JP6205349B2 - Novel bis (4-hydroxyphenyl) cyclohexenes - Google Patents

Description

  The present invention relates to novel bis (4-hydroxyphenyl) cyclohexenes. More specifically, the present invention relates to a novel bis (4-hydroxyphenyl) having excellent solubility in a solvent in which two hydroxyphenyl groups are bonded to the cyclohexene ring skeleton at the 1,3-position or 1,5-position. ) Regarding cyclohexenes.

Conventionally, polyphenols have been used in various fields as raw materials for thermoplastic synthetic resins such as polycarbonate resins, thermosetting resin materials such as epoxy resins, or raw materials for photosensitive materials such as photoresists for semiconductors.
In recent years, with the increasing demand for improvement in various performances in these application fields, the performance required for polyphenols as raw materials has been further advanced and refined. As one of such performance improvement requirements, when polyphenols are used as raw materials for various compositions and resins, they are excellent in solubility and reactivity in solvents, and are heat resistant when used as compositions and resins. There has been a demand for polyphenols having excellent performance and the like.
When used as such a raw material, the present inventors have excellent solubility and reactivity in a solvent, and when used as a composition or resin, bis ( We focused on 4-hydroxyphenyl) cyclohexenes.
Conventionally, as bis (4-hydroxyphenyl) cyclohexenes, for example, several compounds such as 1,4-bis (4-hydroxyphenyl) -1-cyclohexenes (Patent Document 1) are known. However, all of these compounds are not sufficiently soluble in solvents, and improvements have been demanded.

JP 2002-308809 A

  An object of the present invention is to provide bis (4-hydroxyphenyl) cyclohexenes excellent in solubility in solvents and reactivity.

  As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that bis (4-hydroxyphenyl) in which two hydroxyphenyl groups are bonded to the cyclohexene ring skeleton in the 1,3-position or 1,5-position The present inventors have found that cyclohexenes have a low melting point and excellent solubility in a solvent, and that such bis (4-hydroxyphenyl) cyclohexenes have not been known so far.

That is, according to the present invention,
General formula (1)
(Wherein, R _1, R ₂ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group, a hydroxyl group or a halogen atom, R ₃ Represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyloxy group or a halogen atom, and n and m each independently represent an integer of 0 to 4, for but 2 or more, R ₁ may be the same or different, when m is 2 or more, R ₂ may be the same or different, k is an integer of 0 to 7, R ₃ is the general In the formula (1), the carbon atom to which the 4-hydroxyphenyl group is bonded is not substituted, and when k is 2 or more, R ₃ may be the same or different, and R ₂ may be substituted. The bonding position of the hydroxyphenyl group is the 3rd or 5th position of the cyclohexene ring There. Bis (4-hydroxyphenyl) cyclohexene compound represented by) is provided.

In addition, the general formula (2)
(In the formula, R ₁ , R ₂ , R ₃ , n, m, k are the same as those in the general formula (1).) 1,3-bis (4-hydroxyphenyl) -1-cyclohexene And general formula (3)
(In the formula, R ₁ , R ₂ , R ₃ , n, m, and k are the same as those in the general formula (1).)
An isomer mixture composed of 1,5-bis (4-hydroxyphenyl) -1-cyclohexene represented by the formula is a preferred embodiment of the bis (4-hydroxyphenyl) cyclohexene of the present invention.
The 1,3-bis (4-hydroxyphenyl) -1-cyclohexene represented by the general formula (2) is an embodiment of the bis (4-hydroxyphenyl) cyclohexene of the present invention.
The 1,5-bis (4-hydroxyphenyl) -1-cyclohexene represented by the general formula (3) is an embodiment of the bis (4-hydroxyphenyl) cyclohexene of the present invention.

Since bis (4-hydroxyphenyl) cyclohexenes according to the present invention have a 1,3- or 1,5-cyclohexenylene structure in the central skeleton, conventional 1,4-bis (4-hydroxyphenyl) -1- The melting point is lower than that of cyclohexenes and the solvent solubility is excellent. Therefore, derivatives and resins obtained from the compounds of the present application are also expected to have a low melting point and excellent solvent solubility.
Therefore, when used as a synthetic raw material, it is easy to handle such as reducing the amount of solvent used, and for example, a polymerization reaction such as an epoxy resin curing reaction can be performed at a lower temperature or in a molten state (no solvent). Also, it has excellent compatibility with other resins, is easy to handle, has excellent operability, and has excellent heat resistance and mechanical properties when used as a resin, or used as a composition In this case, it is expected that crystals are difficult to precipitate and storage stability is excellent.
Therefore, the bis (4-hydroxyphenyl) cyclohexenes according to the present invention are expected to be useful as raw materials for synthetic resins such as polyester, polycarbonate, and polyurethane, and as raw materials for photoresists such as semiconductors. It is also useful as a raw material.

Hereinafter, the bis (4-hydroxyphenyl) cyclohexenes of the present invention will be described in detail.
The bis (4-hydroxyphenyl) cyclohexenes of the present invention are
General formula (1)
(Wherein, R _1, R ₂ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group, a hydroxyl group or a halogen atom, R ₃ Represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyloxy group or a halogen atom, and n and m each independently represent an integer of 0 to 4, for but 2 or more, R ₁ may be the same or different, when m is 2 or more, R ₂ may be the same or different, k is an integer of 0 to 7, R ₃ is the general In the formula (1), the carbon atom to which the 4-hydroxyphenyl group is bonded is not substituted, and when k is 2 or more, R ₃ may be the same or different, and R ₂ may be substituted. The bonding position of the hydroxyphenyl group is the 3rd or 5th position of the cyclohexene ring A.)
It is represented by

Specific examples of the alkyl group having 1 to 8 carbon atoms represented by R ₁ and R ₂ in the bis (4-hydroxyphenyl) cyclohexene represented by the general formula (1) include, for example, methyl group, ethyl Linear or branched alkyl such as a group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, 2-methylpentyl group, n-hexyl group, n-heptyl group And cyclic alkyl groups such as a cyclopentyl group and a cyclohexyl group.
A linear or branched alkyl group having 1 to 4 carbon atoms and a cyclic alkyl group having 5 to 6 carbon atoms are preferable.
In addition, a halogen atom, an alkoxy group, a phenyl group or the like may be substituted on the alkyl group as long as the effects of the present invention are not hindered. Moreover, it does not need to be substituted.
Specific examples of the alkoxy group having 1 to 8 carbon atoms represented by R ₁ and R ₂ include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, t- Linear or branched alkoxy groups such as butoxy group, s-butoxy group, n-heptyloxy group, 2-methylpentyloxy group, n-hexyloxy group, cycloalkoxy such as cyclopentyloxy group or cyclohexyloxy group Groups.
Preferred are a linear or branched alkoxy group having 1 to 4 carbon atoms and a cycloalkoxy group having 5 to 6 carbon atoms.
The alkoxy group may be substituted with a halogen atom, an alkoxy group, a phenyl group, or the like as long as the effects of the present invention are not impaired. Moreover, it does not need to be substituted.
When R ₁ and R ₂ are a phenyl group or a phenyloxy group, the phenyl group, the phenyloxy group may be an alkyl group such as a methyl group, an alkoxy group such as a methoxy group, a halogen atom, etc. May be substituted. Moreover, it does not need to be substituted.
When R ₁ and R ₂ are halogen atoms, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In addition, the substitution numbers n and m of such a substituent to the hydroxyphenyl group are each an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 2, and further preferably 0 or 1. Particularly when R ₁ and R ₂ are a phenyl group, a phenyloxy group, a hydroxyl group or a halogen atom, n and m are preferably 0 or 1.
Further, R _1, the substitution position of R ₂ when n or m is 1 or more, 2-position of the 4-hydroxyphenyl group, 3-position or 5-position is preferred. When 3-substituted (when a is 3 or b is 3), 2-position, 3-position and 5-position of 4-hydroxyphenyl group are preferred, and when 2-substituted (when a is 2 or b is 2) Is preferably the 3-position and 5-position, or the 2-position and 5-position of the 4-hydroxyphenyl group, and when one is substituted (when a is 1 or b is 1), the 3-position of the 4-hydroxyphenyl group is preferred.

