JP2003146925A - New 4-substituted cyclohexylidenebisphenols - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new cyclohexylidenebisphenol containing a phenyl- substituted asymmetric alkyl group at the 4-position of the cyclohexyl group. SOLUTION: This new 4-substituted cyclohexylidenebisphenol is represented by general formula I (R1 and R2 are each independently a hydrogen atom or a 1-8C alkyl group; R3 is a 1-4C alkyl group; n is an integer of 0-3).

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a novel 4-substituted system.
It relates to clohexylidene bisphenols. In detail
Is a phenyl-substituted alkyl at the 4-position of the cyclohexylidene group.
4-Substituted cyclohexylidenebispheno having a kill group
Rules. [0002] Such 4-substituted cyclohexylidenebi
Sphenols include liquid crystal polyester and polycarbonate
Raw materials, synthetic resin raw materials such as polyurethane,
It is useful as a raw material for photoresist such as a conductor. [0003] BACKGROUND OF THE INVENTION Conventionally, 4-substituted cyclohexylidenebis
Regarding phenols, see, for example, JP-A-4-2823.
No. 34, alkyl-substituted cyclohexanone and pheno
And 1,1-bis-
(4-hydroxyphenyl) -4-methylcyclohexa
And 1,1-bis- (4-hydroxyphenyl) -4-
It is described that t-butylcyclohexane is obtained.
You. Also, Japanese Patent Application Laid-Open No. H02-129155 discloses 4-
Starting from n-propylcyclohexanone and phenol
And 1,1-bis (4-hydroxyphenyl) -4-n
-To obtain propylcyclohexane.
You. Further, Japanese Patent Application Laid-Open No. 2000-63308 discloses 4-
(4-hydroxyphenyl) cyclohexanone and pheno
From 1,4,4-tris (4-hydroxy
To give (phenyl) cyclohexane.
You. [0004] Such 4-substituted cyclohexylidenebi
Sphenols are liquid crystalline resin raw materials, polycarbonate
Synthetic resin materials, photoresist for electronic display devices, semiconductors, etc.
It is useful in the field of raw materials for textiles. But these
In the field of 4-substituted cyclohexylidenebisph
The performance required for enols is also diversified and advanced.
And, as mentioned above, those previously known
Is, for example, odor resistance, lipophilicity, solubility in solvents, etc.
Not enough. Therefore, in recent years, performance such as solubility in a solvent has been improved.
Improved 4-substituted cyclohexylidenebisphenols
Kinds are strongly desired. The present inventors have to respond to the above-mentioned demands.
As a result of extensive research, cyclohexylidene
Phenyl-substituted amino at the 4-position of cyclohexyl
By introducing a alkyl group, solubility in a solvent,
Furthermore, a new 4-type which can be expected to improve heat resistance and lipophilicity
Obtaining substituted cyclohexylidenebisphenols
The inventors have found out what can be done and have led to the present invention. [0007] Accordingly, the present invention provides a system
A phenyl-substituted alkyl group at the 4-position of the clohexyl group
Novel 4-Substituted Cyclohexylidenebisphenol
The purpose is to provide a kind. [0008] The present invention provides a novel 4-
Substituted cyclohexylidenebisphenols have the general formula
(I) [0009] Embedded image (Wherein R₁And R_TwoAre independent of each other
A hydrogen atom or an alkyl group having 1 to 8 carbon atoms;
_ThreeRepresents an alkyl group having 1 to 4 carbon atoms, and n represents 0 to 3
Is an integer. ). [0011] DETAILED DESCRIPTION OF THE INVENTION Novel 4-substituted cycle according to the invention
Rohexylidene bisphenols are represented by the general formula (I)
It is represented by Where R₁And R_TwoAre each independently water
A hydrogen atom or an alkyl group having 1 to 8 carbon atoms,₁
And R_TwoMay be the same or different, but only
And preferably different. R₁Specifically,
Hydrogen atom, methyl group, ethyl group, propyl group, butyl
Group, pentyl group, hexyl group, heptyl group or octyl
Group, and when it is an alkyl group having 3 or more carbon atoms,
It may be linear or branched. Preferably, a hydrogen atom or
Is a methyl group. Also, R_TwoIs, specifically, a hydrogen source
, Methyl, ethyl, propyl, butyl, pen
A tyl, hexyl, heptyl or octyl group.
