JPH06135875A - New fluorobisphenol compound and its production - Google Patents

Abstract

PURPOSE:To provide a new compound of low dielectric constant, excellent in low water absorptivity and heat resistance, useful as e.g. a raw material for polyesters, polycarbonates, polyethers, or epoxy resins. CONSTITUTION:The objective compound of formula I or II (X<1> and X<2> are each H or F), e.g. 3,3'-difluoro-4,4'-dihydroxydiphenylmethane. The compound of the formula I can be obtained by reaction (A) 0-fluorophenol or 2,6- difluorophenol and (B) formaldehyde in the presence of an acid catalyst.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel fluorinated bisphenol and a method for producing the same, more specifically, for example,
The present invention relates to novel fluorinated bisphenols useful as intermediates for the production of raw material monomers such as polyesters, polycarbonates, polyethers and epoxy resins and various organic compounds, and a process for producing the same.

[0002]

BACKGROUND OF THE INVENTION Bisphenols are useful compounds as starting monomers for various high molecular weight polymers and intermediates for the production of various organic compounds. In recent years, new functional polymer materials have been actively developed, and as raw materials thereof, development of bisphenols having new properties and unique characteristics has been desired.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in order to meet such a demand, and is to provide a polymeric material having unique characteristics, specifically, a low dielectric constant and a low water absorption. Another object of the present invention is to provide a novel fluorine-containing bisphenol compound useful as a raw material for a polymer material having excellent heat resistance and the like and a method for producing the same.

Conventionally, various methods have already been known for producing 4,4'-dihydroxydiphenylmethane and 4,4'-dihydroxytriphenylmethane which are bisphenols having no fluorine atom in the molecular structure. Has been. For example, regarding the method for producing 4,4′-dihydroxydiphenylmethane, although many methods for reacting phenol and formalin in the presence of various catalysts are known, according to those methods, in most cases, 4,4'-dihydroxydiphenylmethane as a main component, 2,2'- and 2,
A mixture of isomers containing 4'-dihydroxydiphenylmethane is obtained.

Specifically, for example, JP-A-58-177 is used.
According to the method described in Japanese Patent No. 928, 85% phosphoric acid is used as a catalyst to form 2,2′-, 2,4′- and
It is disclosed that an isomer mixture consisting of 4,4'-dihydroxydiphenylmethane can be obtained in a yield of 89 mol% and 4,4'-dihydroxydiphenylmethane in a yield of 49 mol%.

According to US Pat. No. 4,490,27, 4,4'-dihydroxydiphenylmethane can be collected at a formalin conversion of 57 to 78% by using 10 to 30% of dilute sulfuric acid as a catalyst. It is disclosed that it can be obtained at a rate of 28 to 64 mol%. JP-A-55
According to Japanese Unexamined Patent Publication No. 124730/1997, a mixture of isomers of dihydroxydiphenylmethane, based on formalin, with oxalic acid as a catalyst, in a yield of 97 mol%,
It is disclosed that 4'-dihydroxydiphenylmethane can be obtained in a yield of 33 mol%.

On the other hand, a method using a solid catalyst is also known. For example, according to European Patent No. 331173, a mixture of isomers of dihydroxydiphenylmethane is obtained in a yield of 9 by using activated clay as a catalyst.
It is disclosed that 3 mol% and 4,4′-dihydroxydiphenylmethane can be obtained in a yield of 39 mol%. Similarly, European Patent No. 265017 discloses that zeolite can be used as a catalyst to obtain 4,4′-dihydroxydiphenylmethane at a yield of 29 mol%.

However, according to the method for producing 4,4'-dihydroxydiphenylmethane by reacting phenol with formalin in the presence of an acid catalyst as described above, the reactivity of formalin is large, and therefore dihydroxydiphenylmethane is present. A high-boiling point component, that is, a resinous substance is likely to be produced at the same time as the isomer of 1. Therefore, in order to selectively produce 4,4′-dihydroxydiphenylmethane, a method using special conditions has been conventionally proposed. ing.

