JP5752361B2 - Process for producing 1- (4-hydroxyphenyl) -1-cyclohexenes - Google Patents

Description

  The present invention relates to a method for producing 1- (4-hydroxyphenyl) -1-cyclohexenes. Specifically, 1- (4-hydroxyphenyl) -1-cyclohexenes that are useful as raw materials for synthetic resins such as liquid crystal polyesters, polycarbonates, and polyurethanes, and as raw materials for photoresists for display elements, semiconductors, etc. are easily used. The present invention also relates to a production method that can be obtained with high purity and high yield.

Conventionally, as a method for producing 1- (4-hydroxyphenyl) -1-cyclohexene, for example, 4- (4-hydroxyphenyl) -1,1-bis (4-hydroxyphenyl) cyclohexane is thermally decomposed. 1,4-bis (4-hydroxyphenyl) -1-cyclohexenes are known (Patent Documents 1 and 2).
1,1-bis (4-hydroxyphenyl) cyclohexanes, which are starting materials for thermal decomposition, are obtained by reacting corresponding phenols with cyclohexanones, but are conventionally obtained selectively in this condensation reaction. Focusing only on the p, p form [1,1-bis (4-hydroxyphenyl) substituted compound], 1- (4-hydroxyphenyl) -1-cyclohexenes are obtained by thermally decomposing the p, p form. It was.

  However, when implemented industrially, there are problems such as low yield of p and p isomers in the condensation reaction. Therefore, in order to increase the yield of p and p isomers, the reaction time may be extended or acid catalysts may be used. It was necessary to increase the yield of the p- and p-isomers by a method such as using a large amount of or a promoter. However, when a large amount of acid catalyst is used, the use of a large amount of alkaline solution necessary for neutralization after the reaction ends, for example, the volumetric efficiency is deteriorated. Since a high sulfur atom-containing compound is used, there is a problem that undesirable sulfur impurities are mixed into the obtained 1- (4-hydroxyphenyl) -1-cyclohexene.

  Therefore, the present inventors have intensively studied the reaction to obtain 1- (4-hydroxyphenyl) -1-cyclohexene, which is the target product, by thermal decomposition of 1,1-bis (hydroxyphenyl) cyclohexanes. 1- (4-Hydroxyphenyl) -1-cyclohexenes are not obtained only from the thermal decomposition of the conventionally known p, p-form 1,1-bis (4-hydroxyphenyl) cyclohexanes, 1- (4-hydroxyphenyl) -1- (2-hydroxyphenyl) cyclohexanes which are p-form and o, p-form [1- (2-hydroxyphenyl) -1- (4-hydroxyphenyl) substituted compound] It was also found that 1- (4-hydroxyphenyl) -1-cyclohexenes can be obtained in a good yield by pyrolyzing the mixture. In other words, it has been found that 1- (4-hydroxyphenyl) -1-cyclohexenes can also be obtained by thermal decomposition of o, p forms.

  Such a mixture of p, p form and o, p form is industrially easier to implement than the reaction conditions for selectively obtaining p, p form from phenols and cyclohexanones known in the art. It was found that this is a method for producing 1- (4-hydroxyphenyl) -1-cyclohexenes more efficiently because it can be obtained under various reaction conditions.

JP 2002-308809 A JP 2002-234856 A

  The present invention has been made in view of the above-mentioned problems in the method for producing 1- (4-hydroxyphenyl) -1-cyclohexene, and includes 1- (4-hydroxyphenyl) -1-cyclohexenes. It is an object of the present invention to provide a method for easily producing a high-yield product in a high yield and high purity.

（式中、Ｒ_１はアルキル基、アルコキシ基、アリール基、アリールオキシ基またはハロゲンを示し、Ｒ_２は水素原子、アルキル基、アルコキシ基、アリール基、アリールオキシ基またはハロゲンを示し、ａは０又は１〜４の整数を表す。ただし、ａが２以上の場合に、Ｒ_１は同一でも異なっていてもよい。）
で表される１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン（以下、「化合物１」という）と、一般式（２）

（式中、Ｒ_１、Ｒ_２、ａは一般式（１）のそれと同じである。）
で表される１−（４−ヒドロキシフェニル）−１−（２−ヒドロキシフェニル）シクロヘキサン（以下、「化合物２」という）を化合物１／化合物２の重量比で９０／１０〜５０／５０で含む混合物を塩基性触媒の存在下に熱分解することを特徴とする、一般式（３）

（式中、Ｒ_１、Ｒ_２、ａは一般式（１）のそれと同じである。）
で表される１−（４−ヒドロキシフェニル）−１−シクロヘキセン類の製造方法が提供される。 According to the invention, the general formula (1)