And when it is an alkyl group having 3 or more carbon atoms,
However, it may be branched. Preferably, methyl group, ethyl
Group, propyl group or butyl group. In the above general formula (I), R_ThreeIs
Represents an alkyl group having 1 to 4 carbon atoms, specifically, methyl
Group, ethyl group, propyl group or butyl group,
The benzyl group or the butyl group may be linear or branched. R
_ThreeIs an alkyl group, and when n is 2 or 3, R_Three
May be the same or different. R_ThreeIs preferably
Is a hydrogen atom or a methyl group, and n is preferably
0, 1 or 2. Thus, the 4-substituted cyclohexenes according to the invention
Specific examples of the silidene bisphenols include, for example,
1,1-bis (4-hydroxyphenyl) -4- [1-
(4-hydroxyphenyl) methyl] cyclohexane,
1,1-bis (4-hydroxyphenyl) -4- [1-
(4-hydroxyphenyl) ethyl] cyclohexane,
1,1-bis (4-hydroxyphenyl) -4- [1-
(4-hydroxyphenyl) -1-methylethyl] sic
Hexane, 1,1-bis (4-hydroxyphenyl)
-4- [1- (4-hydroxyphenyl) propyl] cy
Chlohexane, 1,1-bis (4-hydroxyphenyl)
) -4- [1- (4-hydroxyphenyl) butyl]
Cyclohexane, 1,1-bis (4-hydroxyphenyl
) -4- [1- (4-hydroxyphenyl) -2-me
Tylpropyl] cyclohexane, 1,1-bis (4-h
Droxyphenyl) -4- [1- (4-hydroxyphen)
Nyl) -1-ethylpropyl] cyclohexane, 1,1
-Bis (4-hydroxyphenyl) -4- [1- (4-
Hydroxyphenyl) pentyl] cyclohexane, 1,
1-bis (4-hydroxyphenyl) -4- [1- (4
-Hydroxyphenyl) -3-methylbutyl] cyclohe
Xane, 1,1-bis (4-hydroxyphenyl) -4
-[1- (4-hydroxyphenyl) -2-methylbutyi
L] cyclohexane, 1,1-bis (4-hydroxy
Enyl) -4- [1- (4-hydroxyphenyl) hexyl
Sil] cyclohexane, 1,1-bis (4-hydroxy
Phenyl) -4- [1- (4-hydroxyphenyl)-
4-methylpentyl] cyclohexane, 1,1-bis
(4-hydroxyphenyl) -4- [1- (4-hydro
[Xyphenyl) -2,3-dimethylbutyl] cyclohexyl
Sun, 1,1-bis (4-hydroxyphenyl) -4-
[1- (4-hydroxyphenyl) -3-methyl pliers
L] cyclohexane, 1,1-bis (4-hydroxy
Enyl) -4- [1- (4-hydroxyphenyl) -1
-Propylbutyl] cyclohexane, 1,1-bis (4
-Hydroxyphenyl) -4- [1- (4-hydroxy
Phenyl) heptyl] cyclohexane, 1,1-bis
(4-hydroxyphenyl) -4- [1- (4-hydro
[Xyphenyl) -5-methylhexyl] cyclohexa
1,1-bis (4-hydroxyphenyl) -4-
[1- (4-hydroxyphenyl) -3,4-dimethyl
Pentyl] cyclohexane, 1,1-bis (4-hydro
Xyphenyl) -4- [1- (4-hydroxyphenyl)
L) -3-ethylpentyl] cyclohexane, 1,1-
Bis (4-hydroxyphenyl) -4- [1- (4-h
[Droxyphenyl) -3-methylhexyl] cyclohex
Sun, 1,1-bis (4-hydroxyphenyl) -4-
[1- (4-hydroxyphenyl) octyl] cyclohe
Xane, 1,1-bis (4-hydroxyphenyl) -4
-[1- (4-hydroxyphenyl) -4-methylhept
Tyl] cyclohexane, 1,1-bis (4-hydroxy
Phenyl) -4- [1- (4-hydroxyphenyl) no
Nil] cyclohexane, 1,1-bis (4-hydroxy
Phenyl) -4- [1- (4-hydroxyphenyl)-
4-ethylheptyl] cyclohexane, 1,1-bis
(4-hydroxyphenyl) -4- [1- (4-hydro
Xylphenyl) -1-methylpropyl] cyclohexa
1,1-bis (4-hydroxyphenyl) -4-
(1- (4-hydroxyphenyl) -1-methylbuty
L] cyclohexane, 1,1-bis (4-hydroxy
Enyl) -4- [1- (4-hydroxyphenyl)-
1,2,2-trimethylpropyl] cyclohexane,
1,1-bis (4-hydroxyphenyl) -4- [1-
(4-hydroxyphenyl) -1-methylpentyl] si
Chlohexane, 1,1-bis (4-hydroxyphenyl)
Ru) -4- [1- (4-hydroxyphenyl) -1,3
-Dimethylbutyl] cyclohexane, 1,1-bis (4
-Hydroxyphenyl) -4- [1- (4-hydroxy
Phenyl) -1,2-dimethylbutyl] cyclohexa
1,1-bis (4-hydroxyphenyl) -4-
[1- (4-hydroxyphenyl) -1-methylhexyl
L] cyclohexane, 1,1-bis (4-hydroxy
Enyl) -4- [1- (4-hydroxyphenyl)-
1,4-dimethylpentyl] cyclohexane, 1,1-
