KR101786888B1 - Method of producing trisphenol derivatives - Google Patents

Abstract

The present invention relates to a process for producing a trisphenol derivative compound, and more particularly, to a process for producing a trisphenol derivative directly at a high yield and at a high purity, without using an intermediate as an starting material, using an acetyl cumene derivative as a starting material.

Description

[0001] The present invention relates to a method for producing trisphenol derivatives,

The present invention relates to a process for producing a trisphenol derivative compound, and more particularly, to a process for producing a trisphenol derivative directly at a high yield and at a high purity, without using an intermediate as an starting material, using an acetyl cumene derivative as a starting material.

The trisphenol derivative compound is widely used as a raw material for an epoxy resin used for a photosensitive resist raw material, an electric insulating material, etc., a raw material for a developing agent used for a heat-sensitive recording material, a raw material for a discoloration inhibitor, furthermore a raw material for a fungicide and a sterilizing fungicide .

Especially, as a representative compound of the trisphenol derivative, 1- [α-methyl- α- (4'-hydroxyphenyl) ethyl] -4- [α ', α'-bis (4 " Hydroxyphenyl) ethyl] benzene (hereinafter abbreviated as TPPA) is widely known.

[TPPA]

Conventionally, TPPA may be prepared by synthesizing TPPA using a styrene intermediate having the structure [styrene intermediate] shown below as a step material before TPPA production (Patent Document 1) or by synthesizing the following structure of [acetophenone intermediate] TPPA was synthesized through a phenol condensation reaction with an acetophenone intermediate having a hydroxyl group (Patent Document 2).

[Styrene intermediate]

[Acetophenone intermediate]

However, the method of producing an intermediate as described above has a problem in that the process steps are complicated and the process efficiency is low and the synthesis yield is low. Therefore, there is a need to develop a method for producing a trisphenol derivative from a starting material in high yield and high purity without producing an intermediate.

U.S. Pat. No. 4,778,936 Korean Patent Publication No. 10-2012-0015322

Therefore, a problem to be solved by the present invention is to improve the process efficiency by simplifying the process so that the acetyl cumene derivative, which is excellent in storage stability and can be obtained industrially easily, can be directly prepared as a starting material , And a method for producing a trisphenol derivative compound with high efficiency and high purity by carrying out a reaction under industrially easy reaction conditions.

The present invention provides a process for producing a trisphenol derivative represented by the following formula (1), wherein the starting material is an acetylcumin derivative represented by the following formula (2).

[Chemical Formula 1]

In the above formula (1)

Wherein R ₁ is a hydrogen atom, a heavy hydrogen atom, an alkoxy group, a phenyl group or the hydroxy group of the alkyl group having 1 to 8 carbon atoms, having 1 to 8 carbon atoms, wherein R ₂ is a hydrogen atom, a heavy hydrogen atom, an alkyl group having 1 to 8 carbon atoms, having 1 to 8 alkoxy group of said R ₃ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and n is 0 or an integer of 1 to 4, R ₁ is the same or different when n is 2 or more, wherein m is 0 or an integer of 1 to 4, and when m is 2 or more, R ₂ is the same or different.

(2)

In the above formula (2)

The R < ₂ & R ₃ is the same as defined in Formula 1,

R ₄ is a hydrogen atom, a deuterium atom, a halogen group, a hydroxy group, a phenyl group, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms.

According to one embodiment of the present invention, the preparation method can be carried out by condensation reaction of the acetylcimine derivative represented by the formula (2) with phenols represented by the following formula (3).

(3)

In the above formula 3,

Wherein R < ₁ > and n are the same as defined in the above formula (1).

The present invention can be directly prepared without the production of an intermediate by using an acetylcimine derivative which can be easily prepared from cucumber as a starting material, is relatively stable against acid or heat and is excellent in preservation safety and is advantageous for industrial production as a starting material, The process is simplified and the process efficiency is improved, and a process for producing the trisphenol derivative compound with high efficiency and high purity can be provided.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a process for producing a trisphenol derivative, and more particularly, to a process for producing a trisphenol derivative directly from a acetyl cumene derivative as a starting material without producing an intermediate at a high yield and a high purity.

