JP2002284726A - METHOD FOR PRODUCING alpha,alpha',alpha"-TRIS (4-HYDROXYPHENYL)-1,3,5- TRIALKYLBENZENE - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing several kinds of α,α',α"-tris(4- hydroxyphenyl)-1,3,5-trialkylbenzenes at a high selectivity, high yield and high purity under industrially easy conditions. SOLUTION: This method comprises performing condensation reaction of an α,α',α"-trihydroxy-1,3,5-trialkylbenzene of the general formula I (R1 and R2 are each independently H, methyl or ethyl.) with an alkylphenol of the general formula II (R3 is a 1-6C alkyl or a 5-7C cycloalkyl; and n is a 0-3 integer.) to obtain the objective α,α',α"-tris (4-hydroxyphenyl)-1,3,5-trialkylbenzene of the general formula III (R1 , R2 , R3 and n are each the same as mentioned above.).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to α, α ′, α ″-
Regarding a method for producing tris (4-hydroxyphenyl) -1,3,5-trialkylbenzenes (hereinafter sometimes referred to as TAB), for example, epoxy resin, phenol resin, polycarbonate resin, polyester resin, polyimide resin, etc. Raw materials, antioxidants,
The present invention relates to a method for producing TAB useful as a raw material of a photosensitive resist or the like in a high yield under mild conditions.

[0002]

2. Description of the Related Art Recently, TAB is an epoxy resin, a phenol resin, a polycarbonate resin, a polyester resin,
In addition to raw materials for the production of synthetic resins such as polyimide resins, they are attracting attention as functional raw materials for adding functions such as heat resistance to antioxidants and photosensitive resists.

[0003] However, in the past, only a few production examples of TAB are known, and the yield in such a small production example is low. For example, U.S. Pat. No. 3,309,339
In the publication, α, α ′, α ″-
Using trihydroxy-1,3,5-triethylbenzene or α, α ′, α ″ -trihydroxy-1,3,5-triisopropylbenzene, and using phenol or o-cresol as an alkyl phenol,
A method for producing a corresponding TAB by performing a condensation reaction in the presence of an acid catalyst in a solvent-free or toluene solvent at a temperature of 0 to 65 ° C is described. However, according to this production method, both the selectivity and the yield of the target p-adduct, that is, TAB, are low. In addition, α, α ′, α ″ -trihydroxy-1,3,5-trialkylbenzenes, which are one of the raw materials, are also expensive.
It is difficult to employ TAB as an industrial production method.

[0004] On the other hand, in order to use TAB as a functional raw material, any of various TABs having improved structures such as solubility and heat resistance can be easily produced depending on the purpose. It is necessary, for that purpose, by reacting various alkylphenols and trisphenols under reaction conditions that are industrially easy, with high selectivity and high yield,
It is desired to develop a manufacturing method capable of manufacturing the target TAB.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a conventional TA
The present invention has been made to solve the above-mentioned problems in the production of B, and various TABs can be produced under various industrially easy production conditions using various alkylphenols and trisphenols. Is to provide a method which can produce high purity with high selectivity and high yield.

[0006]

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

[0007]

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(Wherein R ₁ and R ₂ each independently represent a hydrogen atom, a methyl group or an ethyl group.) Α, α ′, α ″ -trihydroxy-1,3,5- Trialkylbenzenes and general formula (II)

[0009]

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Wherein R ₃ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms, and n represents 0 to
It is an integer of 3. Wherein the alkylphenol represented by the general formula (III) is subjected to a condensation reaction using an acid catalyst at a temperature in the range of 10 to 40 ° C.

[0011]

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(Wherein R ₁ , R ₂ , R ₃ and n are the same as above), α, α ′, α ″ -tris (4
-Hydroxyphenyl) -1,3,5-trialkylbenzenes are provided.

[0013]

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

[0014]

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(Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, a methyl group or an ethyl group.) Α, α ′, α ″ -trihydroxy-1,3,5- Trialkylbenzenes and general formula (II)

[0016]

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Wherein R ₃ represents an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms, and n represents 0 to
It is an integer of 3. ) By the condensation reaction with the alkylphenols represented by the general formula (III)

[0018]

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(Wherein R ₁ , R ₂ , R ₃ and n are the same as above), α, α ′, α ″ -tris (4
-Hydroxyphenyl) -1,3,5-trialkylbenzenes are obtained.

