JP2021001219A - Method for manufacturing hydroxy substituted aromatic compound - Google Patents

Abstract

To provide an industrially advantageous method for manufacturing a hydroxy substituted aromatic compound, for example, dihydroxynaphthalene.SOLUTION: A method for manufacturing a hydroxy substituted aromatic compound includes extracting metal components in a hydroxy substituted aromatic compound by causing contact between a solution (a) including an organic solvent that is not optionally mixed with water and a hydroxy substituted aromatic compound, and an acid solution.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene).

Hydroxy-substituted aromatic compounds such as dihydroxynaphthalene are useful as raw materials for compounds or resins used as encapsulants for semiconductors, coating agents, resist materials, and semiconductor underlayer film forming materials (for example, Patent Document 1). See ~ 2). Further, a specific method is known as a method for purifying a hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene (see, for example, Patent Document 3).

International Publication No. 2013/024778 International Publication No. 2013/024779 Chinese Patent Application Publication No. 10347249

Conventionally disclosed methods for purifying hydroxy-substituted aromatic compounds such as dihydroxynaphthalene have problems such as limited improvement in purity or variations in purity and yield, and hydroxy-substituted aromatic compounds such as dihydroxynaphthalene. , Improvement of the purification method of dihydroxynaphthalene is required.
Further, in the above-mentioned applications described in the background technology, the metal content is an important performance evaluation item for improving the yield. That is, when a large amount of metal is contained in a hydroxy-substituted aromatic compound, for example, a compound or resin obtained by using dihydroxynaphthalene as a raw material, the metal remains in the semiconductor and deteriorates the electrical characteristics of the semiconductor. It is required to reduce the content of the metal as a metal.
As a method for purifying a hydroxy-substituted aromatic compound, for example, a compound or resin obtained from dihydroxynaphthalene for the purpose of reducing the metal content, a mixture containing the compound or resin and an organic solvent is brought into contact with an ion exchange resin. A method, a method of filtering with a filter, etc. can be considered. However, when a hydroxy-substituted aromatic compound having a high metal content, for example, dihydroxynaphthalene is used as a raw material, the above method has a problem that the load on metal removal is large and the cost is high.
Therefore, it is desired to establish an industrially advantageous purification method for a high-purity hydroxy-substituted aromatic compound having a reduced metal content, for example, dihydroxynaphthalene.
Further, when the purity of the hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene is low, there is a problem that the yield of the hydroxy-substituted aromatic compound, for example, the compound or resin obtained from dihydroxynaphthalene decreases or the yield varies.
Further, conventionally disclosed methods for purifying hydroxy-substituted aromatic compounds such as dihydroxynaphthalene do not describe reduction of metal content, and reduction of metal content is insufficient.
An object of the present invention is to provide an industrially advantageous method for producing a hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene.

As a result of diligent studies to solve the above problems, the present inventors have purified a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) under specific conditions to obtain high purity, high yield, and stability. They have found that a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) can be produced, and have reached the present invention.
In addition, as a result of diligent studies to solve the above problems, the present inventors have brought a solution containing a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) and a specific organic solvent into contact with an acidic aqueous solution for extraction treatment. As a result, they have found that the content of various metals in a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) can be reduced, leading to the present invention.