The present invention provides a process for producing a trisphenol derivative represented by the following formula (1), wherein the starting material is an acetylcimine derivative represented by the following formula (2).

[Chemical Formula 1]

In the above formula (1)

Wherein R ₁ is a hydrogen atom, a heavy hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, a phenyl group or a hydroxyl group having 1 to 8 carbon atoms, n is 0 or an integer of 1 to 4, the R ₁ when n is 2 or more May be the same or different. The alkyl group having 1 to 8 carbon atoms may be a linear, branched or cyclic alkyl group, and may be substituted with 1 to 2 phenyl or alkoxy groups.

Specific examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a cyclohexyl group, a cyclopentyl group and a benzyl group as a substituted alkyl group.

The alkoxy group having 1 to 8 carbon atoms is a linear, branched or cyclic alkoxy group, and 1 to 2 phenyl groups may be substituted for these alkoxy groups. Specific examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a t-butoxy group, a cyclohexyloxy group, and a cyclopentyloxy group.

The phenyl group may be substituted with 1 to 3 alkyl groups having 1 to 8 carbon atoms and / or alkoxy groups having 1 to 8 carbon atoms. Specific examples of the phenyl group include a phenyl group, a 4-methylphenyl group and a 4-methoxyphenyl group. , Wherein the number of substituents is preferably 0 or 1.

The n (number of substituted R ₁₎ is 0, 1 or 2 and when n is 1 or 2 and the substitution position of R ₁ is preferably a о- position of the hydroxy group.

Further, n is at least 1, R, if the one or more of the R _{1 1} group or a hydroxy group, can be substituted with a hydroxy group or a phenyl group and is preferably 1 or 2, most preferably 1. When n is 1 or more and at least _one of R ₁ is a hydroxy group and the substitution number of the hydroxy group is 1, the substitution position is preferably the 3-position of the 4-hydroxyphenyl group, and when the substitution number of the hydroxy group is 2, 2-position and 3-position are preferred. When the substitution position of the hydroxy group is 2-position, it is preferable that R ₃ is a hydrogen atom. When n is 1 or more and at least _one of R ₁ is a phenyl group and the phenyl group substitution number is 1, the substitution position is preferably the 3-position or the 5-position of the 4-hydroxyphenyl group, The substitution position is preferably a 3-position and a 5-position.

In the trisphenol derivative compound represented by the general formula (1), R ₃ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, which is a linear or branched alkyl group. Specific examples of the alkyl group include methyl, ethyl, An isopropyl group, a butyl group, and an isobutyl group.

In addition, the R ₂ is a hydrogen atom, a heavy hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, wherein m is 0 or an integer of 1 to 4, R ₂ is the same when m is 2 or more Or may be different. Here, the alkyl group having 1 to 8 carbon atoms is a linear or branched alkyl group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group. The chalcoc group having 1 to 8 carbon atoms is a linear or branched alkoxy group, and specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a t-butoxy group.

(2)

In the above formula (2)

The R < ₂ & R ₃ is the same as defined in Formula 1,

Wherein R ₄ is a hydrogen atom, a deuterium atom, a halogen group, a hydroxy group, a phenyl group, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, wherein the alkyl group having 1 to 8 carbon atoms and the alkoxy group having 1 to 8 carbon atoms may be the same or different, Lt; ₂ > are the same as defined in the alkyl group and the alkoxy group.

The process for producing the trisphenol derivative compound is preferably carried out by condensation reaction of the acetylcimine derivative represented by the formula (2) with phenols represented by the following formula (3).

(3)

In the above formula 3,

Wherein R < ₁ > and n are the same as defined in the above formula (1).