Accordingly, in the bis (4-hydroxyphenyl) cyclohexenes of the present invention represented by the general formula (1), preferred bis (4-hydroxyphenyl) cyclohexenes include R ₁ and R ₂ groups in the general formula (1). Are represented by the following general formula (5) corresponding to compounds which may have 2-position, 3-position and 5-position respectively.
Wherein R ₅ and R ₇ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyloxy group, a hydroxyl group or a halogen atom. , R ₆ , R ₈ , R ₉ and R ₁₀ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyloxy group or a halogen atom. And the bonding position of the hydroxyphenyl group substituted by R ₇ and R ₈ is the 3- or 5-position of the cyclohexene ring, and R ₃ and k are the same as those in the general formula (1).
It is represented by
In the general formula (5), R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are alkyl groups having 1 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, phenyl groups, and phenyloxy groups. In the case of a halogen atom, specific examples, preferred examples and preferred ranges are the same as those for R ₁ and R ₂ , respectively.
R ₅ and R ₆ are preferably not tertiary alkyl groups, and when one is a tertiary alkyl group, the other is preferably a hydrogen atom, primary alkyl group or secondary alkyl group, and R ₇ And R ₈ are preferably not tertiary alkyl groups, and when one is a tertiary alkyl group, the other is preferably a hydrogen atom, a primary alkyl group or a secondary alkyl group.
R ₉ is preferably a hydrogen atom, an alkyl group or an alkoxy group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
In synthetically obtained easily reason, it is preferred that R ₁₀ is a hydrogen atom, an alkyl group or an alkoxy group with R _9, R ₁₀ is more preferably a hydrogen atom, or a methyl group together with R _9, R ₁₀ is A hydrogen atom together with R ₉ is particularly preferred.
In the bis (4-hydroxyphenyl) cyclohexene represented by the general formula (1), an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group represented by R ₃ Specific examples, preferred examples and preferred ranges of the phenyloxy group and halogen atom are the same as those for R _{1 and} R ₂ , respectively. Particularly preferred are a methyl group and an ethyl group.
Moreover, k has shown the integer of 0-7, Among these, k is preferably 0-2, and 0 or 1 is more preferable. When k is 2 or more, it is preferable not to substitute two or more of the same carbon atoms constituting the ring, and bis (4-hydroxyphenyl) cyclohexene represented by the general formula (1) is represented by the general formula (2). In the case where k is 1 or more, R ₃ is preferably bonded to the 4-position carbon atom and / or the 5-position carbon atom of the 1-cyclohexene-1,3-diyl group. In the case where the bis (4-hydroxyphenyl) cyclohexene represented by (1) is represented by the general formula (3), when k is 1 or more, R ₃ is ₃ of 1-cyclohexene-1,5-diyl group. It is preferably bonded to the carbon atom at the position and / or the carbon atom at the 4-position.

  Therefore, specific examples of the bis (4-hydroxyphenyl) cyclohexene represented by the general formula (1) include 1,3-bis (4-hydroxyphenyl) -1-cyclohexene and 1,5-bis ( 4-hydroxyphenyl) -1-cyclohexene, 1,3-bis (3-methyl-4-hydroxyphenyl) -1-cyclohexene, 1,5-bis (3-methyl-4-hydroxyphenyl) -1-cyclohexene, 1,3-bis (3-t-butyl-4-hydroxyphenyl) -1-cyclohexene, 1,5-bis (3-t-butyl-4-hydroxyphenyl) -1-cyclohexene, 1,3-bis ( 2,5-dimethyl-4-hydroxyphenyl) -1-cyclohexene, 1,5-bis (2,5-dimethyl-4-hydroxyphenyl) -1-cyclohex Sene, 1,3-bis (2,3,5-trimethyl-4-hydroxyphenyl) -1-cyclohexene, 1,5-bis (2,3,5-trimethyl-4-hydroxyphenyl) -1-cyclohexene, 1,3-bis (3,5-dimethyl-4-hydroxyphenyl) -1-cyclohexene, 1,5-bis (3,5-dimethyl-4-hydroxyphenyl) -1-cyclohexene, 1,3-bis ( 3-cyclohexyl-4-hydroxyphenyl) -1-cyclohexene, 1,5-bis (3-cyclohexyl-4-hydroxyphenyl) -1-cyclohexene, 1,3-bis (3-phenyl-4-hydroxyphenyl)- 1-cyclohexene, 1,5-bis (3-phenyl-4-hydroxyphenyl) -1-cyclohexene, 1,3-bis (4-hydroxy) Phenyl) -5-methyl-1-cyclohexene, 1,5-bis (4-hydroxyphenyl) -3-methyl-1-cyclohexene, 1,3-bis (4-hydroxyphenyl) -4-methyl-1-cyclohexene 1,5-bis (4-hydroxyphenyl) -4-methyl-1-cyclohexene, 1,3-bis (4-hydroxyphenyl) -2-methyl-1-cyclohexene, 1,5-bis (4-hydroxy) Phenyl) -6-methyl-1-cyclohexene, 1,3-bis (4-hydroxyphenyl) -4,4-dimethyl-1-cyclohexene, 1,5-bis (4-hydroxyphenyl) -4,4-dimethyl Examples include -1-cyclohexene.

