JP5525206B2 - New biscyclohexenylalkanes - Google Patents

Description

  The present invention relates to novel biscyclohexenyl alkanes, and more particularly to a biscyclohexenyl alkane compound having biscyclohexenyl alkane as a central skeleton and having phenol groups bonded to both ends.

Conventionally, 4,4′-dihydroxyphenyl-bicyclohexenes are known as biscyclohexenyls (Patent Document 1). These bicyclohexene compounds are excellent in performance such as high melting point, heat resistance, weather resistance and the like, and since they have a mesogenic skeleton, raw materials for synthetic resins such as liquid crystal polyester, polyurethane, polycarbonate, display elements, semiconductors, etc. It is useful as a raw material for photoresists, and as a raw material for monomers such as oxetane, urethane, epoxy, trimellitic acid ester, and hydroxyalkoxy compound by converting a hydroxyl group into another functional group.
However, in use of these applications, it is usually necessary to dissolve the bicyclohexene compound in various solvents. However, such a bicyclohexene compound has low solubility in the solvent, and improvement is desired.

International Publication No. 2004/035513 Pamphlet

  Accordingly, an object of the present invention is to improve such 4,4'-dihydroxyphenyl-bicyclohexenes, particularly to improve solubility in solvents.

（式中、Ｒ_１、Ｒ_２は各々独立して、炭素原子数１〜８のアルキル基、炭素原子数１〜８のアルコキシ基、フェニル基またはハロゲン原子を表し、ａ、ｂは各々独立して０又は１〜３の整数を示し、Ｒ_１、Ｒ_２、ａ及びｂはそれぞれ同一でも異なっていても良く、Ｘは炭素原子数１〜２０のアルキレン基を表す。）
で表されるビスシクロヘキセニルアルカン類が提供される。
また、一般式（２）

（式中、Ｒ_３、Ｒ_４は各々独立して水素原子又は炭素原子数１〜８のアルキル基を表し、Ｒ_３、Ｒ_４は互いに結合して環を形成してもよく、Ｒ_１、Ｒ_２、ａ、ｂは一般式（１）のそれと同じである。）
で表されるビスシクロヘキセニルアルカン類は本発明の好ましい態様である。 As a result of intensive studies on the improvement of such 4,4′-dihydroxyphenyl-bicyclohexenes, the present inventors have a chemical structure having a (4-hydroxyphenyl) cyclohexene group and an alkylene group in the central skeleton. Bis (4-hydroxyphenyl-cyclohexenyl) alkanes have been found and such biscyclohexenyls are soluble in solvents while having the compound performance characteristics of 4,4′-dihydroxyphenyl-bicyclohexenes. Has been found to be improved and excellent in handling.
That is, according to the present invention, the general formula (1)

Wherein R ₁ and R ₂ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, and a and b are each independently And R ₁ , R ₂ , a and b may be the same or different, and X represents an alkylene group having 1 to 20 carbon atoms.)
The biscyclohexenyl alkane represented by these is provided.
In addition, the general formula (2)

_(Wherein, R 3, _{R 4} represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms each _{independently,} R 3, _{R 4} may be bonded to each other to form a _{ring, R} 1, R ₂ , a and b are the same as those in the general formula (1).)
Biscyclohexenylalkanes represented by the formula are preferred embodiments of the present invention.

The biscyclohexenyl alkanes of the present invention are superior in solubility in a solvent as compared with hydroxyphenylbicyclohexenes having a similar structure having two (4-hydroxyphenyl) cyclohexene groups, and are recrystallized from an organic solvent. Industrial production is easy because the resulting compound can be purified easily and efficiently.
The biscyclohexenyl alkanes of the present invention have a structure having four ring structures in which rigid (4-hydroxyphenyl) cyclohexenyl skeletons are bonded to both ends via an alkylene group in the central skeleton. Some have a high transition temperature, and polycarbonate resins obtained from such bisphenols can be expected to have excellent heat resistance. Other raw materials for synthetic resins such as polyester and polyurethane, as raw materials for photoresists such as display elements and semiconductors, or by converting the hydroxyl group to another functional group, oxetane, urethane, epoxy, trimellitic acid ester, hydroxyalkoxy compound As a monomer raw material, etc., it can be used for improving heat resistance, weather resistance, water resistance, flexibility, transparency, mechanical strength and the like. Moreover, when manufacturing resin using these as monomer raw materials, since it is excellent in the solubility in a solvent, industrial manufacture and processing are easy.