For example, in US Pat. No. 4,400,554, 4,4'-dihydroxydiphenylmethane was obtained in a yield of 6 by a low temperature reaction at 10 ° C. using 85% phosphoric acid as a catalyst.
It is disclosed that it can be obtained at 8 mol%.
According to Japanese Patent Publication No. 48-38694, by using a catalyst composed of a combination of 35% hydrochloric acid and dimethylsulfoxide or dimethylformamide, 4,4'-
It is disclosed that dihydroxydiphenylmethane can be obtained in a yield of 72 mol%. Japanese Patent Laid-Open No. 3-10
According to 9342, it is disclosed whether 4,4'-dihydroxydiphenylmethane can be obtained in a yield of 80 mol% by using a combination of hydrochloric acid and crown ether.

On the other hand, regarding the method for producing 4,4'-dihydroxytriphenylmethane using phenol and benzaldehyde as raw materials, a cation exchange resin is used as a catalyst at 30 ° C.
Japanese Patent Application Laid-Open No. 1-190713 discloses a method of obtaining a target product at a yield of 60 mol% by reacting the solution with phenol for 1 week, and after reacting phenol with boric acid, concentrated sulfuric acid and mercaptopropion are disclosed. 26 to 20 using an acid as a catalyst
Australian Patent No. 489747 discloses a method of obtaining the desired product at a yield of 54 mol% by reacting at 21 ° C. for about 21 hours.

As a result of extensive research on the production of the above-mentioned conventional dihydroxydiphenylmethane and dihydroxytriphenylmethane, the present inventors have compared the reactivity of benzaldehydes with phenols.
Regarding the reactivity to phenols, p-fluorobenzaldehyde is less reactive than benzaldehyde, and the reactivity of phenols to benzaldehyde is lower for o-fluorophenol than phenol, and thus for o-fluorophenol. It was observed that 2,6-difluorophenol was even lower than that. Especially 2,
When 6-difluorophenol and benzaldehydes are used as raw materials, under the reaction conditions according to the conventional method described above,
The reaction was found to be very slow.

Therefore, no fluorine atom is contained in the molecule
Even when the method for producing 4,4′-dihydroxydiphenylmethane and 4,4′-dihydroxytriphenylmethane is applied to the production of fluorinated bisphenols containing a fluorine atom in the molecule, the reaction rate is very low, and thus the yield Is extremely low and its isolation is not easy.

[0013]

The present invention provides a novel fluorinated compound useful as an intermediate for the production of starting monomers such as polyesters, polycarbonates, polyethers, epoxy resins and various organic compounds. It is an object of the present invention to provide bisphenols, and further to provide a method capable of manufacturing the fluorinated bisphenols in a high yield by solving the above-mentioned problems in manufacturing.

[0014]

The first of the novel fluorinated bisphenols according to the present invention is the general formula (I)

[0015]

[Chemical 5]

(Wherein X ¹ represents a hydrogen atom or a fluorine atom). Specific examples of the fluorinated bisphenols include, for example, 3,3'-difluoro-4,4'-dihydroxydiphenylmethane and 3,
3 ', 5,5'-tetrafluoro-4,4'-dihydroxydiphenylmethane etc. can be mentioned.

Such fluorinated bisphenols can be obtained according to the present invention by reacting o-fluorophenol or 2,6-difluorophenol with formalin in the presence of an acid catalyst. The second of the novel fluorinated bisphenols according to the present invention is represented by the general formula (II)

[0018]

[Chemical 6]

(Wherein, X ¹ and X ² each independently represent a hydrogen atom or a fluorine atom). Such fluorinated bisphenols can be obtained according to the present invention by reacting o-fluorophenol or 2,6-difluorophenol with benzaldehyde or p-fluorobenzaldehyde in the presence of an acid catalyst.

Specific examples of the bisphenols include, for example, 3,3'-difluoro-4,4'-dihydroxytriphenylmethane and 3,3 ', 5,5'-tetrafluoro-4,4'-dihydroxytriphenylmethane. Phenylmethane, 3,3 ', 4 "-trifluoro-4,4'-dihydroxytriphenylmethane, 3,3', 4", 5,
Examples thereof include 5'-pentafluoro-4,4'-dihydroxytriphenylmethane.