In the method of the present invention, one of the starting materials, α, α ′, α ″ -trihydroxy-1,3,5-trialkylbenzenes represented by the above general formula (I), comprises R ₁
And R ₂ are each independently a hydrogen atom, a methyl group or an ethyl group. Therefore, such α, α ′, α ″ −
Specific examples of trihydroxy-1,3,5-trialkylbenzenes include, for example, α, α ′, α ″ -trihydroxy-1,3,5-trimethylbenzene, α, α ′,
α ″ -trihydroxy-1,3,5-triethylbenzene, α, α ′, α ″ -trihydroxy-1,3,5-triisopropylbenzene, α, α ′, α ″ -trihydroxy-1,3 , 5-tri-sec-butylbenzene,
α, α ′, α ″ -trihydroxy-1,3,5-tri-
sec-pentylbenzene and the like.

In the method of the present invention, in the alkylphenols represented by the above general formula (II) as the other raw material, R ₃ is an alkyl group having 1 to 6 carbon atoms or 5 to 5 carbon atoms.
7 is a cycloalkyl group. The alkyl group is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, and the alkyl group having 3 or more carbon atoms may be linear or branched. Further, the cycloalkyl group is a cyclopentyl group, a cyclohexyl group or a cycloheptyl group.

Accordingly, specific examples of the alkylphenols represented by the general formula (II) include, for example, phenol, o-cresol, m-cresol, p-cresol, 2,6-dimethylphenol, and 2,5-dimethylphenol. Dimethylphenol, 3,5-dimethylphenol, 2,3,5-
Trimethylphenol, 2,3,6-trimethylphenol, 2-ethylphenol, 2-n-propylphenol, 2-isopropylphenol, 2-sec-butylphenol, 2-t-butylphenol, 2-pentylphenol, 2-hexylphenol , 2-cyclopentylphenol, 2-cyclohexylphenol,
2,6-diethylphenol, 2,6-diisopropylphenol, 2,6-di-t-butylphenol, 2,
6-dicyclohexylphenol, 2-cyclohexyl-5-methylphenol, 2-methyl-6-cyclohexylphenol, 2-methyl-5-ethylphenol,
2-methyl-5-propylphenol, 3-methyl-6
-Isobutylphenol and the like.

In the present invention, among these, phenol, o-cresol, 2-ethylphenol, 2-sec-butylphenol, 2-cyclohexylphenol and 2-cyclohexyl-5-methylphenol are particularly preferably used.

According to the method of the present invention, α, α ′, α ″ -trihydroxy-1,3,5-trialkylbenzenes and alkylphenols as described above are used in 10 to 4 times.
By condensing at a temperature in the range of 0 ° C. using an acid catalyst, the desired α, α ′, α ″ -tris (4-
(Hydroxyphenyl) -1,3,5-trialkylbenzenes are obtained.

Alkyl phenols are α, α ′, α ″
It is preferable to use a theoretical amount of 3 mol parts or more based on 1 mol part of -trihydroxy-1,3,5-trialkylbenzenes, preferably in the range of 4 to 20 mol parts, particularly preferably in the range of 6 to 12 mol parts. It is used in the molar part range.

Examples of the acid catalyst include inorganic acids such as hydrogen chloride gas, hydrochloric acid, sulfuric acid, phosphoric acid, and sulfuric anhydride, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, oxalic acid, formic acid, and trichloromethane. Preferred specific examples include organic acids such as acetic acid, and solid acids such as an acid-type ion exchange resin. Of these,
Hydrogen chloride gas and hydrochloric acid are preferably used.

For example, with respect to hydrogen chloride gas, such an acid catalyst is preferably used after being saturated in the above-mentioned alkylphenols or in a solution or slurry comprising an alkylphenol and a solvent. In the case of 35% hydrochloric acid, the raw material alkylphenols 1
It is preferable to use 1 to 20 parts by weight with respect to 00 parts by weight.

