JP2000159710A - Asymmetric cyclohexylidene-polyhydric phenols and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compounds comprising a specific asymmetric cyclohexylidene-polyhydric phenols and useful as a raw material for polymers having a nonlinear structure or a network structure and as a raw material for photoresist-related materials. SOLUTION: The compounds are represented by formula I [R1 and R2 are each H, a 1-4C alkyl or the like; R3 is H or a 1-3C alkyl; (n) is 1-3; R4 to R6 are each OH or H], e.g. 1-(4-hydroxyphenyl)-1-(3,4-dihydroxyphenyl)cyclohexane. The compounds represented by formula I are produced by reacting 1 mol of cyclohexenylphenols represented by formula II [e.g. 1-(4-hydroxyphenyl)-4- isopropylcyclohexene] with 1-5 mol of polyhydric phenols (e.g. catechol) in the presence of an acidic catalyst (e.g. p-toluenesulfonic acid) in an alcohol solvent (e.g. methanol). The alcohol solvent is used in an amount of preferably 30-100 pts.wt. based on 100 pts.wt. of the polyhydric phenols.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an asymmetric cyclohexylidene polyhydric phenol, and more particularly, to a structure in which a substituted phenol nucleus and a polyhydric phenol skeleton having a plurality of hydroxyl groups are linked by a cyclohexylidene group. It relates to novel asymmetric cyclohexylidene polyhydric phenols. Such polyhydric phenols are useful as raw materials for various polymers having a non-linear structure or a network structure, and also have selective reactivity and selective solubility in various solvents, acids, and alkalis. It is also useful as a raw material of a photoresist-related material having

[0002] The present invention further relates to a process for producing such asymmetric cyclohexylidene polyhydric phenols.

[0003]

2. Description of the Related Art Conventionally, asymmetric alkylidene polyhydric phenols having three or more phenolic hydroxyl groups in a molecule and having no center of symmetry have already been partially used in photoresist-related materials and epoxy resins. It is known that it is useful as a curing agent and the like.

[0004] For example, Japanese Patent Application Laid-Open No. Hei 2-269351 discloses that dioxane is dissolved in dioxane in the presence of an aluminum chloride catalyst.
-(3-hydroxyphenyl) propene or 2- (4-
It is described that various alkylidene polyhydric phenols can be obtained by reacting an alkenyl phenol such as (hydroxyphenyl) propene with a dihydric phenol such as hydroquinone, methylhydroquinone or resorcin. For example, 2- (2,5-dihydroxyphenyl) -2
-(3-hydroxyphenyl) propane, 2- (2,5-
Dihydroxy-3-methylphenyl) -2- (3-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (3-hydroxyphenyl) propane, 2- (2,5-dihydroxyphenyl)- 2- (4-
(Hydroxyphenyl) propane, 2- (2,5-dihydroxy-3-methylphenyl) -2- (4-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) -2- (4-hydroxyphenyl) propane And the like are described as being useful as positive photoresist materials.

However, each of these polyhydric phenols has a structure in which a phenol skeleton and a dihydric phenol skeleton are connected by a propylidene group, and has an asymmetric propylidene polyhydric polyhydric compound having a methyl group in the dihydric phenol skeleton. Phenols.

On the other hand, symmetric alkylidene polyhydric phenols having a symmetry center in the molecule include benzene or methanol solvents such as 36% hydrochloric acid, 47% hydrobromic acid, p-toluenesulfonic acid, and strongly acidic cationic resins. In the presence of an acidic catalyst, 1.4-2.0 mol parts of 2- (4-hydroxyphenyl) propene are reacted with 1 mol part of resorcinol to give 1,
3-dihydroxy-4,6-bis [α-methyl-α- (4 ′
(Hydroxyphenyl) ethyl] benzene is described in JP-A-4-364147.

Japanese Unexamined Patent Publication No. Hei 5-201903 discloses a method for producing 2- (2,4-dihydroxyphenyl) -2- (4-hydroxyphenyl) propane as described above in which 36% benzene or benzene-methanol mixed solvent is used. A method is described in which 1 to 1 mol of resorcinol is reacted with 0.8 to 1.1 mol of 4-isopropenylphenol using hydrochloric acid as a catalyst.

Further, JP-A-6-116191 discloses that the above-mentioned 2- (2,4-dihydroxyphenyl) -2-
Using (4-hydroxyphenyl) propane and 4-isopropenylphenol, 1,3-dihydroxy-4,6-
A method for producing bis [α-methyl-α- (4′-hydroxyphenyl) ethyl] benzene is described.

As described above, conventionally, a molecule has three or more phenolic hydroxyl groups and a phenol skeleton has a substituent such as an alkyl group, a cycloalkyl group, or a phenyl group, and has no center of symmetry. Asymmetric cyclohexylidene polyhydric phenols are not known.

[0010]

The present invention has a structure in which a substituted phenol nucleus and a polyhydric phenol skeleton having a plurality of hydroxyl groups are linked by a cyclohexylidene group. A new asymmetrical material that is useful as a raw material for various polymers having a structure, and also useful as a raw material for photoresist-related materials having selective reactivity and selective solubility in various solvents, acids, and alkalis. An object of the present invention is to provide a cyclohexylidene polyhydric phenol and a method for producing the same.

[0011]

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

[0012]

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(Wherein R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group or a phenyl group, and R ₃ represents a hydrogen atom or 1 to 4 carbon atoms)
3 represents an alkyl group, n represents an integer of 1 to 3,
One or two of R ₄ , R ₅ and R ₆ represent a hydroxyl group, and the remainder represents a hydrogen atom. Where R ₄ and R
Except when both ₅ are hydroxyl groups. The present invention provides an asymmetric cyclohexylidene polyhydric phenol represented by the formula:

Further, according to the present invention, the compound represented by the general formula (II):

[0015]

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(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group or a phenyl group, and R ₃ represents a hydrogen atom or 1 to 4 carbon atoms.
3 represents an alkyl group, and n represents an integer of 1 to 3. Wherein the cyclohexenylphenol represented by the formula (I) is reacted with a polyhydric phenol selected from catechol, resorcinol, pyrogallol and 1,2,4-trihydroxybenzene in the presence of an acid catalyst. )