Such bis (4-hydroxyphenyl) cyclohexenes represented by the general formula (1) according to the present invention include, for example, the following general formula (4):
(In the formula, R ₁ , R ₂ , R ₃ , n, m, and k are the same as those in the general formula (1), and R ₄ each independently represents an alkyl group having 1 to 8 carbon atoms, the number of carbon atoms. 1 to 8 represents an alkoxy group, a phenyl group, a phenyloxy group, a hydroxyl group or a halogen atom, l represents an integer of 0 to 4, and the substitution position of the hydroxyphenyl group whose substitution position is not fixed is the para position of the hydroxy group Or ortho position.)
The bis (4-hydroxyphenyl) cyclohexenes can be obtained by decomposing the trisphenols represented by the formula below under heating and / or in the presence of a catalyst. The production method by the decomposition reaction is preferable for producing bis (4-hydroxyphenyl) cyclohexenes in which R ₉ is a hydrogen atom in general formula (5) from the viewpoint of yield, and R ₉ and R ₁₀ Are more preferable for producing bis (4-hydroxyphenyl) cyclohexenes in which both are hydrogen atoms.

The reaction formula is illustrated below. In this reaction, bis (4-hydroxyphenyl) cyclohexene produced is usually obtained as an isomer mixture of the above general formula (2) and general formula (3).
Reaction formula (1)
The decomposition of the trisphenol represented by the general formula (4) may be performed in the absence of a catalyst, but is preferably performed in the presence of a catalyst. Examples of the catalyst include a basic catalyst and an acid catalyst. Preferably, the catalyst is used 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, Alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, alkali metal phenoxides such as sodium phenoxide and potassium phenoxide, alkaline catalysts such as alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide and barium hydroxide Can be mentioned. Of these, sodium hydroxide or potassium hydroxide is particularly preferably used.
Thus, when using an alkali catalyst, an alkali catalyst is 0.01-50 mol normally with respect to 100 mol of trisphenols, Preferably, it is used in the range of 0.1-20 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.

The above trisphenol decomposition reaction is carried out in order to improve the uniform liquidity when the uniformity of the raw material and catalyst in the reaction vessel is impaired at the decomposition reaction temperature due to the high viscosity of the reaction solution. Is preferably carried out in the presence of a reaction solvent in order to prevent thermal polymerization of the produced target product.
The reaction solvent is not particularly limited as long as it is inert at the decomposition reaction temperature and does not distill from the reaction mixture. For example, triethylene glycol, tetraethylene glycol, pentaethylene glycol, etc. Polyethylene glycols, polypropylene glycols such as tripropylene glycol and tetrapropylene glycol, and polyhydric alcohols such as glycerin are used.
Such a solvent is generally used in an amount of 10 to 150 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the trisphenol to be used.

The decomposition reaction of trisphenols is usually performed at a temperature in the range of 150 to 250 ° C, preferably in the range of 160 to 200 ° C. This is because when the decomposition reaction temperature is too low, the reaction rate is too slow, while when the decomposition reaction temperature is too high, undesirable side reactions increase. Further, the reaction pressure for the decomposition is not particularly limited, but is preferably a pressure range from normal pressure to reduced pressure since it is preferably a pressure capable of reacting while distilling the produced phenols. The range is .32 kPa, more preferably 1 to 10 kPa. The decomposition reaction is preferably performed in an inert atmosphere such as under a nitrogen stream.
Under such reaction conditions, trisphenols are preferably subjected to a decomposition reaction for about 1 to 10 hours. The end point of the decomposition reaction can be, for example, the point in time when the phenols produced by the decomposition reaction are no longer distilled.
According to a preferred embodiment, the trisphenol decomposition reaction is performed, for example, by charging a reaction vessel with a solvent such as trisphenols, an alkali catalyst, and tetraethylene glycol, in an inert atmosphere, at a temperature of 160 to 200 ° C., and a pressure of 1 to 10 kPa. It is carried out by stirring while distilling off phenols produced by the decomposition reaction for about 3 to 6 hours with a gauge.
Thus, by decomposing trisphenols, the bis (4-hydroxyphenyl) cyclohexenes according to the present invention can be usually obtained in a reaction yield of about 90%.

After completion of the decomposition reaction, a water-containing oily reaction mixture can be obtained by adding an aqueous acid solution such as an aqueous acetic acid solution to the resulting reaction mixture to neutralize the alkali catalyst. From such a water-containing oily reaction mixture, separation and purification can be performed according to a conventional method to obtain the target bis (4-hydroxyphenyl) cyclohexene 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 hydrated oily reaction mixture, stirring, and then the salt produced by the neutralization and the solvent used in the decomposition reaction (for example, tetraethylene glycol). ) To the aqueous layer, separated and removed together with the aqueous layer, and if necessary, the operation of adding and stirring the water to the obtained oil layer and separating and removing the aqueous layer once to several times, The organic solvent (for example, methyl isobutyl ketone) and the low-boiling point products such as phenols produced by decomposition are distilled off by distillation or the like, and a crystallization solvent is added to the distillation residue thus obtained for crystallization. Then, the precipitated crystals are separated by filtration. The precipitated crystal may be an adduct crystal (adduct crystal) with a crystallization solvent.
If the crude crystal obtained by the above crystallization is further recrystallized, filtered and dried once to several times, the target reaction product by the decomposition reaction can be obtained as a highly purified product. Preferred crystallization solvents include, for example, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic ketone solvents such as methyl isobutyl ketone, aliphatic saturated hydrocarbon solvents such as n-hexane and n-heptane, cyclohexane, cycloheptane and the like. Examples include alicyclic saturated hydrocarbon solvents.

According to the above production method, the bis (4-hydroxyphenyl) cyclohexene represented by the general formula (1) of the present invention produced by the decomposition of the trisphenol represented by the general formula (4) is usually It is obtained as an isomer mixture of the 1,3-substituted product represented by the general formula (2) and the 1,5-substituted product represented by the general formula (3).
The molar ratio of the resulting isomer mixture is not limited to a specific one depending on the raw material trisphenol, reaction conditions, etc. For example, the 2-position or 2-position of 2-cyclohexen-1-one. If there is no substituent, the isomer molar ratio of the 1,3-substituent and the 1,5-substituent is usually in the range of about 1 to about 0.6 to 1.5.
Further, from the obtained bis (4-hydroxyphenyl) cyclohexene isomer mixture, each isomer can be easily represented by the general formula (2) by a known method such as liquid chromatography or multiple crystallizations. It can be isolated as a 1,3-substituted product and a 1,5-substituted product represented by the general formula (3).
In addition, the 1,3-substituted product represented by the general formula (2) and the 1,5-substituted product represented by the general formula (3) which are bis (4-hydroxyphenyl) cyclohexenes of the present invention include Each enantiomer exists, and each enantiomer can be further isolated by a known separation method such as chromatography on an optically active column.