（式中、Ｒ_１、Ｒ_２は各々独立して、炭素原子数１〜８のアルキル基、炭素原子数１〜８のアルコキシ基、フェニル基またはハロゲン原子を表し、ａ、ｂは各々独立して０又は１〜３の整数を示し、Ｒ_１、Ｒ_２、ａ及びｂはそれぞれ同一でも異なっていても良く、Ｘは炭素原子数１〜２０のアルキレン基を表す。）
で表され、一般式（１）において、Ｒ_１、Ｒ_２は各々独立して、炭素原子数１〜８のアルキル基、炭素原子数１〜８のアルコキシ基、フェニル基またはハロゲン原子を表す。炭素原子数１〜８のアルキル基としては、具体的には、メチル基、エチル基、また、炭素原子数３以上のアルキル基は直鎖状、分岐鎖状また環状であってもよく、例えばｎ−プロピル基、イソプロピル基、ブチル基、ｔ−ブチル基、シクロペンチル基、シクロヘキシル基などが挙げられる。好ましくは炭素原子数１〜４の直鎖状、分岐鎖状のアルキル基、炭素原子数５〜８の環状のアルキル基である。これらのアルキル基には芳香族炭化水素基が置換していてもよく、例えば、ベンジル基、フェネチル基、α−メチルベンジル基などが挙げられる。 The biscyclohexenyl alkanes of the present invention have the following general formula (1)

Wherein R ₁ and R ₂ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, and a and b are each independently And R ₁ , R ₂ , a and b may be the same or different, and X represents an alkylene group having 1 to 20 carbon atoms.)
In general formula (1), R ₁ and R ₂ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, or a halogen atom. Specifically, as the alkyl group having 1 to 8 carbon atoms, a methyl group, an ethyl group, and an alkyl group having 3 or more carbon atoms may be linear, branched, or cyclic. Examples include n-propyl group, isopropyl group, butyl group, t-butyl group, cyclopentyl group, cyclohexyl group and the like. Preferably, it is a linear or branched alkyl group having 1 to 4 carbon atoms or a cyclic alkyl group having 5 to 8 carbon atoms. These alkyl groups may be substituted with an aromatic hydrocarbon group, and examples thereof include a benzyl group, a phenethyl group, and an α-methylbenzyl group.

  Specific examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, and an alkoxy group having 3 or more carbon atoms may be linear, branched, or cyclic. -Propoxy group, isopropoxy group, butoxy group, t-butoxy group, cyclopentyloxy group, cyclohexyloxy group and the like. Preferably, it is a linear or branched alkoxy group having 1 to 4 carbon atoms. The alkoxy group may be substituted with an aromatic hydrocarbon group.

Examples of the phenyl group include a phenyl group, an alkyl group such as a 4-methylphenyl group, a dimethylphenyl group, and a methoxyphenyl group, and an alkoxyl-substituted phenyl group. Examples of the halogen atom include a chlorine atom and a bromine atom.
Further, a, b each independently represents a 0 or an integer of 1 to 3, when R ₁ is more than one on the same or different phenylene groups, or different and each R ₁ is the same, R ₂ If there are two more on the same or different cyclohexene group, or different and each R ₂ is the same, when R ₂ is more than one on the same cyclohexene group, R ₂ is on the cyclohexene ring respectively Substitution with a different carbon atom is preferred.
Moreover, it is preferable that b is the same, More preferably, both are 0 or 1.
If b are both 1, it is preferable substitution position of R ₂ is 3-position with respect to the position of attachment to the X group. R ₂ is preferably an alkyl group, and a methyl group is particularly preferable.
Moreover, it is preferable that a is the same, More preferably, both are 0, 1 or 2. When a is 1 or 2, the substitution position of R ₁ is preferably ortho to the hydroxyl group.