[0017]

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(Wherein R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group or a phenyl group, and R ₃ represents a hydrogen atom or 1 to 4 carbon atoms)
3 represents an alkyl group, n represents an integer of 1 to 3,
One or two of R ₄ , R ₅ and R ₆ represent a hydroxyl group, and the remainder represents a hydrogen atom. Where R ₄ and R
Except when both ₅ are hydroxyl groups. The present invention provides a method for producing an asymmetric cyclohexylidene polyhydric phenol represented by the following formula:

[0019]

DETAILED DESCRIPTION OF THE INVENTION The novel asymmetric cyclohexylidene polyhydric phenols according to the present invention have the general formula (I)

[0020]

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(Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group or a phenyl group, and R ₃ represents a hydrogen atom or 1 to 4 carbon atoms.
3 represents an alkyl group, n represents an integer of 1 to 3,
One or two of R ₄ , R ₅ and R ₆ represent a hydroxyl group, and the remainder represents a hydrogen atom. Where R ₄ and R
Except when both ₅ are hydroxyl groups. ).

In the cyclohexylidene polyhydric phenol represented by the general formula (I), when R ₁ or R ₂ is an alkyl group having 1 to 4 carbon atoms, specific examples thereof include a methyl group, Ethyl, propyl or butyl groups can be mentioned. The propyl group and the butyl group may be linear or branched. When R ₃ is an alkyl group having 1 to ₃ carbon atoms, specific examples thereof include a methyl group, an ethyl group and a propyl group. The propyl group may be linear or branched.

Accordingly, specific examples of the asymmetric cyclohexylidene polyhydric phenols according to the present invention include, for example, 1-
(4-hydroxyphenyl) -1- (2,4-dihydroxyphenyl) -4-isopropylcyclohexane, 1-
(4-hydroxyphenyl) -1- (3,4-dihydroxyphenyl) -4-isopropylcyclohexane, 1-
(4-hydroxyphenyl) -1- (2,3,4-trihydroxyphenyl) -4-isopropylcyclohexane,
1- (4-hydroxyphenyl) -1- (2,4-dihydroxyphenyl) -4-n-propylcyclohexane,
1- (4-hydroxyphenyl) -1- (3,4-dihydroxyphenyl) -4-n-propylcyclohexane,
1- (4-hydroxyphenyl) -1- (2,3,4-trihydroxyphenyl) -4-n-propylcyclohexane, 1- (3-cyclohexyl-4-hydroxyphenyl) -1- (2,4- Dihydroxyphenyl) cyclohexane, 1- (3-cyclohexyl-4-hydroxyphenyl) -1- (3,4-dihydroxyphenyl) cyclohexane, 1- (3-cyclohexyl-4-hydroxyphenyl) -1- (2,3, 4-trihydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -1-
(2,4-dihydroxyphenyl) cyclohexane, 1-
(4-hydroxyphenyl) -1- (3,4-dihydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -1- (2,3,4-trihydroxyphenyl) cyclohexane, 1- (3,5- Dimethyl-4-hydroxyphenyl) -1- (2,4-dihydroxyphenyl) cyclohexane, 1- (3,5-dimethyl-4-hydroxyphenyl) -1- (3,4-dihydroxyphenyl) cyclohexane, 1- ( 3,5-dimethyl-4-hydroxyphenyl) -1- (2,3,4-trihydroxyphenyl) cyclohexane, 1- (3,5-dimethyl-4-hydroxyphenyl) -1- (2,4-dihydroxy Phenyl) -4-
Isopropylcyclohexane, 1- (3,5-dimethyl-
4-hydroxyphenyl) -1- (3,4-dihydroxyphenyl) -4-isopropylcyclohexane, 1-
(3,5-dimethyl-4-hydroxyphenyl) -1-
(2,3,4-trihydroxyphenyl) -4-isopropylcyclohexane, 1- (4-hydroxyphenyl)-
1- (2,4-dihydroxyphenyl) -3,3,5-trimethylcyclohexane, 1- (4-hydroxyphenyl)
-1- (3,4-dihydroxyphenyl) -3,3,5-trimethylcyclohexane, 1- (4-hydroxyphenyl) -1- (2,3,4-trihydroxyphenyl) -3,3,
5-trimethylcyclohexane, 1- (3-tert.-butyl-4-hydroxyphenyl) -1- (2,4-dihydroxyphenyl) cyclohexane, 1- (3-tert.-
Butyl-4-hydroxyphenyl) -1- (3,4-dihydroxyphenyl) cyclohexane, 1- (3-tert.
-Butyl-4-hydroxyphenyl) -1- (2,3,4-
Trihydroxyphenyl) cyclohexane and the like.

The asymmetric cyclohexylidene polyhydric phenols according to the present invention have the general formula (II)

[0025]

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(Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group or a phenyl group, and R ₃ represents a hydrogen atom or 1 to 4 carbon atoms.
3 represents an alkyl group, and n represents an integer of 1 to 3. )) And a polyhydric phenol selected from catechol, resorcinol, pyrogallol and 1,2,4-trihydroxybenzene in the presence of an acid catalyst.

In the cyclohexenylphenol represented by the above general formula (II), R ₁ or R ₂ has 1 carbon atom.
When they are alkyl groups of to 4, as specific examples thereof,
For example, a methyl group, an ethyl group, a propyl group or a butyl group can be mentioned. The propyl group and the butyl group may be linear or branched. R ₃ has 1 carbon atom
When it is an alkyl group of (1) to (3), specific examples thereof include a methyl group, an ethyl group and a propyl group. The propyl group may be linear or branched.

Accordingly, specific examples of such cyclohexenylphenols include 1- (4-hydroxyphenyl) -4-isopropylcyclohexene, 1- (4-hydroxyphenyl) -4-n-propylcyclohexene, 1- ( 3-cyclohexyl-4-hydroxyphenyl) cyclohexene, 1- (3-methyl-4-hydroxyphenyl) cyclohexene, 1- (3-phenyl-4
-Hydroxyphenyl) cyclohexene, 1- (3,5-
Dimethyl-4-hydroxyphenyl) cyclohexene,
1- (3,5-dimethyl-4-hydroxyphenyl) -4
-Isopropylcyclohexene, 1- (3-cyclohexyl-4-hydroxyphenyl) -4-isopropylcyclohexene, 1- (4-hydroxyphenyl) -3,3,
Examples thereof include 5-trimethylcyclohexene and 1- (3-tert.-butyl-4-hydroxyphenyl) cyclohexene.