In the present invention, phosphoric acid, sulfuric acid, hydrochloric acid, hydrogen chloride gas, methanesulfonic acid and trifluoromethanesulfonic acid are used as the acid catalyst in the production of both the first and second fluorinated bisphenols. At least one selected from the following can be used. However, in particular, in order to obtain the first fluorinated bisphenols according to the invention by reaction of o-fluorophenol or 2,6-difluorophenol with formalin, preferably phosphoric acid, hydrochloric acid, sulfuric acid or methane is used. Sulfonic acid is used. Among these, phosphoric acid (preferably about 85%), hydrochloric acid (preferably about 35%), and sulfuric acid (preferably about 70%) are used. By using such a catalyst, with high selectivity, the target 4,
4'-body can be obtained. As described above, although formalin and phenol are likely to react with each other, a mixture of isomers and a resinous substance are likely to be formed.Therefore, in order to obtain 4,4′-form, a special catalyst or reaction condition is required. Needed.

On the other hand, o-fluorophenol or 2,6-
To obtain the second fluorinated bisphenols according to the invention by reaction of difluorophenol with benzaldehyde or p-fluorobenzaldehyde, preferably hydrogen chloride gas or a mixture of hydrogen chloride gas and trifluoromethanesulfonic acid is used. Used as a catalyst. The most preferred high strength catalyst is a mixture of hydrogen chloride gas and trifluoromethanesulfonic acid.

As described above, generally, benzaldehydes and phenols are difficult to react with each other and the yield is low. However, since the fluorinated phenols used in the present invention have a lower reactivity with benzaldehydes than phenol, When acid or sulfuric acid is used alone, the reactivity is low and it is difficult to obtain the desired product advantageously. However, according to the present invention, by using hydrogen chloride gas or a mixture of hydrogen chloride gas and trifluoromethanesulfonic acid as a catalyst to accelerate the reaction rate, the desired 4,4'-
The body can be obtained advantageously, ie with high selectivity and high yield.

Furthermore, according to the present invention, in any of the above cases, it is preferable to use mercaptans such as sodium methyl mercaptan, ethyl mercaptan, octyl mercaptan and lauryl mercaptan as the cocatalyst together with the acid catalyst. In the present invention, the amount of the catalyst used is not particularly limited, but when it is too small, the effect as a catalyst for promoting the reaction is poor,
On the other hand, when used in excess, the treatment after the reaction may be troublesome and the yield of the desired product may be reduced. Therefore, it is usually 0.1 for the fluorophenols charged.
-5 times the molar amount is preferred.

Regarding the charged molar ratio of the raw materials, that is, the fluorophenols / aldehydes, in the present invention,
Although not particularly limited, the above molar ratio is usually 2
It is preferably in the range of -30. When the molar ratio is too small, the production rate of by-products increases, while on the other hand, when the molar ratio is too large, the production efficiency of the target product decreases and the amount of expensive fluorophenols lost is large. Become.

Further, in the present invention, a reaction solvent may be used, but it is preferable to carry out the reaction in the absence of a solvent in consideration of the reaction rate, the production efficiency of the target product and the post-reaction treatment. When carrying out the reaction, it is usually preferable to add a catalyst after charging fluorophenols and aldehydes, or to add aldehydes after charging fluorophenols and catalysts.

The reaction temperature is not particularly limited, but when the reaction temperature is too low, the reaction rate is slow, and when it is too high, tar-like by-products increase and the yield decreases. Therefore, the range of 10 to 200 ° C., preferably 20 to 150 ° C. is suitable. The reaction time is not particularly limited, but it is longer than that required for producing a bisphenol having no fluorine atom in the molecular skeleton corresponding to the fluorinated bisphenol according to the present invention.

The reaction is carried out by high performance liquid chromatography analysis (HPLC analysis) or gas chromatography analysis (G
Since it can be traced by C analysis), the time point when the increase of the target substance is not observed can be regarded as the reaction end point. After the completion of the reaction, in order to isolate the desired product from the obtained reaction solution, separation and purification by rectification may be possible, but from the viewpoint of operability and efficiency of removing impurities, recrystallization purification with alkylbenzenes is preferable. . As the alkylbenzenes, for example, benzene, toluene, xylene, ethylbenzene, trimethylbenzenes, diethylbenzenes and the like are preferably used, but particularly benzene, toluene,
Xylene and the like are preferably used.

Upon recrystallization using an alkylbenzene as a solvent, the catalyst contained in the reaction solution may be used as it is, but preferably, it is preferably washed beforehand with water or neutralized and removed with an alkaline aqueous solution. The amount of the alkylbenzenes used in the recrystallization is not particularly limited, but it is usually preferable to use 1 to 5 times the weight of the residual liquid obtained by collecting the unreacted fluorophenols.