Bis (4-hydroxyphenyl) -4- [1- (4-h
Droxyphenyl) -1,2,3-trimethylbutyl]
Cyclohexane, 1,1-bis (4-hydroxyphenyl
Ru) -4- [1- (4-hydroxyphenyl) -1,3
-Dimethylpentyl] cyclohexane, 1,1-bis
(4-hydroxyphenyl) -4- [1- (4-hydro
Xylphenyl) -1-methylheptyl] cyclohexa
1,1-bis (4-hydroxyphenyl) -4-
[1- (4-hydroxyphenyl) -1,4-dimethyl
Hexyl] cyclohexane, 1,1-bis (4-hydro
Xyphenyl) -4- [1- (4-hydroxyphenyl)
L) -1,3,4-trimethylpentyl] cyclohexa
1,1-bis (4-hydroxyphenyl) -4-
[1- (4-hydroxyphenyl) -1,3-dimethyl
Hexyl] cyclohexane, 1,1-bis (3-methyl
-4-hydroxyphenyl) -4- [1- (4-hydro
Xyphenyl) methyl] cyclohexane, 1,1-bis
(3-methyl-4-hydroxyphenyl) -4- [1-
(4-hydroxyphenyl) -1-methylethyl] sic
Hexane, 1,1-bis (3-methyl-4-hydroxy
Cyphenyl) -4- [1- (4-hydroxyphenyl)
Propyl] cyclohexane, 1,1-bis (3-methyl
-4-hydroxyphenyl) -4- [1- (4-hydro
Xylphenyl) -1-methylpropyl] cyclohexa
1,1-bis (3,5-dimethyl-4-hydroxy
Phenyl) -4- [1- (4-hydroxyphenyl) meth
Tyl] cyclohexane, 1,1-bis (3,5-dimethyl
4-Hydroxyphenyl) -4- [1- (4-hydr)
Roxyphenyl) -1-methylethyl] cyclohexa
1,1-bis (3,5-dimethyl-4-hydroxy
Phenyl) -4- [1- (4-hydroxyphenyl) p
Ropyl] cyclohexane, 1,1-bis (3,5-dimethyl
Tyl-4-hydroxyphenyl) -4- [1- (4-h
Droxyphenyl) -1-methylpropyl] cyclohex
Sun, 1,1-bis (2,3,5-trimethyl-4-hi
Droxyphenyl) -4- [1- (4-hydroxyphen)
Nyl) methyl] cyclohexane, 1,1-bis (2,
3,5-trimethyl-4-hydroxyphenyl) -4-
[1- (4-hydroxyphenyl) -1-methylethyl
L] cyclohexane, 1,1-bis (2,3,5-tri
Methyl-4-hydroxyphenyl) -4- [1- (4-
Hydroxyphenyl) propyl] cyclohexane, 1,
1-bis (2,3,5-trimethyl-4-hydroxyf
Enyl) -4- [1- (4-hydroxyphenyl) -1
-Methylpropyl] cyclohexane, 1,1-bis (3
-Ethyl-4-hydroxyphenyl) -4- [1- (4
-Hydroxyphenyl) methyl] cyclohexane, 1,
1-bis (3-ethyl-4-hydroxyphenyl) -4
-[1- (4-hydroxyphenyl) -1-methylethyl
L] cyclohexane, 1,1-bis (3-ethyl-4-
Hydroxyphenyl) -4- [1- (4-hydroxyf
Enyl) propyl] cyclohexane, 1,1-bis (3
-Ethyl-4-hydroxyphenyl) -4- [1- (4
-Hydroxyphenyl) -1-methylpropyl] cyclo
Hexane, 1,1-bis (3-isopropyl-4-hydride
Roxyphenyl) -4- [1- (4-hydroxyphenyl)
L) propyl] cyclohexane, 1,1-bis (2-meth
Tyl-5-tert-butyl-4-hydroxyphenyl) -4
-[1- (4-hydroxyphenyl) methyl] cyclohe
Xan, 1,1-bis (2-methyl-5-t-butyl-
4-hydroxyphenyl) -4- [1- (4-hydroxy
Cyphenyl) -1-methylethyl] cyclohexane,
1,1-bis (2-methyl-5-t-butyl-4-hydride
Roxyphenyl) -4- [1- (4-hydroxyphenyl)
L) propyl] cyclohexane, 1,1-bis (2-meth
Tyl-5-tert-butyl-4-hydroxyphenyl) -4
-[1- (4-hydroxyphenyl) -1-methylpro
Pill] cyclohexane, 1,1-bis (3,5-di-t
-Butyl-4-hydroxyphenyl) -4- [1- (4
-Hydroxyphenyl) methyl] cyclohexane 1,1-bis (3,5-di-t-butyl-4-hydroxy
Cyphenyl) -4- [1- (4-hydroxyphenyl)
-1-methylethyl] cyclohexane 1,1-bis (3,5-di-t-butyl-4-hydroxy
Cyphenyl) -4- [1- (4-hydroxyphenyl)
Propyl] cyclohexane 1,1-bis (3,5-di-t-butyl-4-hydroxy
Cyphenyl) -4- [1- (4-hydroxyphenyl)
-1-methylethyl] cyclohexane 1,1-bis (3,5-di-t-butyl-4-hydroxy
Cyphenyl) -4- [1- (4-hydroxyphenyl)
-1-methylpropyl] cyclohexane and the like
Can be. The 4-substituted cyclohexane according to the present invention as described above.
Xylidene bisphenols are, for example, represented by the general formula (II) [0015] Embedded image (Wherein R₁And R_TwoIs the same as above
You. ) And the general formula (II)
I) [0017] Embedded image (Wherein R_ThreeAnd n are the same as above.