(Wherein R ₁ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a halogen; R ₂ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a halogen; Or an integer of 1 to 4. However, when a is 2 or more, R ₁ may be the same or different.
1,1-bis (4-hydroxyphenyl) cyclohexane (hereinafter referred to as “compound 1”) represented by the general formula (2)

(In the formula, R _1, R _{2 and} a are the same as those in the general formula (1).)
1- (4-hydroxyphenyl) -1- (2-hydroxyphenyl) cyclohexane (hereinafter referred to as “compound 2”) represented by the formula: The mixture is thermally decomposed in the presence of a basic catalyst and is represented by the general formula (3)

(In the formula, R _1, R _{2 and} a are the same as those in the general formula (1).)
A process for producing 1- (4-hydroxyphenyl) -1-cyclohexenes represented by the formula:

（式中、Ｒ_２は一般式（１）のそれと同じである。）
で表されるフェノール類と、一般式（５）

（式中、Ｒ_１、ａは一般式（１）のそれと同じである。）
で表されるシクロヘキサノン類を、シクロヘキサノン類に対し１〜９０モル％の酸触媒存在下に助触媒を用いずに脱水縮合させて得られたものであることを特徴とする１−（４−ヒドロキシフェニル）−１−シクロヘキセン類の製造方法は、本発明の好ましい態様である。
また、前記フェノール類とシクロヘキサノン類から前記化合物１／化合物２の重量比で９０／１０〜５０／５０で含む混合物を得、次いで、得られた混合物を塩基性触媒の存在下に熱分解することを特徴とする1−（４−ヒドロキシフェニル）−１−シクロヘキセン類の製造方法は、本発明の好ましい態様である。 The mixture of Compound 1 / Compound 2 is represented by the general formula (4).

(Wherein R ₂ is the same as that of general formula (1).)
And phenols represented by general formula (5)

(In the formula, R ₁ and a are the same as those in the general formula (1).)
1- (4-hydroxy) obtained by dehydrating and condensing a cyclohexanone represented by the following formula in the presence of 1 to 90 mol% of an acid catalyst with respect to the cyclohexanone without using a cocatalyst. A method for producing phenyl) -1-cyclohexenes is a preferred embodiment of the present invention.
Also, a mixture containing 90/10 to 50/50 by weight ratio of Compound 1 / Compound 2 is obtained from the phenols and cyclohexanones, and then the obtained mixture is thermally decomposed in the presence of a basic catalyst. The method for producing 1- (4-hydroxyphenyl) -1-cyclohexenes characterized by the above is a preferred embodiment of the present invention.

（式中、Ｒ_１、Ｒ_２は一般式（１）のそれと同じであり、ｃは０又は１〜３の整数を表し、ただし、ｃが２以上の場合、Ｒ_１は同一でも異なっていてもよく、Ｒ_３は独立してＲ_１と同じであり、ｂは０又は１〜４の整数を表し、ｂが２以上の場合に、Ｒ_３は同一でも異なっていてもよい。）
で表され、前記一般式（２）が、一般式（７）

（式中、Ｒ_１、Ｒ_２、Ｒ_３、ｂ及びｃは一般式（６）のそれと同じである。）
で表され、前記一般式（３）が、一般式（８）

（式中、Ｒ_１、Ｒ_２、Ｒ_３、ｂ及びｃは一般式（６）のそれと同じである。）
で表される１−（４−ヒドロキシフェニル）−１−シクロヘキセン類の製造方法は、本発明の好ましい態様である。 In the general formulas (1) to (3), when at least one of R ₁ is an aryl group, the general formula (1) is represented by the general formula (6).

(In the formula, R ₁ and R ₂ are the same as those in the general formula (1), c represents an integer of 0 or 1 to 3, provided that when c is 2 or more, R ₁ is the same or different. R ₃ is independently the same as R ₁ , b represents 0 or an integer of 1 to 4, and when b is 2 or more, R ₃ may be the same or different.
The general formula (2) is represented by the general formula (7)

(In the formula, R ₁ , R _2, R ₃ , b and c are the same as those in the general formula (6).)
The general formula (3) is represented by the general formula (8)

(In the formula, R ₁ , R _2, R ₃ , b and c are the same as those in the general formula (6).)
The method for producing 1- (4-hydroxyphenyl) -1-cyclohexene represented by the formula is a preferred embodiment of the present invention.

（式中、Ｒ_１、Ｒ_３、ｂ及びｃは一般式（６）のそれと同じである。）
で表される１−（４−ヒドロキシフェニル）−１−シクロヘキセン類の製造方法は、本発明の好ましい態様である。 In the cyclohexanones represented by the general formula (5), the general formula (5) when at least one of R ₁ is an aryl group is represented by the general formula (9).