According to the present invention, an asymmetric cyclohexylidene polyhydric phenol is produced by reacting the cyclohexenyl phenol represented by the general formula (II) with the polyhydric phenol in the presence of an acid catalyst. In doing so, the polyhydric phenols are usually used in excess with respect to the cyclohexenyl phenols, and preferably, the polyhydric phenols are 1 to 5 mol parts, more preferably 1 to 5 mol parts, per 1 mol part of the cyclohexenyl phenols. Preferably, it is used in the range of 1.5 to 3 mol parts.

When the molar ratio of polyhydric phenols / cyclohexenylphenols is too small, by-products in which two molecules of cyclohexenylphenol are added to one molecule of polyhydric phenol increase. On the other hand, when the molar ratio of polyhydric phenols / cyclohexenyl phenols is too large, unreacted phenols increase and the production efficiency of the target product decreases.

As the acid catalyst, p-toluenesulfonic acid, cation exchange resin, concentrated hydrochloric acid, sulfuric acid, methanesulfonic acid and the like are used, and particularly, p-toluenesulfonic acid is preferably used. As the p-toluenesulfonic acid, a monohydrate is usually used. Although not particularly limited, the acid catalyst is usually used in a range of 1 to 10 mol% based on cyclohexenylphenol.

In the reaction of cyclohexenyl phenols with polyhydric phenols in the presence of an acid catalyst, cyclohexenyl phenols are liable to self-polymerize under an acid catalyst or in a high temperature environment. The reaction is carried out in a solvent, especially in an alcohol solvent, in order to obtain a high yield of the asymmetric cyclohexylidene polyhydric phenol described above. The alcohol solvent is preferably an aliphatic alcohol having 1 to 10 carbon atoms or a cycloalkanol having 5 to 7 carbon atoms, and specific examples include, for example, methanol, ethanol, isopropanol, n-propanol, and n-propanol.
Examples thereof include butanol, t-butanol, pentanol, n-hexanol, cyclohexanol, and octanol. Among them, according to the present invention, methanol is preferably used.

In the present invention, when the cyclohexenylphenol and the polyhydric phenol are reacted in the presence of an acid catalyst, the mode thereof is not particularly limited. Polyhydric phenols, alcohol solvents and acid catalysts may be charged to the reactor all at once, heated and reacted.
It is preferable that a polyhydric phenol, an alcohol solvent, and an acid catalyst are charged in a reactor in advance, and a mixed solution of cyclohexenylphenol and an alcohol solvent is dropped therein and reacted.

In such a method, the amount of the alcohol solvent to be used is not particularly limited, but at a temperature of ordinary temperature to about 60 ° C., the cyclohexenyl phenol and the polyhydric phenol which are previously charged in the reactor are used. The alcohol solvent and the acid catalyst are selected so as to form a solution, which can be added dropwise to the solution comprising the cyclohexenylphenol and the alcohol solvent. Thus, as an example, for example, the alcohol solvent in the charged solution is usually preferably 30 to 100 parts by weight based on 100 parts by weight of the polyhydric phenol, and in the solution comprising cyclohexenylphenols and the alcohol solvent, The solvent is usually used in a range of 50 to 150 parts by weight based on 100 parts by weight of cyclohexenylphenol.

The reaction temperature of the cyclohexenyl phenol with the polyhydric phenol is not particularly limited either. However, when the reaction temperature is too low, the reaction rate is too slow to be practical. When the reaction temperature is too high, undesirable side reactions occur, and the yield of the desired asymmetric cyclohexylidene polyhydric phenols decreases. Therefore, in the present invention, the reaction between cyclohexenyl phenols and polyhydric phenols is usually 20 to
It is performed in the range of 80 ° C.

The reaction between the cyclohexenyl phenols and the polyhydric phenols can be monitored by liquid chromatography or gas chromatography analysis. Therefore, unreacted cyclohexenyl phenols disappear in the reaction mixture. The end point may be a point in time at which an increase in the desired asymmetric cyclohexylidene polyhydric phenol is no longer observed.

After the cyclohexenyl phenols and the polyhydric phenols are reacted in an alcohol solvent in the presence of an acid catalyst, the resulting reaction mixture is neutralized to pH 5 to 7 with an aqueous alkali solution. The alcohol solvent is recovered by distillation, and then the crystallization solvent in the distillation residue, for example, a mixture of aromatic hydrocarbons and water, or a mixed solvent of aromatic hydrocarbons and saturated hydrocarbons After a mixture with water is added and unreacted polyhydric phenols are extracted and removed from the aqueous layer, the desired cyclohexylidene polyhydric phenols are crystallized in the oil layer, which is filtered and separated.

The alkaline aqueous solution is not limited, and various ones can be used. For example, an aqueous solution of sodium hydroxide, potassium hydroxide, dibasic sodium phosphate or the like is preferably used.

As the above aromatic hydrocarbons, for example, toluene, xylene, mesitylene, pseudocumene and the like are preferably used. As the saturated hydrocarbons, for example, fatty acids such as pentane, n-hexane, heptane and octane are used. And alicyclic hydrocarbons such as cyclohexane. Such a crystallization solvent is usually used in an amount of about 1 to 4 times the weight of the distillation residue after the recovery of the alkali solvent.

Among the cyclohexenylphenols represented by the general formula (II) used in the present invention, for example, 1- (4-hydroxyphenyl) cyclohexene is a known compound, (4-
It can be obtained by thermal decomposition of (hydroxyphenyl) cyclohexane.

In general, the cyclohexenyl phenols represented by the above general formula (II) is

[0042]

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(Wherein R ₁ , R ₂ , R ₃ and n are the same as those described above). The cyclohexylidenebisphenol represented by the formula (I) is heated under an inert atmosphere under reduced pressure in the presence of a basic catalyst. It can be obtained by distilling off the phenols that are decomposed and generated by fractional distillation, and then distilling off cyclohexenylphenols and recovering them.