In the above reaction, if the starting alkylphenol is liquid at the reaction temperature,
Although it may be used, if it is a solid at the reaction temperature, it is preferable to use it in a solution or slurry using a solvent and then subject it to the reaction. The solvent is not particularly limited as long as it is inert to the reaction, and examples thereof include lower aliphatic alcohols such as methanol and ethanol, hydrocarbons such as toluene, xylene and hexane, and ethers such as tetrahydrofuran and dioxolan. . Among these, water is preferably used as a solvent because the raw material alkylphenols are so-called hydrates to lower the melting point and because post-treatment such as purification is easy. Such water is usually added to the starting alkylphenols in an amount of 1: 1.
It is used in the range of 10 to 10% by weight, preferably 3 to 7% by weight.

The other raw material, α, α ′, α ″ -trihydroxy-1,3,5-trialkylbenzene, is also preferably provided as a solution during the reaction. For example, the raw material may be dissolved in alcohols or used as a raw material. It is preferable to dissolve it in an alcohol solution of alkylphenols or to dissolve it in a raw material alkylphenol under heating to form a solution, such as lower aliphatic alcohols such as methanol, ethanol and propanol. Preferred, especially, is methanol.

Such solvents include α, α ′, α ″ -trihydroxy-1,3,5-trialkylbenzenes 10
It is used in an amount of usually 10 to 100 parts by weight, preferably 20 to 50 parts by weight, based on 0 parts by weight.

According to the present invention, α, α ′, α ″ -trihydroxy-1,3,5-trialkylbenzenes and alkylphenols are converted to 10 to 4 with the above-mentioned acid catalyst.
The condensation reaction is carried out at a temperature in the range of 0 ° C, preferably in the range of 20 to 30 ° C. As described above, by performing the reaction at a relatively low temperature, undesirable side reactions are suppressed, and furthermore, there is no problem in industrial production of the target substance, and thus, under reaction conditions that are industrially easy. High selectivity,
The target product can be produced in high yield.

The manner in which the reaction is carried out is not particularly limited. For example, preferably, after introducing hydrogen chloride gas to a hydrated alkylphenol to a saturated concentration, the temperature is reduced to 1%.
A solution of α, α ′, α ″ -trihydroxy-1,3,5-trialkylbenzenes, for example, a solution in which the above-mentioned raw material alkylphenols or alcohol is dissolved is maintained at about 0 to 40 ° C. May be added dropwise with stirring. Under such reaction conditions, the reaction is usually performed in the range of 1 to 2
It ends in about 0 hours. The reaction selectivity is usually 80 to 1
It is about 00%.

After completion of the reaction, an aqueous alkali solution such as sodium hydroxide and ammonia is added to the obtained reaction mixture,
After neutralizing the used acid catalyst, the aqueous layer is separated and removed.Excess raw materials and solvent are removed from the obtained oil layer by distillation and the like, and the obtained residue is crystallized, if necessary. Solvents, for example, aromatic hydrocarbons such as toluene and xylene, aliphatic ketones such as methyl ethyl ketone and diisopropyl ketone or a mixed solvent thereof are added, and crystallization is performed from the resulting solution to obtain the desired α, α ′, Highly purified α ″ -tris (4-hydroxyphenyl) -1,3,5-trimethylbenzenes can be obtained.

Thus, according to the present invention, the α, α ′, α ″ -trihydroxy-1,
According to 3,5-trialkylbenzenes and alkylphenols, a compound represented by the general formula (III)

[0035]

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(Wherein R ₁ , R ₂ , R ₃ and n are the same as above), α, α ′, α ″ -tris (4
-Hydroxyphenyl) -1,3,5-trialkylbenzenes can be obtained.