You. ) Represented by the reaction solvent
By conducting a dehydration condensation reaction in the presence of an acid catalyst
Obtainable. As specific examples of the above substituted cyclohexanone,
And, for example, 1- (4-oxocyclohexyl) -1-
(4-hydroxyphenyl) methane, 1- (4-oxo
Cyclohexyl) -1- (4-hydroxyphenyl) d
Tanne, 1- (4-oxocyclohexyl) -1- (4
-Hydroxyphenyl) propane, 1- (4-oxo)
Clohexyl) -1- (4-hydroxyphenyl) buta
1- (4-oxocyclohexyl) -1- (4-h
Droxyphenyl) pentane, 1- (4-oxocyclo)
Hexyl) -1- (4-hydroxyphenyl) -3-me
Tylbutane, 1- (4-oxocyclohexyl) -1-
(4-hydroxyphenyl) hexane, 1- (4-oxo
Socyclohexyl) -1- (4-hydroxyphenyl)
Heptane, 1- (4-oxocyclohexyl) -1-
(4-hydroxyphenyl) octane, 1- (4-oxo
Socyclohexyl) -1- (4-hydroxyphenyl)
Nonane, 2- (4-oxocyclohexyl) -2- (4
-Hydroxyphenyl) propane, 2- (4-oxo)
Clohexyl) -2- (4-hydroxyphenyl) buta
2- (4-oxocyclohexyl) -2- (4-h
Droxyphenyl) pentane, 2- (4-oxocyclo)
Hexyl) -2- (4-hydroxyphenyl) -3-me
Tylbutane, 2- (4-oxocyclohexyl) -2-
(4-hydroxyphenyl) hexane, 2- (4-oxo
Socyclohexyl) -2- (4-hydroxyphenyl)
-3-methylpentane, 2- (4-oxocyclohexyl)
2-) (4-hydroxyphenyl) heptane, 2-
(4-oxocyclohexyl) -2- (4-hydroxy
Phenyl) octane, 2- (4-oxocyclohexyl)
Ru) -2- (4-hydroxyphenyl) nonane, 3-
(4-oxocyclohexyl) -3- (4-hydroxy
Phenyl) pentane and the like. Further, the above-mentioned (alkyl) phenols
For example, phenol, o-cresol, m
-Cresol, 2,3-xylenol, 2,5-xylen
Knol, 2,6-xylenol, 3,5-xylenol
3,3,5-trimethylphenol, 2,3,5-
Trimethylphenol, 2,3,6-trimethylpheno
, 3-methyl-6-t-butyl-phenol, 2-
Ethylphenol, 2-isopropylphenol, 2-
t-butylphenol, 2,6-di-t-butylpheno
And the like. The above substituted cyclohexanone is, for example,
General formula (IV) [0022] Embedded image (Wherein R₁And R_TwoIs the same as above
You. Bis (4-hydroxyphenyl) al represented by)
Selective cans in reaction solvent in the presence of palladium catalyst
It can be obtained by hydrogenation. The above substituted cyclohexanone and (alkyl
L) In the reaction with phenols, (alkyl)
The anols are used per mole of the substituted cyclohexanone,
Usually, it is used in the range of 4 to 20 mol parts. The above substituted cyclohexanones and (alkyl
B) In the reaction with phenols, the reaction solvent is used
May not be used. When using a reaction solvent
If, for example, aliphatic alcohols, aromatic hydrocarbons or
These mixed solvents are used. As alcohol,
Reaction materials, solubility of the resulting product, reaction conditions,
In consideration of economical efficiency, methanol, ethanol,
Isopropyl alcohol, n-propyl alcohol, t-
Butyl alcohol, isobutyl alcohol, n-butyl
Alcohol and the like can be mentioned. In addition, aromatic carbonization
Examples of the hydrogen solvent include toluene, xylene,
And the like. Such solvents are usually
For 100 parts by weight of the substituted cyclohexanone used, 1
Used in the range of 00 to 500 parts by weight, but limited to this
It is not done. As the acid catalyst, hydrochloric acid or dry chloride water is used.
Raw gas is preferably used. But limited to this
Not sulfuric acid, sulfuric anhydride, p-tolue
Sulfonic acid, methanesulfonic acid, trifluoromethane
Sulfonic acid, oxalic acid, formic acid, phosphoric acid, trichlorovinegar
Acids, trifluoroacetic acid and the like are also used. Furthermore, the present invention
According to the report, mercaptan or the like (eg,
Octyl mercaptan).
Wear. The reaction is usually carried out at a temperature of from 20.degree.
At 20 to 50 ° C, add hydrochloric acid to the reaction mixture in the reactor.
Or dry hydrogen chloride gas
2 to 48 hours under stirring, usually 6 to 24 hours
Just do it. After completion of the reaction, the resulting reaction mixture is usually
After neutralizing the acid catalyst by adding an alkali,
Add a crystallization solvent or separate and remove the aqueous layer.
First, after distilling the obtained organic layer under normal pressure or reduced pressure,
Add a suitable crystallization solvent to this to precipitate coarse crystals.
Then, the crude crystals are collected by filtration and further filtered.
The desired 4-position is obtained by crystallization from the precipitation solvent.
Obtain high purity products of substituted cyclohexylidenebisphenols
Can be As the above-mentioned crystallization solvent, specifically,
Appropriately selected in consideration of conditions, refining effect, economics, etc.