As the above basic catalyst, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is usually used in a range of 0.5 to 20 mol% based on cyclohexylidenebisphenols. Can be

The thermal decomposition of cyclohexylidenebisphenols is preferably performed under reduced pressure, for example, at 30 to 5 mmH.
g of cyclohexylidenebisphenols at a temperature in the range of 160 to 270 ° C. under an inert gas, for example, nitrogen gas atmosphere under reduced pressure of g.
The phenols produced by this thermal decomposition are first distilled off by fractional distillation, and then the desired cyclohexenylphenols are distilled off and recovered.

If the cyclohexenyl phenols thus obtained are crystalline at about normal temperature, a purified product can be obtained by recrystallization from an appropriate solvent. Preferred examples of the solvent for recrystallization include an aqueous methanol solution. On the other hand, if the obtained cyclohexenylphenols are liquid at around normal temperature, purified products can be obtained by distillation, preferably under reduced pressure.

Therefore, for example, by thermal decomposition of 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1- (4-hydroxyphenyl) -4-isopropylcyclohexane is obtained.
Isopropylcyclohexene can be obtained and 1,1-
By thermal decomposition of bis (4-hydroxyphenyl) -4-n-propylcyclohexane, 1- (4-hydroxyphenyl) -4-n-propylcyclohexene can be obtained, and 1,1-bis (3-cyclohexyl-4) can be obtained. -Hydroxyphenyl) cyclohexane by thermal decomposition
(3-Cyclohexyl-4-hydroxyphenyl) cyclohexene can be obtained.

[0048]

As described above, the asymmetric cyclohexylidene polyhydric phenols according to the present invention have an asymmetric structure in which a substituted phenol nucleus and a polyhydric phenol skeleton having a plurality of hydroxyl groups are connected by a cyclohexylidene group. Therefore, by using such an asymmetric cyclohexylidene polyhydric phenol as a raw material, a novel polymer having unprecedented heat resistance, impact resistance, chemical resistance, and the like, It is possible to develop a novel photoresist material having reactivity and selective solubility in various solvents, acids, alkalis, and the like.

Further, according to the present invention, such an asymmetric cyclohexylidene polyhydric phenol is reacted with a cyclohexenyl phenol and the polyhydric phenol in an alcohol solvent in the presence of an acid catalyst, Undesirable side reactions can be suppressed and a high yield can be obtained.

[0050]

The present invention will be described below with reference to Examples and Reference Examples showing production examples of raw materials, but the present invention is not limited to these Examples.

Reference Example 1 (Synthesis of 1- (4-hydroxyphenyl) cyclohexene) 1000 mL equipped with a stirrer, a thermometer and a distillation apparatus
1,2-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z) 972.3 in a four-neck flask having a capacity
g (3.63 mol), the inside of the flask was replaced with nitrogen gas, and then 2.9 g of a 48% aqueous sodium hydroxide solution (0.03 mol) was added.
5 mol) and the temperature was raised. When the internal temperature reaches around 180 ° C., the pressure inside the flask is gradually reduced by a vacuum pump, and while maintaining the internal temperature at 190 to 220 ° C./10 mmHg,
The 1,1-bis (4-hydroxyphenyl) cyclohexane was subjected to alkali pyrolysis to obtain 920.1 g of a fraction.

This fraction was rectified by a distillation apparatus packed with 10 cm of Helipack, and 301.2 g of phenol was recovered.
20 g was added for recrystallization. After cooling to 20 ° C,
After filtration and drying, 577.1 g of 1- (4-hydroxyphenyl) cyclohexene (gas chromatography purity 9) was obtained.
9.9%) as white crystals.

Reference Example 2 (Synthesis of 1- (4-hydroxyphenyl) -4-isopropylcyclohexene) A 500 mL capacity four equipped with a stirrer, a thermometer, a nitrogen gas injection tube, and a distillation distilling tube (filled with Helipack 10 cm). 1 in the neck flask (distillation device)
200 g (0.645 mol) of 1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane was charged,
After the inside of the reactor was replaced with nitrogen gas, 1.0 g (0.012 mol) of a 48% aqueous sodium hydroxide solution was added, and the temperature was raised.

The above starting material was heated at an internal temperature of 190 to 230 ° C. for 2.5 hours under a reduced pressure of 15 to 10 mmHg and thermally decomposed to give 60.2 g of a phenol fraction and a main fraction (distillation temperature of 188). ° C / 10 mmHg) 106.5 g and distillation residue 27.
3 g were obtained.

After adding 150 g of methanol and 50 g of water to the main fraction (main component: 94.3%), the reaction product was recrystallized, filtered at 30 ° C., washed with a 50% aqueous methanol solution, and dried under reduced pressure. To give 1- (4-hydroxyphenyl)-
99.3 g of 4-isopropylcyclohexene (purity by gas chromatography: 98.6%) were obtained as white crystals. Melting point: 154 ° C (DSC method) Mass spec: 216 (M ⁺ ), 201 (M ⁺ -CH ₃ ), 146 (M ⁺ -C
₅ H ₁₀₎ Infrared absorption spectrum (cm ^-1): 3226.7-3028.0 (phenolic hydroxyl group), 2956.7, 2868.0, 2835.2, 2726.2,
1596.0, 1512.1, 1454.2, 1365.5, 1234.4, 1181.3, 80
9.1, 735.8, 623.9 Proton NMR analysis (DMSO solvent, 60 MHz):

[0056]

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[0057]

[Table 1]

Reference Example 3 (Synthesis of 1- (4-hydroxyphenyl) -4-n-propylcyclohexene)
160 g (0.516 mol) of 1-bis (4-hydroxyphenyl) -4-n-propylcyclohexane was charged,
After replacing the inside of the reactor with nitrogen gas, 0.8 g (9.6 mmol) of a 48% aqueous sodium hydroxide solution was added, and the internal temperature was reduced to about 18%.
The temperature was raised until the temperature reached 0 ° C., and then the pressure inside the reactor was gradually reduced, and the internal temperature was changed from 188 ° C./33 mmHg to 220 ° C./8 mm
The starting material was heated under a reduced pressure of Hg for 7 hours and thermally decomposed to obtain 46.6 g of a phenol fraction, 97.0 g of a main fraction, and 9.6 g of a distillation residue.