(In the formula, R ₁ , R ₃ , b and c are the same as those in the general formula (6).)
The method for producing 1- (4-hydroxyphenyl) -1-cyclohexene represented by the formula is a preferred embodiment of the present invention.

  According to the method for producing 1- (4-hydroxyphenyl) -1-cyclohexenes of the present invention, conventional p, p-forms obtained from phenols and cyclohexanones, which are direct raw materials subjected to thermal decomposition, are obtained. Compared with the production method in which 1-bis (4-hydroxyphenyl) cyclohexane is thermally decomposed, by using a mixture of p, p-isomer and o, p-isomer directly as a raw material, such a mixture is The reaction with cyclohexanones can be obtained under milder and simpler conditions, such as a smaller amount of catalyst and reaction conditions such as not using a co-catalyst such as thiols. For example, the amount of alkali required for neutralization is greatly reduced. Thus, the volumetric efficiency is improved, which is advantageous for industrial implementation.

  Moreover, since it is not necessary to use a cocatalyst, it becomes possible to eliminate a trace amount of impurities of the organic sulfur compound in the obtained 1- (4-hydroxyphenyl) -1-cyclohexenes, and the organic sulfur component is not preferable. It is advantageous for use in applications.

（式中、Ｒ_１はアルキル基、アルコキシ基、アリール基、アリールオキシ基またはハロゲンを示し、Ｒ_２は水素原子、アルキル基、アルコキシ基、アリール基、アリールオキシ基またはハロゲンを示し、ａは０又は１〜４の整数を表す。ただし、ａが２以上の場合に、Ｒ_１は同一でも異なっていてもよい。）
で表される１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン（化合物１）と、一般式（２）

（式中、Ｒ_１、Ｒ_２、ａは一般式（１）のそれと同じである。）
で表される１−（４−ヒドロキシフェニル）−１−（２−ヒドロキシフェニル）シクロヘキサン（化合物２）を化合物１／化合物２の重量比で９０／１０〜５０／５０で含む混合物が用いられる。 According to the method for producing 1- (4-hydroxyphenyl) -1-cyclohexenes of the present invention, as a direct raw material to be subjected to a thermal decomposition reaction, the general formula (1)

(Wherein R ₁ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a halogen; R ₂ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a halogen; Or an integer of 1 to 4. However, when a is 2 or more, R ₁ may be the same or different.
1,1-bis (4-hydroxyphenyl) cyclohexane (compound 1) represented by the general formula (2)

(In the formula, R _1, R _{2 and} a are the same as those in the general formula (1).)
1- (4-hydroxyphenyl) -1- (2-hydroxyphenyl) cyclohexane (compound 2) represented by the formula (1) is used at a weight ratio of compound 1 / compound 2 at 90/10 to 50/50.

In the general formulas (1) to (2), in the formula, R ₁ represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a halogen, and R ₂ represents a hydrogen atom, an alkyl group, an alkoxy group or an aryl group. Represents an aryloxy group or halogen.
The alkyl group represented by R _{1 to} R ₂ is an alkyl group having 1 to 12 carbon atoms, and may be linear, branched or cyclic, for example, methyl group, ethyl group, isopropyl group And a linear alkyl group such as a t-butyl group or a cyclic alkyl group such as a cyclohexyl group, a cyclopentyl group, or a 4-methylcyclohexyl group. Such an alkyl group may be substituted with an aryl group such as a phenyl group or an alkoxy group such as a methoxy group, or may be a halogenated alkyl substituted with a halogen group.

  The alkoxy group is an alkoxy group having 1 to 12 carbon atoms, for example, a linear or branched alkoxy group such as a methoxy group, an ethoxy group, or a butoxy group, or a cyclic alkoxy group such as a cyclohexyloxy group or a cyclopentyloxy group. Can be mentioned. Such an alkoxy group may be substituted with an aryl group such as a phenyl group or an alkoxy group such as a methoxy group, or may be a halogenated alkoxy group substituted with chlorine or the like.

  Examples of the aryl group include a phenyl group, a 4-hydroxyphenyl group, a substituted or unsubstituted phenyl group of a 4-methylphenyl group, and the like.

  Examples of the aryloxy group include substituted or unsubstituted phenyloxy groups such as a phenoxy group and 4-methylphenoxy group.

Preferable R ₁ is an alkyl group, an alkoxy group or a phenyl group, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group, a cycloalkyl group having 5 to 8 carbon atoms, It is a cycloalkoxy group or a substituted or unsubstituted phenyl group, and more preferable R ₁ is a 4-hydroxyphenyl group.
The preferred substitution position of R ₁ is the 3-position, 4-position or 5-position with respect to the substitution position of the 1,1- (hydroxyphenyl) group.