That is, the present invention is as follows.
[1]
A method for producing a hydroxy-substituted aromatic compound, which comprises a step (contact step) of contacting the hydroxy-substituted aromatic compound with an organic solvent and / or water in an atmosphere having an oxygen concentration of less than 20% by volume.
[2]
The method for producing a hydroxy-substituted aromatic compound according to [1], wherein the hydroxy-substituted aromatic compound is a hydroxy-substituted aromatic compound represented by the following formulas (A ₀ ) and / or (B ₀ ).
(In the above equation (A ₀ ), n ⁰ is an integer of ⁰ to 9, m ⁰ is an integer of ⁰ to 2, p ⁰ is an integer of ⁰ to 9, and Ra is independently hydrogen. An atom, a hydroxyl group, a halogen group, a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms which may have a substituent, or an aryl group having 2 to 40 carbon atoms. It is a group consisting of an alkenyl group and a combination thereof, and the alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond.
In the above formula (B ₀ ), n ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and R _b is independently a hydrogen atom, a hydroxyl group, a halogen group, and 1 to 1 carbon atoms. A group consisting of 40 linear, branched or cyclic alkyl groups, aryl groups having 6 to 40 carbon atoms which may have substituents, or alkenyl groups having 2 to 40 carbon atoms and combinations thereof. , The alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond. )
[3]
The hydroxy-substituted aromatic compound represented by the formula (A ₀ ) is a compound represented by the following formula (A), and the hydroxy-substituted aromatic compound represented by the formula (B ₀ ) is the following formula (B). The production method according to [2], which is a compound represented by.
(In the above equation (A), n ⁰ is an integer of ⁰ to 9, m ⁰ is an integer of ⁰ to 2, p ⁰ is an integer of ⁰ to 9, and R ₀ is an independent carbon. A linear, branched or cyclic alkyl group of number 1 to 30, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms.
In the above formula (B), n ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and R ₁ is independently linear, branched or branched with 1 to 30 carbon atoms. It is a cyclic alkyl group, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms. )
[4]
The hydroxy-substituted aromatic compound represented by the formula (A) is a compound represented by the following formula (A-1), a compound represented by the following formula (A-2), and a compound represented by the following formula (A-3). It is one or more selected from the group consisting of the compound represented by the compound and the compound represented by the following formula (A-4).
The production method according to [3], wherein the hydroxy-substituted aromatic compound represented by the formula (B) is a compound represented by the following formula (B-1).
(In the above formulas (A-1) to (A-4), n ⁰ is an integer of ⁰ to 9, and in the above formula (B-1), n ¹ is an integer of 0 to 9.)
[5]
The production method according to [3], wherein the hydroxy-substituted aromatic compound represented by the formula (A) is a compound represented by the following formula (1).
[6]
The production method according to any one of [1] to [5], which comprises a step of dissolving the hydroxy-substituted aromatic compound in an organic solvent.
[7]
The production method according to [6], which comprises a step of dissolving the hydroxy-substituted aromatic compound in an organic solvent and then bringing activated carbon into contact with a solution of the hydroxy-substituted aromatic compound.
[8]
The production method according to [6] or [7], which comprises a step of dissolving the hydroxy-substituted aromatic compound in an organic solvent and then crystallizing the hydroxy-substituted aromatic compound.
[9]
The group in which the organic solvent consists of methanol, ethanol, isopropanol, acetone, N-methylpyrrolidone, propylene glycol monomethyl ether, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate and ethyl acetate. The production method according to any one of [1] to [8], which is one or more selected from the above.
[10]
A hydroxy-substituted aromatic compound comprising a step of contacting a solution (α) containing an organic solvent and a hydroxy-substituted aromatic compound that is optionally immiscible with water with an acidic aqueous solution to extract a metal component in the hydroxy-substituted aromatic compound. Manufacturing method.
[11]
The production method according to [10], wherein the hydroxy-substituted aromatic compound is a hydroxy-substituted aromatic compound represented by the following formulas (A ₀ ) and / or (B ₀ ).
(In the above equation (A ₀ ), n ⁰ is an integer of ⁰ to 9, m ⁰ is an integer of ⁰ to 2, p ⁰ is an integer of ⁰ to 9, and Ra is independently hydrogen. An atom, a hydroxyl group, a halogen group, a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms which may have a substituent, or an aryl group having 2 to 40 carbon atoms. It is a group consisting of an alkenyl group and a combination thereof, and the alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond.
In the above formula (B ₀ ), n ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and R _b is independently a hydrogen atom, a hydroxyl group, a halogen group, and 1 to 1 carbon atoms. A group consisting of 40 linear, branched or cyclic alkyl groups, aryl groups having 6 to 40 carbon atoms which may have substituents, or alkenyl groups having 2 to 40 carbon atoms and combinations thereof. , The alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond. )
[12]
The hydroxy-substituted aromatic compound represented by the formula (A ₀ ) is a compound represented by the following formula (A), and the hydroxy-substituted aromatic compound represented by the formula (B ₀ ) is the following formula (B). The production method according to [11], which is a compound represented by).
(In the above equation (A), n ⁰ is an integer of ⁰ to 9, m ⁰ is an integer of ⁰ to 2, p ⁰ is an integer of ⁰ to 9, and R ₀ is an independent carbon. A linear, branched or cyclic alkyl group of numbers 1 to 30, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms.
In the above formula (B), n ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and R ₁ is independently linear, branched or branched with 1 to 30 carbon atoms. It is a cyclic alkyl group, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms. )
[13]
The hydroxy-substituted aromatic compound represented by the formula (A) is a compound represented by the following formula (A-1), a compound represented by the following formula (A-2), and a compound represented by the following formula (A-3). It is one or more selected from the group consisting of the compound represented by the compound and the compound represented by the following formula (A-4).
The production method according to [12], wherein the hydroxy-substituted aromatic compound represented by the formula (B) is a compound represented by the following formula (B-1).
(In the above formulas (A-1) to (A-4), n ⁰ is an integer of ⁰ to 9, and in the above formula (B-1), n ¹ is an integer of 0 to 9.)
[14]
The production method according to [12], wherein the hydroxy-substituted aromatic compound represented by the formula (A) is a compound represented by the following formula (1).
[15]
The production method according to any one of [10] to [14], which is carried out in an atmosphere having an oxygen concentration of less than 20% by volume.
[16]
The production method according to any one of [10] to [15], which comprises a step of extracting a metal component in a hydroxy-substituted aromatic compound with water after the extraction step.
[17]
The organic solvent that is optionally immiscible with water is at least one selected from the group consisting of toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate and ethyl acetate, [10] to The production method according to any one of [16].
[18]
The acidic aqueous solution is one or more mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid and maleic acid. , Tartrate, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and one or more organic acid aqueous solutions selected from the group consisting of trifluoroacetic acid, according to any one of [10] to [17]. The manufacturing method described.
[19]
The production method according to any one of [10] to [18], wherein the hydroxy-substituted aromatic compound is at least one selected from the group consisting of 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene.