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments and the like. It will be apparent to those skilled in the art, however, that these examples are provided for further illustrating the present invention and that the scope of the present invention is not limited thereto.

Example

Example 1

According to the following Reaction Scheme 1, 4,4 '- (1- (4- (2- (4- (2-hydroxyphenyl) 2-yl) phenyl) ethane-1,1-diyl) bis (2-phenol).

[Reaction Scheme 1]

Specifically, 1- (4- (2-hydroxypropan-2-yl) phenyl) ethanone (100 g, 0.556 mol) was dissolved in phenol (475 g, 5.0 mmol) followed by dodecyl mercaptan , And methanol (25 g, 1.4 mol) were added. After stirring at 60 ° C for 1 hour, hydrogen chloride (HCl) gas was blown to saturate, followed by reaction at 60 ° C for 12 hours. After completion of the reaction, the reaction mixture was neutralized with a 10% sodium hydroxide solution, and 276 g of methyl isobutyl ketone toluene mixed solvent and 100 g of water were added thereto. The reaction mixture was washed with water, separated from the aqueous layer and further washed with water. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain a white solid 4,4 '- (1- (4- (2- (4-hydroxyphenyl) propan-2- Phenyl) ethane-1,1-diyl) bis (2-phenol).

Purity: 99.1% (High Performance Liquid Chromatography)

Melting point: 222-225 DEG C

¹ H-NMR (400MHz) measurement (CDCl ₃₎ Shift value (ppm) Proton number signal 1.6 6 s 2.02 3 s 4.9 3 s 6.6 ~ 7.2 16 m

Using the process for preparing a trisphenol derivative according to the present invention, the acetylcimine derivative can be directly used as a starting material without the production of an intermediate, and a high purity (99.1%) trisphenol derivative compound Can be obtained.

Example  2

According to the following reaction scheme 2, 4,4 '- (l- (4- (2- (4-hydroxycyclohexyl) phenyl) ethanone was obtained by using 1- (4- Yl) phenyl) ethane-1,1-diyl) bis (2-phenol) was synthesized.

[Reaction Scheme 2]

Specifically, l- (4- (2-chloropropan-2-yl) phenyl) ethanone (108 g, 0.556 mol) was dissolved in phenol (475 g, 5.0 mmol) followed by dodecyl mercaptan (19.2 g, 0.169 mol ) And methanol (25 g, 1.4 mol) were added. After stirring at 60 ° C for 1 hour, hydrogen chloride (HCl) gas was blown to saturation, and the reaction was carried out at 60 ° C for 12 hours. After completion of the reaction, the reaction mixture was neutralized with a 10% sodium hydroxide solution, and 276 g of methyl isobutyl ketone toluene mixed solvent and 100 g of water were added thereto. The reaction mixture was washed with water, separated from the aqueous layer and further washed with water. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain a white solid 4,4 '- (1- (4- (2- (4-hydroxyphenyl) propan-2- Phenyl) ethane-1,1-diyl) bis (2-phenol).

Purity: 98.9% (High Performance Liquid Chromatography)

Melting point: 222-225 ° C

¹ H-NMR (400MHz) measurement (CDCl ₃₎ Shift value (ppm) Proton number signal 1.6 6 s 2.02 3 s 4.9 3 s 6.6 ~ 7.2 16 m

Using the process for preparing a trisphenol derivative compound according to the present invention, it is possible to produce a trisphenol derivative compound having a high purity (98.9%) without using an intermediate, by using an acetylcumin derivative as a starting material, Can be obtained.

Example 3

According to the following reaction scheme 3, 4,4 '- (1- (4- (2- (4- (2-hydroxyphenyl) Methylphenyl) propan-2-yl) phenyl) ethane-1,1-diyl) bis (2-methylphenol).