However, as the aromatic hydrocarbon, for example, toluene, xylene
Len, cumene or the like is used. Also aliphatic alcohol
As aliphatic ketones such as methanol and ethanol
For example, acetone, methyl isopropyl keto
, Methyl ethyl ketone, methyl isobutyl ketone,
Tetracyclic ethers such as isopropyl ketone
Hydrofuran, dioxane and the like are used. The novel 4-substituted cyclohexyl according to the invention
Riden bisphenols have three aromatic rings in the molecule.
And a cyclohexane ring and an alkyl substituent in the molecule.
Has high heat resistance, lipophilicity, and solvent affinity
Is expected. Further, the 4-substituted cycle according to the present invention
Rohexylidene bisphenols are used as raw materials
And various reactions, for example, on phenolic aromatic rings
Substitution reaction, hydrogenation reaction, reaction against phenolic hydroxyl group
Various derivatives can be obtained by performing
Wear. [0031] The present invention will be described below with reference to examples.
The present invention is not limited by these examples.
No. In the following, the reaction product which is the object of the present invention
Purity is the value of area percentage by liquid chromatography.
is there. Reference Example 1 (1- (4-oxocyclohexyl) -1- (4-hydr)
Production of loxyphenyl) propane 1,1-di (4-hydroxyphenyl) propane 100
g (0.439 mol) and 150 g of ethyl acetate.
About 1.5% by weight of thorium and 5% by weight of palladium
Palladium-carbon catalyst supported on carbon powder
3.0 g (equivalent to the dry weight of the hydrous catalyst) was added to a 1 L gas
Charge into a lath autoclave.
After the temperature has risen to 0 ° C, the internal pressure is released and the pressure (gauge
Pressure) was set to 0 MPa. Next, the autoclave is closed, and the internal temperature is reduced.
After heating to 140 ° C, hydrogen was introduced into the autoclave.
It was introduced up to 0.5 MPa. After this, in the autoclave
Hydrogen as appropriate so as to maintain the hydrogen pressure at 0.5 MPa.
While replenishing in the autoclave, 1,1-di (4-H
Hydrogenation of (doxyphenyl) propane
The amount of hydrogen absorbed in the reave is the theoretical amount of hydrogen absorbed (
When the amount becomes 1.1 times the molar amount (2 times the molar amount)
5 hours later). As a result, conversion of raw materials
The rate was 94.2% and the selectivity of the target was 92.2%.
there were. After the completion of the reaction, the temperature in the autoclave is reduced to 70 ° C.
After the temperature was reduced and the atmosphere was replaced with nitrogen gas, the catalyst was filtered off at 65 ° C.
Was. The obtained filtrate was concentrated by heating, and 50 g of ethyl acetate was distilled off.
After discharging, the concentrate was cooled to room temperature, and the precipitated crystals were collected.
It is collected by filtration, dried and 1- (4-oxocyclohexyl)
58.0 g of -1- (4-hydroxyphenyl) propane
Was obtained as white crystals. Purity is 99.2% (gas chroma
By tomographic analysis. ) And the yield is 56.5%.
Met. Embodiment 1 (1,1-bis (4-hydroxyphenyl) -4- [1
-(4-hydroxyphenyl) propyl] cyclohexa
Manufacturing) 2 L equipped with thermometer, dropping funnel, reflux condenser and stirrer
Phenol 307.2 g (3.2
Mol) and 243.1 g of 35% hydrochloric acid in a reaction vessel.
Was replaced with nitrogen, and the temperature was raised to 40 ° C. under normal pressure. The 1- (4-oxocyclohexene obtained in Reference Example 1
Xyl) -1- (4-hydroxyphenyl) propane 1
50.0 g (0.65 mol) of phenol 193.0 g
(2.1 mol) to prepare a solution. Hula above
This solution was added to 1.
It was added dropwise over 5 hours. After dropping, the temperature is further increased to 40 ° C.
For 16 hours with stirring. After completion of the reaction, 16% was added to the obtained reaction mixture.
An aqueous sodium hydroxide solution was added for neutralization. After neutralization
The aqueous layer was separated and removed from the reaction mixture to obtain an oil layer mixture.
Next, phenol was removed from the oil layer mixture by distillation under reduced pressure.
After removal, the desired 1,1-bis (4-hydroxy
Enyl) -4- [1- (4-hydroxyphenyl) pro
[Pyr] cyclohexane was obtained. to this
A mixed solution of toluene, methyl isobutyl ketone and water
In addition, crystallization filtration is performed.
Certain 1,1-bis (4-hydroxyphenyl) -4-
[1- (4-hydroxyphenyl) propyl] cyclohe
110 g of xane was obtained as white crystals. Purity 94.9
%Met. This is further treated with heptane and methyl isobutyl ketone.
Tons and a mixture of water, crystallize, filter, dry and
1,1-bis (4-hydroxyphenyl) having a purity of 99.0%
) -4- [1- (4-Hydroxyphenyl) propyl
L] cyclohexane was obtained as white crystals. 1
-(4-oxocyclohexyl) -1- (4-hydroxy
The yield based on (cyphenyl) propane was 40.2 mol%.
there were. Melting point (differential thermal analysis): 149 ° C., 133
° C Molecular weight (mass spectrometry, M⁺): 402 Infrared absorption spectrum (KBr method): Hydroxyl group: 3510.2cm^-1, 1243.0cm^-1 Benzene ring: 1612.4 to 1510.2 cm^-1 Cyclohexane ring: 1451.3cm^-1 Proton NMR (400 MHz, solvent DMSO-d): [0040] Embedded image[0041] [Table 1] Reference Example 2 (2- (4-oxocyclohexyl) -2- (4-hydrido
Production of roxyphenyl) butane) 100 g of 2,2-di (4-hydroxyphenyl) butane
(0.413 mol) as a raw material
The medium was changed from ethyl acetate to 2-butanol.