INDUSTRIAL APPLICABILITY According to the present invention, a method for producing a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) can be provided industrially advantageously, and a high-purity hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) can be stably produced in a high yield. It will be possible.
Further, according to the present invention, a method for producing a hydroxy-substituted aromatic compound (for example, dihydroxynaphthalene) capable of reducing the content of various metals can be provided industrially advantageously.

Hereinafter, embodiments of the present invention (hereinafter, also referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and the present invention is not limited to the embodiments.

<Method for producing hydroxy-substituted aromatic compounds>
The first method for producing a hydroxy-substituted aromatic compound of the present embodiment is a step of contacting the hydroxy-substituted aromatic compound with an organic solvent and / or water in an atmosphere having an oxygen concentration of less than 20% by volume (contact step). including.

In the first production method of the present embodiment, the hydroxy-substituted aromatic compound is not particularly limited as long as it is an aromatic compound having at least one phenolic hydroxy group, and for example, the following formula (A ₀ ) and / or It is preferably a hydroxy-substituted aromatic compound represented by (B ₀ ).

(In the above equation (A ₀ ), n ⁰ is an integer of ⁰ to 9, m ⁰ is an integer of ⁰ to 2, p ⁰ is an integer of ⁰ to 9, and Ra is independently hydrogen. An atom, a hydroxyl group, a halogen group, a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms which may have a substituent, or an aryl group having 2 to 40 carbon atoms. It is a group consisting of an alkenyl group and a combination thereof, and the alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond.
In the above formula (B ₀ ), n ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and R _b is independently a hydrogen atom, a hydroxyl group, a halogen group, and 1 to 1 carbon atoms. A group consisting of 40 linear, branched or cyclic alkyl groups, aryl groups having 6 to 40 carbon atoms which may have substituents, or alkenyl groups having 2 to 40 carbon atoms and combinations thereof. , The alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond. )

In the first production method of the present embodiment, the hydroxy-substituted aromatic compound represented by the formula (A ₀ ) is preferably a compound represented by the following formula (A).
Further, in the first production method of the present embodiment, the hydroxy-substituted aromatic compound represented by the above formula (B ₀ ) is preferably a compound represented by the following formula (B).

(In the above equation (A), n ⁰ is an integer of ⁰ to 9, m ⁰ is an integer of ⁰ to 2, p ⁰ is an integer of ⁰ to 9, and R ₀ is an independent carbon. A linear, branched or cyclic alkyl group of numbers 1 to 30, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms.
In the above formula (B), n ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and R ₁ is independently linear, branched or branched with 1 to 30 carbon atoms. It is a cyclic alkyl group, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms. )

In the first production method of the present embodiment, the hydroxy-substituted aromatic compound represented by the formula (A) is represented by the compound represented by the following formula (A-1) and the following formula (A-2). It is preferable that the compound is one or more selected from the group consisting of a compound represented by the following formula (A-3), a compound represented by the following formula (A-4), and a compound represented by the following formula (A-4).
Further, in the first production method of the present embodiment, the hydroxy-substituted aromatic compound represented by the formula (B) is preferably a compound represented by the following formula (B-1).

(In the above formulas (A-1) to (A-4), n ⁰ is an integer of ⁰ to 9, and in the above formula (B-1), n ¹ is an integer of 0 to 9.)

According to the first production method of the present embodiment, the hydroxy-substituted aromatic compound is brought into contact with an organic solvent and / or water in an atmosphere having an oxygen concentration of less than 20% by volume, for example, impurities in the hydroxy-substituted aromatic compound. Is dissolved in an organic solvent and / or water and separated, so that the hydroxy-substituted aromatic compound can be stably and highly purified in a high yield.

Further, a hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene has a problem that a dimer is particularly easy to be produced. However, by performing the above contact step in an atmosphere where the oxygen concentration is less than 20% by volume, the hydroxy-substituted aromatic compound is produced. The formation of by-products such as dimers due to the oxidation of group compounds such as dihydroxynaphthalene can be suppressed, and hydroxy-substituted aromatic compounds such as dihydroxynaphthalene can be stably produced with high purity and high yield. become.

