms is an ethyl group, a propyl group or a butyl group, and is preferably An alkyl group having 3 or more carbon atoms, and an alkyl group having 3 or more carbon atoms may be linear or branched, but is preferably a branched, cycloalkyl group having 5 or 6 carbon atoms. Is a cyclopentyl group or a cyclohexyl group, preferably a cyclohexyl group, and n is 1 or 2.

On the other hand, when R ₁ is a methyl group, R ₂ represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms, and the alkyl group having 1 to 4 carbon atoms is
Specifically, it is a methyl group, an ethyl group, a propyl group or a butyl group, and the alkyl group having 3 or more carbon atoms may be linear or branched, but is preferably a branched chain, The cycloalkyl group of Formula 5 or 6 is a cyclopentyl group or a cyclohexyl group, preferably
A cyclohexyl group, and n is 1 or 2.

Accordingly, a preferred specific example of such 9,9-bis (alkyl-4-hydroxyphenyl) fluorenes according to the present invention is, for example, 9,9-bis (4-hydroxy-3-isopropylphenyl) fluorene. , 9,
9-bis (4-hydroxy-3-sec.-butylphenyl) fluorene, 9,9-bis (4-hydroxy-3-
tert. -Butylphenyl) fluorene, 9,9-bis (4-hydroxy-3-cyclopentylphenyl) fluorene, 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, 9,9-bis (4-hydroxy- 3,5-diisopropylphenyl) fluorene, 9,9
-Bis (4-hydroxy-3,5-di-tert.-butylphenyl) fluorene, 9,9-bis (4-hydroxy-2,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy- 2-methyl-5-cyclohexylphenyl) fluorene 9,9-bis (4-hydroxy-2-methyl-5-ter
t. -Butylphenyl) fluorene, 9,9-bis (4-
(Hydroxy-2,3,5-trimethylphenyl) fluorene and the like.

Such 9,9-bis (alkyl-substituted-4-hydroxyphenyl) fluorenes according to the present invention are:
According to the present invention, 9-fluorenone has the general formula (II) in the presence of an acid catalyst:

[0019]

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(Wherein R ₁ represents a hydrogen atom or a methyl group, and when R ₁ is a hydrogen atom, R ₂ represents an alkyl group having 2 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms) , N is 1 or 2, and when R ₁ is a methyl group, R ₂ represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms, and n is 1 or 2. ) Can be obtained by reacting an alkylphenol represented by the formula (1).

In the alkylphenols represented by the general formula (II), when R ₁ is a hydrogen atom, R ₂
Represents an alkyl group having 2 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms, and the alkyl group having 2 to 4 carbon atoms is specifically an ethyl group, a propyl group or a butyl group, and is preferably , An alkyl group having 3 or more carbon atoms,
The alkyl group having 3 or more carbon atoms may be linear or branched, but is preferably branched, and a cycloalkyl group having 5 or 6 carbon atoms is specifically a cyclopentyl group or a cyclohexyl group. A cyclohexyl group, and n is 1 or 2.

On the other hand, when R ₁ is a methyl group, R ₂ represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms, and the alkyl group having 1 to 4 carbon atoms is
Specifically, it is a methyl group, an ethyl group, a propyl group or a butyl group, and the alkyl group having 3 or more carbon atoms may be linear or branched, but is preferably a branched chain, The cycloalkyl group of Formula 5 or 6 is specifically a cyclopentyl group or a cyclohexyl group,
Preferably, it is a cyclohexyl group, and n is 1 or 2.

Accordingly, preferred specific examples of such alkylphenols include, for example, o-isopropylphenol, o-sec. -Butylphenol, o-te
rt. -Butylphenol, 2,5-xylenol, 2-
Cyclohexyl-5-methylphenol and the like can be mentioned.

According to the invention, 9,9-bis (alkyl-4-)
In the production of (hydroxyphenyl) fluorenes, alkylphenols are usually, but not limited to, at least 2 parts per mole of 9-fluorenone.
A mole part is used, and preferably 4 to 8 mole parts are used for 1 mole part of 9-fluorenone. When the amount of the alkylphenol is less than 2 parts by mole per 1 part by mole of 9-fluorenone, the amount of by-products increases and the yield of the target product decreases. However, even if the alkylphenol is used in an amount of more than 8 parts by mole relative to 1 part by mole of 9-fluorenone, the productivity is low and the amount of the raw material alkylphenols recovered is large, which is disadvantageous in process economy.