The unreacted fluorophenols remaining in the reaction solution may be used as they are, but preferably, they are recovered in advance by vacuum distillation or the like, and then, as described above,
The target fluorinated bisphenols are preferably recrystallized from alkylbenzenes.

[0031]

According to the present invention, there are provided novel fluorinated bisphenols represented by the above general formulas (I) and (II). The fluorinated bisphenols are characterized in that they are diphenylmethanes and triphenylmethanes having a fluorine atom at the o-position of the hydroxyl group of the benzene nucleus. As described above, bisphenols having a fluorine atom at the o-position of the hydroxyl group have a low dielectric constant in various polymer materials obtained by using the bisphenols having a strong electron-withdrawing property and hydrophobic property of the fluorine atom. And low water absorption can be provided.

Further, the heat resistance of the polymer material can be improved by the strong bonding force of the fluorine atom to the carbon atom, which is superior to the hydrogen atom.

[0033]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. Example 1 A stirrer, a thermometer and a dropping funnel were provided, and a reflux condenser connected to a hydrogen chloride gas absorption device was also provided.
O-Fluorophenol 1 in a 4-neck flask with a capacity of 00 ml
68 g (1.5 mol), 35% formalin 13 g (0.15)
Mol) and 173 g (1.5 mol) of 85% phosphoric acid, and the mixture was reacted at an internal temperature of 40 to 42 ° C. for 25 hours.

After the reaction was completed, the phosphoric acid layer was separated from the obtained reaction solution, the oil layer was neutralized with a 20% sodium carbonate aqueous solution, and then washed with water, and then unreacted o-fluorophenol was recovered by distillation. did. The composition of the distillation residue (35.7 g) was analyzed by liquid chromatography.
-Fluorophenol 1.87%, by-product (2,2'-form) 3.
The yield was 79%, the by-product (2,4′-form) 12.56%, and the main component (target product) 76.09% (the existing yield based on the charged formalin was 76.7 mol%). This distillation residue was mixed with toluene 7
The crystals were recrystallized twice from 0 g to give 21.9 g of 3,3'-difluoro-4,4'-dihydroxydiphenylmethane, melting point 102.3.
C., white powder crystals having a GC analysis purity of 99.6% were obtained.

The analytical data are shown below. Mass spectrum (m / z) 236 (M ⁺ ), 235 (MH), 125 (M-fluorophenol) Infrared absorption spectrum (KBr tablet method, cm ^-1 ) Strong absorption peak peculiar to phenolic hydroxyl group: 3320 (3600)
~ 3100) Strong absorption peaks other than the above: 1600, 1510, 1440, 1340,
1280, 1190, 1100, 950, 800 NMR (270 MHz, CDCl ₃ solvent used, δ value, signal type
And proton integral ratio) 3.83 (s, 2H), 5.19-5.20 (d, 2H), 6.86-7.04 (m, 6H) Quantitative analysis of fluorine Actual value 15.40% Theoretical value 16.10%

Example 2 The same apparatus as in Example 1 was used, except that o-fluorophenol 33.6 was used.
g (0.3 mol), 35% formalin 5.1 g (0.06 mol) and 70% sulfuric acid 26 g (0.18 mol) were charged and reacted at an internal temperature of 40 to 42 ° C. for 20 hours. After the reaction,
The catalyst layer was separated and removed from the resulting reaction solution, followed by washing with neutralized water to obtain a yellowish brown oil layer (37.3 g). When this oil layer was analyzed by liquid chromatography, the composition was found to include unreacted o-fluorophenol 61.51% and by-products (2,2 '
-Form) 2.99%, by-product (2,4'-form) 6.71% and target product (3,3'-difluoro-4,4'-dihydroxydiphenylmethane) 27.0% (based on formalin charged) The yield in existence was 71.1 mol%).

Example 3 2,6-difluorophenol 6 was placed in the same apparatus as in Example 1.
5 g (0.5 mol), 8.6 g (0.1 mol) of 35% formalin and 50 g (0.36 mol) of 70% sulfuric acid were charged and reacted at an internal temperature of 48 to 53 ° C. for 23 hours. After the reaction,
The sulfuric acid layer was separated and removed from the obtained reaction solution, and the oil layer was reduced to 20%
After neutralizing with an aqueous solution of sodium carbonate, the mixture was washed with water, and unreacted 2,6-difluorophenol was recovered by distillation from it.