Moreover, in the trisphenol represented by the above general formula (4) which is a starting material for the production of the bis (4-hydroxyphenyl) cyclohexenes of the present invention, preferred trisphenols include those represented by the general formula (6). Or it represents with General formula (7).
(R ₅ , R ₆ , R ₇ and R ₈ are the same as those in formula (5), R ₁₁ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, R ₁₂ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyloxy group or a halogen atom. R ₃ and k are the same as those in general formula (1).)
Therefore, as preferable trisphenols, specifically, for example,
1,1,3-tris (4-hydroxyphenyl) cyclohexane, 1,1,3-tris (4-hydroxy-3-methylphenyl) cyclohexane, 1,1,3-tris (3,5-dimethyl-4- Hydroxyphenyl) cyclohexane, 1- (2-hydroxyphenyl) -1,3-bis (4-hydroxyphenyl) cyclohexane, 1- (2-hydroxy-3-methylphenyl) -1,3-bis (4-hydroxy-) 3-methylphenyl) cyclohexane, 1,1,3-tris (4-hydroxyphenyl) -2-methylcyclohexane, 1,1,3-tris (4-hydroxyphenyl) -4-methylcyclohexane, 1,1,3 -Tris (4-hydroxyphenyl) -6-methylcyclohexane, 1,1,3-tris (4-hydroxyphenyl) 5-methylcyclohexane, 1,1,3-tris (4-hydroxyphenyl) -5-chlorocyclohexane, 1,1,3-tris (4-hydroxy-3-methylphenyl) -4-methylcyclohexane, 1,1 , 3-tris (4-hydroxyphenyl) -4,4-dimethylcyclohexane and the like.

As a preferable method for producing such raw material trisphenols, for example, 2-cyclohexen-1-one, 3-hydroxy-cyclohexane-1-one corresponding to the production of the target raw material trisphenol, 3-hydroxycyclohexane-1-one or 3 It can be obtained by reacting-(4-hydroxyphenyl) -cyclohexane-1-one with phenols in the presence of an acid catalyst.
The reaction formula is illustrated below.
Reaction formula (2)
In the reaction formula (2), the phenols may be reacted with two or more different phenols simultaneously or sequentially.
In that case, in the three hydroxyphenyl groups, trisphenol and the same trisphenol having the same substituent, substitution position and / or number of substitutions are formed.
Another method for producing the bis (4-hydroxyphenyl) cyclohexene represented by the general formula (1) according to the present invention includes phenols and 2-cyclohexen-1-one in the reaction formula (2). Reaction with 3-hydroxycyclohexane-1-one or 3- (4-hydroxyphenyl) cyclohexane-1-one in the presence of an acid catalyst, apparently without going through trisphenol In the general formula (5), R ₉ is not a hydrogen atom, that is, R ₉ is an alkyl group having 1 to 8 carbon atoms or an alkoxyl group having 1 to 8 carbon atoms. In the production of bis (4-hydroxyphenyl) cyclohexene which is a phenyl group, a phenyloxy group or a halogen atom, 2-cyclohexene is preferable. In the case of producing by reacting -1-one or 3-hydroxycyclohexane-1-one and phenol, bis (4-hydroxy) in which R ₉ and R ₁₀ are not hydrogen atoms in general formula (5). More preferably, phenyl) cyclohexenes are produced.
It illustrates as reaction formula (3) below.
Reaction formula (3)

Reaction formula (2) in a preferred production method of the raw material trisphenols, or a reaction formula (1) in a method of producing bis (4-hydroxyphenyl) cyclohexenes of general formula (1) from phenols in one reaction step ( In the following phenols in 3), y is preferably 0 or 1-3, more preferably 0, 1 or 2, and R is not substituted at the para position of the hydroxyl group.
General formula (8)
(In the formula, each R independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyloxy group, a hydroxyl group or a halogen atom, and y represents 0 to 4) Represents an integer.)
Further, phenols in which R is not substituted in at least one of the meta positions of the hydroxyl group are preferable. When y is 1 or more, it is more preferable that R is substituted in the ortho position of the hydroxyl group.
Preferred phenols are represented by the following general formula (9).
General formula (9)
(Wherein R ₁₃ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyloxy group, a hydroxyl group or a halogen atom, and R ₁₄ and R ₁₅ are (Represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyloxy group or a halogen atom.)
From the viewpoint of yield, phenols and 2-cyclohexen-1-ones, 3-hydroxycyclohexane-1-ones or 3- (4-hydroxyphenyl) cyclohexane-1-ones are reacted in the presence of an acid catalyst. In the production method for obtaining the bis (4-hydroxyphenyl) cyclohexene of the general formula (1) in one reaction, the phenol of the general formula (9) in which R ₁₅ is not a hydrogen atom is preferable, and the general formula (4) In the preferable production method for obtaining the raw material trisphenol, the phenol of the formula (9) in which R ₁₅ is a hydrogen atom is preferable.
Specific examples of such phenols include:
Phenol, o-cresol, m-cresol, 2,6-xylenol, 2,5-xylenol, 2,3,6-trimethylphenol, 2-chlorophenol, 2-cyclohexylphenol, 2-phenylphenol, 2-isopropylphenol , 2-t-butylphenol, 2-cyclohexylphenol and the like.
Specific examples of 2-cyclohexen-1-ones include, for example,
2-cyclohexen-1-one, 6-methyl-2-cyclohexen-1-one, 2-methyl-2-cyclohexen-1-one, 2-methoxy-2-cyclohexen-1-one, 2-phenyl-2- Cyclohexen-1-one, 4-methyl-2-cyclohexen-1-one, 4-ethyl-2-cyclohexen-1-one, 4-isopropyl-2-cyclohexen-1-one, 4-t-butyl-2- Cyclohexen-1-one, 4-cyclohexyl-2-cyclohexen-1-one, 4-phenyl-2-cyclohexen-1-one, 4-phenylmethyl-2-cyclohexen-1-one, 5-methyl-2-cyclohexene -1-one, 5-ethyl-2-cyclohexen-1-one, 5-isopropyl-2-cyclohexen-1-one, 5-t-butyl Lu-2-cyclohexen-1-one, 5-n-butyl-2-cyclohexen-1-one, 5-phenyl-2-cyclohexen-1-one, 4,4-dimethyl-2-cyclohexen-1-one, Examples include 4,5-dimethyl-2-cyclohexen-1-one, 2,5-dimethyl-2-cyclohexen-1-one, 4,4,5-trimethyl-2-cyclohexen-1-one, and the like.
Specific examples of 3-hydroxycyclohexane-1-ones include 3-hydroxycyclohexane-1-one, 3-hydroxy-6-methylcyclohexane-1-one, and 3-hydroxy-2-methylcyclohexane- 1-one, 3-hydroxy-2-methoxycyclohexane-1-one, 3-hydroxy-2- (4-methoxyphenyl) cyclohexane-1-one, 3-hydroxy-4-methylcyclohexane-1-one, 3- Hydroxy-4-ethylcyclohexane-1-one, 3-hydroxy-4-isopropylcyclohexane-1-one, 3-hydroxy-4-tert-butylcyclohexane-1-one, 3-hydroxy-4-cyclohexylcyclohexane-1- ON, 3-hydroxy-4-phenylcyclohexane-1- 3-hydroxy-4-phenylmethylcyclohexane-1-one, 3-hydroxy-5-methylcyclohexane-1-one, 3-hydroxy-5-ethylcyclohexane-1-one, 3-hydroxy-5-isopropylcyclohexane -1-one, 3-hydroxy-5-t-butylcyclohexane-1-one, 3-hydroxy-5-n-butylcyclohexane-1-one, 3-hydroxy-5-phenylcyclohexane-1-one, 3- Hydroxy-2,6-dimethylcyclohexane-1-one, 3-hydroxy-4,5-dimethylcyclohexane-1-one, 3-hydroxy-5-isopropyl-2-methylcyclohexane-1-one, 3-hydroxy-5 , 5-Dimethylcyclohexane-1-one, 3-hydroxy-2,5,6- Trimethyl cyclohexane-1-one, and the like.

