JP2002234856A - METHOD FOR PRODUCING 4,4"-DIHYDROXY-p-TERPHENYL COMPOUNDS - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a highly pure 4,4"-dihydroxy-p- terphenyl compound, especially having one to three substituents on one terminal 4-hydroxyphenyl group of the molecule, in a high yield by a reaction using industrially easily available raw materials and under industrially easily performable reaction conditions. SOLUTION: This method for producing the 4,4"-dihydroxy-p-terphenyl compound represented by general formula (II) [R groups are each a 1 to 12C alkyl, alkoxy or haloalkoxy, a 5 to 5C cycloalkyl, cycloalkoxy or halocycloalkoxy, phenyl or hydroxy; (n) is an integer of 0 to 3] comprises thermally decomposing a hydroxyphenyl-substituted cyclohexylidenebisphenol compound represented by general formula (I) and then subjecting the obtained reaction mixture to a dehydrogenation reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing 4,4 "-dihydroxy-p-terphenyls, and more particularly, to synthetic resin materials such as liquid crystal polyesters, polycarbonates and polyurethanes, display devices, and photoconductors such as semiconductors. The present invention relates to a production method capable of obtaining 4,4 "-dihydroxy-p-terphenyls, which are expected to be useful for applications such as resist raw materials, with high purity and high yield.

[0002]

2. Description of the Related Art Conventionally, methods for producing 4,4 "-dihydroxy-p-terphenyls are described in, for example,
Japanese Patent No. 212449 discloses a method in which 4-methoxy-4'-bromobiphenyl and 4-methoxy-3-phenylmagnesium bromide are subjected to Grignard coupling and then demethylated. However, according to this method, a special raw material is used, and the Grignard reaction is performed. Therefore, the production cost is extremely high, and it is difficult to implement industrially.

Japanese Patent Application Laid-Open No. 1-168632 discloses that 1,1,4,4-tetrakis (4-hydroxyphenyl) cyclohexane is produced from 1,4-cyclohexanedione and phenol, and is thermally decomposed. Later, a method for dehydrogenation is disclosed. However, according to this method, the production of 1,1,4,4-tetrakis (4-hydroxyphenyl) cyclohexane from 1,4-cyclohexanedione and phenol has a low reaction yield and a high raw material production cost. Further, according to this method, it is necessary to carry out the reaction at a high temperature under pressure using an autoclave. Moreover, due to the thermal decomposition and dehydrogenation of 1,1,4,4-tetrakis (4-hydroxyphenyl) cyclohexane, an asymmetric 4,4 group having a substituent only at one terminal 4-hydroxyphenyl group of the molecule. "-Dihydroxy-p-terphenyls cannot be prepared.

[0004]

SUMMARY OF THE INVENTION The present invention is directed to a 4,4 "-
The present invention has been made in order to solve the above-mentioned problems in the production of dihydroxy-p-terphenyls, and an object of the present invention is to use raw materials that are easily available industrially and to make industrially easy to use. The reaction is carried out under a variety of reaction conditions, in particular, an asymmetrical 4,4 ″ -dihydroxy-p-terter having only a 4-hydroxyphenyl group at one end of the molecule, for example, having a substituent such as an alkyl group. An object of the present invention is to provide a method for producing phenyls with high yield and high purity.

[0005]

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

[0006]

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Wherein R is an alkyl group having 1 to 12 carbon atoms, an alkoxyl group or a haloalkoxyl group, a cycloalkyl group having 5 or 6 carbon atoms,
A cycloalkoxyl group, a halocycloalkoxyl group, a phenyl group or a hydroxyl group;
Is an integer. ), Wherein the hydroxyphenyl-substituted cyclohexylidenebisphenols are thermally decomposed, and the resulting reaction mixture is subjected to a dehydrogenation reaction.

[0008]

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(Wherein R and n are the same as above)
And a method for producing 4,4 "-dihydroxy-p-terphenyls represented by the formula:

Further, according to the present invention, there is provided a compound of formula (III)

[0011]

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4- (4-hydroxyphenyl) cyclohexanone represented by the general formula (IV)

[0013]

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Wherein R is an alkyl group, an alkoxyl group or a haloalkoxyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 or 6 carbon atoms,
A cycloalkoxyl group, a halocycloalkoxyl group, a phenyl group or a hydroxyl group;
Is an integer. Is reacted in the presence of an acid catalyst to give a compound of the general formula (I)

[0015]

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(Wherein, R and n are the same as above)
Producing a hydroxyphenyl-substituted cyclohexylidenebisphenol represented by the following formula, pyrolyzing it, and subjecting the resulting reaction mixture to a dehydrogenation reaction:

[0017]

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(Wherein, R and n are the same as above)
And a method for producing 4,4 "-dihydroxy-p-terphenyls represented by the formula:

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION According to the process for producing 4,4 "-dihydroxy-p-terphenyls of the present invention, a starting material represented by the general formula (I)

[0020]

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(Wherein R is an alkyl group having 1 to 12 carbon atoms, an alkoxyl group or a haloalkoxyl group, a cycloalkyl group having 5 or 6 carbon atoms,
A cycloalkoxyl group, a halocycloalkoxyl group, a phenyl group or a hydroxyl group;
Is an integer. The hydroxyphenyl-substituted cyclohexylidenebisphenols represented by the formula (1) are used.

In the hydroxyphenyl-substituted cyclohexylidenebisphenols represented by the above general formula (I), R represents an alkyl group having 1 to 12 carbon atoms, an alkoxyl group or a haloalkoxyl group, each having 5 or 6 carbon atoms. It represents a cycloalkyl group, a cycloalkoxyl group or a halocycloalkoxyl group, a phenyl group or a hydroxyl group, and n is an integer of 0 to 3.