In the first production method of the present embodiment, the oxygen concentration in the contact step is preferably less than 10% by volume, more preferably less than 5% by volume, still more preferably less than 1% by volume. The lower the oxygen concentration in the contact step, the greater the effect of suppressing alteration of the hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene. The lower limit of the oxygen concentration in the drying step is not particularly limited, but is, for example, 0.01% by volume.

A known method can be applied to reduce the oxygen concentration, and the method is not particularly limited. For example, gas replacement can be performed by flowing nitrogen gas into a kettle for purification or by reducing the pressure and then introducing nitrogen gas. There are ways to do it. Alternatively, a method of reducing the pressure and performing under vacuum can be mentioned. A method of depressurizing the pot for purification and then introducing nitrogen gas is convenient, reliable and preferable.

The oxygen concentration can be confirmed by a known method and is not particularly limited. For example, nitrogen gas is flowed through a kettle for purification, and the oxygen concentration of the gas discharged from the vent is measured with an oxygen concentration meter. The method of doing this can be mentioned. Another method is to install an oxygen concentration meter in the pot for refining.

In the above contact step, the contact temperature is not particularly limited as long as it can suppress the alteration of the hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene, but is preferably in the range of 0 to 150 ° C, more preferably in the range of 5 to 100 ° C, and 5 to 60. The ° C range is even more preferred. When the contact temperature is within the above range, the purity and yield tend to be good, and the temperature adjustment tends to be easy.

In the above contact step, the contact time is not particularly limited as long as the alteration of the hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene can be suppressed, but is preferably in the range of 1 minute to 120 minutes, more preferably in the range of 1 minute to 60 minutes, 1 The range of minutes to 30 minutes is more preferable. When the contact time is within the above range, the purity and yield tend to be good, and the productivity tends to be improved.
Further, the pressure in the contact step can be applied to any of reduced pressure, normal pressure and pressurization.

The hydroxy-substituted aromatic compound represented by the formula (A) used in the first production method of the present embodiment is particularly preferably a compound represented by the following formula (1).

Here, the compound represented by the above formula (1) is not particularly limited, but from the viewpoint of raw material supply, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1 , 5-Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene. One or more selected from the above is preferable.

The compound represented by the above formula (1) is not particularly limited, but is derived from 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene from the viewpoint of heat resistance of the compound or resin obtained from the compound as a raw material. One or more selected from the group is more preferable.

The compound represented by the above formula (1) is not particularly limited, but 2,6-dihydroxynaphthalene is more preferable from the viewpoint of further heat resistance of the compound or resin obtained from the compound as a raw material.

The compound represented by the above formula (1) can be easily obtained by known means such as a manufacturer and a reagent manufacturer. Further, a known method can be applied and appropriately synthesized, and the synthesis method is not particularly limited.

The hydroxy-substituted aromatic compound used in the first production method of the present embodiment may be used alone or in combination of two or more. Further, the hydroxy-substituted aromatic compound may contain various surfactants, various cross-linking agents, various acid generators, various stabilizers and the like.

The organic solvent and / or water used in the first production method of the present embodiment is not particularly limited, but for example, an organic solvent and / or water that can be safely applied to the semiconductor manufacturing process is preferable. The amount of the organic solvent and / or water used is usually preferably about 0.1 to 1000 times by mass with respect to the hydroxy-substituted aromatic compound used, and more preferably 0.5 to 500 from the viewpoint of economy. It is mass times, more preferably 1 to 100 times by mass.

Specific examples of the organic solvent used in the first production method of the present embodiment are not limited to the following, but for example, ethers such as tetrahydrofuran and 1,3-dioxolane, and alcohols such as methanol, ethanol and isopropanol. , Acetone, Methyl Ethyl Ketone, Methyl Isobutyl Ketone, Ethyl Isobutyl Ketone, Cyclohexanone, Cyclopentanone, 2-Heptanone, 2-Pentanone, N-Methylpyrrolidone and other ketones, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl Glycol ethers such as ether (PGME) and propylene glycol monoethyl ether, ethers such as diethyl ether and diisopropyl ether, esters such as ethyl acetate, n-butyl acetate and isoamyl acetate, ethylene glycol monoethyl ether acetate and ethylene glycol. Glycol ether acetates such as monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate, aliphatic hydrocarbons such as n-hexane and n-heptane, and aromatic hydrocarbons such as toluene and xylene. Examples include halogenated hydrocarbons such as methylene chloride and chloroform.
Among these, from the group consisting of methanol, ethanol, isopropanol, acetone, N-methylpyrrolidone, propylene glycol monomethyl ether, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate and ethyl acetate. One or more selected are preferable, and one or more selected from the group consisting of methanol, ethanol, isopropanol, acetone, N-methylpyrrolidone, propylene glycol monomethyl ether, cyclohexanone and propylene glycol monomethyl ether acetate is more preferable.