The main fraction was 1- (4-hydroxyphenyl) -4-n-propylcyclohexene (purity of liquid chromatography: 98.8%).

In the above main fraction, 145.5 g of methanol and 7
After adding 7.6 g and recrystallizing, the obtained crystals were cooled to 25 ° C.
, Washed with 65% methanol, and dried under reduced pressure to give 93.2 g of 1- (4-hydroxyphenyl) -4-n-propylcyclohexene (purity of gas chromatography 99.0%) as yellow crystals. Obtained. Mp: 115.2 ° C. (DSC method) Mass ^{spectrometry: 216 (M +), 201} (M + -CH 3), 187 (M + -C 2 H 5),
173 (M ⁺ -C ₃ H ₇ ), 159 (M ⁺ -C ₄ H ₉ ), 146 (M ⁺ -C ₅ H ₁₀ ) Infrared absorption spectrum (cm ^-1 ): 3287.2-3027.1 (phenolic hydroxyl group), 2954.7, 2912.3, 2840.0, 2622.0,
1646.1, 1594.1, 1514.0, 1453.3, 1379.0, 1239.2, 11
79.4, 1134.1, 1110.9, 1077.2, 1011.6, 915.2, 838.0,
809.1, 715.5, 631.6, 519.8 Proton NMR analysis (CDCl ₃ solvent, 60 MHz):

[0061]

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[0062]

[Table 2]

Reference Example 4 (Synthesis of 1- (3-cyclohexyl-4-hydroxyphenyl) cyclohexene) Stirrer, thermometer, nitrogen gas injection pipe, and distillation distillation pipe (filled with Helipack 10 cm).
500 mL four-necked flask with distillation (distillation apparatus)
250 g (0.58 mol) of 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane was charged into the reactor, and the inside of the reactor was purged with nitrogen gas. Then, 1.25 g (0.015 mol) of a 48% aqueous sodium hydroxide solution was added. Mol) was added and the temperature was raised.

Under reduced pressure conditions of 10 to 5 mmHg, the starting material was heated at an internal temperature of 196 to 250 ° C. for 7 hours and thermally decomposed to obtain 101.4 g of an o-cyclohexylphenol fraction,
98.5 g of a main fraction (distillation temperature: 180 ° C./5 mmHg) and 31.0 g of a distillation residue were obtained.

The main fraction was a red-brown viscous liquid of 1- (3-cyclohexyl-4-hydroxyphenyl) cyclohexene containing a small amount (8.2%) of 2,4-dicyclohexylphenol (gas 90.7% purity by chromatography). It did not solidify at room temperature. Boiling point: 180 ° C./5 mmHg Mass spectrometry: 256 (M ⁺ ), 173 (M ⁺ −C ₆ H ₁₁ ) Infrared absorption spectrum (cm ⁻¹ ): 3429.2-2851.6 (phenolic hydroxyl group), 2925.8, 2851.6, 1604.7, 1504.4 ,
1447.5, 1435.9, 1418.5, 1343.3, 1300.9, 1272.0, 12
50.8, 1177.5, 1137.0, 1098.4, 881.4, 847.7, 812.0,
620.1, 418.5 Proton NMR analysis (DMSO solvent, 60 MHz):

[0066]

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[0067]

[Table 3]

Example 1 (Synthesis of 1- (4-hydroxyphenyl) -1- (3,4-dihydroxyphenyl) cyclohexane) 300 mL equipped with a stirrer, thermometer, dropping funnel and reflux condenser
In a four-neck flask having a capacity, 22.0 g (0.20 mol) of catechol and 0.6 g (3.2 mmol) of p-toluenesulfonic acid monohydrate were charged together with 11.0 g of methanol, and dissolved therein. Then, 17.4 g (0.1 mol) of 1- (4-hydroxyphenyl) cyclohexene was added to 17.4 g of methanol.
g, and keeping this solution at 30 ° C.
The mixture was dropped into the flask in 2 hours, and thereafter, the mixture was further stirred for 2 hours.

After the completion of the reaction, 22 g of toluene was added to the obtained green reaction mixture, an 8% aqueous sodium hydroxide solution was added to neutralize the mixture to pH 6 to 7, and the mixture was heated to 60 ° C. and dissolved. Recrystallize, filter at 25 ° C., dry under reduced pressure, and wash 1- (4-hydroxyphenyl) -1- (3,4-dihydroxyphenyl) cyclohexane 12.1 g (high-performance liquid chromatography purity 99.2%). Was obtained as white crystals. Melting point: 167.9 ° C (Mettler method) Mass spec: 284 (M ⁺ ), 267 (M ⁺ -OH), 241, 215 (M ⁺ -C ₅
H ₁₀ ) Infrared absorption spectrum (cm ⁻¹ ): 3477.4-3400.3 (phenolic hydroxyl group), 2940.3-2859.3, 1611.4, 1594.1, 1
512.1, 1468.7, 1453.3, 1431.1, 1340.4, 1268.1, 124
7.9, 1218.9, 1182.3, 1112.9, 1024.7, 1011.6, 952.8,
930.6, 901.7, 840.9, 818.7, 777.3, 636,5, 610.4, 5
45.7, 551.6 Proton NMR analysis (DMSO solvent, 60 MHz):

[0070]

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[0071]

[Table 4]

Example 2 (Synthesis of 1- (4-hydroxyphenyl) -1- (2,4-dihydroxyphenyl) cyclohexane) 300 mL equipped with a stirrer, thermometer, dropping funnel and reflux condenser
In a four-neck flask having a capacity, 22.0 g (0.20 mol) of resorcinol and 0.6 g (3.2 mmol) of p-toluenesulfonic acid monohydrate were charged together with 11.0 g of methanol, and dissolved therein. Then, 17.4 g (0.1 mol) of 1- (4-hydroxyphenyl) cyclohexene was added to 17.4 g of methanol.
g, and keeping this solution at 30 ° C.
The mixture was added dropwise to the flask in 1.5 hours, and thereafter, the mixture was further stirred for 5 hours.