As the above alkyl group having 1 to 12 carbon atoms,
Specific examples include, in addition to a methyl group or an ethyl group, a linear or branched alkyl group having 3 or more carbon atoms. Specific examples thereof include, for example, an isopropyl group and a t-butyl group. , N-heptyl group, n-decyl group and the like. Examples of the cycloalkyl group having 5 or 6 carbon atoms include a cyclopentyl group and a cyclohexyl group.

Specific examples of the alkoxyl group having 1 to 12 carbon atoms include a methoxyl group or an ethoxyl group and a linear or branched alkoxyl group having 3 or more carbon atoms, such as a propoxyl group, Examples include an isopropoxyl group, a t-butoxyl group, a s-butoxyl group, an n-heptoxyl group, and an n-decyloxyl group. Examples of the cycloalkoxy group having 5 or 6 carbon atoms include a cyclopentoxyl group and a cyclohexoxy group.

Examples of the haloalkoxyl group having 1 to 12 carbon atoms include, for example, monochloromethoxyl, dichloromethoxyl, monochloroethoxyl, monochloroisopropoxyl, monobromomethoxyl, dibromomethoxyl Group, monobromoethoxyl group, difluoromethoxyl group, trifluoromethoxyl group and the like. Examples of the halocycloalkoxyl group having 5 or 6 carbon atoms include a chlorocyclopentoxyl group and a chlorocyclohexoxy group.

Among these, R is preferably an alkyl group having 1 to 6 carbon atoms, an alkoxyl group, a haloalkoxyl group, a phenyl group or a hydroxyl group.

Accordingly, specific examples of the hydroxyphenyl-substituted cyclohexylidenebisphenols represented by the general formula (I) include, for example, 1- (4-hydroxyphenyl) -4,4-bis (4- (Hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl)
-4,4-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl)
-4,4-bis (2-methyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl)
-4,4-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (3,6-dimethyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (2,3,5-trimethyl-4
-Hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (2,3,6-trimethyl-4-hydroxyphenyl) cyclohexane,
-(4-hydroxyphenyl) -4,4-bis (3-ethyl-4-hydroxyphenyl) cyclohexane, 1-
(4-hydroxyphenyl) -4,4-bis (2-ethyl-4-hydroxyphenyl) cyclohexane, 1-
(4-hydroxyphenyl) -4,4-bis (3-isopropyl-4-hydroxyphenyl) cyclohexane,
1- (4-hydroxyphenyl) -4,4-bis (2-
Isopropyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (3-isobutyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis ( 2-isobutyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-
Bis (3-s-butyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4
-Bis (2-s-butyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,
4-bis (3-isopropyl-6-methyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (3-isopropyl-5-methyl) -4-hydroxyphenyl) cyclohexane, 1
-(4-hydroxyphenyl) -4,4-bis (3-t
-Butyl-6-methyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4
-Bis (3,5-di-t-butyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (3-n-heptyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (3-cyclohexyl-
6-methyl-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (3,5-dicyclohexyl-4-hydroxyphenyl) cyclohexane 1- (4-hydroxyphenyl) -4,4 -Screw (3-
Methoxy-4-hydroxyphenyl) cyclohexane,
1- (4-hydroxyphenyl) -4,4-bis (2-
Methoxy-4-hydroxyphenyl) cyclohexane,
1- (4-hydroxyphenyl) -4,4-bis (3-
t-butoxy-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (2-monochloromethoxy-4-hydroxyphenyl)
Cyclohexane, 1- (4-hydroxyphenyl)-
4,4-bis (3-trifluoromethoxy-4-hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (3-phenyl-4-hydroxyphenyl) cyclohexane, 1- (4- (Hydroxyphenyl) -4,4-bis (3,5-diphenyl-4-
(Hydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (2,4-dihydroxyphenyl) cyclohexane, 1- (4-hydroxyphenyl) -4,4-bis (3,4-dihydroxyphenyl) ) Cyclohexane, 1- (4-hydroxyphenyl)
-4,4-bis (2,3,4-trihydroxyphenyl) cyclohexane and the like can be mentioned.

In the method of the present invention, the starting material, that is, the hydroxyphenyl-substituted cyclohexylidenebisphenol represented by the above general formula (I) is, for example, disclosed in
As described in JP-A-00-63308, it can be easily obtained by reacting 4- (4-hydroxyphenyl) cyclohexanone with a substituted phenol in the presence of an acid catalyst.

In the present invention, the thermal decomposition of the above hydroxyphenyl-substituted cyclohexylidenebisphenols is
The reaction may be performed in the absence of a catalyst, but is preferably performed in the presence of an alkali catalyst. Examples of the alkali catalyst include, but are not particularly limited to, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; Sodium hydrogen, alkali metal bicarbonates such as potassium bicarbonate, sodium phenoxide, alkali metal phenoxides such as potassium phenoxide, magnesium hydroxide, calcium hydroxide, alkaline earth metal hydroxides such as barium hydroxide and the like. it can. Among these, sodium hydroxide or potassium hydroxide is particularly preferably used.

In the present invention, when an alkali catalyst is used, the alkali catalyst is usually used in an amount of 0.01 to 30 parts by weight, preferably 100 parts by weight, based on 100 parts by weight of the hydroxyphenyl-substituted cyclohexylidenebisphenol.
It is used in the range of 0.1 to 10 parts by weight. The form of use of the catalyst is not particularly limited, but is preferably used as an aqueous solution of 10 to 50% by weight from the viewpoint of easy charging operation.