Specific examples of water used in the first production method of the present embodiment include, but are not limited to, tap water, industrial water, ion-exchanged water, ultrapure water, and the like. Further, an acidic aqueous solution may be used. The acidic aqueous solution is not particularly limited, and is appropriately selected from an aqueous solution in which a generally known organic or inorganic compound is dissolved in water. For example, an aqueous solution in which mineral acids such as hydrochloric acid, sulfuric acid, nitrate and phosphoric acid are dissolved in water, or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid and methanesulfone. Examples thereof include an aqueous solution in which an organic acid such as an acid, phenol sulfonic acid, p-toluene sulfonic acid, or trifluoroacetic acid is dissolved in water. The pH of the acidic aqueous solution is not particularly limited, but it is preferable to adjust the acidity of the aqueous solution in consideration of the adverse effect on the hydroxy-substituted aromatic compound. Generally, the pH range of the acidic aqueous solution is preferably about 0 to 5, more preferably about pH 0 to 4, and even more preferably about pH 0 to 3.
Among these, ion-exchanged water, ultrapure water and the like are preferable in order to suppress contamination of metals and chlorine.
These organic solvents and water can be used alone or in combination of two or more.
Further, it is preferable to reduce dissolved oxygen in advance from these organic solvents and / or water. The method for reducing dissolved oxygen is not particularly limited, and a known method can be applied. However, an inert gas such as nitrogen gas is passed through an organic solvent and / or water under normal pressure or reduced pressure, or ultrasonic waves are used. The method of adding is effective.

The first production method of the present embodiment preferably includes a step of dissolving the hydroxy-substituted aromatic compound in an organic solvent.

In the first production method of the present embodiment, the hydroxy-substituted aromatic compound is dissolved in an organic solvent for the purpose of decolorization, demetallization, deimpurity, etc., and then the activated carbon is brought into contact with the solution of the hydroxy-substituted aromatic compound. It is preferable to include a step. Further, it is more preferable that the contacting step of the activated carbon is performed in an atmosphere having an oxygen concentration of less than 20% by volume. The method for reducing the oxygen remaining in the activated carbon is not particularly limited, and a known method can be applied. However, by adding the activated carbon to the purification pot, flowing nitrogen gas, or reducing the pressure and then introducing nitrogen. There are ways to do it.
On the other hand, when the contacting step of activated carbon is carried out in an atmosphere having an oxygen concentration of less than 20% by volume, the deterioration of the hydroxy-substituted aromatic compound, for example, dihydroxynaphthalene is suppressed, and the purity of the hydroxy-substituted aromatic compound tends to be further improved. There is, or it suppresses variations in purity and yield, making it an industrially more advantageous process.

The first production method of the present embodiment preferably includes a step of dissolving the hydroxy-substituted aromatic compound in an organic solvent and then crystallizing the hydroxy-substituted aromatic compound.

As a method for isolating the hydroxy-substituted aromatic compound, known methods such as removal under reduced pressure, separation by reprecipitation, and a combination thereof can be applied. If necessary, known treatments such as concentration operation, filtration operation, centrifugation operation, and drying operation can be performed.
It is preferable to carry out these operations in an atmosphere having an oxygen concentration of less than 20% by volume in order to improve the purity or suppress variations in purity and yield.

In the second method for producing a hydroxy-substituted aromatic compound of the present embodiment, a solution (α) containing an organic solvent and a hydroxy-substituted aromatic compound that is not arbitrarily mixed with water is brought into contact with an acidic aqueous solution to bring the hydroxy-substituted aromatic compound into contact with each other. The step of extracting the metal content in the compound is included.

In the second production method of the present embodiment, the hydroxy-substituted aromatic compound is not particularly limited as long as it is an aromatic compound having at least one phenolic hydroxy group, and for example, the following formula (A ₀ ) and / or It is preferably a hydroxy-substituted aromatic compound represented by (B ₀ ).

(In the above equation (A ₀ ), n ⁰ is an integer of ⁰ to 9, m ⁰ is an integer of ⁰ to 2, p ⁰ is an integer of ⁰ to 9, and Ra is independently hydrogen. An atom, a hydroxyl group, a halogen group, a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms which may have a substituent, or an aryl group having 2 to 40 carbon atoms. It is a group consisting of an alkenyl group and a combination thereof, and the alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond.
In the above formula (B ₀ ), n ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and R _b is independently a hydrogen atom, a hydroxyl group, a halogen group, and 1 to 1 carbon atoms. A group consisting of 40 linear, branched or cyclic alkyl groups, aryl groups having 6 to 40 carbon atoms which may have substituents, or alkenyl groups having 2 to 40 carbon atoms and combinations thereof. , The alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond. )

In the second production method of the present embodiment, the hydroxy-substituted aromatic compound represented by the formula (A ₀ ) is preferably a compound represented by the following formula (A).
Further, in the second production method of the present embodiment, the hydroxy-substituted aromatic compound represented by the above formula (B ₀ ) is preferably a compound represented by the following formula (B).