[Reaction Scheme 3]

Specifically, l- [4- (2-hydroxypropan-2-yl) phenyl] ethanone (100 g, 0.556 mol) was dissolved in o-cresol (546.46 g, 5.0 mmol) and dodecyl mercaptan 19.2 g, 0.169 mol) and methanol (25 g, 1.4 mol) were added. After stirring at 60 ° C for 1 hour, hydrogen chloride (HCl) gas was blown to saturation, and the mixture was allowed to react at 60 ° C for 12 hours . After completion of the reaction, the reaction mixture was neutralized with a 10% sodium hydroxide solution, and 276 g of methyl isobutyl ketone toluene mixed solvent and 100 g of water were added thereto. The reaction mixture was washed with water, separated from the aqueous layer and further washed with water. The precipitated crystals were separated by filtration and dried under reduced pressure to give pale yellow solid 4,4 '- (1- (4- (2- (4-hydroxy-3-methylphenyl) -Yl) phenyl) ethane-1,1-diyl) bis (2-methylphenol).

Purity: 98.3% (High Performance Liquid Chromatography)

Melting point: 87-91 ° C

¹ H-NMR (400MHz) measurement (CDCl ₃₎ Shift value Proton number signal 1.6 6 s 2.05 3 s 2.18 9 s 2.24 3 s 4.8 3 s 6.6 ~ 7.2 13 m

Using the process for preparing a trisphenol derivative according to the present invention, the acetylcumin derivative can be directly used as a starting material without the production of an intermediate, and a high purity (98.3%) trisphenol derivative compound Can be obtained.

Example  4

According to the following reaction scheme 4, 4,4 '- (1- (4- (2- (4-Hydroxyphenyl) ethanone was obtained from 1- [4- (2- Methylphenyl) propan-2-yl) phenyl) ethane-1,1-diyl) bis (2-methylphenol).

[Reaction Scheme 4]

Specifically, l- [4- (2-chloropropan-2-yl) phenyl] ethanone (108 g, 0.556 mol) was dissolved in o-cresol (546.46 g, 5.0 mmol) followed by dodecyl mercaptan g, 0.169 mol) and methanol (25 g, 1.4 mol) were added. The mixture was stirred at 60 ° C for 1 hour, and hydrogen chloride (HCl) gas was blown to saturation, followed by reaction at 60 ° C for 12 hours. After completion of the reaction, the reaction mixture was neutralized with a 10% sodium hydroxide solution, and 276 g of methyl isobutyl ketone toluene mixed solvent and 100 g of water were added thereto. The reaction mixture was washed with water and the aqueous layer was separated and further washed with water. The precipitated crystals were separated by filtration and dried under reduced pressure to give pale yellow solid 4,4 '- (1- (4- (2- (4-hydroxy-3-methylphenyl) Yl) phenyl) ethane-1,1-diyl) bis (2-methylphenol).

Purity: 98.0% (High Performance Liquid Chromatography)

Melting point: 87-91 ° C

¹ H-NMR (400MHz) measurement (CDCl ₃₎ Shift value Proton number signal 1.6 6 s 2.05 3 s 2.18 9 s 2.24 3 s 4.8 3 s 6.6 ~ 7.2 13 m

Using the process for preparing the trisphenol derivative compound according to the present invention, it is possible to produce the trisphenol derivative compound having a high purity (98.0%) without using an intermediate, by using the acetylcumin derivative as a starting material. Can be obtained.

Example 5

According to the following Reaction Scheme 5, using 4,4 '- (1- (4- (2- (4- (2-hydroxypropyl) Dimethylphenyl) propan-2-yl) phenyl) ethane-1,1-diyl) bis (3,5-dimethylphenol).

[Reaction Scheme 5]

(100 g, 0.556 mol) was dissolved in 2,6-xylenol (617 g, 5.0 mmol), and then dodecyl mercaptan (19.2 g, 0.169 mol) and methanol (25 g, 1.4 mol) were added. After stirring at 60 ° C for 1 hour, hydrogen chloride (HCl) gas was blown to saturation, . After completion of the reaction, the reaction mixture was neutralized with a 10% sodium hydroxide solution, and 276 g of methyl isobutyl ketone toluene mixed solvent and 100 g of water were added thereto. The reaction mixture was washed with water and the aqueous layer was separated and further washed with water. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain a white solid 4,4 '- (1- (4- (2- (4-hydroxy-3,5-dimethylphenyl) Propane-2-yl) phenyl) ethane-1,1-diyl) bis (3,5-dimethylphenol).