In the present invention, the reaction between 9-fluorenone and the above-mentioned alkylphenols is carried out in the presence of an acid catalyst. This catalyst includes hydrogen chloride gas, concentrated hydrochloric acid,
Although 60 to 98% sulfuric acid, 85% phosphoric acid, and methanesulfonic acid are used alone or in combination of two or more, hydrogen chloride gas is preferably used in a state where the inside of the reaction system is saturated.

According to the present invention, in order to further promote the reaction, thiols are preferably used in combination with the above acid catalyst. As the thiols, alkyl mercaptans having 1 to 12 carbon atoms are preferable. For example, sodium methyl mercaptan, sodium ethyl mercaptan, n-
Octyl mercaptan sodium, n-lauryl mercaptan sodium and the like are used. Such alkyl mercaptans usually have 3 to 9-fluorenone.
It is used in the range of ２０20 mol%.

According to the invention, 9,9-bis (alkyl-4-)
In the production of (hydroxyphenyl) fluorenes, 9
-Since fluorenone is a solid at ordinary temperature (melting point: 85 ° C), a reaction solvent is preferably used when the alkylphenols, which are other raw materials, are also solid at ordinary temperature. As the reaction solvent, for example, an aliphatic alcohol, an aromatic hydrocarbon or a mixture thereof is preferable, and particularly, methanol, toluene or a mixture thereof is preferable.

According to the present invention, hydrogen chloride gas may be blown into the reaction system in which the raw material, the reaction solvent and the alkyl mercaptan are charged into the reaction vessel at a time.
After charging an alkylphenol, an alkylmercaptan and a solvent into a reaction vessel, hydrogen chloride gas is blown until the inside of the reaction system is saturated, and then a mixture of 9-fluorenone and an alkylphenol, or 9-fluorenone and an alkylphenol It is desirable to drop a mixture of and a solvent.

The reaction temperature is not particularly limited, but when the reaction temperature is too low, the reaction rate is slow. On the other hand, when the reaction temperature is too high, undesirable side reactions occur, and Usually leads to a decrease in the yield of
The range of 0-80 degreeC is preferable. The reaction can be monitored by liquid chromatography analysis or gas chromatography analysis, and the time when no unreacted 9-fluorenone is present in the reaction mixture and no increase in the amount of the target product is observed is determined as the end point of the reaction. And

After the completion of the reaction, an alkaline aqueous solution is added to the reaction mixture to neutralize the reaction mixture, and then an appropriate organic solvent, for example, an aliphatic ketone is added thereto. , Can be separated. In some cases,
The desired product obtained in this manner is a suitable solvent, for example,
By recrystallizing from an aliphatic ketone or a mixed solvent of water and an aliphatic ketone, it is possible to obtain a higher-purity target substance.

As the alkaline aqueous solution for neutralizing the reaction mixture, for example, an aqueous solution of sodium hydroxide or an aqueous solution of dibasic sodium phosphate is preferable.
These are usually neutralized to pH 3-6.

Examples of the aliphatic ketone solvent for recrystallization of the target substance include acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, and the like.
Examples thereof include dibutyl ketone, octanones, nonanones, decanones, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, methylcyclohexanone, and 3,3,5-trimethylcyclohexanone. Among these, acetone, methyl isobutyl ketone or cyclohexanone is particularly preferred. These recrystallization solvents are not particularly limited, but are usually used in a range of 5 to 50 times the weight of the crude product.

[0033]

As described above, the 9,9-bis (alkyl-substituted-4-hydroxyphenyl) fluorenes according to the present invention have a fluorenylidene group in the molecular skeleton, through which two alkyl-substituted phenol skeletons are formed. Bisphenols bonded, in a preferred embodiment,
The phenolic hydroxyl group has an alkyl group at the ortho position (and meta position). In particular, bisphenols having an alkyl group at the meta position of a phenolic hydroxyl group have not been known.

Accordingly, such novel bisphenols, when used as a raw material, have the characteristics of high heat resistance and high refractive index due to the fluorene skeleton, as well as solubility and flexibility in various organic solvents. A new resin can be obtained, and thus, the 9,9-bis (alkyl-substituted-4-hydroxyphenyl) fluorenes according to the present invention enable the production of a new resin and an optical material having functions and characteristics which have not existed before. It is assumed that.

[0035]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples.