Moreover, as 3- (4-hydroxyphenyl) -cyclohexane-1-one, specifically, for example,
3- (4-hydroxyphenyl) -cyclohexane-1-one,
3- (4-hydroxy-3-methylphenyl) cyclohexane-1-one, 3- (4-hydroxy-3,5-dimethylphenyl) cyclohexane-1-one, 3- (4-hydroxy-3-tert-butyl Phenyl) cyclohexane-1-one, 3- (4-hydroxy-3-phenylphenyl) cyclohexane-1-one, 3- (4-hydroxyphenyl) -6-methylcyclohexane-1-one, 3- (4-hydroxy) Phenyl) -2-methylcyclohexane-1-one, 3- (4-hydroxyphenyl) -4-methylcyclohexane-1-one, 3- (4-hydroxyphenyl) -5-methylcyclohexane-1-one, and the like. It is done.

In the preferred method of obtaining the raw material trisphenols or the method of obtaining the bis (4-hydroxyphenyl) cyclohexenes of the present invention from the phenols in one reaction step, the phenols and, for example, 2-cyclohexen-1-ones or The reaction with 3-hydroxycyclohexane-1-one will be specifically described. In the reaction, the phenol is preferably 5 to 5-cyclohexen-1-one or 3-hydroxycyclohexane-1-one. It is used in a range of 30 mol times, more preferably 8 to 20 mol times. Examples of the acid catalyst include hydrochloric acid, hydrogen chloride gas, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, aluminum chloride and the like. Hydrochloric acid or hydrogen chloride gas is preferred, hydrochloric acid and / or hydrogen chloride gas is particularly preferred, and preferred usage of 35% hydrochloric acid is 2-cyclohexen-1-one or 3-hydroxycyclohexane-1-one. Preferably, it is used in a range of 0.1 to 3 mol times, more preferably 0.2 to 1 mol times, particularly preferably 0.3 to 0.6 mol times relative to the class.
Furthermore, in order to accelerate | stimulate reaction, the compound which has mercapto groups, such as alkyl mercaptans, can be used as a co-catalyst. Examples of the alkyl mercaptans include methyl mercaptan, ethyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan and the like, and the amount used is preferably 0.5 to 50 mol% with respect to 2-cyclohexen-1-ones. More preferably, it is the range of 2-30 mol%.
The reaction temperature is preferably 0 to 80 ° C, more preferably 15 to 50 ° C.
In the reaction, a solvent such as water, lower aliphatic alcohols, aromatic hydrocarbons, ethers and saturated aliphatic hydrocarbons may be used as necessary.

The reaction is carried out, for example, by charging a predetermined amount of phenols, an acid catalyst and, if necessary, a co-catalyst and a reaction solvent in a reaction vessel, raising the temperature to a predetermined reaction temperature while stirring under a nitrogen stream, A method in which 2-cyclohexen-1-ones or 3-hydroxyphenylcyclohexanes are added sequentially is preferable.
In order to isolate or purify the raw material trisphenols or the bis (4-hydroxyphenyl) cyclohexene of the present invention from the obtained reaction-terminated liquid after completion of the reaction, a known isolation or purification method can be applied. . For example, an alkaline aqueous solution is added to the reaction completion liquid to neutralize the acid catalyst, and then a solvent such as an aromatic hydrocarbon that separates from water is added, the aqueous layer is separated and removed, and the resulting oil layer is cooled. After crystallization or precipitation, the risphenols or bis (4-hydroxyphenyl) cyclohexenes of the present invention can be obtained as crystals or solids by filtration. The oil layer obtained by separating and removing the aqueous layer was added with water as necessary, stirred and washed with water, and then the operation of separating and removing the aqueous layer was repeated once or multiple times, and the washed oil layer was crystallized. The solvent and unreacted phenols are removed by distillation from the oil layer obtained by precipitation, filtration, or separation and removal of the aqueous layer, and then the solvent is added to the residue to dissolve, and the crystal is cooled and crystallized. Trisphenols or bis (4-hydroxyphenyl) cyclohexenes may be obtained by precipitation or precipitation.
When crystallization is difficult, the residue obtained by distillation can be cooled to obtain a crude product.
In the crystallization process, depending on the target trisphenol or bis (4-hydroxyphenyl) cyclohexene, it may be obtained as an adduct crystal (adduct crystal) with the solvent or raw material phenol used.
The crude crystals, solids or crude products of the trisphenols or bis (4-hydroxyphenyl) cyclohexenes obtained above can be further purified by a known purification method such as recrystallization with a solvent.
For bis (4-hydroxyphenyl) cyclohexenes obtained from phenols in a single reaction, specific examples of isomer separation / purification methods and recrystallization solvents include bis (4 Same as those described for -hydroxyphenyl) cyclohexenes.
As the raw material trisphenol used in the preferred production method of the bis (4-hydroxyphenyl) cyclohexenes of the present invention, any of the above-mentioned crude crystals, high-purity crystals, solids, compositions or adduct crystals can be used.
Moreover, about the present-application compound obtained by making it above, the use and the derivative | guide_body obtained by well-known methods, such as substituting a phenolic hydroxyl group, are demonstrated concretely.
For example, by reacting the present compound with ethylene carbonate, 1,3-bis [4- (2-hydroxyethoxy) phenyl] -1-cyclohexene or 1,5-bis [4- (2-hydroxyethoxy) phenyl] -1-cyclohexene or the like, or a mixture of isomers thereof can be obtained, and these can be used for resin raw materials such as polyester and polycarbonate.
Alternatively, by reacting with 2- (3-oxetanyl) butyl tosylate, 1,3-bis {4- [2- (3-oxetanyl)] butoxyphenyl} cyclohexene or 1,5-bis {4- [2 -(3-Oxetanyl)] butoxyphenyl} -1-cyclohexene and the like can be obtained, and an oxetane resin can be obtained using these as raw materials.
Alternatively, by reacting with 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,3-bis {4-[(6-diazo-5-oxonaphthyl) sulfonyloxy] phenyl} -1-cyclohexene or 1 , 5-bis {4-[(6-diazo-5-oxonaphthyl) sulfonyloxy] phenyl} -1-cyclohexene and the like can be used in the photosensitive composition.
Moreover, by reacting with cyanogen chloride, 1,3-bis (4-cyanatophenyl) -1-cyclohexene or 1,5-bis (4-cyanatophenyl) -1-cyclohexene is obtained, and these are It can be used as a cyanate resin raw material.
Further, 1,3-bis [4- (4-aminophenoxy) phenyl] -1-cyclohexene or 1,5-bis [4- (4) obtained by reducing a nitro compound obtained by reacting with parachloronitrobenzene. 1,3-bis [4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-yl] obtained by reacting with -aminophenoxy) phenyl] -1-cyclohexene or the like or trimellitic anhydride chloride Carbonyloxy) phenyl] -1-cyclohexene or 1,5-bis [4- (1,3-dioxo-1,3-dihydroisobenzofuran-5-ylcarbonyloxy) phenyl] -1-cyclohexene is a polyimide resin. It can be used for raw materials and epoxy resin curing agents.
Further, by reacting with acrylic acid (or methacrylic acid), 1,3-bis (4- (meth) acryloxyphenyl) -1-cyclohexene or 1,5-bis (4- (meth) acryloxyphenyl)- 1-cyclohexene and the like can be obtained, and these can be used as a raw material for a resin.
Alternatively, by reacting with methylamine and formaldehyde, 1,3-bis (3-methyl (2H, 4H-benzo [3,4-e] 1,3-oxazin-6-yl)) cyclohexene or 1,5- Bis (3-methyl (2H, 4H-benzo [3,4-e] 1,3-oxazin-6-yl)) cyclohexene or the like is obtained, and these can be used as a raw material for a resin.
Also, by reacting with formaldehyde, 1,3-bis (3,5-dihydroxymethyl-4-hydroxyphenyl) -1-cyclohexene or 1,5-bis (3,5-dihydroxymethyl-4-hydroxyphenyl)- 1-cyclohexene and the like can be obtained. Further, by reacting these compounds with methanol, 1,3-bis (3,5-dimethoxymethyl-4-hydroxyphenyl) -1-cyclohexene or 1,5-bis (3,5-dimethoxymethyl-4- Hydroxyphenyl) -1-cyclohexene and the like can be obtained. It can be used as a cross-linking material or the like in various applications including a precursor compound obtained by a reaction with formalin.
Since the compound of the present application has a plurality of phenolic hydroxyl groups as other uses, resin raw materials such as polycarbonate, polyester, polyarylate, polyetheretherketone, polyethersulfone (or polysulfone, polyphenylsulfone), novolak, and resole Also, it can be expected to be used as a curing agent for epoxy resins, a raw material for epoxy resins obtained by reacting an epoxy compound with a phenolic compound such as the present compound, other i-line resist additives, developers, and antioxidants.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not restrict | limited only to a following example.