（式中、Ｒ_３、Ｒ_４は一般式（２）のそれと同じである。）
一般式（３）で表されるアルキレン基において、Ｒ_３、Ｒ_４は、各々独立して水素原子または炭素原子数１〜８のアルキル基を表し、Ｒ_３、Ｒ_４は互いに結合して環を形成してもよいが、環を形成しない場合には、Ｒ_３、Ｒ_４の少なくとも一方または両方が水素原子、１級アルキル基または２級アルキル基であることが好ましい。炭素原子数１〜８のアルキル基としては直鎖状または分岐鎖状が好ましく、１級アルキル基または２級アルキル基であることが好ましい。より好ましくは炭素原子数１〜４の直鎖状、分岐鎖状の、例えばメチル基、エチル基、イソプロピル基、イソブチル基等の１級アルキル基または２級アルキル基である。従って、一般式（３）で表されるアルキレン基としては具体的には、メチレン基、１−メチルメチリデン基、１−エチルメチリデン基、１−イソプロピルメチリデン基、２，２−プロピリデン基などを挙げることができる。Ｒ_３、Ｒ_４は互いに結合して環を形成する場合には、Ｒ_３＋Ｒ_４の合計炭素原子数は１６以下であり、４〜１０が好ましい。従って、Ｒ_３、Ｒ_４は互いに結合して環を形成する場合の一般式（３）で表されるアルキレン基としては具体的には、１，１−シクロペンチリデン基、１，１−シクロヘキシリデン基、４−メチル−１，１−シクロヘキシリデン基、３，３，５−トリメチル−１，１−シクロヘキシリデン基などを挙げることができ、１，１−シクロヘキシリデン基が好ましい。 In the general formula (1), X represents an alkylene group having 1 to 20 carbon atoms. Examples of the alkylene group having 1 to 20 carbon atoms include linear, branched or cyclic alkylene groups, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. .
Further, the alkylene group having a preferred structure is specifically represented by the following general formula (3).

(In the formula, R ₃ and R ₄ are the same as those in the general formula (2).)
In the alkylene group represented by the general formula (3), R ₃ and R ₄ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ₃ and R ₄ are bonded to each other to form a ring. However, when no ring is formed, at least one or both of R ₃ and R ₄ are preferably a hydrogen atom, a primary alkyl group, or a secondary alkyl group. The alkyl group having 1 to 8 carbon atoms is preferably linear or branched, and is preferably a primary alkyl group or a secondary alkyl group. More preferably, it is a linear or branched alkyl group having 1 to 4 carbon atoms, for example, a primary alkyl group or a secondary alkyl group such as a methyl group, an ethyl group, an isopropyl group or an isobutyl group. Therefore, specific examples of the alkylene group represented by the general formula (3) include a methylene group, a 1-methylmethylidene group, a 1-ethylmethylidene group, a 1-isopropylmethylidene group, and a 2,2-propylidene group. Can do. When R ₃ and R ₄ are bonded to each other to form a ring, the total number of carbon atoms of R ₃ + R ₄ is 16 or less, preferably 4 to 10. Therefore, specific examples of the alkylene group represented by the general formula (3) when R ₃ and R ₄ are bonded to each other to form a ring include a 1,1-cyclopentylidene group, a 1,1-cyclohexene group. Examples include a silidene group, a 4-methyl-1,1-cyclohexylidene group, a 3,3,5-trimethyl-1,1-cyclohexylidene group, and a 1,1-cyclohexylidene group is preferable. .