According to the present invention, the thermal decomposition of the above hydroxyphenyl-substituted cyclohexylidenebisphenols is
In order to improve the liquidity of the hydroxyphenyl-substituted cyclohexylidenebisphenols at the thermal decomposition temperature, since the melting points of the raw materials, ie, the hydroxyphenyl-substituted cyclohexylidenebisphenols and / or the reaction products obtained by the thermal decomposition thereof, are high. In order to prevent thermal polymerization of the reaction product due to the thermal decomposition, the reaction is preferably performed in the presence of a reaction solvent. According to the present invention, the reaction product obtained by the thermal decomposition of the above-mentioned hydroxyphenyl-substituted cyclohexylidenebisphenols is 1,4-bis (4) based on the structure of the reaction product obtained by the dehydrogenation reaction.
-Hydroxyphenyl) -1-cyclohexene.

The reaction solvent is not particularly limited as long as it is inert at the thermal decomposition temperature and does not distill from the reaction mixture.
Triethylene glycol, tetraethylene glycol,
Polyethylene glycols such as pentaethylene glycol, polypropylene glycols such as tripropylene glycol and tetrapropylene glycol, and polyhydric alcohols such as glycerin are used. In addition, commercially available organic heat mediums such as "Therm S" (manufactured by Nippon Steel Chemical Co., Ltd.) and "SK-OIL" (manufactured by Soken Chemical Co., Ltd.) are also used.

According to the present invention, such a solvent is used in an amount of usually 10 to 150 parts by weight, preferably 30 to 100 parts by weight, based on 100 parts by weight of the hydroxyphenyl-substituted cyclohexylidenebisphenol used. Used.

According to the invention, the thermal decomposition of the hydroxyphenyl-substituted cyclohexylidenebisphenols is usually in the range from 150 to 300 ° C., preferably from 180 to 300 ° C.
It is performed at a temperature in the range of 50 ° C. If the thermal decomposition temperature is too low, the reaction rate is too low, while if the thermal decomposition temperature is too high, undesirable side reactions increase.
The reaction pressure of the thermal decomposition is not particularly limited, but is usually in a range from normal pressure to reduced pressure, for example,
1 to 760 mmHg gauge range, preferably 30 to
It is in the range of 50 mmHg gauge.

Under such reaction conditions, the thermal decomposition of the hydroxyphenyl-substituted cyclohexylidenebisphenols is usually completed in about 1 to 6 hours. The end point of the thermal decomposition reaction can be, for example, the point at which the distillation of the alkylphenols generated by the decomposition reaction stops.

According to a preferred embodiment, the thermal decomposition reaction of the hydroxyphenyl-substituted cyclohexylidenebisphenol is carried out, for example, by charging a hydroxyphenyl-substituted cyclohexylidenebisphenol, an alkali catalyst and a solvent such as tetraethylene glycol into a reaction vessel. 190-
This is carried out by stirring at 220 ° C. under a pressure of 30 to 50 mmHg gauge for about 3 to 6 hours while distilling off the alkylphenols generated by the decomposition reaction.

According to the present invention, after completion of the thermal decomposition reaction of such hydroxyphenyl-substituted cyclohexylidenebisphenols, when an alkali catalyst is used for the thermal decomposition, an acid is added to the obtained reaction mixture. By neutralizing the alkali with an alkali, a water-containing oily reaction mixture can be obtained. According to the present invention, a reaction product can be separated and purified from such a water-containing oily reaction mixture, if necessary, and then subjected to the next step of dehydrogenation.

That is, an organic solvent such as methyl isobutyl ketone and water are added to the above water-containing oily reaction mixture, and the salt formed by the above neutralization is mixed with the solvent used in the thermal decomposition reaction (for example,
Tetraethylene glycol) as an aqueous layer, and the above-mentioned organic solvent (for example, methyl isobutyl ketone) is distilled off from the obtained oil layer by distillation or the like. A reaction product by a thermal decomposition reaction can be obtained as a purified product by adding a precipitation solvent to cause crystallization and purification. As a result of various analyses, this reaction product was converted to a compound represented by the general formula (V) corresponding to the starting material, hydroxyphenyl-substituted cyclohexylidenebisphenols.

[0039]

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(In the formula, R and n are the same as described above.)
1,4-bis (4-hydroxyphenyl)-represented by
It is estimated to be 1-cyclohexenes. In this way, the reaction product obtained by the thermal decomposition reaction of the hydroxyphenyl-substituted cyclohexylidenebisphenols is separated, purified if necessary, and then subjected to the next step of dehydrogenation. .

However, according to the present invention, when an alkali catalyst is used for the thermal decomposition of the above-mentioned hydroxyphenyl-substituted cyclohexylidenebisphenols, after the reaction is completed, the resulting reaction mixture is added with an acid. After neutralizing the alkali, it is used as it is for the next step of dehydrogenation without purification, such as crystallization and filtration.
When an alkali catalyst was not used for the thermal decomposition of the above-mentioned hydroxyphenyl-substituted cyclohexylidenebisphenols, after completion of the reaction, the obtained reaction mixture was directly subjected to the next step without purification such as crystallization filtration. From the viewpoint of simplifying the reaction process.

Thus, according to the present invention, preferably
By subjecting the hydroxyphenyl-substituted cyclohexylidenebisphenols to thermal decomposition and subjecting the resulting reaction mixture to a dehydrogenation reaction, the desired 4,4 ″ -dihydroxy-p-terphenyl can be obtained. According to the invention, the starting 4,4 "-dihydroxy-p-terphenyls are thus obtained starting from hydroxyphenyl-substituted cyclohexylidenebisphenols,
Usually, a yield of about 75% or more can be obtained.