Reference example 1
[Synthesis of 1,1,3-tris (4-hydroxyphenyl) cyclohexane]
1412 g of phenol, 78.2 g of 35% hydrochloric acid, 15.2 g of dodecyl mercaptan, and 144 g of methanol were charged into a 3 liter four-necked flask, and while maintaining the liquid temperature at 30 to 35 ° C. in a nitrogen atmosphere, 2-cyclohexene-1 -144g of ON was dripped in 10 hours, and after completion | finish of dripping, it stirred at 30 degreeC for 46 hours. After completion of the reaction, an aqueous sodium hydroxide solution was added for neutralization, and then the temperature was raised and methanol was distilled off. Thereafter, methyl isobutyl ketone and water were added to the oil layer obtained by separating and removing the aqueous layer, and the mixture was stirred and washed with water to separate the aqueous layer. Methyl isobutyl ketone and unreacted phenol were distilled off under reduced pressure from the obtained oil layer. Toluene was added to the residue, and the precipitated crystals were filtered off at room temperature and dried to obtain crude crystals (purity 95%, high performance liquid chromatography method).
The crude crystals were dissolved in methyl isobutyl ketone, water was added, stirred and washed with water, and then the aqueous layer was separated. After concentrating the obtained oil layer, toluene was added to the residue, and the precipitated crystals were filtered off at room temperature and dried to obtain 1,1,3-purity having a target purity of 99.4% (high performance liquid chromatography method). 223.2 g of tris (4-hydroxyphenyl) cyclohexane was obtained as white crystals.
Molecular weight: 359 (MH) ^- (liquid chromatography mass spectrometry)
Melting point: 202 ° C. (differential scanning calorimetry)
¹ H-NMR (400 MHz) measurement (solvent: DMSO-d6): see Table 1

Example 1
[Synthesis of a mixture of 1,3-bis (4-hydroxyphenyl) -1-cyclohexene and 1,5-bis (4-hydroxyphenyl) -1-cyclohexene]
14.0 g (49.9 mmol) of 1,1,3-tris (4-hydroxyphenyl) cyclohexane obtained in Reference Example 1 in a four-necked flask equipped with a thermometer, a condenser and a stirring blade, tetraethylene glycol After charging 9.0 g and 1.3 g (5.0 mmol) of 16% aqueous sodium hydroxide solution, the temperature was raised to 170 ° C. with stirring while reducing the pressure to 10 kPa, and then the phenol produced under reduced pressure was distilled under stirring. The decomposition reaction was further performed for 9 hours at the same temperature.
After completion of the reaction, the reaction mixture was cooled to 100 ° C. and neutralized by adding acetic acid. Further, methyl isobutyl ketone and water were added and stirred, and then the aqueous layer was separated. Water was added to the obtained oil layer and stirred, and a water washing operation for separating the water layer was performed three times. Then, after removing the solvent from the water-washed oil layer by distillation, 18 g of toluene was added for crystallization, filtration, drying, and 1,3-bis (4 with a purity of 91% (by high performance liquid chromatography). -Hydroxyphenyl) -1-cyclohexene and 1,5-bis (4-hydroxyphenyl) -1-cyclohexene mixture 6 g crystals (isomer ratio A / B = 49/51 by high performance liquid chromatography analysis) It was. Further purification was performed by preparative liquid chromatography, and 1,3-bis (4-hydroxyphenyl) -1-cyclohexene (A) and 1,5-bis (4- A mixture of hydroxyphenyl) -1-cyclohexene (B) was obtained (isomer ratio by high performance liquid chromatography analysis: A / B = 50/50).
Molecular weight: 265 (M−H) ⁻ (liquid chromatography mass spectrometry)
Melting point: 159 ° C (differential scanning calorimetry)
¹ H-NMR (400 MHz) measurement (solvent: CD3OD): see Table 2

Reference example 2
[Synthesis of 1,1,3-tris (4-hydroxy-3-methylphenyl) cyclohexane]
Orthocresol 1513.4 g, 35% hydrochloric acid 73 g, dodecyl mercaptan 14.2 g, and methanol 134.4 g were charged into a 3 liter four-necked flask and maintained at a temperature of 30 to 32 ° C. in a nitrogen atmosphere. 134.5 g of cyclohexen-1-one was added dropwise over 3.5 hours. After completion of the addition, the mixture was stirred at 30 to 32 ° C. for 22 hours. After completion of the reaction, an aqueous sodium hydroxide solution was added for neutralization, and then the temperature was raised and methanol was distilled off. Thereafter, methyl isobutyl ketone and water were added to the oil layer obtained by separating and removing the aqueous layer, followed by stirring and washing, and the aqueous layer was separated and removed. Methyl isobutyl ketone and unreacted orthocresol were distilled off under reduced pressure from the obtained oil layer. The residue was dissolved in 1-octanol, crystallized by adding cyclohexane, and the precipitated adduct crystal was filtered off at room temperature and dried to a purity of 99.2% (high performance liquid chromatography, excluding solvent). 522.5 g of white adduct crystals of 1,3-tris (4-hydroxy-3-methylphenyl) cyclohexane were obtained. As a result of analyzing this adduct crystal by gas chromatography, the amount of solvent in the adduct crystal was 16% by weight.