(In the above equation (A), n ⁰ is an integer of ⁰ to 9, m ⁰ is an integer of ⁰ to 2, p ⁰ is an integer of ⁰ to 9, and R ₀ is an independent carbon. A linear, branched or cyclic alkyl group of numbers 1 to 30, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms.
In the above formula (B), n ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and R ₁ is independently linear, branched or branched with 1 to 30 carbon atoms. It is a cyclic alkyl group, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms. )

In the second production method of the present embodiment, the hydroxy-substituted aromatic compound represented by the formula (A) is represented by the compound represented by the following formula (A-1) and the following formula (A-2). It is preferable that the compound is one or more selected from the group consisting of a compound represented by the following formula (A-3), a compound represented by the following formula (A-4), and a compound represented by the following formula (A-4).
Further, in the second production method of the present embodiment, the hydroxy-substituted aromatic compound represented by the formula (B) is preferably a compound represented by the following formula (B-1).

(In the above formulas (A-1) to (A-4), n ⁰ is an integer of ⁰ to 9, and in the above formula (B-1), n ¹ is an integer of 0 to 9.)

According to the second production method of the present embodiment, the hydroxy-substituted aromatic compound is dissolved in an organic solvent that is not arbitrarily mixed with water, and the solution is brought into contact with an acidic aqueous solution to carry out an extraction treatment. After transferring the metal content contained in the solution (α) containing the compound and the organic solvent to the aqueous phase, the organic phase and the aqueous phase are separated to obtain a hydroxy-substituted aromatic compound having a reduced metal content. Can be done.

The hydroxy-substituted aromatic compound represented by the formula (A) used in the second production method of the present embodiment is particularly preferably a compound represented by the following formula (1).

Here, the compound represented by the above formula (1) is not particularly limited, but from the viewpoint of raw material supply, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1 , 5-Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene. One or more selected from the above is preferable.

Further, the compound represented by the above formula (1) is more than one selected from the group consisting of 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene from the viewpoint of the heat resistance of the obtained compound or resin. preferable.

The compound represented by the above formula (1) is more preferably 2,6-dihydroxynaphthalene from the viewpoint of further heat resistance of the obtained compound or resin.

The compound represented by the above formula (1) can be easily obtained by known means such as a manufacturer and a reagent manufacturer. Further, a known method can be applied and appropriately synthesized, and the synthesis method is not particularly limited.

The hydroxy-substituted aromatic compound used in the second production method of the present embodiment may be used alone or in combination of two or more. Further, the hydroxy-substituted aromatic compound may contain various surfactants, various cross-linking agents, various acid generators, various stabilizers and the like.

The organic solvent used in the second production method of the present embodiment, which is not arbitrarily miscible with water, is not particularly limited, but an organic solvent that can be safely applied to the semiconductor manufacturing process is preferable.
The organic solvent that is not miscible with water means an organic solvent having a solubility in water at room temperature of less than 30%, more preferably less than 20%, and particularly preferably less than 10%.
Specific examples of the organic solvent used in the second production method of the present embodiment are not limited to the following, but for example, ethers such as diethyl ether and diisopropyl ether, ethyl acetate, n-butyl acetate, isoamyl acetate and the like. Esters, methyl ethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 2-pentanone and other ketones, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), glycol ether acetates such as propylene glycol monoethyl ether acetate, aliphatic hydrocarbons such as n-hexane and n-heptane, aromatic hydrocarbons such as toluene and xylene, halogens such as methylene chloride and chloroform. Examples include chemical hydrocarbons. Among these, one or more selected from the group consisting of toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate and ethyl acetate is preferable, and cyclohexanone, propylene glycol monomethyl ether acetate and ethyl acetate are preferable. More preferably, one or more selected from the group consisting of.
Each of these organic solvents can be used alone, or two or more of them can be mixed and used.

The amount of the organic solvent used is usually preferably about 0.1 to 1000 times by mass, more preferably 0.5 to 500 times by mass, and further preferably from the viewpoint of economy, with respect to the hydroxy-substituted aromatic compound to be used. It is preferably 1 to 100 times by mass.

In the second production method of the present embodiment, it may be preferable that the solution (α) further contains an organic solvent that is optionally miscible with water. By containing an organic solvent that is arbitrarily miscible with water, the amount of the hydroxy-substituted aromatic compound charged can be increased, the liquid separation property can be improved, and the production can be performed with high pot efficiency. The method of adding an organic solvent that is arbitrarily miscible with water is not particularly limited. For example, a method of adding to a solution containing an organic solvent in advance, a method of adding to water or an acidic aqueous solution in advance, and a method of adding after contacting a solution containing an organic solvent with water or an acidic aqueous solution are all possible, but in advance. The method of adding to a solution containing an organic solvent is preferable in terms of workability of operation and ease of control of the amount to be charged.