After completion of the reaction, 22 g of toluene was added to the obtained reaction mixture, an 8% aqueous solution of sodium hydroxide was added to neutralize the mixture to pH 6 to 7, and the mixture was heated to 60 ° C., dissolved, and then recrystallized. And filtered at 20 ° C., dried under reduced pressure,
21.5 g of 1- (4-hydroxyphenyl) -1- (2,4-dihydroxyphenyl) cyclohexane (purity of high performance liquid chromatography: 98.4%) was obtained as white crystals. Melting point: 206.6 ° C (Mettler method) Mass spec: 284 (M ⁺ ), 241 (M ⁺ -C ₃ H ₇ ), 215 (M ⁺ -C
_{5 H 10), 190 (M} + - phenol), 175 (M ⁺ - resorcinol) Infrared absorption spectrum (cm ^-1): 3482.2-3392.6 (phenolic hydroxyl group), 2940.3, 2858.3, 1613.3, 1593.1,
1559.3, 1540.1, 1511.1, 1471.6, 1455.2, 1435.9, 13
40.4, 1298.0, 1264.3, 1218.9, 1182.3, 1165.9, 1137.
9, 1126.4, 1108.0, 1081.0, 1023.2, 975.9, 815.8, 79
1.7, 743.5, 624.9, 590.2, 557.4, 514,0, 468.7,418.
5 Proton NMR analysis (DMSO solvent, 60 MHz):

[0074]

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[0075]

[Table 5]

Example 3 (Synthesis of 1- (4-hydroxyphenyl) -1- (2,3,4-trihydroxyphenyl) cyclohexane) 30 equipped with a stirrer, thermometer, dropping funnel and reflux condenser.
Pyrogallol 25.2 g in a 0 mL four-necked flask
(0.20 mol) and p-toluenesulfonic acid monohydrate 0.6
g (3.2 mmol) together with 12.6 g of methanol were charged and dissolved therein. Next, 17.4 g (0.1 mol) of 1- (4-hydroxyphenyl) cyclohexene was dissolved in 17.4 g of methanol, and this solution was added dropwise to the flask over 2 hours while maintaining the internal temperature at 30 ° C. Thereafter, the mixture was further stirred for 18 hours.

After the completion of the reaction, 22 g of toluene was added to the obtained reaction mixture, and an aqueous 8% sodium hydroxide solution was added to neutralize the mixture to pH 6 to 7, and the temperature was raised to 70 ° C., followed by cooling to 20 ° C. , And dried under reduced pressure, and 14.8 g of 1- (4-hydroxyphenyl) -1- (2,3,4-trihydroxyphenyl) cyclohexane (high-performance liquid chromatography purity: 96.3%) was obtained as white crystals. Obtained. Melting point: 227.6 ° C (Mettler method) Mass spec: 300 (M ⁺ ), 257, 206 (M ⁺ -phenol), 174
(M ⁺ -pyrogallol) Infrared absorption spectrum (cm ^-1 ): 3471.6-3200.6 (phenolic hydroxyl group), 2931.6, 3007.8, 2917.1, 2860.2,
1613.3, 1595.0, 1505.3, 1472.5, 1459.0, 1447.5, 14
36.9, 1344.3, 1315.4, 1260.4, 1228.6, 1177.5, 1136.
0, 1125.4, 1110.9, 1064.6,1032.8, 951.8, 929.6, 87
3.7, 818.7, 799.4, 715.5, 623.0, 582,5, 547.7,516.
9, 418.5 Proton NMR analysis (DMSO solvent, 60 MHz):

[0078]

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[0079]

[Table 6]

Example 4 (Synthesis of 1- (3-cyclohexyl-4-hydroxyphenyl) -1- (2,4-dihydroxyphenyl) cyclohexane) A 300 mL capacity equipped with a stirrer, thermometer, dropping funnel and reflux condenser was prepared. In a four-necked flask, 22.0 g (0.20 mol) of resorcinol and 0.6 g (3.2 mmol) of p-toluenesulfonic acid monohydrate were added to 11.0 g of methanol.
And dissolved in it. Then, 1- (3-
28.7 g (0.1 mol) of cyclohexyl-4-hydroxyphenyl) cyclohexene was dissolved in 28.7 g of methanol, and this solution was added dropwise to the flask over 1.5 hours while maintaining the internal temperature at 30 ° C. Thereafter, the mixture was further stirred for 7 hours.

After completion of the reaction, 1.9 g of an 8% aqueous sodium hydroxide solution was added to the obtained reaction mixture to neutralize the solution to pH 5 to 6, and methanol was recovered by distillation at normal pressure. 104.6 g of toluene and 26.2 g of water were added to 52.3 g of the distillation residue, washed with water at 45 ° C., separated twice, and then 26.2 g of water.
Was added for recrystallization, cooled to 20 ° C., and centrifuged.
The obtained cake is washed with toluene, dried and dried.
-(3-cyclohexyl-4-hydroxyphenyl)-
1- (2,4-dihydroxyphenyl) cyclohexane 1
9.5 g (93.0% high performance liquid chromatography purity) was obtained as a white powder. Melting point: 159.1 ° C (DSC method) Mass analysis: 366 (M ⁺ ) Infrared absorption spectrum (cm ^-1 ): 3397.4-3180.4 (phenolic hydroxyl group), 3042.5, 2924.8, 2852.5, 2795.6-
2666.4, 1624.9, 1600.8, 1559.3, 1540.1, 1503.4, 14
52.3, 1419.6, 1351.0, 1299.9, 1276.8, 1248.8, 1221.
8, 1178.4, 1163.0, 1138.9,1085.8, 976.9, 839.9, 81
3.9, 800.4, 631.6, 600.8-457.1 Proton NMR analysis (DMSO solvent, 60 MHz):

[0082]

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[0083]

[Table 7]

Example 5 (Synthesis of 1- (3-cyclohexyl-4-hydroxyphenyl) -1- (3,4-dihydroxyphenyl) cyclohexane) A 300 mL capacity equipped with a stirrer, thermometer, dropping funnel and reflux condenser was prepared. In a four-necked flask, 22.0 g (0.20 mol) of catechol and 0.6 g (3.2 mmol) of p-toluenesulfonic acid monohydrate were added to 11.0 g of methanol.
And dissolved in it. Then, 1- (3-
28.7 g (0.1 mol) of cyclohexyl-4-hydroxyphenyl) cyclohexene was dissolved in 28.7 g of methanol, and this solution was added dropwise to the flask over 1.5 hours while maintaining the internal temperature at 55 ° C. Thereafter, the mixture was further stirred at 50 ° C. for 27 hours.