R ₂ is preferably an alkyl group, an alkoxy group or a phenyl group, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group, a cycloalkyl group having 5 to 8 carbon atoms, A cycloalkoxy group, a substituted or unsubstituted phenyl group, and more preferable R ₂ is a linear or branched alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms.

Moreover, in formula, a represents the integer of 0 or 1-4, Preferably it is 0 or 1-3, More preferably, it is 1. When a is 2 or more, R _{1 s} may be the same or different, and may be substituted with the same carbon atom or with different carbon atoms, but are preferably substituted with different carbon atoms. preferable.

（式中、Ｒ_１、Ｒ_２は一般式（１）のそれと同じであり、ｃは０又は１〜３の整数を表し、ただし、ｃが２以上の場合、Ｒ_１は同一でも異なっていてもよく、Ｒ_３は独立してＲ_１と同じであり、ｂは０又は１〜４の整数を表し、ｂが２以上の場合に、Ｒ_３は同一でも異なっていてもよい。）
一般式（７）

（式中、Ｒ_１、Ｒ_２、Ｒ_３、ｂ及びｃは一般式（６）のそれと同じである。） Accordingly, 1,1-bis (4-hydroxyphenyl) cyclohexane (compound 1) represented by the general formula (1) to 1- (4-hydroxyphenyl) -1- (2 represented by the general formula (2) -Hydroxyphenyl) cyclohexane (compound 2) is more preferably represented by the following general formula (6) to general formula (7).
General formula (6)

(In the formula, R ₁ and R ₂ are the same as those in the general formula (1), c represents an integer of 0 or 1 to 3, provided that when c is 2 or more, R ₁ is the same or different. R ₃ is independently the same as R ₁ , b represents 0 or an integer of 1 to 4, and when b is 2 or more, R ₃ may be the same or different.
General formula (7)

(In the formula, R ₁ , R _2, R ₃ , b and c are the same as those in the general formula (6).)

In the general formulas (6) to (7), R ₁ and R ₂ are the same as those in the general formula (1), R ₃ is independently the same as R ₁ , and therefore R ₃ is An alkyl group, an alkoxy group, an aryl group, an aryloxy group or a halogen; R ₃ is preferably an alkyl group or an alkoxy group, more preferably a linear or branched alkyl group or alkoxy group having 1 to 8 carbon atoms, or a cycloalkyl group or cycloalkoxy group having 5 to 8 carbon atoms. .

In the formula, c represents an integer of 0 or 1 to 3, preferably 0 or 1 to 2, provided that when c is 2 or more, R ₁ may be the same or different, and b is 0 Or it represents the integer of 1-4, Preferably it is 0 or 1-3, When b is 2 or more, R < ₃ > may be same or different.

Therefore, it is represented by 1,1-bis (4-hydroxyphenyl) cyclohexane (compound 1) to general formula (2) or general formula (7) represented by general formula (1) or general formula (6). As 1- (4-hydroxyphenyl) -1- (2-hydroxyphenyl) cyclohexane (compound 2), specifically, for example,
As general formula (1) or general formula (6),
1,1-bis (4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane, 1-bis (3-isopropyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, etc. Named,
As general formula (2) or general formula (7),
1- (4-hydroxyphenyl) -1- (2-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane, 1- (3-methyl-4-hydroxyphenyl) -1- (3-methyl-2- Hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane, 1- (3-isopropyl-4-hydroxyphenyl) -1- (3-isopropyl-2-hydroxyphenyl) -4- (4-hydroxyphenyl) cyclohexane, Examples include 1- (3-methyl-4-hydroxyphenyl) -1- (3-methyl-2-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

In the production method of the present invention, such compound 1 and compound 2 contain 90/10 to 50/50, preferably 70/30 to 85/15, more preferably 75/25 to 80/20 by weight ratio. 1- (4-hydroxyphenyl) -1-cyclohexene, which is the target product, is obtained by thermally decomposing the mixture directly as a raw material in the presence of a basic catalyst.
In the production method of the present invention, by using a mixture containing compound 1 and compound 2 in such a weight ratio range as a raw material, the raw material compound is used as a raw material rather than using the p and p bodies used in the conventional production method. Can be obtained easily and efficiently industrially, and preferably, it is equivalent to or more than that obtained in the conventional thermal decomposition reaction using p and p isomers in a high yield and high purity. -(4-Hydroxyphenyl) -1-cyclohexenes can be obtained.

As a thermal decomposition method, for example, the same method as described in JP-A-2002-308809 can be used.
Specifically, for example, the thermal decomposition of the mixture containing Compound 1 and Compound 2 is performed in the presence of a basic catalyst. Examples of the basic catalyst include, but are not limited to, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, List alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, alkali metal phenoxides such as sodium phenoxide and potassium phenoxide, alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide and barium hydroxide Can do. Of these, sodium hydroxide or potassium hydroxide is particularly preferably used.