More specifically, according to the present invention, the reaction mixture obtained by the thermal decomposition of hydroxyphenyl-substituted cyclohexylidenebisphenols is usually subjected to a dehydrogenation treatment in the presence of a dehydrogenation catalyst. As the dehydrogenation catalyst, a conventionally known dehydrogenation catalyst can be used. Therefore, for example, nickel catalysts such as Raney nickel, reduced nickel, nickel supported catalysts, cobalt catalysts such as Raney cobalt, reduced cobalt, cobalt supported catalysts, copper catalysts such as Raney copper, palladium oxide, palladium black, palladium such as palladium / carbon A catalyst, a platinum catalyst such as platinum black or platinum / carbon, a rhodium catalyst, a chromium catalyst, a copper chromium catalyst or the like is used. Among these, a platinum group catalyst such as palladium is particularly preferable, and a palladium catalyst is particularly preferably used.

Such a dehydrogenation catalyst is generally used in an amount of 0.1 to 20 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of a reaction mixture obtained by thermal decomposition of hydroxyphenyl-substituted cyclohexylidenebisphenols. It is used in the range of 2 to 10 parts by weight.

In this dehydrogenation treatment, a hydrogen acceptor may or may not be allowed to coexist. However, in order to obtain a desired product in a higher yield, it is preferable to coexist with a hydrogen acceptor. Examples of such a hydrogen acceptor include, but are not particularly limited to, styrenes such as α-methylstyrene, nitrobenzene, methyl isobutyl ketone, and phenol. The reaction temperature of the dehydrogenation reaction is usually in the range of 100 to 250 ° C, preferably in the range of 130 to 200 ° C.

The dehydrogenation treatment of the reaction mixture obtained by the thermal decomposition of the hydroxyphenyl-substituted cyclohexylidenebisphenols can be carried out in a gas phase, but from the viewpoint of operability, it is preferably carried out in a solution state. Is preferable, and in that case, it is preferable to use a reaction solvent. As the reaction solvent, the solvent used in the thermal decomposition reaction of the above-mentioned hydroxyphenyl-substituted cyclohexylidenebisphenol is preferably used as it is from the viewpoint of simplification of the process. The reaction is preferably performed under normal pressure. Under such reaction conditions, the dehydrogenation of the reaction mixture obtained by the thermal decomposition of the hydroxyphenyl-substituted cyclohexylidenebisphenols is usually performed by
The process is completed in about 3 to 6 hours.

The reaction mixture obtained by the thermal decomposition of the hydroxyphenyl-substituted cyclohexylidenebisphenols is subjected to a dehydrogenation reaction, and after completion of the reaction, the obtained reaction mixture is subjected to a catalyst treatment according to a conventional method. After separation, a crude product of 4,4 ″ -dihydroxy terphenyls, which is the object of the present invention, can be obtained by a method such as crystallization filtration. If purified by a method such as crystallization filtration, a highly purified product can be obtained.

Accordingly, the 4,4 "-dihydroxy-p represented by the above general formula (II) obtained by the method of the present invention.
Specific examples of the terphenyls include, for example, 4,4 ″ -dihydroxy-p-terphenyl corresponding to the hydroxyphenyl-substituted cyclohexylidenebisphenols represented by the general formula (I) as a raw material. Phenyl, 4-
Hydroxy-3 "-methyl-4" -hydroxy-p-terphenyl, 4-hydroxy-2 "-methyl-4" -hydroxy-p-terphenyl, 4-hydroxy-3 ",
5 "-dimethyl-4" -hydroxy-p-terphenyl, 4-hydroxy-3 ", 6" -dimethyl-4 "-hydroxy-p-terphenyl, 4-hydroxy-2",
3 ", 5" -trimethyl-4 "-hydroxy-p-terphenyl, 4-hydroxy-2", 3 ", 6" -trimethyl-4 "-hydroxy-p-terphenyl, 4-hydroxy-3"- Ethyl-4 "-hydroxy-p-terphenyl, 4-hydroxy-2" -ethyl-4 "-hydroxy-p-terphenyl, 4-hydroxy-3" -isopropyl-4 "-hydroxy-p-terphenyl, 4-
Hydroxy-2 "-isopropyl-4" -hydroxy-
p-terphenyl, 4-hydroxy-3 "-isobutyl-4" -hydroxy-p-terphenyl, 4-hydroxy-2 "-isobutyl-4" -hydroxy-p-terphenyl, 4-hydroxy-3 "- s-butyl-4 "-hydroxy-p-terphenyl, 4-hydroxy-2"-
s-butyl-4 "-hydroxy-p-terphenyl, 4
-Hydroxy-3 "-isopropyl-6" -methyl-
4 "-hydroxy-p-terphenyl, 4-hydroxy-3" -t-butyl-5 "-methyl-4" -hydroxy-p-terphenyl, 4-hydroxy-3 "-t-butyl-6"- Methyl-4 "-hydroxy-p-terphenyl, 4-hydroxy-3", 5 "-di-t-butyl-
4 "-hydroxy-p-terphenyl, 4-hydroxy-3" -trifluoromethoxy-4 "-hydroxy-p
-Terphenyl, 4-hydroxy-3 "-cyclohexyl-6" -methyl-4 "-hydroxy-p-terphenyl, 4-hydroxy-3" -n-heptyl-4 "-hydroxy-p-terphenyl, -Hydroxy-3 "-cyclohexyl-4" -hydroxy-p-terphenyl,
4-hydroxy-3 ", 5" -dicyclohexyl-4 "
-Hydroxy-p-terphenyl, 4-hydroxy-
3 "-methoxy-4" -hydroxy-p-terphenyl, 4-hydroxy-2 "-methoxy-4" -hydroxy-p-terphenyl, 4-hydroxy-3 "-t-butoxy-4" -hydroxy- p-terphenyl, 4-hydroxy-2 "-monochloromethoxy-4" -hydroxy-p-terphenyl, 4-hydroxy-3 "-phenyl-4" -hydroxy-p-terphenyl, 4-hydroxy-3 " , 5 "-diphenyl-4" -hydroxy-p
-Terphenyl, 4-hydroxy-2 ", 4" -dihydroxy-p-terphenyl, 4-hydroxy-3 ",
4 "-dihydroxy-p-terphenyl, 4-hydroxy-2", 3 ", 4" -trihydroxy-p-terphenyl and the like can be mentioned.