Accordingly, in the general formula (1), when X is an alkylene group represented by the general formula (3), the general formula (1) is represented by the general formula (2).
General formula (2)

２，２−ビス［４−（４−ヒドロキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］プロパン、

２，２−ビス［４−（４−ヒドロキシ−３−フェニルフェニル）−３−シクロヘキセン−１−イル］プロパン、

２，２−ビス［４−（４−ヒドロキシ−２−メチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシ−３−エチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシ−３−イソプロピルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシ−３−t−ブチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシ−３−シクロヘキシルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシ−３−メトキシフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシ−３−クロロフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシ−３，５−ジメチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシ−２，３，５−トリメチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
２，２−ビス［４−（４−ヒドロキシフェニル）−３−メチル−３−シクロヘキセン−１−イル］プロパン、
ビス［４−（４−ヒドロキシフェニル）−３−シクロヘキセン−１−イル］メタン、
ビス［４−（４−ヒドロキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］メタン、
１，１−ビス［４−（４−ヒドロキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］エタン、
１，２−ビス［４−（４−ヒドロキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］エタン、
３−メチル−２，２−ビス［４−（４−ヒドロキシフェニル）−３−シクロヘキセン−１−イル］ペンタン、
１，１−ビス［４−（４−ヒドロキシフェニル）−３−シクロヘキセン−１−イル］シクロヘキサン、
１，１−ビス［４−（４−ヒドロキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］シクロヘキサン、
１，１−ビス［４−（４−ヒドロキシフェニル）−３−シクロヘキセン−１−イル］−３，３，５−トリメチルシクロヘキサン、
２−［４−（４−ヒドロキシフェニル）−３−シクロヘキセン−１−イル］−２−［４−（４−ヒドロキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］プロパン、
等を挙げることができる。 Accordingly, preferred specific examples of the biscyclohexenyl alkanes of the present invention include, for example,
2,2-bis [4- (4-hydroxyphenyl) -3-cyclohexen-1-yl] propane,

2,2-bis [4- (4-hydroxy-3-methylphenyl) -3-cyclohexen-1-yl] propane,

2,2-bis [4- (4-hydroxy-3-phenylphenyl) -3-cyclohexen-1-yl] propane,

2,2-bis [4- (4-hydroxy-2-methylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxy-3-ethylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxy-3-isopropylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxy-3-tert-butylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxy-3-cyclohexylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxy-3-methoxyphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxy-3-chlorophenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxy-3,5-dimethylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxy-2,3,5-trimethylphenyl) -3-cyclohexen-1-yl] propane,
2,2-bis [4- (4-hydroxyphenyl) -3-methyl-3-cyclohexen-1-yl] propane,
Bis [4- (4-hydroxyphenyl) -3-cyclohexen-1-yl] methane,
Bis [4- (4-hydroxy-3-methylphenyl) -3-cyclohexen-1-yl] methane,
1,1-bis [4- (4-hydroxy-3-methylphenyl) -3-cyclohexen-1-yl] ethane,
1,2-bis [4- (4-hydroxy-3-methylphenyl) -3-cyclohexen-1-yl] ethane,
3-methyl-2,2-bis [4- (4-hydroxyphenyl) -3-cyclohexen-1-yl] pentane,
1,1-bis [4- (4-hydroxyphenyl) -3-cyclohexen-1-yl] cyclohexane,
1,1-bis [4- (4-hydroxy-3-methylphenyl) -3-cyclohexen-1-yl] cyclohexane,
1,1-bis [4- (4-hydroxyphenyl) -3-cyclohexen-1-yl] -3,3,5-trimethylcyclohexane,
2- [4- (4-hydroxyphenyl) -3-cyclohexen-1-yl] -2- [4- (4-hydroxy-3-methylphenyl) -3-cyclohexen-1-yl] propane,
Etc.

  Such a biscyclohexenylalkane represented by the general formula (1) of the present invention is not particularly limited in its production method. For example, a known method according to the method described in JP-A-2005-247809 is used. Can be easily obtained.