  In the production method of the present invention, the basic catalysts are 1,1-bis (4-hydroxyphenyl) cyclohexane (compound 1) and 1- (4-hydroxyphenyl) -1- (2-hydroxyphenyl) cyclohexane (compound 2). ) Is usually used in the range of 0.5 to 20 mol%, preferably 0.8 to 4.0 mol%. Although there is no restriction | limiting in particular in the usage form of a catalyst, From the point that preparation operation is easy, Preferably, it uses as a 50 to 50 weight% aqueous solution.

According to the present invention, the thermal decomposition of the mixture of the compound 1 and the compound 2 has a high melting point of the mixture of the raw material compound 1 and the compound 2 and / or the reaction product resulting from the thermal decomposition. In order to improve the liquid property at the thermal decomposition temperature of the mixture of 2, and further to prevent thermal polymerization of the reaction product due to the thermal decomposition, it is preferably carried out in the presence of a reaction solvent.
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. For example, triethylene glycol, tetraethylene glycol, pentaethylene glycol Polyethylene glycols such as, polypropylene glycols such as tripropylene glycol and tetrapropylene glycol, and polyhydric alcohols such as glycerin are used. Further, “Therm S” (manufactured by Nippon Steel Chemical Co., Ltd.) and “SK-OIL” (manufactured by Soken Chemical Co., Ltd.), which are commercially available organic heat transfer media, are also used.

According to the present invention, such a solvent is usually used in an amount of 10 to 150 parts by weight, preferably 30 to 100 parts by weight, based on 100 parts by weight of the mixture of Compound 1 and Compound 2 to be used.
According to the invention, the thermal decomposition of the mixture of compound 1 and compound 2 is usually carried out at a temperature in the range of 150-300 ° C, preferably in the range of 180-250 ° C. This is because when the thermal decomposition temperature is too low, the reaction rate is too slow, while when the thermal decomposition temperature is too high, undesirable side reactions increase. The reaction pressure for thermal decomposition is not particularly limited, but is usually in the range from normal pressure to reduced pressure, preferably under reduced pressure such that phenols to be decomposed are distilled off, For example, it is in the range of 0.1 to 101.3 kPa (absolute pressure), preferably in the range of 2.6 to 6.7 kPa (absolute pressure).

Under such reaction conditions, the thermal decomposition of the mixture of Compound 1 and Compound 2 is usually completed in about 1 to 6 hours. The end point of the thermal decomposition reaction can be, for example, the point in time when phenols produced by the decomposition reaction are no longer distilled.
According to a preferred embodiment, the thermal decomposition reaction of the mixture of Compound 1 and Compound 2 is carried out, for example, by charging a reaction vessel with a mixture of Compound 1 and Compound 2, a basic catalyst, a solvent such as tetraethylene glycol, and the temperature of 190 to 220 ° C. The reaction is carried out by stirring while distilling off the phenols produced by the decomposition reaction at a pressure of 2.6 to 6.7 kPa (absolute pressure) for about 3 to 6 hours.

According to the present invention, after completion of the thermal decomposition reaction of such a mixture of compound 1 and compound 2, the aqueous catalyst is neutralized by adding an aqueous acid solution to the obtained reaction mixture to thereby neutralize the basic catalyst. Can be obtained. According to the present invention, from such a water-containing oily reaction mixture, the reaction product is separated and purified according to a conventional method, if necessary, to obtain the desired 1- (4-hydroxyphenyl) -1-cyclohexene. Can be obtained as a high-purity product.
Separation and purification methods include, for example, adding an organic solvent such as methyl isobutyl ketone and water to the water-containing oily reaction mixture, and the salt produced by the neutralization and the solvent used in the thermal decomposition reaction (for example, tetraethylene glycol). Separated as an aqueous layer, the organic solvent (for example, methyl isobutyl ketone) was distilled from the obtained oil layer by distillation or the like, and then a crystallization solvent was added to the distillation residue thus obtained, By crystallizing and purifying, a reaction product by a thermal decomposition reaction can be obtained as a refined product.