According to the present invention, 4- (4-hydroxyphenyl) represented by the general formula (III) is used as a starting material.
Using cyclohexanone and a substituted phenol represented by the general formula (IV), and reacting them in the presence of an acid catalyst to produce a hydroxyphenyl-substituted cyclohexylidenebisphenol represented by the general formula (I) Then, as described above, this is thermally decomposed, and the thus obtained reaction mixture is subjected to a dehydrogenation reaction as described above to obtain the desired compound represented by the general formula (II) 4 , 4 "-
Dihydroxy-p-terphenyls can be obtained.

Also in the above-mentioned method, the hydroxyphenyl-substituted cyclohexylidenebisphenols, which are intermediate products, and the pyrolysis products thereof are isolated after completion of the respective reactions, and, if necessary, purified. After completion of each reaction, the reaction product obtained may be neutralized, or the catalyst may be separated, if necessary, without isolation and purification. In accordance with the above, after separating the aqueous layer or separating and removing the organic solvent, reaction raw materials, and volatile by-products by distillation under reduced pressure or the like, as a raw material for the next step (before the purification step by crystallization filtration or the like) May be used.

However, according to the present invention, according to the latter, after completion of each reaction, the obtained reaction product is neutralized without isolating and purifying the obtained reaction product, Alternatively, after separating the catalyst, it is preferable to use the reaction mixture containing each reaction product as a starting material for the next step (before the purification step), since there is no need to separate or purify the intermediate reaction product.

In the presence of an acid catalyst, 4- (4-hydroxyphenyl) cyclohexanone represented by the general formula (III) is reacted with a substituted phenol represented by the general formula (IV) to give In order to obtain the hydroxyphenyl-substituted cyclohexylidenebisphenol represented by the formula (I), for example, a method similar to the method described in JP-A-2000-63308 may be used.

In the substituted phenols represented by the general formula (IV), R and n are the same as those in the general formula (I). Therefore, specific examples of the substituted phenols include phenol, o- or m-cresol, 2,3-, 2,5-, 2,6-, 3,5- or 3,
6-xylenol, 2,3,5- or 2,3,6-trimethylphenol, 2-ethylphenol, 3-ethylphenol, 2-n-propylphenol, 3-n-propylphenol, 2-isopropylphenol, −
Isopropylphenol, 2-n-butylphenol,
3-n-butylphenol, 2-isobutylphenol, 3-isobutylphenol, 2-s-butylphenol, 3-s-butylphenol, 2-isopropyl-
5-methylphenol, 2-t-butyl-5-methylphenol, 2,6-di-t-butylphenol, 2-n
-Heptylphenol, 2-cyclohexylphenol, 2,6-dicyclohexylphenol, 3-methyl-6-cyclohexylphenol, 2-methoxyphenol, 3-methoxyphenol, 2-t-butoxyphenol, 3-chloromethoxyphenol, Trifluoromethoxyphenol, o-phenylphenol,
Examples thereof include 2,6-diphenylphenol, resorcinol, catechol, and pyrogal.

Such substituted phenols and 4- (4-
In the reaction with (hydroxyphenyl) cyclohexanone, the substituted phenol is usually added in an amount of 4 to 2 parts per mole of 4- (4-hydroxyphenyl) cyclohexanone.
It is used in a range of 0 mol part.

In the reaction between the above substituted phenols and 4- (4-hydroxyphenyl) cyclohexanone, a reaction solvent may or may not be used. When a reaction solvent is used, for example, an aliphatic alcohol, an aromatic hydrocarbon, or a mixed solvent thereof is used. As the alcohol, methanol, ethanol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol, isobutyl alcohol, n-butyl alcohol are used in consideration of the reaction raw materials to be used, the solubility of the obtained product, the reaction conditions, the economics of the reaction, and the like. Butyl alcohol and the like can be mentioned. Examples of the aromatic hydrocarbon solvent include toluene, xylene, cumene and the like. Such a solvent is generally used in an amount of 10 to 100 parts by weight of 4- (4-hydroxyphenyl) cyclohexanone used.
It is used in the range of 0 to 500 parts by weight, but is not limited thereto.

In the present invention, dry hydrogen chloride gas is preferably used as the acid catalyst, but is not limited thereto. For example, hydrochloric acid, sulfuric acid, sulfuric anhydride, p-toluenesulfonic acid, methane Sulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid and the like are also used. In the case of dry hydrogen chloride gas, for example, such an acid catalyst is preferably used in an amount that saturates the inside of the reaction system. Further, according to the present invention, in order to promote the reaction, a mercaptan or the like (for example, octyl mercaptan)
Can be used.

The reaction is usually carried out at a temperature in the range of 20 to 80 ° C., preferably 20 to 50 ° C., while blowing dry hydrogen chloride gas into the reaction mixture in the reactor under stirring.
It may be performed for about 48 hours, usually about 6 to 24 hours.