When 25.7 g of the distillation residue was analyzed by gas chromatography, its composition was found to be 0.66% of 2,6-difluorophenol and 97.56 of the main component (target product).
% (The existing yield based on the charged formalin was 92.2 mol%). The distillation residue was recrystallized twice from 50 g of toluene, and 19.0 g of 3,3 ', 5,5'-tetrafluoro-4,4'-dihydroxydiphenylmethane was melted at 133.4 ° C.
Obtained as pale yellow powdery crystals with a GC analysis purity of 99.8%.

The analytical data are shown below. Mass spectrum (m / z) 272 (M ⁺ ), 271 (MH), 143 (M-difluorophenol) Infrared absorption spectrum (cm ^-1 ) Strong absorption peak peculiar to phenolic hydroxyl group: 3300 (3600)
Strong absorption peak other than the above: 1610, 1520, 1450, 1400,
1340, 1230, 1200, 1020, 840 NMR (270 MHz, CDCl ₃ solvent used, δ value, signal type
And proton integral ratio) 3.83 (s, 2H), 5.19 (s, 2H), 6.70 to 6.81 (m, 4H) Quantitative analysis of fluorine 26.80% Theoretical 27.94%

Example 4 An o-fluorophenol 112 was added to the same apparatus as in Example 1.
g (1.0 mol), benzaldehyde 21.2 g (0.2 mol) and 15% sodium methyl mercaptan aqueous solution 2
I charged g. After this, while blowing hydrogen chloride gas,
The reaction was carried out at an internal temperature of 40 ° C for 4 hours.

After the reaction was completed, the reddish brown reaction solution obtained was added to 2
After neutralizing with a 0% sodium carbonate aqueous solution, the mixture was washed with water, and unreacted o-fluorophenol was recovered by distillation.
A gas chromatographic analysis of 58.5 g of the distillation residue revealed that the composition was o-fluorophenol 0.69.
% And the main component (target product) was 89.90% (the existing yield based on the charged benzaldehyde was 84.3 mol%). The distillation residue was recrystallized twice from 150 g of toluene to give 3,
45.5 g of 3'-difluoro-4,4'-dihydroxytriphenylmethane was obtained as light brown powder crystals with a melting point of 123.3 ° C and a GC analysis purity of 99.5%.

The analytical data are shown below. Mass spectrum (m / z) 312 (M ⁺ ), 235 (M-phenyl), 201 (M-fluorophenol) Infrared absorption spectrum analysis (KBr tablet method, cm ⁻¹ ) Strong absorption peak peculiar to phenolic hydroxyl group: 3300 (3600
~ 3100) Strong absorption peaks other than the above: 1600, 1600, 1510, 1440,
1360, 1290, 1200, 1100, 700 NMR (270 MHz, CDCl ₃ solvent used, δ value, signal type
And proton integral ratio) 5.26-5.27 (d, 2H), 5.45 (s, 1H), 6.81-7.43 (m, 11
H) Quantitative analysis of fluorine Actual value 11.96% Theoretical value 12.18%

Example 5 Raw materials were charged in the same manner as in Example 3 except that 1 g of lauryl mercaptan and 2.8 g of concentrated hydrochloric acid were used as catalysts. After reacting at an internal temperature of 40 ° C. for 31 hours, post-treatment was carried out in the same manner as in Example 3 to obtain the desired product, 3,3′-
Difluoro-4,4'-dihydroxytriphenylmethane was obtained in a yield of 67.0 mol%.

Example 6 An o-fluorophenol 112 was added to the same apparatus as in Example 1.
g (1.0 mol), p-fluorobenzaldehyde 24.8
g (0.2 mol) and water 5.6 g were charged. Then, the reaction was performed at an internal temperature of 39 to 41 ° C. for 69 hours while blowing hydrogen chloride gas. After completion of the reaction, the obtained reddish brown reaction solution was neutralized with a 20% sodium carbonate aqueous solution, and then washed with water,
Then, unreacted o-fluorophenol was recovered by distillation.

When 65.2 g of the distillation residue was analyzed by gas chromatography, the composition was found to be 3.50% o-fluorophenol and 87.0% main component (target product) (based on the charged p-fluorobenzaldehyde). The existence yield was 85.9 mol%). This distillation residue was mixed with toluene 13
Recrystallized twice from 0 g to give 3,3 ', 4 "-trifluoro-4,
40 'of 4'-dihydroxytriphenylmethane, melting point 11
It was obtained as beige powder crystals having a GC analysis purity of 99.2% at 5.7 ° C.