（式中、Ｒ_１、Ｒ_２、ａは一般式（１）のそれと同じである。）
で表される。 In the production method of the present invention, 1- (4-hydroxyphenyl) -1-cyclohexene, which is the target product obtained from the thermal decomposition reaction of the mixture of compound 1 and compound 2 in this way, is the starting compound 1 And corresponding to compound 2 general formula (3)

(In the formula, R _1, R _{2 and} a are the same as those in the general formula (1).)
It is represented by

In the above formula, in the formula, R _1, R _{2 and} a are the same as those in the general formula (1).
Accordingly, preferred R ₁ is an alkyl group, an alkoxy group or a phenyl group, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group, or a cycloalkyl having 5 to 8 carbon atoms. Group, a cycloalkoxy group, a substituted or unsubstituted phenyl group, and more preferable R ₁ is a 4-hydroxyphenyl group.
The preferred substitution position of R ₁ is the 3-position, 4-position or 5-position with respect to the substitution position of the 1,1- (hydroxyphenyl) group.
R ₂ is preferably an alkyl group, an alkoxy group or a phenyl group, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group, a cycloalkyl group having 5 to 8 carbon atoms, A cycloalkoxy group, a substituted or unsubstituted phenyl group, and more preferable R ₂ is a linear or branched alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms.
In the formula, a is preferably 0 or 1 to 3, more preferably 1. When a is 2 or more, R _{1 s} may be the same or different, and may be substituted with the same carbon atom or with different carbon atoms, but are preferably substituted with different carbon atoms. preferable.

（式中、Ｒ_１、Ｒ_２、Ｒ_３、ｂ及びｃは一般式（６）のそれと同じである。）
で表される。上記式において、式中、Ｒ_１、Ｒ_２、Ｒ_３、ｂ及びｃは一般式（６）のそれと同じである。 Similarly, in the 1- (4-hydroxyphenyl) -1-cyclohexenes represented by the general formula (3), a preferable example is the general formula (8).

(In the formula, R ₁ , R _2, R ₃ , b and c are the same as those in the general formula (6).)
It is represented by In the above formula, in the formula, R ₁ , R _2, R ₃ , b and c are the same as those in the general formula (6).

  Accordingly, specific examples of 1- (4-hydroxyphenyl) -1-cyclohexene include 1,4-bis (4-hydroxyphenyl) -1-cyclohexene and 1- (4-hydroxy-3-methyl). Phenyl) -4- (4-hydroxyphenyl) -1-cyclohexene, 1- (4-hydroxyphenyl) -3,3,5-trimethyl-1-cyclohexene, and the like.

（式中、Ｒ_２は一般式（１）のそれと同じである。）
で表されるフェノール類と、一般式（５）

（式中、Ｒ_１、ａは一般式（１）のそれと同じである。）
で表されるシクロヘキサノン類を、シクロヘキサノン類に対し１〜９０モル％の酸触媒存在下に脱水縮合させることにより、得ることができる。 In the production method of the present invention, such 1,1-bis (4-hydroxyphenyl) cyclohexane (Compound 1) and 1- (4-hydroxyphenyl) -1- (2-hydroxyphenyl) cyclohexane (Compound 2) Although there is no restriction | limiting in particular about the method of obtaining the mixture containing 90/10-50/50 by weight ratio, For example, Preferably the following manufacturing methods can be illustrated. That is, the general formula (4)

(Wherein R ₂ is the same as that of general formula (1).)
And phenols represented by general formula (5)

(In the formula, R ₁ and a are the same as those in the general formula (1).)
Can be obtained by dehydration condensation in the presence of 1 to 90 mol% of an acid catalyst with respect to the cyclohexanone.

In the raw material phenol represented by the general formula (4), in the formula, R ₂ is the same as that of the general formula (1). Specific examples of the phenols represented by the general formula (4) include, for example, , Phenol, o-cresol, ot-butylphenol, o-isopropylphenol, on-propylphenol, 2-methoxyphenol, 2-phenylphenol, 2-chlorophenol and the like.
In addition, in the cyclohexanones represented by the general formula (5), which is another raw material, in the formula, R ₁ and a are the same as those in the general formula (1). Therefore, preferable R ₁ is an alkyl group, an alkoxy group. Or a phenyl group, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkoxy group, substituted or unsubstituted phenyl. More preferably R ₁ is a 4-hydroxyphenyl group. In the formula, a is preferably 0 or 1 to 3, more preferably 1.

（式中、Ｒ_１、Ｒ_３、ｂ及びｃは一般式（６）のそれと同じである。）
で表される４−（４−ヒドロキシフェニル）シクロヘキサン−１−オン類である。従って、一般式（５）又は一般式（９）で表されるシクロヘキサノン類としては、具体的には例えば、
３，３，５−トリメチルシクロヘキサノン、４−イソプロピルシクロヘキサノン、４−（４−ヒドロキシフェニル）シクロヘキサノンなどが挙げられる。 Among the cyclohexanones represented by the general formula (5), it is preferable that at least one R ₁ is an aryl group.

(In the formula, R ₁ , R ₃ , b and c are the same as those in the general formula (6).)
It is 4- (4-hydroxyphenyl) cyclohexane-1-one represented by these. Therefore, as the cyclohexanones represented by the general formula (5) or the general formula (9), specifically, for example,
3,3,5-trimethylcyclohexanone, 4-isopropylcyclohexanone, 4- (4-hydroxyphenyl) cyclohexanone and the like can be mentioned.