Example 1 (Synthesis of 9,9-bis (4-hydroxy-3-isopropylphenyl) fluorene) A 1000 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with o-isopropyl. Phenol 274g (2.01mo
After l) and 4.5 g of n-octyl mercaptan were charged and the inside of the system was replaced with nitrogen gas, hydrogen chloride gas was blown into the system while maintaining the internal temperature at 45 to 50 ° C until the system was saturated. Then, 136 g of o-isopropylphenol (1.00 m
ol) and 90 g (0.50 mol) of 9-fluorenone were added dropwise over 2 hours, and the mixture was reacted for 2 hours with stirring to obtain a white reaction mixture (slurry). It was confirmed by liquid chromatography that no unreacted 9-fluorenone remained. To this slurry, 84.7 g of a 16% aqueous sodium hydroxide solution was added dropwise, and the reaction mixture was adjusted to pH 4 to 4.
Neutralized to 5.

Next, 180 g of acetone was added to the thus neutralized reaction mixture to dissolve and recrystallize the crystals, followed by centrifugal filtration at room temperature and washing with water to obtain 263.7 g of a crude cake. After adding 527 g of methyl isobutyl ketone and 264 g of water to the cake, the temperature was raised, and the aqueous layer was separated and removed.
Recrystallized, filtered at 20 ° C., washed with water, dried under reduced pressure,
-Bis (4-hydroxy-3-isopropylphenyl)
188.2 g of fluorene were obtained as white crystals. 99.9% purity by high performance liquid chromatography.

Melting point: 207.0 ° C. (Mettler method) Mass spectrometry (m / z): 434 (M ⁺ ), 391 (M-propyl), 299 (M-propylphenol) Infrared absorption spectrum (cm ⁻¹ ): (A) Strong absorption peak specific to phenolic hydroxyl group: 3
541.1 (B) Strong absorption peak other than the above: 1606.6, 150
2.4, 1463.9, 1447.5, 1413.7, 136
0.7-1082.0, 942.2, 833.2, 808.1, 7
43.5, 658.6, 616.2 (C) Absorption peak peculiar to benzene ring: 2964.4 to 28
66 Proton NMR spectrum (DMSO solvent, 60 MH
z) chemical shifts ([delta] value, ppm), the signal type and the integral ratio: (A) 0.98~1.08 (2 _{doublets, 12H, -CH 3) (B} ) 2.91~3.32 ( Multiple Line, 2H, -CH <) (C) 6.55 to 7.89 (multiple line, 14H, aromatic nucleus hydrogen) (D) 9.09 (single line, 2H, -OH)

Example 2 (Synthesis of 9,9-bis (4-hydroxy-3-sec.-butylphenyl) fluorene) A 2000 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser was used. o-sec. 315 g of butylphenol (2.1
0 mol), water 4.5 g, n-dodecyl mercaptan 6.5
g and 45 g of toluene were charged, and the inside of the system was replaced with nitrogen gas. Then, while maintaining the internal temperature at 45 to 50 ° C, hydrogen chloride gas was blown into the system until the inside of the system was saturated. Then, o-se
c. 135 g (0.90 mol) of butylphenol and 9
A mixture of 90 g (0.50 mol) of fluorenone with 1
After dropwise addition over a period of time, 45 g of toluene was added, and the internal temperature was reduced to 50
The temperature was raised to ５５55 ° C., and the mixture was further reacted under stirring for 3 hours.
Unreacted 9 in the reaction mixture by liquid chromatography
-Confirmed that no fluorenone remained.

Thereafter, in the same manner as in Example 1, the reaction mixture was neutralized, the internal temperature was raised to 75 to 80 ° C., the aqueous layer was separated and removed, and 180 g of acetone was added to recrystallize. Thereafter, the mixture was cooled to room temperature, filtered, washed with water, and the crude cake was washed with 203.
8 g were obtained. Methyl isobutyl ketone 20
After adding 0 g and 200 g of water and raising the temperature, the aqueous layer was separated and removed, recrystallized, filtered at 20 ° C., washed with water, dried under reduced pressure, and dried with 9,9-bis (4-hydroxy-3- sec-butylphenyl) fluorene (140 g) was obtained as white crystals. 99.9% purity by high performance liquid chromatography.