After completion of the reaction, an alkali is added to the obtained reaction mixture to neutralize the acid catalyst, and then an appropriate crystallization solvent is added to the aqueous layer, or the aqueous layer is separated and removed. ,
After distilling the obtained organic layer under normal pressure or reduced pressure, an appropriate crystallization solvent is added thereto to precipitate crude crystals, and then the crude crystals are collected by filtration. By crystallizing from a crystallization solvent, a purified product of hydroxyphenyl-substituted cyclohexylidenebisphenols can be obtained. According to the present invention, the above crude crystals and purified products can be used as a raw material for thermal decomposition in the next step.

However, according to the present invention, as described above, in order to simplify the reaction process, after the reaction is completed, an alkali is added to the obtained reaction mixture to neutralize the acid catalyst, and then the aqueous layer is neutralized. It is desirable that the oily reaction mixture thus obtained is used as a raw material for the next step of thermal decomposition.

The oily reaction mixture containing the hydroxyphenyl-substituted cyclohexylidenebisphenols is thermally decomposed as described above, preferably in the presence of an alkali catalyst, and then the resulting reaction mixture is dehydrogenated. To give the desired general formula (II)
4,4 "-dihydroxy-p-terphenyls represented by the following formula:

[0061]

As described above, according to the method of the present invention,
Since all reactions can be carried out under normal pressure or reduced pressure, including the case starting from substituted phenols and 4- (4-hydroxyphenyl) cyclohexanone, a special reactor such as a pressurized reactor is used. Not necessary, and thus, according to the present invention, the reaction is carried out under industrially easy-to-implement reaction conditions using industrially available raw materials,
The desired 4,4 "-dihydroxy-p-terphenyls can be obtained in high yield and high purity.

Further, according to the present invention, as a starting material,
By using hydroxyphenyl-substituted cyclohexylidenebisphenols having a substituent such as an alkyl group only at one terminal hydroxyphenyl group of the molecule, only at one terminal hydroxyphenyl group of the molecule, for example, Asymmetric 4,4 "-dihydroxy-p-terphenyls having a substituent such as an alkyl group can be obtained.

Such asymmetric 4,4 ″ -dihydroxy-p-terphenyls have a symmetrical 4,4 ″ -p-terphenyl.
Compared to dihydroxy-p-terphenyls, for example,
It is expected to have excellent solubility in organic solvents.

[0064]

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

Example 1 (Production of 4,4 "-dihydroxy-p-terphenyl) Thermal decomposition step (Production of 1,4-bis (4-hydroxyphenyl) cyclohexene-1) 1- (4-hydroxyphenyl) −
76.0 g (0.211 mol) of 4,4-bis (4-hydroxyphenyl) cyclohexane, 0.6 g of a 48% aqueous sodium hydroxide solution, and 63.4 g of tetraethylene glycol.
4 g was charged into a reaction vessel (200 mL four-necked flask), the inside of the reaction vessel was replaced with nitrogen, and then the pressure inside the reaction vessel was reduced to 100 to 150 mmHg. Was done. The point at which no distillate was distilled was regarded as the end point of the thermal decomposition reaction. After completion of the reaction, a 50% aqueous acetic acid solution was added to the obtained reaction mixture to neutralize the mixture to a pH of about 6, thereby obtaining a water-containing oily reaction mixture.

Dehydrogenation step (Production of 4,4 "-dihydroxy-p-terphenyl)
49.8 g of α-methylstyrene (2 times the molar amount of the theoretical yield of 4,4 ″ -hydroxyphenyl-p-cyclohexene-1) was added to 119 g of the above water-containing oily reaction mixture and 5% palladium / carbon supported catalyst (50% by weight). 5.8)
g was further added, and the inside of the reaction vessel was replaced with nitrogen. Then, the temperature was raised to 163 ° C. under normal pressure, and the reaction was performed with stirring for 3 hours.

After completion of the reaction, 1400 g of dimethylformamide was added to the obtained reaction mixture and mixed. After this,
The palladium / carbon catalyst was filtered off from this mixture, and the solvent was distilled off by distillation to obtain a distillation residue containing the target product. Methanol was added to the distillation residue, crystallization filtration was performed, and the obtained solid was dried, and 4,4 ″ -dihydroxy-p-terphenyl having a purity of 98.8% (by high performance liquid chromatography analysis). 7 g were obtained as white crystals, and the yield based on 1- (4-hydroxyphenyl) -4,4-bis (4-hydroxyphenyl) cyclohexane was 74.5 mol%.

Example 2 (Production of 4-hydroxy-3 "-methyl-4" -hydroxyterphenyl) Pyrolysis Step 1- (4-hydroxyphenyl) -4,4-bis (3-
Methyl-4-hydroxyphenyl) cyclohexane 5
0.2 g (0.129 mol), 0.3 g of a 48% aqueous sodium hydroxide solution and 26.3 g of tetraethylene glycol
Into a reaction vessel (300 mL four-necked flask), and the inside of the reaction vessel is purged with nitrogen.
The thermal decomposition reaction was performed at about 210 ° C. for about 4 hours at a reduced pressure of 0 mmHg. The point at which the distillate stopped being distilled was regarded as the end point of the reaction.

After completion of the reaction, 50% was added to the obtained reaction mixture.
An aqueous acetic acid solution was added to neutralize the solution to a pH of about 6, and 64.7 g of a water-containing oily reaction mixture was obtained.

Dehydrogenation Step To 64.7 g of the above water-containing oily reaction mixture, 60.0 g of α-methylstyrene and 3.5 g of a 5% palladium / carbon-supported catalyst (50% by weight water-containing product) were additionally added. After purging with nitrogen, the temperature was raised to 165 ° C. under normal pressure, and the reaction was carried out for 3 hours with stirring.