In the production method of the present invention, 1,1-bis (4-hydroxyphenyl) cyclohexane (compound 1) and 1- (4-hydroxyphenyl) -1- (2- A method for obtaining a mixture containing 90/10 to 50/50 by weight of hydroxyphenyl) cyclohexane (compound 2) will be specifically described.
In the reaction of such phenols with cyclohexanones, the molar ratio of phenols / cyclohexanones is usually in the range of 2/1 to 10/1, preferably in the range of 4/1 to 8/1, more preferably It is used in the range of 6/1 to 4/1.

  In the reaction of the phenols with cyclohexanones, a reaction solvent may or may not be used. When using a reaction solvent, for example, an aliphatic alcohol, an aromatic hydrocarbon, or a mixed solvent thereof is used. Alcohols include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, t-butyl alcohol, isobutyl alcohol, n-, considering the reaction raw materials used, solubility of the resulting product, reaction conditions, economics of the reaction, and the like. A butyl alcohol etc. can be mentioned. Examples of the aromatic hydrocarbon solvent include toluene, xylene, cumene and the like. Such a solvent is usually used in the range of 100 to 500 parts by weight with respect to 100 parts by weight of cyclohexanone to be used, but is not limited thereto.

In the present invention, the acid catalyst is used in the range of 1 to 90 mol%, preferably 5 to 50%, more preferably 10 to 20 mol% with respect to the cyclohexanone. Examples of the acid catalyst include hydrochloric acid, dry hydrogen chloride gas, sulfuric acid, p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, and Lewis acid such as aluminum chloride. Preferred is hydrochloric acid or hydrogen chloride gas. Conventionally, in order to selectively produce p and p isomers, the condensation reaction has been performed in a region where the acid catalyst concentration is high, but the o, p isomer produced by performing the condensation reaction in a region where the acid catalyst concentration is low. It is considered that the rearrangement of p, p form is suppressed and the mixture of p, p form and o, p form is obtained in good yield.
Furthermore, according to the present invention, a cocatalyst such as mercaptan (for example, octyl mercaptan), which has been conventionally used to promote the reaction, is not used.

The reaction is usually 0-100 ° C., preferably 40-80 ° C., more preferably 50-70 ° C., with stirring, usually 5-30 hours, preferably 10-23 hours. Just do it.
After completion of the reaction, an alkali is added to the resulting 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, and obtained as necessary. After the organic layer is distilled under normal pressure or reduced pressure, an appropriate crystallization solvent is added thereto to precipitate a crude crystal, and then the crude crystal is collected by filtration. By crystallization from a solvent, a mixture of 1,1-bis (4-hydroxyphenyl) cyclohexane (Compound 1) and 1- (4-hydroxyphenyl) -1- (2-hydroxyphenyl) cyclohexane (Compound 2) A refined product can be obtained. The molar ratio of compound 1 / compound 2 in the mixture of compound 1 and compound 2 thus obtained is usually in the range of 90/10 to 50/50. In the production method of the present invention, as described above, since the amount of the acid catalyst used is small, the amount of alkali used for neutralization is also small, and the volume efficiency is excellent.

In addition, according to the present invention, the above-mentioned crude crystals and refined products can be used as raw materials for thermal decomposition in the next step. However, according to the present invention, in order to simplify the reaction step, After adding an alkali to the obtained reaction mixture to neutralize the acid catalyst, the aqueous layer is separated and removed, and thus the obtained oily reaction mixture is preferably used as a raw material for thermal decomposition in the next step.
The oily reaction mixture containing the mixture of compound 1 and compound 2 is pyrolyzed in the presence of a basic catalyst as described above to give the target 1- (4 -Hydroxyphenyl) -1-cyclohexenes can be obtained.

  Hereinafter, the present invention will be described in detail with reference to examples.