The analytical data are shown below. Mass spectrum (m / z) 330 (M ⁺ ), 235 (M-fluorophenyl), 219 (M-fluorophenol) Infrared absorption spectrum analysis (cm ^-1 ) Strong absorption peak with phenolic hydroxyl group: 3300 (3600 ~
3100) Strong absorption peaks other than the above: 1600, 1510, 1430, 1360,
1290, 1230, 1100, 750 NMR (200 MHz, DMSO solvent used, δ value, signal shape
And proton integral ratio) 5.41 (s, 1H), 6.66-6.92 (m, 6H), 7.04-7.14 (m, 4H) Quantitative analysis of fluorine Actual value 17.0% Theoretical value 17.27%

Example 7 In a 200 ml four-necked flask equipped with the same apparatus as in Example 1, 65 g (0.5 mol) of 2,6-difluorophenol, 1.5 g (0.01 mol) of trifluoromethanesulfonic acid and Benzaldehyde (10.6 g, 0.1 mol) was charged. Thereafter, while blowing hydrogen chloride gas, the temperature is raised to an internal temperature of 78
The reaction was carried out at 103 ° C for 67 hours. After the reaction was completed, the obtained reddish brown reaction solution was neutralized with a 15% sodium carbonate aqueous solution and then washed with water, and unreacted 2,6-difluorophenol was recovered by distillation.

When 33.3 g of the distillation residue was analyzed by gas chromatography, the composition was 2,6-difluorophenol 27.6%, benzaldehyde 9.2% and the main component (target product) 54.4%. (The existing yield based on the charged benzaldehyde was 52.1 mol%). This distillation residue was recrystallized twice from 100 g of toluene to give 3,3'-difluoro-4,4'-dihydroxytriphenylmethane 12.5.
g was obtained as pale green powder crystals having a melting point of 101.2 ° C. and a GC analysis purity of 98.9%.

The analytical data are shown below. Mass spectrum (m / z) 348 (M ⁺ ), 271 (M-phenyl), 219 (M-difluorophenol) Infrared absorption spectrum analysis (KBr tablet method, cm ⁻¹ ) Strong absorption peak peculiar to phenolic hydroxyl group: 3380 (3600
~ 3100) Strong absorption peaks other than the above: 1600, 1518, 1440, 1320,
1010, 800, 700 NMR (270 MHz, CDCl ₃ solvent used, δ value, signal type
And proton integral ratio) 1.68 (s, 2H), 5.32 (s, 1H), 6.57-6.69 (m, 4H), 7.0
4-7.07 (m, 2H), 7.28-7.36 (m, 3H) Quantitative analysis of fluorine Actual value 21.01% Theoretical value 21.84%

Example 8 2,6-difluorophenol 6 was placed in the same apparatus as in Example 1.
5 g (0.5 mol), p-fluorobenzaldehyde 12.
4 g (0.1 mol) and trifluoromethanesulfonic acid 3.
0 g (0.02 mol) was charged, the temperature was raised while blowing hydrogen chloride gas, and the reaction was carried out at an internal temperature of 120 to 125 ° C. for 9 hours. After the reaction was completed, the obtained reddish brown reaction solution was washed with neutralized water, and unreacted 2,6-difluorophenol was recovered by distillation from the solution.

When 30.0 g of this distillation residue was analyzed by gas chromatography, its composition was found to be 2,6-difluorophenol (0.85% and main component (target product) 76.5).
It was 5% (the existing yield based on the charged p-fluorobenzaldehyde was 62.7 mol%). The distillation residue was recrystallized twice from toluene, and 12.0 g of 3,3 ′, 5,5 ′, 4 ″ -pentafluoro-4,4′-dihydroxytriphenylmethane was melted at 92.2 ° C. by GC analysis. Obtained as light yellow powder crystals with a purity of 97.3%.