Example 2
[Synthesis of 1,3-bis (3-methyl-4-hydroxyphenyl) -1-cyclohexene and 1,5-bis (3-methyl-4-hydroxyphenyl) -1-cyclohexene mixture]
In a four-necked flask equipped with a thermometer, a condenser, and a stirring blade, 236.8 g of adduct crystals of 1,1,3-tris (4-hydroxy-3-methylphenyl) cyclohexane obtained in Reference Example 2, After charging 50.3 g of ethylene glycol and 12.5 g of a 16% aqueous sodium hydroxide solution and raising the liquid temperature to 190 ° C., the decomposition reaction was carried out for 2 hours while distilling out orthocresol from the reaction system under reduced pressure. . After completion of the reaction, the reaction mixture was neutralized with acetic acid, methyl isobutyl ketone and water were added and stirred, and then the aqueous layer was separated and removed. Methyl isobutyl ketone was distilled off from the obtained oil layer, and 1,3-bis (3-methyl-4-hydroxyphenyl) -1-cyclohexene (C) having a purity of 86.8% (high performance liquid chromatography method) and 1 , 5-bis (3-methyl-4-hydroxyphenyl) -1-cyclohexene (D) (132.3 g) was obtained (isomer ratio by high performance liquid chromatography analysis: C / D = 56/44). Further purification was performed by preparative liquid chromatography, and 1,3-bis (3-methyl-4-hydroxyphenyl) -1-cyclohexene and 1,5-bis having a purity of 96.8% (high performance liquid chromatography method) were obtained. A (3-methyl-4-hydroxyphenyl) -1-cyclohexene mixture was obtained (isomer ratio by high performance liquid chromatography analysis: C / D = 59/41).
Molecular weight: 293 (MH) ^- (liquid chromatography mass spectrometry)
Melting point: not confirmed
¹ H-NMR (400 MHz) measurement (solvent: CDCl ₃ ): see Table 3

Reference example 3
[Synthesis of 1,1,3-tris (3-phenyl-4-hydroxyphenyl) cyclohexane]
2-phenylphenol 177 g, dodecyl mercaptan 0.5 g, and methanol 17.7 g were charged into a 1-liter four-necked flask and the temperature was raised to 42 ° C. in a nitrogen atmosphere, then the system was saturated with hydrogen chloride gas. I blew until I did. While maintaining the internal temperature at 39 to 41 ° C., 10.1 g of 2-cyclohexen-1-one was added dropwise thereto over 2 hours, and after completion of the dropwise addition, the mixture was stirred at 39 to 41 ° C. for 25 hours while blowing hydrogen chloride gas. . After completion of the reaction, an aqueous sodium hydroxide solution was added for neutralization, and then toluene was added to separate and remove the aqueous layer. Then, water was added, stirred and washed, and toluene and unreacted 2-phenylphenol were removed by distillation under reduced pressure from the oil layer obtained by separating the aqueous layer, and the purity was 77.0% (high-speed liquid). Chromatographic method) 1,1,3-tris (3-phenyl-4-hydroxyphenyl) cyclohexane 93.6 g was obtained.

Example 3
[Synthesis of 1,3-bis (3-phenyl-4-hydroxyphenyl) -1-cyclohexene and 1,5-bis (3-phenyl-4-hydroxyphenyl) -1-cyclohexene mixture]
In a 200 ml four-necked flask equipped with a thermometer, a condenser and a stirring blade, 31.0 g of 1,1,3-tris (3-phenyl-4-hydroxyphenyl) cyclohexane obtained in Reference Example 3, tetraethylene After charging 6.1 g of glycol and 1.0 g of 16% sodium hydroxide aqueous solution and raising the liquid temperature to 200 ° C., the decomposition reaction was carried out for 3 hours while distilling 2-phenylphenol out of the reaction system under reduced pressure. It was. After completion of the reaction, the reaction mixture was neutralized by adding acetic acid, methyl isobutyl ketone and water were added and stirred to dissolve, and the aqueous layer was separated and removed. Methyl isobutyl ketone was distilled off from the obtained oil layer, and 1,3-bis (3-phenyl-4-hydroxyphenyl) -1-cyclohexene (compound E) having a purity of 64.6% (high performance liquid chromatography method) and 21.3 g of a mixture of 1,5-bis (3-phenyl-4-hydroxyphenyl) -1-cyclohexene (compound F) was obtained as a distillation residue. Further purification was performed by preparative liquid chromatography, and 1,3-bis (3-phenyl-4-hydroxyphenyl) -1-cyclohexene and 1,5-bis having a purity of 94.2% (high performance liquid chromatography method) were obtained. A (3-phenyl-4-hydroxyphenyl) -1-cyclohexene mixture was obtained (ratio by hydrogen integral value in ¹ H-NMR analysis: E / F = 51/49).
Molecular weight: 417 (M−H) ⁻ (liquid chromatography mass spectrometry)
Melting point: not confirmed
¹ H-NMR (400 MHz) measurement (solvent: CDCl ₃ ): see Table 4

Example 4
[Synthesis of 1,3-bis (2,5-dimethyl-4-hydroxyphenyl) -1-cyclohexene or 1,5-bis (2,5-dimethyl-4-hydroxyphenyl) -1-cyclohexene]
After charging 114.7 g of 2,5-xylenol, 0.5 g of dodecyl mercaptan and 51.0 g of methanol into a 500 ml four-necked flask and raising the liquid temperature to 39 ° C. in a nitrogen atmosphere, the system was filled with hydrogen chloride gas. Boiled until saturated. While maintaining the internal temperature at 39 to 40 ° C., a mixture of 10.0 g of 2-cyclohexen-1-one, 12.8 g of 2,5-xylenol and 12.8 g of methanol was added dropwise over 2 hours, and the addition was completed. Then, it stirred at 39 degreeC for 24 hours, blowing in hydrogen chloride gas. A part of the reaction solution was collected during the reaction and analyzed by a high performance liquid chromatograph mass spectrometer. As a result, two peaks having the same molecular weight as the target product were detected at almost the same retention time. After completion of the reaction, an aqueous sodium hydroxide solution was added for neutralization. Methyl isobutyl ketone was added thereto and stirred, and then filtered to obtain crystals. The crystal was mainly composed of a peak component having a slightly longer retention time among the same molecular weight peak components as those of the two detected objects. After adding methyl isobutyl ketone and water to the obtained crystals and stirring to dissolve and allowing to stand, the aqueous layer was separated and removed. After adding water to the obtained oil layer and stirring and standing, the aqueous layer was separated and removed. . The obtained oil layer was cooled and the precipitated crystals were filtered out and dried to obtain 1,5-bis (2,5-dimethyl-4-hydroxyphenyl)-with a purity of 99.7% (high performance liquid chromatography method). 9.4 g of an isomer mixture of 1-cyclohexene was obtained.
Molecular weight: 323 (M + H) ⁺ (liquid chromatography mass spectrometry)
Melting point: 247 ° C. (differential scanning calorimetry)
¹ H-NMR (400 MHz) measurement (solvent: DMSO-d6): see Table 5