Accordingly, as such α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-trialkylbenzenes, specifically, for example, α,
α ′, α ″ -tris (4-hydroxyphenyl) -1,
3,5-trimethylbenzene, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triethylbenzene, α, α ′, α ″ -tris (4-hydroxyphenyl) -1, 3,5-triisopropylbenzene,
α, α ', α "-tris (4-hydroxyphenyl)-
1,3,5-tri-sec-butylbenzene, α,
α ′, α ″ -tris (4-hydroxyphenyl) -1,
3,5-tri-sec-pentylbenzene, α, α ′,
α "-tris (3-methyl-4-hydroxyphenyl)
-1,3,5-trimethylbenzene, α, α ', α "-
Tris (3-methyl-4-hydroxyphenyl) -1,
3,5-triethylbenzene, α, α ′, α ″ -tris (3-methyl-4-hydroxyphenyl) -1,3,5
-Triisopropylbenzene, α, α ′, α ″ -tris (3-methyl-4-hydroxyphenyl) -1,3,5
-Tri-sec-butylbenzene, α, α ′, α ″ -tris (3-methyl-4-hydroxyphenyl) -1,
3,5-tri-sec-pentylbenzene, α, α ′,
α ″ -tris (3,5-dimethyl-methyl-4-hydroxyphenyl) -1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (3,6-dimethyl-4-
(Hydroxyphenyl) -1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (2,3,6-trimethyl-4-hydroxyphenyl) -1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (3-
Ethyl-4-hydroxyphenyl) -1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (3-
Isopropyl-4-hydroxyphenyl) -1,3,5
-Triisopropylbenzene, α, α ′, α ″ -tris (3-t-butyl-4-hydroxyphenyl) -1,
3,5-triisopropylbenzene, α, α ', α "-
Tris (3-cyclohexyl-4-hydroxyphenyl) -1,3,5-triisopropylbenzene, α,
α ′, α ″ -tris (3-methyl-5-cyclohexyl-4-hydroxyphenyl) -1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (3-cyclohexyl-6-methyl- 4-hydroxyphenyl)-
1,3,5-triisopropylbenzene, α, α ′,
α "-tris (3,5-dicyclohexyl-4-hydroxyphenyl) -1,3,5-triisopropylbenzene and the like.

In the present invention, α, α ′, α ″ -trihydroxy- represented by the general formula (I) as a raw material is used.
The purity of the 1,3,5-trialkylbenzenes is not particularly limited as long as they do not contain a reaction inhibitor, but usually, about 60 to 100% is purified after the reaction. It is preferably used for reasons such as easiness of production and securing the purity of the target product.

The above α, α ′, α ″ -trihydroxy-
For example, 1,3,5-trialkylbenzenes are represented by the general formula (IV)

[0040]

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(Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, a methyl group or an ethyl group.) A 1,3,5-trialkylbenzene represented by the following formula: It can be obtained by air oxidation in the presence and then reduction with a reducing agent.

The 1,3,5- represented by the general formula (IV)
Examples of the trialkylbenzene include, for example, 1,3,5-
Trimethylbenzene, 1,3,5-triethylbenzene, 1,3,5-triisopropylbenzene, 1,3
5-tri-sec-butylbenzene, 1,3,5-tri-sec-pentylbenzene and the like are used.

Starting from 1,3,5-trialkylbenzene, α, α ′, α ″ -trihydroxy-1,
In order to produce 3,5-trialkylbenzenes, they are usually obtained by oxidizing 1,3,5-trialkylbenzenes and then reducing the obtained reaction product.

Thus, the 1,3,5-trialkylbenzenes are oxidized, and the obtained reaction product is reduced to obtain α, α ′, α ″ -trihydroxy-1,3,5-
The method for producing trialkylbenzenes is not particularly limited, and may be a conventionally known method. For example, Japanese Patent Application Laid-Open No. 61-145246 discloses that 1,3,5-triisopropylbenzene is air-oxidized to hydroperoxide, which is then reduced with hydrogen to obtain α, α ′, α ″ -trihydroxy. -1,3,5-
A method for obtaining triisopropylbenzene is described.

Japanese Patent Application Laid-Open No. 61-10522 discloses that 1,3,5-triisopropylbenzene is oxidized with a molecular oxygen-containing gas to obtain a peroxide, which is then reduced with a sulfite to obtain a peroxide. α, α ′, α ″ -trihydroxy-1,
A method for obtaining 3,5-triisopropylbenzene is described.