一般式（４）において、式中、Ｒ_１、Ｒ_２、ａ、ｂ、Ｘは一般式（１）のそれと同じである。
直接原料であるビス｛４，４−ジ（ヒドロキシフェニル）シクロヘキシル｝アルカンとしては、一般式（４）で示されるように４，４−位の２つの末端ヒドロキシフェニルが同一であるものが好ましいが、これに限らず相互に異なっていてもよい。 Specifically, for example, as shown in reaction formula (1), bis {4,4-di (hydroxyphenyl) cyclohexyl} represented by the following general formula (4) corresponding to general formula (1) of the present invention} It can be obtained by using alkane directly as a raw material and thermally decomposing it in a solvent, preferably in the presence of an alkali.
Reaction formula (1)

In the general formula (4), in the formula, R ₁ , R ₂ , a, b, and X are the same as those in the general formula (1).
The direct raw material bis {4,4-di (hydroxyphenyl) cyclohexyl} alkane is preferably one in which the two terminal hydroxyphenyls in the 4,4-position are the same as shown in the general formula (4). Not limited to this, they may be different from each other.

More preferable raw material bis {4,4-di (hydroxyphenyl) cyclohexyl} alkane is a case where all four terminal hydroxyphenyls are the same and X is an alkylene group of the general formula (3). For example, a, b The thermal decomposition reaction of bis (4,4-dihydroxyphenylcyclohexyl) alkane in which all are 0 and X is a 2,2-propylidene group is represented by the following reaction formula (2).
Reaction formula (2)

As the bis (4,4-dihydroxyphenylcyclohexyl) alkane represented by the general formula (4), specifically, for example,
2,2-bis [4,4-di (4-hydroxyphenyl) cyclohexyl] propane,
2,2-bis [4,4-di (4-hydroxy-3-methylphenyl) cyclohexyl] propane,
2,2-bis [4,4-di (4-hydroxy-3-phenylphenyl) cyclohexyl] propane,
2,2-bis [4,4-di (4-hydroxy-3,5-dimethylphenyl) cyclohexyl] propane,
2,2-bis [4,4-di (4-hydroxy-3-methylphenyl) -3-methylcyclohexyl] propane,
2,2-bis [4,4-di (4-hydroxy-3-methylphenyl) cyclohexyl] methane,
1,1-bis [4,4-di (4-hydroxyphenyl) cyclohexyl] cyclohexane,
2- [4,4-di (4-hydroxyphenyl) cyclohexyl] -2- [4,4-di (4-hydroxy-3-methylphenyl) cyclohexyl] propane,
Etc.

ａ及び／又はＲ_１が非対称な原料ビス{４，４−ジ（ヒドロキシフェニル）シクロヘキシルアルカンを得る場合には、２種類のフェノール類を併用すればよい。 Such a raw material bis {4,4-di (hydroxyphenyl) cyclohexyl} alkane is prepared in accordance with a known method described in JP-A-2001-199920, for example, bis {4,4-di (hydroxyphenyl). When the cyclohexyl} alkane is identical in all four terminal hydroxyphenyls and X is an alkylene group of the general formula (3), as shown in the reaction formula (3), the corresponding biscyclohexanone and phenols in an organic solvent, It can be obtained by dehydration condensation in the presence of an acid catalyst.
Reaction formula (3)

When obtaining raw material bis {4,4-di (hydroxyphenyl) cyclohexylalkane in which a and / or R ₁ is asymmetric, two types of phenols may be used in combination.

  The thermal decomposition of the raw material bis {4,4-di (hydroxyphenyl) cyclohexyl} alkane represented by the general formula (4) may be performed in the absence of a catalyst. Done in the presence. The alkali catalyst is not particularly limited, but examples thereof include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and hydrogen carbonate. Examples thereof include alkali metal hydrogen carbonates such as sodium and potassium hydrogen carbonate, alkali metal phenoxides such as sodium phenoxide and potassium phenoxide, and alkaline earth metal hydroxides such as magnesium hydroxide and barium hydroxide. Among these, sodium hydroxide or potassium hydroxide is particularly preferably used.