The organic solvent used in the second production method of the present embodiment, which is optionally miscible with water, is not particularly limited, but an organic solvent that can be safely applied to the semiconductor manufacturing process is preferable. The organic solvent that is arbitrarily miscible with water means an organic solvent having a solubility in water at room temperature of 70% or more, more preferably 80% or more, and particularly preferably 90% or more.

Specific examples of the organic solvent that is optionally mixed with water are not limited to the following, but for example, ethers such as tetrahydrofuran and 1,3-dioxolane, alcohols such as methanol, ethanol and isopropanol, acetone and N-methylpyrrolidone. Examples thereof include ketones such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), and glycol ethers such as propylene glycol monoethyl ether. Among these, N-methylpyrrolidone, propylene glycol monomethyl ether and the like are preferable, and one or more selected from the group consisting of N-methylpyrrolidone and propylene glycol monomethyl ether is more preferable.
Each of the above organic solvents can be used alone, or two or more kinds can be mixed and used.

The amount of the organic solvent that is arbitrarily miscible with water is not particularly limited as long as the solution phase and the aqueous phase are separated from each other, but is usually 0.1 to 1000 mass by mass with respect to the hydroxy-substituted aromatic compound used. It is preferably about twice, more preferably 0.5 to 500 times by mass, and further preferably 1 to 100 times by mass from the viewpoint of economic efficiency.

The acidic aqueous solution used in the second production method of the present embodiment is not limited to the following, and is appropriately selected from a generally known aqueous solution in which an organic or inorganic compound is dissolved in water. For example, an aqueous solution in which mineral acids such as hydrochloric acid, sulfuric acid, nitrate and phosphoric acid are dissolved in water, or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid and methanesulfone. Examples thereof include an aqueous solution in which an organic acid such as an acid, phenol sulfonic acid, p-toluene sulfonic acid, or trifluoroacetic acid is dissolved in water. Each of these acidic aqueous solutions can be used alone, or two or more of them can be used in combination.

Among these acidic aqueous solutions, one or more mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitrate and phosphoric acid, or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid and malein. It is preferably one or more aqueous organic acid solutions selected from the group consisting of acids, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and trifluoroacetic acid, preferably sulfuric acid, nitrate and acetic acid. An aqueous solution of a carboxylic acid such as oxalic acid, tartaric acid, or citric acid is more preferable, an aqueous solution of sulfuric acid, oxalic acid, tartaric acid, or citric acid is more preferable, and an aqueous solution of oxalic acid is particularly preferable. It is considered that polyvalent carboxylic acids such as oxalic acid, tartaric acid, and citric acid coordinate to metal ions and produce a chelating effect, so that the metal can be removed more effectively. Further, the water used here is preferably water having a low metal content, for example, ion-exchanged water, etc., in line with the object of the present embodiment.

The pH of the acidic aqueous solution used in the present embodiment is not particularly limited, but it is preferable to adjust the acidity of the aqueous solution in consideration of the adverse effect on the hydroxy-substituted aromatic compound. Generally, the pH range of the acidic aqueous solution is preferably about 0 to 5, more preferably about pH 0 to 4, and even more preferably about 0 to 3.

The amount of the acidic aqueous solution used in the second production method of the present embodiment is not particularly limited, but from the viewpoint of reducing the number of extractions for removing metals and from the viewpoint of ensuring operability in consideration of the total amount of liquid. It is preferable to adjust the amount used from the above. From this point of view, the amount of the acidic aqueous solution used is usually preferably 0.01 to 200% by mass with respect to the solution (α) containing the organic solvent and the hydroxy-substituted aromatic compound which are not miscible with water. It is more preferably 0.05 to 20% by mass, still more preferably 0.1 to 10% by mass.

In the second production method of the present embodiment, hydroxy substitution is performed by contacting the above-mentioned acidic aqueous solution with a solution (α) containing a hydroxy-substituted aromatic compound and an organic solvent that is arbitrarily immiscible with water. The metal content in the aromatic compound can be extracted.

In the second production method of the present embodiment, the temperature at which the extraction treatment is performed is usually preferably in the range of 0 to 90 ° C, more preferably in the range of 10 to 85 ° C, and further preferably in the range of 20 to 80 ° C. The extraction operation is not particularly limited, but is performed by, for example, mixing well by stirring or the like and then allowing the mixture to stand. As a result, the metal content contained in the solution containing the hydroxy-substituted aromatic compound and the organic solvent is transferred to the aqueous phase. In addition, this operation reduces the acidity of the solution and suppresses the alteration of the hydroxy-substituted aromatic compound.

Since the solution phase containing the hydroxy-substituted aromatic compound and the organic solvent and the aqueous phase are separated by the above operation, the solution containing the hydroxy-substituted aromatic compound and the organic solvent is recovered by decantation or the like. The standing time is not particularly limited, but it is preferable to adjust the standing time from the viewpoint of improving the separation between the solution phase containing the organic solvent and the aqueous phase. Usually, the standing time is preferably 1 minute or more, more preferably 10 minutes or more, and further preferably 30 minutes or more.
Further, although the extraction process may be performed only once, it is also effective to repeat the operations of mixing, standing, and separating a plurality of times.