The analytical data are shown below. Mass spectrometry (m / z) 366 (M ⁺ ), 271 (M-fluorophenyl), 237 (M-difluorophenol) Infrared absorption spectrum analysis (KBr
Tablet method, cm ^-1 ) Strong absorption peak with phenolic hydroxyl group: 3360 (3600 ~
3100) Strong absorption peaks other than the above: 1600, 1520, 1440, 1320,
1220, 1020, 850 NMR (270 MHz, CDCl ₃ solvent used, δ value, signal type
And proton integral ratio) 5.22 (s, 1H), 5.28 (s, 1H), 6.52-6.63 (m, 4H), 6.9
7-7.00 (m, 4H) Quantitative analysis of fluorine Actual value 25.53% Theoretical value 25.95%

Example 9 2,6-difluorophenol 2 was placed in the same apparatus as in Example 1.
6 g (0.2 mol), 35% formalin 3.4 g (0.040)
Mol) and 15% aqueous solution of methyl mercaptan sodium
2.6 g was charged, and the reaction was performed for 24 hours while blowing hydrogen chloride gas at an internal temperature of 51 to 70 ° C.

After completion of the reaction, benzene 4 was added to the resulting reaction solution.
After adding 0 g and 30 g of water and neutralizing with 20% sodium carbonate aqueous solution, it was washed with water, and then benzene and unreacted 2,
6-difluorophenol was recovered by distillation. When 8.4 g of the distillation residue was analyzed by gas chromatography, its composition was 2,6-difluorophenol (6.61).
%) And the main component (target product) was 68.0% (the existing yield based on the charged formalin was 52.5 mol%).

Comparative Example 1 In Example 4, as a catalyst, 112 g of 85% phosphoric acid was used.
The raw materials and the catalyst were charged in the same manner as in Example 4 except that (0.97 mol) was used, and the reaction was carried out at 130 ° C. for 44 hours.
Liquid chromatography analysis of the resulting reaction liquid revealed that the yield of the desired 3,3′-difluoro-4,4′-dihydroxytriphenylmethane was only 27.5 mol%.

Comparative Example 2 85% phosphoric acid 115.3 was used as the catalyst in Example 6.
Raw materials were charged in the same manner as in Example 6 except that g (1.0 mol) was used, and the mixture was reacted at 50 to 70 ° C. for 96 hours. When the obtained reaction solution was analyzed by liquid chromatography, the desired 3,3 ', 4 "-trifluoro-4,4' was obtained.
-The existence yield of dihydroxytriphenylmethane was only 7.3 mol%, and the desired product could not be isolated.

Comparative Example 3 In the same manner as in Example 7, except that 6.5 g of a 15% sodium methyl mercaptan aqueous solution was charged as a catalyst in Example 7, the raw materials were charged and the temperature was raised to 40 ° C. while blowing hydrogen chloride gas. For 48 hours. However, it was confirmed that the target 3,3 ′, 5,5′-tetrafluoro-4,4′-dihydroxytriphenylmethane was hardly produced.

Claims (8)

[Claims] 1. A compound represented by the general formula (I): (In the formula, X ¹ represents a hydrogen atom or a fluorine atom.) A fluorinated bisphenol. 2. O-fluorophenol or 2,6-difluorophenol and formalin are reacted in the presence of an acid catalyst to give a compound of the general formula (I): (In the formula, X ¹ represents a hydrogen atom or a fluorine atom.) A method for producing a fluorinated bisphenol. 3. The method for producing fluorinated bisphenols according to claim 2, wherein the acid catalyst is phosphoric acid, hydrochloric acid, sulfuric acid or methanesulfonic acid. 4. A compound represented by the general formula (II): (In the formula, X ¹ and X ² each independently represent a hydrogen atom or a fluorine atom.) A fluorinated bisphenol. 5. A compound represented by the general formula (II): wherein o-fluorophenol or 2,6-difluorophenol and benzaldehyde or p-fluorobenzaldehyde are reacted in the presence of an acid catalyst. (In the formula, X ¹ and X ² each independently represent a hydrogen atom or a fluorine atom.) A method for producing a fluorinated bisphenol. 6. The method for producing fluorinated bisphenols according to claim 5, wherein the acid catalyst is hydrogen chloride gas or a mixture of hydrogen chloride gas and methanesulfonic acid. 7. After the completion of the reaction, unreacted o-fluorophenol and / or 2,6-
The difluorophenol is recovered by distillation, and then the desired bisphenols are extracted with alkylbenzenes from the obtained distillation residue.
5. The method for producing a fluorinated bisphenol according to 5 or 6. 8. The method for producing fluorinated bisphenols according to claim 2, 3, 5, 6 or 7, wherein the reaction is carried out in the absence of a solvent.