Melting point: 153.4 ° C. (Mettler method) Mass spectrometry (m / z): 462 (M ⁺ ), 405 (M-butyl), 313 (M-butylphenol) Infrared absorption spectrum (cm ⁻¹ ): ( A) Strong absorption peak specific to phenolic hydroxyl group: 3
529.5-3438.8 (B) Strong absorption peak other than the above: 1606.6, 150
1.5, 1447.5, 1413.7, 1378.0-1084.
9, 811.0, 736.8, 659.6, 618.1 (C) Absorption peak specific to benzene ring: 2960.5 to 28
71.8 Proton NMR spectrum (CDCl ₃ solvent, 60 MH
z) Chemical shift (δ value, ppm), signal form and integration ratio: (A) 0.65-1.73 (multiplet, 16H, —CH ₃ , C
_{H 2 -) (B) 2.57~3.17} ( multiplet, 2H, -CH <) (C ) 4.64 ( solid wire, 2H, -OH) (D) 6.33~7.72 ( Multiple Wire, 14H, aromatic nucleus hydrogen)

Example 3 (Synthesis of 9,9-bis (4-hydroxy-3-tert.-butylphenyl) fluorene) A 1000 mL four-neck flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser was used. o-tert. -278 g of butylphenol
(1.85 mol), 4.8 g of water and 45 g of toluene were charged, and the inside of the system was replaced with nitrogen gas. Then, while maintaining the internal temperature at 20 to 25 ° C., hydrogen chloride gas was blown into the system until the system was saturated. Then, 5 g of a 10% sodium methyl mercaptan solution was charged. Then, o-tert. 135 g (0.90 mol) of butylphenol and 9-fluorenone 9
A mixture with 0 g (0.50 mol) was added dropwise over 3 hours, and further reacted for 2 hours with stirring. After confirming that no unreacted 9-fluorenone remained in the reaction mixture by liquid chromatography, a 16% aqueous sodium hydroxide solution and 180 g of acetone were added dropwise, and the reaction mixture was adjusted to pH6.
Neutralized to ~ 7.

After the internal temperature was raised to 70 ° C., the mixture was cooled to 20 ° C., filtered by centrifugation, washed with water, and 330.2 g of a crude cake was obtained.
I got 650 g of methyl isobutyl ketone
And 325 g of water were added, the temperature was raised, the aqueous layer was separated and removed, and then recrystallized, filtered at 20 ° C., washed with water, and dried under reduced pressure.
200.2 g of 9,9-bis (4-hydroxy-3-tert.-butylphenyl) fluorene was obtained as white crystals. 99.5% purity by high performance liquid chromatography.

Melting point: 247.5 ° C. (Mettler method) Mass spectrometry (m / z): 462 (M ⁺ ), 405 (M-butyl), 313 (M-butylphenol) Infrared absorption spectrum (cm ⁻¹ ): ( A) Strong absorption peak specific to phenolic hydroxyl group: 3
544.9 (B) Strong absorption peak other than the above: 1603.7, 150
3.4, 1484.1, 1446.5, 1388.7 to 1083.
0, 884.3, 803.3, 755.1, 732.9, 746.
4, 658.6, 615.2 (C) Absorption peak peculiar to benzene ring: 2959.6 to 28
64.1 Proton NMR spectrum (DMSO solvent, 60 MH
z) Chemical shift (δ value, ppm), signal form and integration ratio: (A) 1.21 (single line, 18H, —CH ₃ ) (B) 6.56 to 7.90 (multiple line, 14H, aromatic nucleus) Hydrogen) (C) 9.14 (single line, 2H, -OH)

Example 4 (Synthesis of 9,9-bis (4-hydroxy-2,5-dimethylphenyl) fluorene) A 2000 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser was used.
215 g (1.76 mol) of 2,5-xylenol, 4.5 g of n-octylmercaptan and 92.1 g of methanol were charged, and the inside of the system was replaced with nitrogen gas.
, And hydrogen chloride gas was blown until the inside of the system was saturated. Then, 90 g of 2,5-xylenol (0.74 m
ol), 90 g (0.50 mol) of 9-fluorenone and 38.6 g of methanol were added dropwise over 1.5 hours, and the mixture was further reacted under stirring for 1.5 hours.
An additional 3 g was added, and a 16% aqueous sodium hydroxide solution and 72 g of acetone were added dropwise to neutralize the reaction mixture to pH 5-6.

After the internal temperature was raised to 70 ° C., it was cooled to 20 ° C., centrifugally filtered, washed with water, and 222.4 g of a crude cake.
I got Add methyl isobutyl ketone 220 to this cake.
g, acetone 105 g and water 220 g, heated to 80 ° C., filtered at 20 ° C., washed with acetone, dried under reduced pressure, and 9,9-bis (4-hydroxy-2,5-dimethylphenyl) 155.0 g of fluorene were obtained as pale beige crystals. 99.0% purity by high performance liquid chromatography.