However, according to the present invention,
To oxidize 5-trialkylbenzenes and then reduce the resulting reaction product to obtain α, α ′, α ″ -trihydroxy-1,3,5-trialkylbenzenes, refer to Japanese Patent Application No. It is preferable to use the method of the present inventors disclosed in Japanese Patent Application Publication No. 11-200457. For example, 1,3,5-trialkylbenzenes such as 1,3,5-triisopropylbenzene are dissolved in an aqueous alkaline solution in the presence of 80%. ~ 1
At a temperature of 20 ° C., the reaction mixture is oxidized with molecular oxygen or a gas containing molecular oxygen so that the peroxide concentration in the reaction mixture is 7 to 5 mg equivalent / g, and then, for example, an aqueous solution of sulfite is used in an equivalent ratio. (Mol number of sulfite / g equivalent number of hydroperoxyoxide group) It is present at a concentration of 0.90 to 3.0 and is reduced at a temperature of 50 to 150 ° C. to convert 1,3,5-triisopropylbenzene. To obtain a reaction mixture containing the target substance, α, α ′, α ″ -trihydroxy-1,3,5-triisopropylbenzene, at a high concentration.

After completion of the reaction, an inorganic salt such as a catalyst was filtered off from the obtained reaction mixture, a reaction solvent such as methanol was distilled off from the obtained filtrate, and a residue such as methyl isobutyl ketone was added to the obtained residue. A crystallization solvent and water are added, and the mixture is washed with water, the aqueous layer is separated, and the resulting oil layer is crystallized to obtain a crude product of the intended product.

The purity of the crude product is usually about 80 to 95% by weight. In the present invention, a high-purity product can be easily obtained by using such a crude product as a raw material. However, if necessary, the crude product may be further purified to use a purified product having a purity of 95 to 100% by weight, and an inorganic salt such as a catalyst may be filtered from the reaction mixture after completion of the reaction. Thereafter, the reaction solvent may be distilled off, and the residue thus obtained may be used as a raw material. In this case, the purity of the raw material is usually about 60 to 80% by weight.

[0049]

According to the present invention, various TABs can be produced at high selectivity under various industrially easy production conditions using various alkylphenols and trisphenols.
It can be produced in high yield and high purity.

[0050]

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

Example 1 A 1 L four-necked flask equipped with a thermometer, a stirrer, and a dropping funnel was charged with 188 g of phenol and 14.1 g of distilled water, and the temperature was raised to 30 ° C., and hydrogen chloride was added to the wet phenol. Gas was blown in until saturation concentration was reached.

Then, 1,3,5-tris (α-hydroxyisopropyl) benzene (purity: 98.5% by weight)
A solution prepared by dissolving 3 g in 141 g of phenol was added under stirring.
At a temperature of 30 ° C., the solution was dropped into the hydrous phenol over 3 hours. Thereafter, the mixture was further stirred at the above temperature for 20 hours to carry out a reaction.

After completion of the reaction, the obtained reaction mixture was subjected to high performance liquid chromatography analysis and NMR analysis to obtain the target product α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5- The production of triisopropylbenzene was confirmed, and the reaction selectivity to 1,3,5-tris (α-hydroxyisopropyl) benzene was 95.
3%.

After neutralizing the reaction mixture by adding an aqueous sodium hydroxide solution, the aqueous layer was separated and removed. After adding xylene to the obtained oil layer, it was washed with water and furthermore inorganic salts were removed. Then, after distilling off xylene and residual raw material phenol under reduced pressure, xylene is added to the residue, and the target substance is filtered off by recrystallization, dried, and the target substances α, α ′,
α "-tris (4-hydroxyphenyl) -1,3,5
96.2 g of triisopropylbenzene were obtained as white crystals (purity 97.5% by weight, melting point 189 ° C.). 1,
The yield based on 3,5-tris (α-hydroxyisopropyl) benzene) was 79.4%.

Example 2 216 g of o-cresol and 16.2 g of distilled water were charged into a 1 L four-necked flask equipped with a thermometer, a stirrer and a dropping funnel, and the temperature was raised to 30 ° C. Hydrogen chloride gas was blown into the flask until a saturated concentration was reached.

Then, 63 g of 1,3,5-tris (α-hydroxyisopropyl) benzene (purity: 97% by weight)
Was dissolved in 108 g of o-cresol under stirring.
At a temperature of 30 ° C., the solution was added dropwise over 3 hours. afterwards,
Further, the reaction was carried out by stirring at the above temperature for 16 hours.