5% by weight of palladium on carbon powder
3g of palladium-carbon catalyst (dry of hydrous catalyst)
0.1 g of sodium carbonate as co-catalyst
Reference Example except that the reaction pressure was set to 0.4 MPa using
Reaction was carried out in the same manner as in Example 1 for 2.5 hours. as a result,
The conversion rate of the raw material is 95.5%, and the selectivity of the target substance is 9%.
It was 4.9%. After the completion of the reaction, the temperature in the autoclave was reduced to 90 ° C.
After the temperature was reduced and the atmosphere was replaced with nitrogen gas, the catalyst was filtered off at 80 ° C.
Was. The obtained filtrate is heated and concentrated to give 2-butanol 75.
After distilling g, the concentrate was cooled to room temperature and precipitated.
The crystals are collected by filtration, dried and dried to give 2- (4-oxocyclohexyl).
Sil) -2- (4-hydroxyphenyl) butane
9 g were obtained as white crystals. Purity is 98.8% (gask
By chromatographic analysis. ) And the yield is 56.
3%. Embodiment 2 (1,1-bis (4-hydroxyphenyl) -4- [1
-(4-hydroxyphenyl) -1-methylpropyl]
Production of cyclohexane) 30 equipped with thermometer, dropping funnel, reflux condenser and stirrer
Phenol 47.0 g in a 0 mL four-necked flask
(0.5 mol) and 37.6 g of 35% hydrochloric acid
After the atmosphere in the vessel was replaced with nitrogen, the temperature was raised to 40 ° C under normal pressure.
Was. The 2- (4-oxocyclohexene obtained in Reference Example 2
Xyl) -2- (4-hydroxyphenyl) butane 2
4.6 g (0.1 mol) dissolved in 28.2 g of phenol
Thus, a solution was prepared. Under stirring in the flask, 40
The solution was added dropwise over 2 hours while maintaining the temperature. drop
After completion of the lower step, the mixture is further stirred at a temperature of 40 ° C. for 23 hours.
The reaction was performed. After the completion of the reaction, 16% was added to the obtained reaction mixture.
An aqueous sodium hydroxide solution was added for neutralization. After neutralization
The aqueous layer was separated and removed from the reaction mixture to obtain an oil layer mixture.
Next, phenol was removed from the oil layer mixture by distillation under reduced pressure.
After removal, the desired 1,1-bis (4-hydroxy
Enyl) -4- [1- (4-hydroxyphenyl) -1
-Methylpropyl] cyclohexane
Obtained. This is mixed with toluene and methyl isobutyl ketone.
The combined solution was added, and the mixture was crystallized and filtered.
The desired 1,1-bis (4-hydroxyphenyl)
) -4- [1- (4-hydroxyphenyl) -1-me
Tylpropyl] cyclohexane as white crystals
I got it. Purity is 91.7%, 2- (4-oxo)
Cyclohexyl) -2- (4-hydroxyphenyl) bu
The yield based on tan was 50.7 mol%. Melting point (differential thermal analysis): 224 ° C. Molecular weight (mass spectrometry, M⁺): 416 Infrared absorption spectrum (KBr method): Hydroxyl group: 3304.8 cm^-1, 1242.1cm^-1 Benzene ring: 1612.4 to 1510.2 cm^-1 Cyclohexane ring: 1458.1 to 1448.4 cm^-1 Proton NMR (400 MHz, solvent DMSO-d): [0048] Embedded image[0049] [Table 2] Reference Example 3 (2- (4-oxocyclohexyl) -2- (4-hydrido
Production of roxyphenyl) octane) 2,2-di (4-hydroxyphenyl) octane 100
g (0.336 mol) and 150 g of 2-butanol
About 1.5% by weight of sodium and 5% by weight of palladium
Carbon supported on carbon powder
3.0 g of catalyst (equivalent to dry weight of hydrous catalyst) in 1 L capacity
Into a glass autoclave, inside the autoclave
After the temperature is raised to 70 ° C, the internal pressure is released and the pressure
Pressure) was set to 0 MPa. Next, the autoclave was closed, and the internal temperature was reduced.
After heating to 140 ° C, hydrogen was introduced into the autoclave.
It was introduced up to 0.4 MPa. After this, in the autoclave
Hydrogen as appropriate to keep the hydrogen pressure of 0.4 MPa
While replenishing in the autoclave, 2,2-di (4-H
Hydrogenation of (doxyphenyl) octane
The amount of hydrogen absorbed in the reave is the theoretical amount of hydrogen absorbed (
When the amount becomes 1.1 times the molar amount (2 times the molar amount)
4.5 hours later). As a result,
The conversion was 98.5%, and the selectivity of the target product was 86.3.
%Met. After the completion of the reaction, the inside of the autoclave is kept at 90 ° C.
After the temperature was reduced and the atmosphere was replaced with nitrogen gas, the catalyst was filtered off at 80 ° C.