When an alkali catalyst is used, the alkali catalyst is usually 0.01 to 30 parts by weight, preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of bis {4,4-di (hydroxyphenyl) cyclohexyl} alkane. Used in the range of parts. 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.
The thermal decomposition of the bis {4,4-di (hydroxyphenyl) cyclohexyl} alkane may be used with or without a solvent if there is no problem in operability during the reaction. , 4-di (hydroxyphenyl) cyclohexyl} alkanes and the target product, biscyclohexenylalkanes, have a high melting point. Therefore, in order to improve the liquidity at the thermal decomposition temperature, further, It is preferred to use it to prevent thermal polymerization.
In the case of using a solvent, the solvent used is not particularly limited as long as it is inert to the reaction at the thermal decomposition temperature, and one kind or a mixture of two or more kinds may be used.

Examples of such solvents include polyethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and pentaethylene glycol, and polyhydric alcohols such as tripropylene glycol, tetrapropylene glycol, and glycerin.
Also, “Therm S” (manufactured by Nippon Steel Chemical Co., Ltd.) or “SK-OIL” (manufactured by Soken Chemical Co., Ltd.), which is a commercially available organic heat medium, can be used.

Such a solvent is generally used in an amount of 20 to 2000 parts by weight, preferably 100 to 800 parts by weight, based on 100 parts by weight of bis {4,4-di (hydroxyphenyl) cyclohexyl} alkanes.
The thermal decomposition of bis (4,4-dihydroxyphenylcyclohexyl) alkanes generally has a reaction rate of slow when the thermal decomposition temperature is too low, and many undesirable side reactions occur when the thermal decomposition temperature is too high. It is carried out at a temperature in the range of -300 ° C, preferably in the range of 180-250 ° C.
In addition, the reaction pressure for the pyrolysis is not particularly limited, but is preferably a pressure at which the generated phenols can be distilled while performing the pyrolysis reaction, and is usually in the range of normal pressure to reduced pressure. Yes, for example, in the range of 1 to 101 kPa (gauge pressure), preferably in the range of 10 to 70 kPa (gauge pressure).

Under such reaction conditions, the thermal decomposition of bis {4,4-di (hydroxyphenyl) cyclohexyl} alkanes is usually completed in about 1 to 6 hours. The end point of the thermal decomposition reaction can be, for example, a point in time when phenol produced by the decomposition reaction is no longer distilled.
According to a preferred embodiment, for example, a reaction vessel is charged with a solvent such as bis {4,4-di (hydroxyphenyl) cyclohexyl} alkanes, tetraethylene glycol and sodium hydroxide, at a temperature of 190 to 220 ° C., and a pressure of 10 to 40 kPa. It is carried out by stirring while distilling off the phenols produced by the decomposition reaction at (gauge pressure) for about 3 to 6 hours. After completion of the reaction, a method for taking out the target product from the obtained reaction completion liquid can be performed by a known method. For example, neutralize the reaction completion liquid as necessary, add distilled water and a solvent as necessary, wash with water, concentrate if necessary, and collect the precipitated crystalline or amorphous solid by filtration. To do. When the purity of the obtained crystals and solids is low, such crystallization or precipitation filtration may be further performed once to plural times as necessary.

Thus, by thermally decomposing bis {4,4-di (hydroxyphenyl) cyclohexyl} alkane having a corresponding structure, the biscyclohexenylalkane of the present invention represented by the general formula (1) is obtained. It can be obtained with high yield and high purity.
As another specific example of the method for producing the biscyclohexenylalkane represented by the general formula (1) of the present invention, Journal of American Chemical Society, vol. 74, p.5631-5632 (1952) Bis (4-oxocyclohexyl) alkanes and 4-alkoxybenzenemagnesium bromides are reacted to give bis {4- (4-alkoxyphenyl) -3-cyclohexen-1-yl } Alkanes are synthesized, and then the alkyl group of the alkoxyl group of the obtained bis {4- (4-alkoxyphenyl) -3-cyclohexen-1-yl} alkanes is obtained by a known method, for example, boron tribromide. The biscyclohexenyl alkanes represented by the general formula (1) of the present invention can also be obtained by elimination with hydrogen atoms and substitution with hydrogen atoms.