After completion of the reaction, 1.9 g of an 8% aqueous sodium hydroxide solution was added to the obtained reaction mixture to neutralize the solution to pH 5 to 6, and methanol was recovered by distillation at normal pressure. To 53.5 g of the distillation residue were added 53.5 g of xylene and 26.3 g of water, and the mixture was washed with water at 60 ° C. and separated four times. Then, after removing water from the mixture by azeotropic dehydration, the mixture was recrystallized, cooled to 27 ° C., and centrifugally filtered. The obtained cake was washed with xylene and dried, and 23.1 g of 1- (3-cyclohexyl-4-hydroxyphenyl) -1- (3,4-dihydroxyphenyl) cyclohexane (purity of high-performance liquid chromatography 97. 2%) as a white powder. Melting point: 181.0 ° C. (DSC method) Mass spectrometry: 366 (M ⁺ ) Infrared absorption spectrum (cm ⁻¹ ): 3521.8-3264.3 (phenolic hydroxyl group), 3034.8, 2926.8, 2848.7, 2666.4,
2361.7, 2341.4, 2064.7, 1604.7, 1521.7, 1495.7, 14
32.0, 1349.1, 1326.9, 1297.0, 1272.0, 1237.3, 1187.
1, 1135.0, 1115.7, 1093.6,1026.1, 1002.9, 955.7, 9
32.5, 896.8, 872.7, 878.6, 810.0, 783.0, 761.8, 73
8.7, 649.0, 621.0, 591.1, 549.7, 485.1 Proton NMR analysis (DMSO solvent, 60 MHz):

[0086]

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[0087]

[Table 8]

Example 6 (Synthesis of 1- (3-cyclohexyl-4-hydroxyphenyl) -1- (2,3,4-trihydroxyphenyl) cyclohexane) A stirrer, a thermometer, a dropping funnel and a reflux condenser were provided. In a 300 mL four-necked flask, 22.2 g (0.20 mol) of pyrogallol and 0.6 g (3.2 mmol) of p-toluenesulfonic acid monohydrate were added to methanol 1
It was charged together with 2.6 g and dissolved therein. Then, 1-
28.7 g (0.1 mol) of (3-cyclohexyl-4-hydroxyphenyl) cyclohexene was converted to 28.7 g of methanol
The solution was added dropwise to the flask over 1.5 hours while maintaining the internal temperature at 30 ° C., followed by stirring for further 7 hours.

After completion of the reaction, an 8% aqueous sodium hydroxide solution was added to the obtained reaction mixture to neutralize the solution to pH 5 to 6, and methanol was recovered by distillation at normal pressure. To 56.3 g of the distillation residue, 56.3 g of toluene and 28.2 g of water were added, and 50
Water washing and liquid separation were performed three times at ６０60 ° C. Then, after removing water from the mixture by azeotropic dehydration, 143.7 g of cyclohexane was added for recrystallization, cooled to 27 ° C., and centrifugally filtered. The obtained cake was washed with cyclohexane and then dried, and 16.4 g of 1- (3-cyclohexyl-4-hydroxyphenyl) -1- (2,3,4-trihydroxyphenyl) cyclohexane (high-performance liquid chromatography). (Purity 90.8%) as a white powder. Melting point: 176.0 ° C. (DSC method) Mass spectrometry: 382 (M ⁺ ) Infrared absorption spectrum (cm ⁻¹ ): 3478.1 (phenolic hydroxyl group), 2942.8, 2853.5, 2657.7, 1624.9, 1503.4,
1449.4, 1351.0, 1301.9, 1274.9, 1253.6, 1190.0, 11
37.9, 1123.5, 1092.6, 1064.6, 1015.5, 947.9, 866.9,
847.7, 816.8, 793.7, 643.2, 671.2, 617.2, 569.0, 4
03.1 Proton NMR analysis (DMSO solvent, 60 MHz):

[0090]

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[0091]

[Table 9]

Example 7 (Synthesis of 1- (4-hydroxyphenyl) -1- (3,4-dihydroxyphenyl) -4-isopropylcyclohexane) A 300 mL capacity equipped with a stirrer, thermometer, dropping funnel and reflux condenser was prepared. In a four-necked flask, 22.0 g (0.20 mol) of catechol, 0.6 g (3.2 mmol) of p-toluenesulfonic acid monohydrate, 1- (4-hydroxyphenyl) -4-isopropylcyclohexene 21. 6g
(0.10 mol) and 32.0 g of methanol,
The reaction was carried out at 50 ° C. for 24 hours, and further at 60 ° C. for 3 hours.
Reacted.

After completion of the reaction, the obtained reaction mixture was neutralized to pH 5 to 6 by adding an 8% aqueous sodium hydroxide solution, recrystallized, cooled to room temperature and centrifugally filtered. The obtained cake was washed with water and dried, and 21.8 g of 1- (4-hydroxyphenyl) -1- (3,4-dihydroxyphenyl) -4-isopropylcyclohexane (purity of high performance liquid chromatography 95. 9%) as a white powder. Melting point: 194.8 ° C. (DSC method) Mass spectrometry: 326 (M ⁺ ) Infrared absorption spectrum (cm ⁻¹ ): 3499.9-3243.1 (phenolic hydroxyl group), 3048.3, 3017.4, 2931.6, 2855.4,
2834.2, 2680.9, 2580.6, 1611.4, 1558.4, 1511.1, 14
42.7, 1364.5, 1334.6, 1276.8, 1243.0, 1186.1, 1144.
7, 1116.7, 1094.5, 1009.7,960.5, 948.9, 879.5, 85
1.5, 823.5, 808.1, 790.8, 782.1, 724.2, 670.2,630.
7, 618.1, 594.0, 541.0, 435.9 Proton NMR analysis (DMSO solvent, 60 MHz):

[0094]

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[0095]

[Table 10]

Example 8 (Synthesis of 1- (4-hydroxyphenyl) -1- (2,4-dihydroxyphenyl) -4-n-propylcyclohexane) 300 mL equipped with a stirrer, thermometer, dropping funnel and reflux condenser In a four-neck flask having a capacity, 22.0 g (0.20 mol) of resorcinol, 1.2 g (6.3 mmol) of p-toluenesulfonic acid monohydrate and 11.0 g of methanol were charged, and the internal temperature was adjusted to 25 to 30. While maintaining the temperature at
21.6 g (0.10 mol) of (4-hydroxyphenyl) -4-n-propylcyclohexene and 21.6 g of methanol
Was added dropwise over 1 hour, and further reacted at the same temperature for 7 hours.