Was. The obtained filtrate was evaporated to dryness to give 2- (4-oxo).
Cyclohexyl) -2- (4-hydroxyphenyl) o
83.0% by weight of octane (for gas chromatography analysis)
According to ) Was obtained. Embodiment 3 (1,1-bis (4-hydroxyphenyl) -4- [1
-(4-hydroxyphenyl) -1-methylheptyl]
Production of cyclohexane) 50 equipped with thermometer, dropping funnel, reflux condenser and stirrer
18.2 g of phenol in a 0 mL four-necked flask
(0.2 mol) and 18.0 g of 35% hydrochloric acid
After the atmosphere in the vessel was replaced with nitrogen, the temperature was raised to 40 ° C under normal pressure.
Was. The 2- (4-oxocyclohexene obtained in Reference Example 3 was obtained.
Xyl) -2- (4-hydroxyphenyl) octane 1
6.5 g (0.1 mol) dissolved in 18.9 g of phenol
Thus, a solution was prepared. Under stirring in the flask, 40
The solution was added dropwise over 1 hour while maintaining the temperature. drop
After completion of the lower step, the mixture is further stirred under
The reaction was performed. After completion of the reaction, 16% was added to the obtained reaction mixture.
An aqueous sodium hydroxide solution was added for neutralization. After neutralization
The aqueous layer was separated and removed from the reaction mixture to obtain an oil layer mixture.
Next, phenol was removed from the oil layer mixture by distillation under reduced pressure.
After removal, the desired 1,1-bis (4-hydroxy
Enyl) -4- [1- (4-hydroxyphenyl) -1
-Methylheptyl] cyclohexane
Obtained. This was purified by preparative liquid chromatography,
After drying, the desired 1,1-bis (4-hydroxy
Phenyl) -4- [1- (4-hydroxyphenyl)-
1-Methylheptyl] cyclohexane 198 mg in white
Obtained as crystals. Purity was 97.2%. Melting point (differential thermal analysis): 73.7 ° C. Molecular weight (mass spectrometry, M⁺): 472 Infrared absorption spectrum (KBr method): Hydroxyl group: 3253.7 cm^-1, 1238.2cm^-1 Benzene ring: 1611.4cm^-1, 1511.1c
m^-1, 1489.9 cm^-1 Cyclohexane ring: 1489.9 cm^-1 Proton NMR (400 MHz, solvent DMSO-d): [0057] Embedded image[0058] [Table 3] Reference Example 4 (2- (4-oxocyclohexyl) -2- (4-hydrido
Production of loxyphenyl) propane 2,2-bis (4-hydroxyphenyl) propane 10
0 g (0.439 mol) and 150 g of butyl acetate,
About 1.5% by weight of sodium and 5% by weight of palladium
Palladium-carbon catalyst supported on carbon powder
3.0 g (equivalent to the dry weight of the hydrous catalyst) was added to a 1 L gas
Charge into a lath autoclave.
After the temperature has risen to 0 ° C, the internal pressure is released and the pressure (gauge
Pressure) was set to 0 MPa. Next, the autoclave is closed, and the internal temperature is reduced.
1 After heating to 25 ° C, hydrogen was
It was introduced up to 0.2 MPa. After this, in the autoclave
Hydrogen as appropriate to keep the hydrogen pressure of 0.2 MPa
While replenishing in the autoclave, 2,2-bis (4-
Hydrogenation of (hydroxyphenyl) propane and auto
The amount of hydrogen absorbed in the clave is the theoretical amount of hydrogen absorbed
0.86 times the amount (2 times the molar amount of
(1.9 hours after the beginning), the reaction was completed. After completion of the reaction, the internal temperature of the autoclave was raised to 80 ° C.
After the temperature has been lowered and the system has been replaced with nitrogen gas, the catalyst is filtered off.
did. The obtained filtrate containing the target substance is subjected to crystallization filtration and dried.
To obtain the desired product, 2- (4-oxocyclohexyl)-
48.7 g of 2- (4-hydroxyphenyl) propane
Obtained as white crystals. Purity is 97.7%, 2,2-bis
The yield based on (4-hydroxyphenyl) propane is 4
It was 6.8%. Embodiment 4 (1,1-bis (4-hydroxyphenyl) -4- [1
-(4-hydroxyphenyl) -1-methylethyl] si
Production of Clohexane) 1 L equipped with thermometer, dropping funnel, reflux condenser and stirrer
Phenol 42.3 g (0.45
Mol) and 56.3 g of 35% hydrochloric acid.
After purging with nitrogen, the temperature was raised to 40 ° C. under normal pressure. The 2- (4-oxocyclohexene) obtained in Reference Example 4 was obtained.
Xyl) -2- (4-hydroxyphenyl) propane 3
5.6 g (0.15 mol) of phenol 70.5 g
(0.75 mol) to prepare a solution. Above
While stirring at 40 ° C. in a Lasco, add this solution to 2
It was dropped over time. After dropping, further raise the temperature to 40 ° C.
The reaction was carried out with stirring for 22 hours. After completion of the reaction, 16% was added to the obtained reaction mixture.
An aqueous sodium hydroxide solution was added for neutralization. After neutralization
The aqueous layer was separated and removed from the reaction mixture to obtain an oil layer mixture.