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

温度計、撹拌器、蒸留装置を備えた２００ｍＬ容量の四つ口フラスコに、２，２−ビス［４，４−ジ（４−ヒドロキシフェニル）シクロヘキシル］プロパン２０ｇとエチレングリコール５０ｇと水酸化ナトリウム０．６ｇを仕込み、系内を窒素ガス置換した後、撹拌下に内温１８９℃、３０ｋＰａを保ち、フェノールを留出させながら５時間反応を行った。反応終了後、得られた反応液を９０℃まで冷却した後、酢酸０．９ｇを加えて中和し、メチルイソブチルケトン８０ｇ、蒸留水４０ｇを順に加えて撹拌した後、静置して水層を分離、除去した。得られた油層に水を加えて撹拌した後、静置して水層を除去した。
さらに、同様の操作を行い、油層を水洗した。得られた油層を減圧下に濃縮し、残った液にトルエン４０ｇを加え、晶析を行った。析出した結晶をろ別して回収し、得られた結晶を減圧下、１５０℃で乾燥させ、目的物の２，２−ビス［４−（４−ヒドロキシフェニル）−３−シクロヘキセン−１−イル］プロパン８．６ｇを純度９７％（高速液体クロマトグラフィー分析による）の薄茶色結晶として得た。
原料の２，２−ビス［４，４−ジ（４−ヒドロキシフェニル）シクロヘキシル］プロパンに対する収率は６４モル％であった。 Synthesis of 2,2-bis [4- (4-hydroxyphenyl) -3-cyclohexen-1-yl] propane

In a 200 mL capacity four-necked flask equipped with a thermometer, stirrer and distillation apparatus, 20 g of 2,2-bis [4,4-di (4-hydroxyphenyl) cyclohexyl] propane, 50 g of ethylene glycol and 0 sodium hydroxide were added. Then, the inside of the system was purged with nitrogen gas, and the reaction was carried out for 5 hours while distilling phenol while keeping the internal temperature at 189 ° C. and 30 kPa with stirring. After completion of the reaction, the resulting reaction solution was cooled to 90 ° C., neutralized by adding 0.9 g of acetic acid, 80 g of methyl isobutyl ketone and 40 g of distilled water were sequentially added and stirred, and then left to stand to form an aqueous layer. Was separated and removed. Water was added to the obtained oil layer and stirred, and then allowed to stand to remove the water layer.
Furthermore, the same operation was performed and the oil layer was washed with water. The obtained oil layer was concentrated under reduced pressure, and 40 g of toluene was added to the remaining liquid for crystallization. The precipitated crystals were collected by filtration, and the obtained crystals were dried at 150 ° C. under reduced pressure to obtain the desired 2,2-bis [4- (4-hydroxyphenyl) -3-cyclohexen-1-yl] propane. 8.6 g was obtained as light brown crystals with a purity of 97% (according to high performance liquid chromatography analysis).
The yield based on 2,2-bis [4,4-di (4-hydroxyphenyl) cyclohexyl] propane as a raw material was 64 mol%.

Melting point: 243.5 ° C. (differential scanning calorimetry (DSC))
Glass transition temperature: 88 ° C. (differential scanning calorimetry (DSC),
Measuring method: After heating up to a temperature 20 ° C. higher than the melting point of the crystals of each compound and melting, this is quenched and then heated and measured. Measurement start temperature 40 ° C., measurement end temperature: melting point + 20 ° C., heating rate: 10.0 ° C./min.
Molecular weight: 387 (M−H) ^−
1 H-NMR (400 MHz, solvent: DMSO-d6) measurement