Comparative Example 1
1,3-bis (4-hydroxyphenyl) -1-cyclohexene and 1,5-bis (4-hydroxyphenyl) -1-cyclohexene isomer mixture synthesized by the method of Example 1 (Example 1 compound) and Table 6 shows a comparison of melting point and solubility with 1,4-bis (4-hydroxyphenyl) -1-cyclohexene (Comparative Compound 1) synthesized by a known method.

Comparative compound 1

(Solubility measurement method)
A saturated solution was prepared by adding 3 g of a solvent to a test tube and adding a compound to be measured for solubility at 30 ° C.
After adding the target compound and stirring for 30 minutes, confirming that it is not completely dissolved, stop the stirring and settle the undissolved product, and then determine the concentration of the supernatant using a calibration curve by high performance liquid chromatography. Measure and evaluate solubility.

Application example 1
The isomer mixture of 1,3-bis (4-hydroxyphenyl) -1-cyclohexene and 1,5-bis (4-hydroxyphenyl) -1-cyclohexene synthesized in Example 1 was glycidyl etherified by a known method. The resulting 1,3-bis (4-glycidyloxyphenyl) -1-cyclohexene and 1,5-bis (4-glycidyloxyphenyl) -1-cyclohexene mixture (application example compound) and 1,4- Table 7 shows a comparison of melting points with bis (4-glycidyloxyphenyl) -1-cyclohexene (Comparative Compound 2).

Application Example Compound Synthesis Example In addition, a mixture of [1,3-bis (4- (glycidyloxy) phenyl) -1-cyclohexene and 1,5-bis (4- (glycidyloxy) phenyl) -1-cyclohexene is as follows. Synthesized according to the procedure.
A 300 ml four-necked flask equipped with a stirrer was charged with 97.0% pure 1,3-bis (4-hydroxyphenyl) -1-cyclohexene and 1,5-bis (4-hydroxyphenyl) -1-cyclohexene. 13.8 g of a mixture (isomer ratio by high performance liquid chromatography-analysis method: 49/51), 3.2 g of tetrabutylammonium bromide and 138.1 g of epichlorohydrin were charged, and the system was replaced with nitrogen gas. Stir at 22 ° C. for 22 hours. To the reaction solution, 6.0 g of sodium hydroxide was added at 20 ° C., and the mixture was further stirred for 3 hours. Next, after excess epichlorohydrin was recovered by concentration under reduced pressure, 110.4 g of methyl isobutyl ketone was added, and washing with distilled water was repeated until the pH of the aqueous layer became around 7. This oil layer was concentrated by distillation, and the precipitated crystals were separated by filtration. The obtained crystals were dried under reduced pressure at 40 ° C., and the purity was 94.6% (high performance liquid chromatography analysis method). -Bis (4- (oxiranylmethoxy) phenyl) -1-cyclohexene and 1,5-bis (4- (oxiranylmethoxy) phenyl) -1-cyclohexene mixture (hydrogen integral value in ¹ H-NMR analysis Ratio: 52/48) 8.0 g was obtained. The yield based on the raw material mixture of 1,3-bis (4-hydroxyphenyl) -1-cyclohexene and 1,5-bis (4-hydroxyphenyl) -1-cyclohexene was 42.1 mol%.
Melting point: 75 ° C (differential scanning calorimetry)

Claims (4)

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, a phenyloxy group, a hydroxyl group or a halogen atom; R ₃ Represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyloxy group or a halogen atom, and n and m each independently represent an integer of 0 to 4, When R is 2 or more, R ₁ may be the same or different, and when m is 2 or more, R ₂ may be the same or different, k represents an integer of 0 to 7, and R ₃ represents the above general formula In the formula (1), the carbon atom to which the 4-hydroxyphenyl group is bonded is not substituted, and when k is 2 or more, R ₃ may be the same or different, and R ₂ may be substituted. The bonding position of the hydroxyphenyl group is 3 in the cyclohexene ring. Or 5-position.)
The bis (4-hydroxyphenyl) cyclohexene represented by these. General formula (2)
(In the formula, R _1, R _2, R ₃ , n, m, and k are the same as those in the general formula (1).)
1,3-bis (4-hydroxyphenyl) -1-cyclohexene represented by the general formula (3)
(In the formula, R _1, R _2, R ₃ , n, m and k are the same as those in the general formula (1).)
The mixture of bis (4-hydroxyphenyl) cyclohexenes according to claim 1, which is an isomer mixture consisting of 1,5-bis (4-hydroxyphenyl) -1-cyclohexenes represented by formula (1). General formula (2)
(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, a phenyloxy group, a hydroxyl group or a halogen atom, R ₃ Represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyloxy group or a halogen atom, n and m each independently represent an integer of 0 to 4; R ₁ may be the same or different when m is 2 or more, R ₂ may be the same or different when m is 2 or more , k represents an integer of 0 to 7, and R ₃ represents the above general formula In the formula (1), the carbon atom to which the 4-hydroxyphenyl group is bonded is not substituted, and when k is 2 or more, R ₃ may be the same or different, and R ₂ may be substituted. The bonding position of the hydroxyphenyl group is the cyclohexene ring. A position or 5-position.)
1,3-bis (4-hydroxyphenyl) -1-cyclohexene represented by General formula (3)
(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, a phenyloxy group, a hydroxyl group or a halogen atom, R ₃ Represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyloxy group or a halogen atom, n and m each independently represent an integer of 0 to 4; R ₁ may be the same or different when m is 2 or more, R ₂ may be the same or different when m is 2 or more , k represents an integer of 0 to 7, and R ₃ represents the above general formula In the formula (1), the carbon atom to which the 4-hydroxyphenyl group is bonded is not substituted, and when k is 2 or more, R ₃ may be the same or different, and R ₂ may be substituted. The bonding position of the hydroxyphenyl group is the cyclohexene ring. A position or 5-position.)
1,5-bis (4-hydroxyphenyl) -1-cyclohexene represented by