After completion of the reaction, the obtained reaction mixture was subjected to high performance liquid chromatography analysis and NMR analysis to obtain the desired product α, α ′, α ″ -tris (3-methyl-4
-Hydroxyphenyl) -1,3,5-triisopropylbenzene was confirmed. 1,3,5-tris (α
The reaction selectivity for (-hydroxyisopropyl) benzene was 87.6%.

After neutralizing the reaction mixture by adding an aqueous sodium hydroxide solution, the aqueous layer was separated and removed. Toluene was added to the obtained oil layer, washed with water, and further, inorganic salts were removed. Then, after distilling off the solvent and the residual raw material o-cresol under reduced pressure, toluene is added to the residue, the target substance is collected by recrystallization, filtered and dried, and the target substances α, α ′,
α "-tris (3-methyl-4-hydroxyphenyl)
―10,3 g of 1,3,5-triisopropylbenzene
Was obtained as white crystals (purity 98.4 mol%, melting point 15).
1.2 ° C). The yield based on 1,3,5-tris (α-hydroxyisopropyl) benzene) was 80.5%.

Example 3 404 g of 1,3,5-triisopropylbenzene, 245 g of water, 25 g of a 48% aqueous sodium hydroxide solution and 25 g of a reaction initiator were placed in a 1.5 L capacity stainless steel autoclave equipped with a stirrer, a gas inlet tube and a pressure relief valve. Benzoyl peroxide, and heated to 95 ° C., and then air was blown into this under stirring, and at the same time, 0.737 NL /
The air was evacuated at a rate of 1 minute, and the oxidation reaction was performed for 46 hours while maintaining the internal pressure of the container at 0.4 MPa. After completion of the reaction, the content was diluted with 120 g of methanol to obtain a reaction mixture.

Next, sodium 446 was added to a 2 L four-necked flask equipped with a stirrer, a dropping funnel and a thermometer.
g, 150 g of water and 60 g of methanol, the temperature was maintained at 85 ° C., and the above reaction mixture was added to 1. under stirring.
It was added dropwise over 5 hours. After the completion of the dropwise addition, a reduction reaction was performed at the above temperature for 1.5 hours.

After completion of the reaction, the inorganic salt was filtered off from the obtained reaction mixture, methanol was distilled off from the obtained filtrate, and methyl isobutyl ketone and water were added to the obtained residue.
After washing with water, methanol water was separated and removed to obtain a methyl isobutyl ketone solution containing the target product 1,3,5-tris (α-hydroxyisopropyl) benzene. The solution was cooled and filtered by crystallization to obtain a crude product as a crude product.

Separately, 47 g of phenol was placed in a 300 mL four-necked flask equipped with a thermometer, a stirrer and a dropping funnel.
And 5 g of distilled water were charged to obtain a water-containing phenol, the temperature was raised to 30 ° C., and hydrogen chloride gas was blown into the phenol until the saturated concentration was reached.

Next, 25.2 g of the above-mentioned 1,3,5-tris (α-hydroxyisopropyl) benzene crude cake (purity of 90% by weight) and 37.6 g of phenol were mixed to form a solution. At 0 ° C, the solution was added dropwise to the above-mentioned hydrous phenol over 3 hours. Thereafter, the reaction was further performed at the above temperature for 20 hours with stirring.

After completion of the reaction, the obtained reaction mixture was subjected to high performance liquid chromatography analysis and NMR analysis to obtain the desired product α, α ′, α ″ -tris (4-hydroxyphenyl).
Generation of -1,3,5-triisopropylbenzene was confirmed. The reaction selectivity for 1,3,5-tris (α-hydroxyisopropyl) benzene was 82.6%.

After neutralizing the reaction mixture by adding an aqueous sodium hydroxide solution, the aqueous layer was separated and removed. After adding xylene to the obtained oil layer, it was washed with water to remove inorganic salts. Thereafter, xylene and residual raw material phenol are distilled off under reduced pressure. Then, xylene is added to the residue, the target substance is collected by recrystallization, filtered, and dried to obtain the target substance α, α ′, α ″.
30.7 g of -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene was obtained as white crystals (purity 95.5 mol%, 1,3,5-tris (α-hydroxyisopropyl) benzene). Yield of 6
It was 7.9%.

Example 4 70.4 g of o-cyclohexylphenol and 3.2 g of methanol were charged into a 1 L four-necked flask equipped with a thermometer, a stirrer and a dropping funnel, and the temperature was raised to 55 ° C. Hydrogen gas was blown in until a saturated concentration was reached.