After completion of the reaction, 50 g of dimethylformamide was added to the obtained reaction mixture and mixed. Thereafter, the palladium / carbon catalyst was filtered off from the mixture,
The solvent was distilled off to obtain a distillation residue containing the target substance. Methanol was added to the distillation residue to dissolve the residue, water was further added, and then crystallization filtration was performed. The obtained solid was dried to a purity of 99.1% (by high performance liquid chromatography analysis). 30.5 g of 4,4 "-dihydroxy-3" -methyl terphenyl was obtained as white crystals. 1
The yield based on-(4-hydroxyphenyl) -4,4-bis (3-methyl-4-hydroxyphenyl) cyclohexane was 85.8 mol%.

Melting point: 251.4 ° C. (DSC method) Molecular weight: 276 (M ⁺ ) (by mass spectrometry) Proton NMR (400 MHz, solvent DMSO-d)
(Δ (ppm): 2.19 (s, 3H), 6.86 (d
d, 3H, J = 8.0 Hz, J = 3.2 Hz), 7.3
2 (dd, 1H, J = 10.2 Hz, 2.4 Hz),
7.41 (d, 1H, J = 2.4 Hz), 7.50
(D, 2H, J = 8.8 Hz), 7.58 (s, 4
H), 9.48 (brs. 2H)

Example 3 (Production of 4-hydroxy-3 ″, 5 ″ -dimethyl-4 ″ -hydroxyterphenyl) Pyrolysis Step 1- (4-hydroxyphenyl) -4,4-bis (3,3
83.2 g (0.200 mol) of 5-dimethyl-4-hydroxyphenyl) cyclohexane, 0.4 g of a 48% aqueous sodium hydroxide solution and 32 g of tetraethylene glycol
Into a reaction vessel (300 mL capacity four-necked flask), and the inside of the reaction vessel is purged with nitrogen.
The thermal decomposition reaction was performed at about 210 ° C. for about 4 hours at a reduced pressure of 0 mmHg. The point at which the distillate stopped being distilled was regarded as the end point of the reaction. After completion of the reaction, a 50% aqueous acetic acid solution was added to the obtained reaction mixture to neutralize the solution to about pH 6, and 88.0 g of a water-containing oily reaction mixture was obtained.

Dehydrogenation Step To 88.0 g of the above water-containing oily reaction mixture, 90.0 g of α-methylstyrene and 0.56 g of a 5% palladium / carbon-supported catalyst (50% by weight water-containing product) were added, and the inside of the reaction vessel was added. After purging with nitrogen, the temperature was raised to 160 ° C. under normal pressure, and the reaction was carried out for 6 hours with stirring.

After the reaction was completed, 96 g of dimethylformamide was added to the obtained reaction mixture and mixed. Thereafter, the palladium / carbon catalyst was filtered off from the mixture,
The solvent was distilled off to obtain a distillation residue containing the target substance. Water was added to the distillation residue, crystallization filtration was performed, and the obtained solid was slurried by adding isopropanol. Then, crystallization filtration was performed again, followed by drying to obtain a purity of 98.1% (by high performance liquid chromatography analysis). )) 4-Hydroxy-
47.4 g of 3 ", 5" -dimethyl-4 "-hydroxy-p-terphenyl were obtained as white crystals. 1- (4-hydroxyphenyl) -4,4-bis (3,5-dimethyl-4-) The yield based on (hydroxyphenyl) cyclohexane was 81.7 mol%.

Melting point: 231 ° C. (DSC method) Molecular weight: 290 (M ⁺ ) (by mass spectrometry) Proton NMR (400 MHz, solvent DMSO-d)
(Δ (ppm): 2.25 (s, 6H), 6.88
(D, 2H, J = 8.0 Hz), 7.25 (s, 2
H), 7.50 (d, 2H, J = 8.8 Hz), 7.5
8 (s, 4H), 8.80 (brs, 2H)

Example 4 (Production of 4-hydroxy-3 "-isopropyl-4" -hydroxy-p-terphenyl) Thermal decomposition step 1- (4-hydroxyphenyl) -4,4-bis (3-
29.3 g (0.0660 mol) of isopropyl-4-hydroxyphenyl) cyclohexane, 0.2 g of a 48% aqueous sodium hydroxide solution and tetraethylene glycol 1
2.0 g was charged into a reaction vessel (300 mL capacity four-necked flask), and the inside of the reaction vessel was replaced with nitrogen. Then, the pressure inside the reaction vessel was reduced to 40 mmHg. Was done. The point at which the distillate stopped being distilled was regarded as the end point of the reaction.

After completion of the reaction, 50% was added to the obtained reaction mixture.
An aqueous acetic acid solution was added to neutralize the solution to a pH of about 6, and 33.6 g of a water-containing oily reaction mixture was obtained.

Dehydrogenation Step To 33.6 g of the above water-containing oily reaction mixture, 31.2 g of α-methylstyrene and 0.2 g of a 5% palladium / carbon-supported catalyst (50% by weight water-containing product) were additionally added, and the inside of the reaction vessel was added. After purging with nitrogen, the temperature was raised to 160 ° C. under normal pressure, and the reaction was carried out for 4 hours with stirring.

After completion of the reaction, 31.2 g of dimethylformamide was added to the obtained reaction mixture and mixed. After this,
The palladium / carbon catalyst was filtered off from this mixture, and the solvent was distilled off by distillation to obtain a distillation residue containing the target substance. Methyl isobutyl ketone and water were added to this distillation residue, the aqueous layer was separated and removed, and the solvent was distilled off from the obtained oil layer. Toluene was added for crystallization filtration, followed by drying, and the purity was 99.0. % (By high performance liquid chromatography analysis) of 4-hydroxy-3 "-isopropyl-4"-
16.5 g of hydroxy-p-terphenyl were obtained as white crystals. The reaction yield of the starting material, 1- (4-hydroxyphenyl) -4,4-bis (3-isopropyl-4-hydroxyphenyl) cyclohexane, was 81.
It was 2 mol%.