Purity: 98.7% (High Performance Liquid Chromatography)

Melting point: 191-194 DEG C

¹ H-NMR (400MHz) measurement (CDCl ₃₎ Shift value Proton number signal 1.6 6 s 2.06 3 s 2.15 18 s 2.19 6 s 4.4 One s 4.45 2 s 6.6 ~ 7.2 10 m

Using the process for preparing a trisphenol derivative compound according to the present invention as described in Example 5, it is possible to produce a trisphenol derivative compound having a high purity (98.7%) without using an intermediate, by using an acetylcumin derivative as a starting material. Can be obtained.

Example 6

According to the following Reaction Scheme 6, 4,4 '- (1- (4- (2- (4-Hydroxyphenyl) ethanone was obtained from 1- [4- (2- Phenyl) ethane-1,1-diyl) bis (3,5-dimethylphenol) was synthesized.

[Reaction Scheme 6]

(100 g, 0.556 mol) was dissolved in 2,6-xylenol (617 g, 5.0 mmol), and then dodecyl mercaptan ( 19.2 g, 0.169 mol) and methanol (25 g, 1.4 mol) were added. After stirring at 60 ° C for 1 hour, hydrogen chloride (HCl) gas was blown to saturation, and the mixture was allowed to react at 60 ° C for 12 hours . After completion of the reaction, the reaction mixture was neutralized with a 10% sodium hydroxide solution, and 276 g of methyl isobutyl ketone toluene mixed solvent and 100 g of water were added thereto. The reaction mixture was washed with water and the aqueous layer was separated and further washed with water. The precipitated crystals were separated by filtration and dried under reduced pressure to obtain a white solid 4,4 '- (1- (4- (2- (4-hydroxy-3,5-dimethylphenyl) Propan-2-yl) phenyl) ethane-1,1-diyl) bis (3,5-dimethylphenol).

Purity: 98.1% (High Performance Liquid Chromatography)

Melting point: 191-194 DEG C

¹ H-NMR (400MHz) measurement (CDCl ₃₎ Shift value Proton number signal 1.6 6 s 2.06 3 s 2.15 18 s 2.19 6 s 4.4 One s 4.45 2 s 6.6 ~ 7.2 10 m

Using the process for preparing a trisphenol derivative compound according to the present invention as described in Example 6, an acetylcumin derivative can be directly used as a starting material without the production of an intermediate, and a high purity (98.1%) trisphenol derivative compound Can be obtained.

Claims (2)

delete A process for producing a trisphenol derivative represented by the following formula (1), wherein an acetyl cumene derivative represented by the following formula (2) is condensed with a phenol represented by the following formula (3)
[Chemical Formula 1]

In the above formula (1), R ₁ is a methyl group, R ₂ is hydrogen,
Wherein n is an integer of 0 to 2, the (R ₂ ) _m is not present,
When n is 1, R < 1 > is bonded to one of two carbon atoms adjacent to the carbon substituted by a hydroxy group,
When n is 2, R < ₁ > is bonded to two carbons adjacent to the carbon substituted by a hydroxy group,
R ₃ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms;
(2)

In the above formula (2), R ₂ and Wherein R ₃ is the same as defined in Formula 1, and (R ₂ ) _m is not present;
R ₄ is selected from a halogen group and a hydroxy group;
(3)

In Formula 3, R ₁ and n are the same as defined in Formula 1;
Wherein the condensation reaction is carried out for 12 hours while keeping the temperature of 60 占 폚 in the saturated state of the hydrogen chloride gas.