Then, 1,3,5-tris (α-hydroxyisopropyl) benzene (purity: 97% by weight)
6 g was dissolved in a solution consisting of 35.2 g of o-cyclohexylphenol and 12.6 g of methanol to form a solution, which was added dropwise with stirring over 2 hours. During this time,
The temperature of the mixture was gradually reduced to 30 ° C. Thereafter, the mixture was further stirred for 21 hours at the above temperature to carry out a reaction.

After completion of the reaction, the obtained reaction mixture was analyzed by high performance liquid chromatography to find the desired product α, α ′, α ″ -tris (3-cyclohexyl-4-hydroxyphenyl) -1,3,5. The formation of -triisopropylbenzene was confirmed, and the reaction selectivity to 1,3,5-tris (α-hydroxyisopropyl) benzene was 72.2%.

After neutralizing the reaction mixture by adding an aqueous sodium hydroxide solution, the aqueous layer was separated and removed. Toluene was added to the obtained oil layer and washed with water to remove inorganic salts. Thereafter, toluene and the residual starting material o-cyclohexylphenol were distilled off under reduced pressure, and then the target product was separated from the residue by using high performance liquid chromatography. This was dried to obtain 68.3 mg of the target product α, α ′, α ″ -tris (3-cyclohexyl-4-hydroxyphenyl) -1,3,5-triisopropylbenzene as a colorless starch syrup ( The purity based on 1,3,5-tris (α-hydroxyisopropyl) benzene was 42.4% Molecular weight (mass spectrum analysis): 726 Proton NMR analysis (DMSO solvent, 400MHz):

[0070]

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[0071]

[Table 1]

Comparative Example 1 188 g of phenol and 14.1 g of distilled water were charged into a 1 L four-necked flask equipped with a thermometer, a stirrer, and a dropping funnel. Blow in until the concentration reaches saturation.

Then, 63 g of 1,3,5-tris (α-hydroxyisopropyl) benzene (purity: 97% by weight)
Was dissolved in 94 g of phenol and added dropwise to the hydrous phenol at a temperature of 60 ° C. over 30 minutes with stirring. Thereafter, the mixture was further stirred at the above temperature for 20 hours to carry out a reaction. After completion of the reaction, the obtained reaction mixture was subjected to high performance liquid chromatography analysis and NMR analysis to obtain the target compound α,
α ′, α ″ -tris (4-hydroxyphenyl) -1,
Generation of 3,5-triisopropylbenzene was confirmed.
The reaction selectivity for 1,3,5-tris (α-hydroxyisopropyl) benzene was 86.2%.

Continued on the front page (72) Inventor Hiroyasu Ohno 2-115, Kozaiga, Wakayama-shi F-term in Honshu Kagaku Kogyo Co., Ltd. F-term (reference) 4H006 AA02 AC25 AC41 BA66 BD70 BE20 BE30 BE90 FC52 FE13 4H039 CA10 CA41 CD10 CD40

Claims (2)

[Claims] 1. A compound of the general formula (I) (Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, a methyl group or an ethyl group.)
α "-trihydroxy-1,3,5-trialkylbenzenes and a compound of the general formula (II) Wherein R ₃ is an alkyl group having 1 to 6 carbon atoms or 5 carbon atoms.
Represents a cycloalkyl group of 7 to 7, and n is an integer of 0 to 3. ) At 10 to 40 ° C
Wherein the condensation reaction is carried out using an acid catalyst at a temperature in the range of the general formula (III): (In the formula, R ₁ , R ₂ , R ₃ and n are the same as above.) Α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-trialkylbenzene Manufacturing methods. 2. A compound of the general formula (IV) (Wherein, R ₁ and R ₂ each independently represent a hydrogen atom, a methyl group or an ethyl group.)
Α, α ′, α ″ -trihydroxy- obtained by oxidizing a trialkylbenzene and then reducing it
The α according to claim 1, wherein the reaction mixture containing 1,3,5-trialkylbenzenes is used as α, α ', α "-trihydroxy-1,3,5-trialkylbenzenes to react with alkylphenols. , Α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-trialkylbenzenes.