Next, phenol was removed from the oil layer mixture by distillation under reduced pressure.
After removal, the desired 1,1-bis (4-hydroxy
Enyl) -4- [1- (4-hydroxyphenyl) -1
-Methylethyl] cyclohexane
Was. This is mixed with a mixed solution of methyl isobutyl ketone and water.
And wash with water, then add toluene to the oil layer after separation of the aqueous layer.
, Followed by crystallization filtration and drying.
Bis (4-hydroxyphenyl) -4- [1- (4-h
Droxyphenyl-1-methylethyl)] cyclohexa
Thus, 24.5 g of crude crystals containing the compound were obtained. This crude crystal is
It was dissolved again in ethyl ketone, and toluene was further added.
Thereafter, the resultant was subjected to crystallization filtration and drying, and the mixture was dried at a purity of 92.6%.
2- (4-hydroxyphenyl) -4- [1- (4-hydrido)
Roxyphenyl-1-methylethyl)] cyclohexane
16.6 g of purified product was obtained as white crystals. 2- (4-
Oxocyclohexyl) -2- (4-hydroxyphenyl)
G) The yield based on propane was 24.5 mol%. Melting point (differential thermal analysis): 233 ° C. Molecular weight (mass spectrometry, M⁺): 402 Infrared absorption spectrum (KBr method): Hydroxyl group: 3357.8 cm^-1, 1239.2cm^-1 Benzene ring: 1610.5 to 1510.2cm^-1 Cyclohexane ring: 1465.8 cm^-1 Proton NMR (400 MHz, solvent DMSO-d): [0066] Embedded image [0067] [Table 4] Embodiment 5 (1,1-bis (3,5-dimethyl-4-hydroxyf
Enyl) -4- [1- (4-hydroxyphenyl) pro
Production of pill] cyclohexane 2 L equipped with thermometer, dropping funnel, reflux condenser and stirrer
2,6-dimethylphenol 6 in a four-neck flask
6.2 g (0.54 mol) were charged, and the inside of the reaction vessel was filled with nitrogen.
After the replacement, the temperature was raised to 50 ° C. under normal pressure. Next, dry hydrogen chloride gas is placed in the reaction vessel.
While blowing 1- in the same manner as in Reference Example 1.
(4-oxocyclohexyl) -1- (4-hydroxy
Phenyl) propane 30.8 g (0.13 mol, purity 9)
7.5%) in 60 g of 2,6-dimethylphenol (0.5%).
49 mol) was kept at 50 ° C. while stirring.
The solution was dropped over 2 hours. After completion of dropping,
The reaction was carried out at 50 ° C. with stirring for 21 hours. After completion of the reaction, 16%
An aqueous sodium hydroxide solution was added for neutralization. After neutralization
The aqueous layer was separated and removed from the reaction mixture to obtain an oil layer mixture.
Next, 2,6-dimethyl was obtained from the oil layer mixture by distillation under reduced pressure.
By removing tylphenol, the desired 1,1-bis
(4-hydroxyphenyl) -4- [1- (4-hydro
Distillation residue containing (xylphenyl) propyl] cyclohexane
A distillate was obtained. Add a mixed solution of toluene and water
To remove water from the oil layer after separation of the aqueous layer.
After distilling off a portion, crystallization filtration and drying were performed to obtain the target product 1,
1-bis (3,5-dimethyl-4-hydroxyphenyl)
) -4- [1- (4-Hydroxyphenyl) propyl
[1] 43.3 g of crude crystals containing cyclohexane were obtained. This
Was re-dissolved in methyl ethyl ketone.
After adding ruene, crystallization filtration and drying were carried out to give a purity of 95.1.
% Of 1,1-bis (3,5-dimethyl-4-hydroxy
Phenyl) -4- [1- (4-hydroxyphenyl) p
[Ropyl] cyclohexane 23.7 g as white crystals
As obtained. 1- (4-oxocyclohexyl) -1-
The yield based on (4-hydroxyphenyl) propane is 3
It was 7.5 mol%. Melting point (differential thermal analysis): 138.4 ° C., 1
52.8 ° C Molecular weight (mass spectrometry, M⁺): 458 Infrared absorption spectrum (KBr method): Hydroxyl group: 3379.1 cm^-1 Benzene ring: 1611.4-1488.9 cm^-1 Cyclohexane ring: 1451.3cm^-1 Proton NMR (400 MHz, solvent CD_ThreeOD) [0072] Embedded image [0073] [Table 5]

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Miwa             5-115 Kozaiga, Wakayama-shi Honshu             Gaku Kogyo Co., Ltd. (72) Inventor Mikio Kawahara             5-115 Kozaiga, Wakayama-shi Honshu             Gaku Kogyo Co., Ltd. (72) Inventor Takeshi Egawa             5-115 Kozaiga, Wakayama-shi Honshu             Gaku Kogyo Co., Ltd. F-term (reference) 4H006 AA01 AA03 AB46 AB64 AB91                       FC22 FC50 FE13

Claims (1)

[Claim 1] A compound represented by the general formula (I): (Wherein, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ₃ represents an alkyl group having 1 to 4 carbon atoms, and n represents 0 to 3 4-substituted cyclohexylidenebisphenols represented by an integer.).