温度計、撹拌器、蒸留装置を備えた２００ｍＬ容量の四つ口フラスコに、２，２−ビス［４，４−ジ（４−ヒドロキシ−３−メチルフェニル）シクロヘキシル］プロパン２０ｇとテトラエチレングリコール３５ｇと水酸化ナトリウム０．６ｇを仕込み、系内を窒素ガス置換した後、撹拌下に、内温２００℃、１０ｋＰａでｏ−クレゾールを留出させながら４時間反応を行った。反応終了後、得られた反応液を４５℃まで冷却した後、酢酸０．９ｇを加えて中和し、メチルイソブチルケトン８０ｇ、蒸留水４０ｇを順に加えて撹拌した後、静置して水層を分離、除去した。得られた油層に水を加えて撹拌した後、静置して水層を除去した。
さらに、同様の操作を２回行い、油層を水洗した。得られた油層を減圧下に濃縮し、残った液にトルエン４０ｇを加え、晶析を行った。析出した結晶をろ別して回収し、得られた結晶を減圧下、１５０℃で乾燥させ、目的物の２，２−ビス［４−（４−ヒドロキシ−３−メチルフェニル）−３−シクロヘキセン−１−イル］プロパン７．４ｇを純度９８％（高速液体クロマトグラフィー分析による）の薄茶色結晶として得た。
原料の２，２−ビス［４，４−ジ（４−ヒドロキシ−３−メチルフェニル）シクロヘキシル］プロパンに対する収率は５６モル％であった。 Synthesis of 2,2-bis [4- (4-hydroxy-3-methylphenyl) -3-cyclohexen-1-yl] propane

In a 200 mL four-necked flask equipped with a thermometer, stirrer and distillation apparatus, 20 g of 2,2-bis [4,4-di (4-hydroxy-3-methylphenyl) cyclohexyl] propane and 35 g of tetraethylene glycol were added. And 0.6 g of sodium hydroxide were charged, and the system was purged with nitrogen gas. Then, the reaction was carried out for 4 hours while stirring and distilling o-cresol at an internal temperature of 200 ° C. and 10 kPa. After completion of the reaction, the resulting reaction liquid was cooled to 45 ° C., neutralized by adding 0.9 g of acetic acid, added with 80 g of methyl isobutyl ketone and 40 g of distilled water in this order and stirred, and then left to stand to form an aqueous layer. Was separated and removed. Water was added to the obtained oil layer and stirred, and then allowed to stand to remove the water layer.
Furthermore, the same operation was performed twice and the oil layer was washed with water. The obtained oil layer was concentrated under reduced pressure, and 40 g of toluene was added to the remaining liquid for crystallization. The precipitated crystals were collected by filtration, and the obtained crystals were dried at 150 ° C. under reduced pressure to obtain the desired 2,2-bis [4- (4-hydroxy-3-methylphenyl) -3-cyclohexene-1 7.4 g of yl] propane were obtained as pale brown crystals with a purity of 98% (according to high performance liquid chromatography analysis).
The yield based on the raw material 2,2-bis [4,4-di (4-hydroxy-3-methylphenyl) cyclohexyl] propane was 56 mol%.

Melting point: 185.9 ° C. (differential scanning calorimetry (DSC))
Molecular weight: 415 (M−H) ^−
1 H-NMR (400 MHz, solvent: DMSO-d6) measurement

溶解度測定方法：溶液温度２２℃で各化合物の飽和溶液を作成し、この飽和溶液の濃度を液体クロマトグラフィーによる検量線で測定した。 [Comparative example]
2,2-bis [4- (4-hydroxy-3-methylphenyl) -3-cyclohexen-1-yl] propane (compound (1)) obtained in Example 2 and 4,4-bis (4- The solubility of hydroxy-3-methylphenyl) -1,1′-bicyclohexane-3,3′-diene (compound (2)) in a solvent was measured.

Solubility measurement method: A saturated solution of each compound was prepared at a solution temperature of 22 ° C., and the concentration of the saturated solution was measured with a calibration curve by liquid chromatography.

Claims (2)

General formula (1)

Wherein R ₁ and R ₂ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, and a and b are each independently And R ₁ , R ₂ , a and b may be the same or different, and X represents an alkylene group having 1 to 20 carbon atoms.)
Biscyclohexenylalkanes represented by General formula (2)

_(Wherein, R 3, _{R 4} represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms each _{independently,} R 3, _{R 4} may be bonded to each other to form a _{ring, R} 1, R ₂ , a and b are the same as those in the general formula (1).)
The biscyclohexenyl alkane of Claim 1 represented by these.