Melting point: 179 ° C. (DSC method) Molecular weight: 304 (M ⁺ ) (by mass spectrometry) Proton NMR (400 MHz, solvent DMSO-d)
(Δ (ppm): 1.24 (d, 6H, J = 6.8H)
z), 3.25-3.29 (m, 1H), 6.87-
6.90 (m, 3H), 7.33 (dd, 1H, J =
8.4 Hz, 2.0 Hz), 7.43 (d, 1H, J =
2.4 Hz), 7.52 (d, 2H, J = 8.8H)
z), 7.61 (s, 4H), 9.46 (brs, 1
H), 9.56 (brs, 1H)

Example 5 (4-hydroxy-3 "-methyl-4" -hydroxy-
Production of p-terphenyl) 1- (4-hydroxyphenyl) -4,4-bis (3-
Production process of methyl-4-hydroxyphenyl) cyclohexane 136 g of o-cresol (8 times mol of 4- (4′-hydroxyphenyl) cyclohexane), concentrated hydrochloric acid 53.9
g, octyl mercaptan 0.3 g and methanol 2
7.2 g of a reaction vessel (500 mL four-necked flask)
And stirred at 40 ° C., and 29.0 g of 4- (4′-hydroxyphenyl) cyclohexane powder was added thereto.
The mixture was added over a period of time, and the mixture was further stirred at 40 ° C. for 4 hours. The reaction selectivity was 98% (by high performance liquid chromatography analysis).

After the completion of the reaction, 16% was added to the obtained reaction mixture.
The solution was neutralized by adding 135 g of an aqueous sodium hydroxide solution, and further adjusted to pH 6 by adding a few drops of 75% phosphoric acid. Thereafter, 100 g of methyl isobutyl ketone was added, and the aqueous layer was separated and removed. 50 g of water was added to the obtained oil layer, and the mixture was separated to obtain an oil layer. Methanol and methyl isobutyl ketone were removed from the oil layer by distillation to obtain 244 g of a reddish brown liquid as a residue.

Pyrolysis Step: To 244 g of the above reddish brown liquid, 0.60 g of a 48% aqueous sodium hydroxide solution and 18 g of tetraethylene glycol were added, and o-cresol was distilled off at a reduced pressure of 40 mmHg and a temperature of 182 to 204 ° C. While heating for 3 hours
1- (4-hydroxyphenyl) -4,4-bis (3-
Thermal decomposition of (methyl-4-hydroxyphenyl) cyclohexane was performed to obtain 63.4 g of a reddish brown oil as a residue. The reaction selectivity was 91% (by high performance liquid chromatography analysis).

To 63.4 g of this reddish-brown oil, 1.0 g of a 50% aqueous acetic acid solution was added for neutralization, and the mixture was stirred at 90 ° C. for 20 minutes to obtain 64 g of a cream-colored slurry.

Dehydrogenation Step 72 g of α-methylstyrene and 4.2 g of a 5% palladium / carbon supported catalyst (50% by weight water-containing product) were added to 64 g of the cream-colored slurry, and the mixture was refluxed under normal pressure at a temperature of 165 ° C. The reaction was performed for 3 hours. Reaction selectivity is 89%
(By high performance liquid chromatography analysis).

Thereafter, the reaction mixture was cooled to room temperature, and dissolved by adding 60 g of dimethylformamide. After removing the catalyst by filtration, dimethylformamide was distilled off.
98 g of a residue were obtained. Methanol was added thereto, and the mixture was heated to 60 ° C. to dissolve, then water was added for crystallization, and the mixture was filtered at room temperature, dried, and dried to give 99.1% pure 4,4 ″ -dihydroxy-3 ″. 35.7 g of -methyl-p-terphenyl were obtained. The reaction yield with respect to 4- (4′-hydroxyphenyl) cyclohexane was 84 mol%.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hiroyasu Ohno 2-115, Kozaiga, Wakayama-shi F-term in Honshu Kagaku Kogyo Co., Ltd. 4H006 AA02 AC12 AC25 AC26 BA25 BA66 BD70 FC22 FC52 FE13 4H039 CA40 CC10

Claims (2)

[Claims] 1. A compound of the general formula (I) (Wherein, R represents an alkyl group having 1 to 12 carbon atoms,
It represents an alkoxyl group or a haloalkoxyl group, a cycloalkyl group having 5 or 6 carbon atoms, a cycloalkoxyl group or a halocycloalkoxyl group, a phenyl group or a hydroxyl group, respectively, and n is an integer of 0-3. Wherein the hydroxyphenyl-substituted cyclohexylidenebisphenols represented by the formula (1) are thermally decomposed, and the resulting reaction mixture is subjected to a dehydrogenation reaction. (Wherein, R and n are the same as those described above.) A method for producing 4,4 ″ -dihydroxy-p-terphenyls represented by the formula: 2. A compound of the formula (III) And 4- (4-hydroxyphenyl) cyclohexanone represented by the general formula (IV): (Wherein, R represents an alkyl group having 1 to 12 carbon atoms,
An alkoxyl group or a haloalkoxyl group, a cycloalkyl group having 5 or 6 carbon atoms, a cycloalkoxyl group or a halocycloalkoxyl group, a phenyl group or a hydroxyl group, respectively, and n is an integer of 0-3. ) Is reacted in the presence of an acid catalyst to give a compound of the general formula (I) (Wherein R and n are the same as defined above) to produce the hydroxyphenyl-substituted cyclohexylidenebisphenols, pyrolyze them, and then dehydrogenate the resulting reaction mixture. Characteristic general formula (II) (Wherein, R and n are the same as described above).