Melting point: 277.9 ° C. (DSC method) Mass spectrometry (m / z): 286 (M ⁺ ), 271 (M-methyl), 165 (M-2,5-xylenol) Infrared absorption spectrum (cm ^{−) 1} ): (A) Strong absorption peak specific to phenolic hydroxyl group: 3
530.5 (B) Strong absorption peak other than the above: 1614.3, 157
7.7, 1507.3, 1448.4, 1386.7 to 1076.
2,755.1,742.5,616.2 (C) Absorption peak peculiar to benzene ring: 2969.2-29
25.8 Proton NMR spectrum (DMSO solvent, 60 MH
z) Chemical shift (δ value, ppm), signal form and integration ratio: (A) 1.84 (single line, 12H, —CH ₃ ) (B) 6.47-7.88 (multiple line, 12H, aromatic nucleus) Hydrogen) (C) 8.95 (single line, 2H, -OH)

Example 5 (Synthesis of 9,9-bis (4-hydroxy-2-methyl-5-cyclohexylphenyl) fluorene) A 1000 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser Then, 108.6 g (0.4 mol) of 2-cyclohexyl-5-methylphenol, 0.9 g of n-octylmercaptan and 53 g of methanol were charged, and the system was purged with nitrogen gas. ,
Hydrogen chloride gas was blown in until the inside of the system was saturated. Subsequently, 2-cyclohexyl-5-methylphenol 27.2
g (0.1 mol), 18 g of 9-fluorenone (0.1 mol)
l) and methanol (8.2 g) were added dropwise over 1.5 hours, and the mixture was further reacted under stirring for 2 hours, and then 95.4 g of 16% aqueous sodium hydroxide solution was added dropwise to bring the reaction mixture to pH 5-6. Until neutralized.

The internal temperature was raised to 80 ° C., the aqueous layer was separated and removed, and methanol was recovered by distillation. Then, 240 g of cyclohexane and 36 g of water were added to recrystallize, and cooled to 20 ° C. After centrifugal filtration, washing with water and drying under reduced pressure, 59.1 g of a crude cake was obtained. The cake was dried under reduced pressure to obtain 32 g of 9,9-bis (4-hydroxy-2-methyl-5-cyclohexylphenyl) fluorene as pale brown crystals.
98.0% purity by high performance liquid chromatography.

Melting point: 221.2 ° C. (DSC method) Mass spectrometry (m / z): 542 (M ⁺ ), 527 (M-methyl), 459 (M-cyclohexyl), 269 (M-z)
2-cyclohexyl-5-methylphenyl) Infrared absorption spectrum (cm ^-1 ): (A) Strong absorption peak specific to phenolic hydroxyl group: 3
396.4 (B) Strong absorption peak other than the above: 1696.3, 150
7.3, 1447.5, 1404.1, 1363.6 to 1082.
0, 998.1, 862.1, 744.5 (C) Absorption peak peculiar to benzene ring: 2924.8 to 28
50.6 Proton NMR spectrum (CDCl ₃ solvent, 60 MH
z):

[0051]

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[0052]

[Table 1]

Continued on the front page (72) Inventor Tomoyuki Maruyama 2-115 Kozaiga, Wakayama-shi F-term in Honshu Kagaku Kogyo Co., Ltd. F-term (reference) 4H006 AA01 AA02 AB46 AC25 BA52 BA66 FC22 FC52 FC56 FE13 4H039 CA40 CA41 CD10 CD40

Claims (3)

[Claims] 1. A compound of the general formula (I) (Wherein, R ₁ represents a hydrogen atom or a methyl group, and when R ₁ is a hydrogen atom, R ₂ represents an alkyl group having 2 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms, and n represents 1 or 2, and when R ₁ is a methyl group, R ₂ represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms, and n is 1 or 2.) 9,9-bis (alkyl-substituted-4-hydroxyphenyl) fluorenes. 2. In the presence of an acid catalyst, 9-fluorenone is converted to a compound of the general formula (II). (Wherein, R ₁ represents a hydrogen atom or a methyl group, and when R ₁ is a hydrogen atom, R ₂ represents an alkyl group having 2 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms, and n represents 1 or 2, and when R ₁ is a methyl group, R ₂ represents an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 or 6 carbon atoms, and n is 1 or 2.) The method for producing 9,9-bis (alkyl-4-hydroxyphenyl) fluorenes according to claim 1, wherein the alkylphenols are reacted. 3. The method according to claim 2, wherein an alkyl mercaptan is used in combination with the acid catalyst.