Example 1;
Preparation of 1- (3-methyl-4-hydroxyphenyl) -4- (4-hydroxyphenyl) -1-cyclohexene 270.0 g (2.5 mol) of o-cresol and 8.2 g of 35% hydrochloric acid were used in a volume of 1 L. The flask was charged and the temperature in the flask was raised to 50 ° C. While maintaining 50 ° C., 95.0 g (0.5 mol) of 4- (4-hydroxyphenyl) cyclohexanone was added to this solution over 1 hour, followed by reaction at the same temperature for 23 hours.
After completion of the reaction, the resulting reaction mixture was neutralized with 16% aqueous sodium hydroxide solution, 200 g of methyl isobutyl ketone was added, and the temperature was raised to 97 ° C. to dissolve the reaction product. After separating and removing the aqueous layer from the dissolved liquid, water was added to the oil layer and washed with water, and the aqueous layer was separated and removed. The composition of the obtained residual oil layer was 70.1% for the p and p isomers and 20.3% for the o and p isomers (measured by liquid chromatography analysis). To this, 3.1 g of 16% aqueous sodium hydroxide solution was added, the pressure in the reaction vessel was reduced to 3.0 kPa [abs], and a thermal decomposition reaction was performed for 3 hours while distilling o-cresol generated at 195 ° C. . The time when the distillate stopped distilling was regarded as the end point of the reaction. After adding o-cresol and methyl isobutyl ketone to the resulting distillation residue, an aqueous acetic acid solution was added to neutralize to about pH 6.
After completion of neutralization, the aqueous layer was removed, and water was added to the obtained oil layer and washed with water to remove the aqueous layer. Thereafter, methyl isobutyl ketone was distilled off under reduced pressure from the obtained oil layer, and toluene was added to the resulting concentrated residual liquid for crystallization. The crystallized liquid was cooled and filtered, and the resulting crystal was dried to give 1- (3-methyl-4-hydroxyphenyl) -4- (4) having a purity of 98.1% (measured by high performance liquid chromatography analysis). 100.2 g of -hydroxyphenyl) -1-cyclohexene was obtained as a white powder. The yield based on the raw material 4- (4-hydroxyphenyl) cyclohexanone was 71.5%.

Reference Example 1;
135 g (1.25 mol) of o-cresol, 1.5 g of methanol, and 4.07 g (0.04 mol) of 35% hydrochloric acid were charged into a 500 mL four-necked flask, and the temperature in the flask was raised to 40 ° C. While maintaining 40 ° C., 47.5 g (0.25 mol) of 4- (4-hydroxyphenyl) cyclohexanone was added to this solution over 1 hour, followed by reaction at 50 to 55 ° C. for 1 hour, and then 75 ° C. The temperature was raised to about 2 hours. Thereafter, the mixture was further reacted at 74 to 78 ° C. for 2.5 hours.
The composition of the reaction solution after completion of the reaction is 77.4% for the p and p isomers and 12.7% for the o and p isomers (p, p isomer / o, p isomer = 85.9 / 14.1) (Measurement by liquid chromatography analysis).

Reference Example 2;
A reaction vessel was charged with 10 g (93 mmol) of o-cresol, 0.1 g (0.5 mmol) of p-toluenesulfonic acid, and 3.5 g (18 mmol) of 4- (4-hydroxyphenyl) cyclohexanone. The reaction was carried out at 0 ° C. for 8 hours.
The composition of the reaction solution at the end of the reaction was 39.7% for the p and p isomers and 27% for the o and p isomers (p, p / o, p = 59.5 / 40.5). (Measured by liquid chromatography analysis).

Claims (4)

General formula (6)

(Wherein R ₁ and R ₃ each independently represents an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a halogen, and R ₂ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or Represents halogen, c represents an integer of 0 or 1 to 3, provided that when c is 2 or more, R ₁ may be the same or different; b represents an integer of 0 or 1 to 4; In the case of 2 or more, R ₃ may be the same or different from each other.)
1,1-bis (4-hydroxyphenyl) cyclohexane (compound 1) represented by the general formula (7)

(In the formula, R ₁ , R _2, R ₃ , b and c are the same as those in the general formula (6).)
A mixture of 1 / (4-hydroxyphenyl) -1- (2-hydroxyphenyl) cyclohexane (compound 2) represented by the formula (1) with a weight ratio of compound 1 / compound 2 of 90/10 to 50/50 is a basic catalyst. Which is thermally decomposed in the presence of the general formula (8)

(In the formula, R ₁ , R _2, R ₃ , b and c are the same as those in the general formula (6).)
The manufacturing method of 1- (4-hydroxyphenyl) -1-cyclohexene represented by these. As a step of obtaining a mixture of the compound 1 and the compound 2,
General formula (4)

(In the formula, R ₂ is the same as that in the general formula (6).)
And phenols represented by the general formula (9)

(In the formula, R ₁ , R ₃ , b and c are the same as those in the general formula (6).)
The process according to claim 1, wherein the process comprises a step of dehydrating and condensing the cyclohexanone represented by the following formula in the presence of 1 to 90 mol% of an acid catalyst with respect to the cyclohexanone without using a cocatalyst. A process for producing-(4-hydroxyphenyl) -1-cyclohexenes.   The method for producing 1- (4-hydroxyphenyl) -1-cyclohexene according to claim 2, wherein the acid catalyst is hydrochloric acid and / or hydrogen chloride.   The method for producing 1- (4-hydroxyphenyl) -1-cyclohexene according to claim 2 or 3, wherein a reaction temperature of the dehydration condensation is 50C to 70C.