After completion of the reaction, an 8% aqueous sodium hydroxide solution was added to the obtained reaction mixture to neutralize the solution to pH 5 to 6, 21.6 g of methanol and 50 g of water were added, and the mixture was cooled to 25 ° C. and suctioned. After filtration, the obtained cake was washed with a 50% aqueous methanol solution to obtain 24.5 g of a wet crude cake. 20 g of the wet crude cake was purified by recrystallization with 100 g of toluene to give 1- (4-hydroxyphenyl) -1-
14.5 g of (2,4-dihydroxyphenyl) -4-n-propylcyclohexane (purity of high performance liquid chromatography: 96.4%) was obtained as white crystals. Melting point: 240.0 ° C (DSC method) Mass spectrometry: 326 (M ⁺ ), 241 (M ⁺ -C ₆ H ₁₃ ) Infrared absorption spectrum (cm ^-1 ): 3496.7-3357.8 (phenolic hydroxyl group), 2923.9, 2888.2 , 1596.9, 1514.0,
1441.7, 1373.2, 1293.2, 1240.1, 1186.1, 1158.2, 11
38.9, 1115.7, 981.7,836.1, 815.8, 800.4, 640.3, 62
6.8, 560.3, 542.9 Proton NMR analysis (DMSO solvent, 60 MHz):

[0098]

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[0099]

[Table 11]

Example 9 (Synthesis of 1- (4-hydroxyphenyl) -1- (2,3,4-trihydroxyphenyl) -4-n-propylcyclohexane) A stirrer, thermometer, dropping funnel and reflux condenser were used. 25.2 g (0.20 mol) of pyrogallol, 0.7 g (3.7 mmol) of p-toluenesulfonic acid monohydrate and 25.5 g of methanol were placed in a 300 mL four-necked flask provided.
2 g of 1- (4-hydroxyphenyl) -4-n-propylcyclohexene, 21.6 g (0.10 mol) of methanol and 2 g of methanol were added.
After a mixed solution with 1.6 g was dropped in 1 hour, the mixture was further reacted at the same temperature for 22 hours.

After completion of the reaction, an 8% aqueous sodium hydroxide solution was added to the obtained reaction mixture to neutralize the mixture to pH 5 to 6, 21.6 g of methanol and 50 g of water were added, and the mixture was cooled to 25 ° C. and suctioned. After filtration, the obtained cake was washed with a 50% aqueous methanol solution and dried to obtain 16.9 g of a crude cake. After dissolving 10 g of this crude cake in a mixed solvent of 50 g of toluene and 18 g of methanol, methanol was recovered by distillation, and then purified by recrystallization to obtain 1- (4-hydroxyphenyl) -1- (2,3 8.5 g of (, 4-trihydroxyphenyl) -4-n-propylcyclohexane (high-performance liquid chromatography purity: 96.4%) were obtained as white crystals. Melting point: 223.0 ° C (DSC method) Mass spectrometry: 342 (M ⁺ ), 257 (M ⁺ -C ₆ H ₁₃ ), 257 (M ⁺ -phenol), 216 (M ⁺ -phenol) Infrared absorption spectrum (cm) ^-1 ): 3458.1-3309.6 (phenolic hydroxyl group), 3068.5, 2923.9, 2859.3, 1609.5,
1595.0, 1559.3, 1507.3, 1458.1, 1437.8, 1349.1, 13
15.4, 1264.3, 1232.4, 1183.2, 1140.8, 1112.9, 1037.
6, 1022.2, 987.5, 941.2, 820.7, 793.7, 716.5, 695.
3, 669.3, 627.8, 584.5, 554.5, 531.4, 518.8, 419.5 Proton NMR analysis (DMSO solvent, 60 MHz):

[0102]

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[0103]

[Table 12]

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toru Nakaguchi 2-5-1115 Kosaga, Wakayama City Inside Honshu Kagaku Kogyo Co., Ltd. (72) Inventor Hiroyuki Kojima 2-115-5 Kosiga, Wakayama No. F-term in Honshu Kagaku Kogyo Co., Ltd. (Reference) 4H006 AA01 AA02 AB76 AC21 BA52 BA66 BB14 BC31 FC22 FC52 FE13 4H039 CA40 CA41 CF10

Claims (3)

[Claims] 1. A compound of the general formula (I) (Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group or a phenyl group, R ₃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, n represents an integer of 1 to 3, and R ₄ , R ₅ and R
₆ , one or two of these represent a hydroxyl group, and the remainder represents a hydrogen atom. However, the case where both R ₄ and R ₅ are hydroxyl groups is excluded. Asymmetric cyclohexylidene polyhydric phenols represented by the formula: 2. A compound of the general formula (II) (Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group or a phenyl group, R ₃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, n represents an integer of 1 to 3) and a polyhydric phenol selected from catechol, resorcinol, pyrogallol and 1,2,4-trihydroxybenzene in the presence of an acid catalyst. General formula (I) characterized by the following: (Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group or a phenyl group, R ₃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, n represents an integer of 1 to 3, and R ₄ , R ₅ and R
₆ , one or two of these represent a hydroxyl group, and the remainder represents a hydrogen atom. However, the case where both R ₄ and R ₅ are hydroxyl groups is excluded. A method for producing an asymmetric cyclohexylidene polyhydric phenol represented by the formula: 3. The method according to claim 2, wherein p-toluenesulfonic acid is used as an acid catalyst, and a polyhydric phenol is reacted in an alcohol solvent in a range of 1 to 5 parts by mole with respect to 1 part by mole of cyclohexenylphenol. For producing an asymmetric cyclohexylidene polyhydric phenol.