In the second production method of the present embodiment, an extraction treatment is performed by a step of bringing the solution (α) into contact with an acidic aqueous solution, and then a step of extracting a metal component in the hydroxy-substituted aromatic compound with water. Is preferably included. That is, it is preferable that the extraction treatment is performed using an acidic aqueous solution, and then the recovered solution containing the hydroxy-substituted aromatic compound and the organic solvent is further subjected to the extraction treatment with water. The extraction treatment with water is not particularly limited, but can be carried out by, for example, mixing well by stirring or the like and then allowing the mixture to stand. Since the solution obtained after the standing is separated into a solution phase containing the hydroxy-substituted aromatic compound and the organic solvent and an aqueous phase, the solution phase containing the hydroxy-substituted aromatic compound and the organic solvent can be recovered by decantation or the like. it can.
Further, the water used here is preferably water having a low metal content, for example, ion-exchanged water, ultrapure water, or the like, in line with the object of the present embodiment. The extraction process with water may be performed only once, but it is also effective to repeat the operations of mixing, standing, and separating a plurality of times. Further, the conditions such as the ratio of use of both in the extraction treatment with water, the temperature, and the time are not particularly limited, but the same as in the case of the contact treatment with the acidic aqueous solution may be used.

Moisture that can be mixed in the solution containing the hydroxy-substituted aromatic compound and the organic solvent thus obtained can be easily removed by performing an operation such as vacuum distillation.
Further, if necessary, an organic solvent can be added to adjust the concentration of the hydroxy-substituted aromatic compound to an arbitrary concentration.

The method for isolating the hydroxy-substituted aromatic compound from the obtained solution containing the hydroxy-substituted aromatic compound and the organic solvent is not particularly limited, and for example, removal under reduced pressure, separation by reprecipitation, and a combination thereof are known. It can be done by the method of. Further, if necessary, known treatments such as concentration operation, filtration operation, centrifugation operation, and drying operation can be performed.

Further, the second production method of the present embodiment is preferably performed in an atmosphere having an oxygen concentration of less than 20% by volume. By setting the oxygen concentration to less than 20% by volume, alteration of the hydroxy-substituted aromatic compound can be suppressed, and a high-purity hydroxy-substituted aromatic compound can be obtained.

In the second production method of the present embodiment, the oxygen concentration is more preferably less than 10% by volume, further preferably less than 5% by volume, and particularly preferably less than 1% by volume. The lower the oxygen concentration, the more the alteration of the second production method of the present embodiment can be suppressed. The lower limit of the oxygen concentration in the second production method of the present embodiment is not particularly limited, but is, for example, 0.01% by volume.

A known method can be applied to reduce the oxygen concentration, and the method is not particularly limited. For example, gas replacement is performed by flowing nitrogen gas into a kettle for purification or by reducing the pressure and then introducing nitrogen gas. The method can be mentioned. Alternatively, a method of reducing the pressure and performing under vacuum can be mentioned. A method of depressurizing the pot for purification and then introducing nitrogen gas is convenient, reliable and preferable.

A known method can be applied to confirm the oxygen concentration, and the confirmation is not particularly limited. For example, nitrogen gas is flowed through a kettle for purification, and the oxygen concentration of the gas discharged from the vent is measured with an oxygen concentration meter. The method to be performed by In addition, a method of installing an oxygen concentration meter in a kettle for refining can also be mentioned.

Hereinafter, the present embodiment will be described in more detail with reference to examples. However, this embodiment is not limited to these examples.

(Example 1)
In a 3000 L capacity glass-lined refiner, 100 kg of a 90% pure 2,6-dihydroxynaphthalene (hereinafter also referred to as "2,6-DHN") crude is charged in 220 kg of acetone and 280 g of ion-exchanged water, and then in the pot. The air inside was removed under reduced pressure, nitrogen gas was introduced, and the solution was obtained by heating and dissolving to 50 ° C. with stirring. In this step, the oxygen concentration in the purification pot was less than 1% by volume.
Next, 10 kg of activated carbon that had been deoxidized in advance was added to the obtained solution, the mixture was cooled to room temperature, stirred for 1 hour, and then the activated carbon was filtered off. Subsequently, the filtrate was rinsed with 100 kg of acetone / ion-exchanged water (1/1).
Then, acetone was removed from the filtrate under reduced pressure, filtered by centrifugation, and then vacuum dried to obtain 90 kg (yield 90%) of 2,6-DHN having a purity of 99%.
It is believed that this process can be refined industrially favorably.

(Example 2)
In a 5000 mL glass-lined purification kettle, 500 g of a 90% pure 2,6-dihydroxynaphthalene (2,6-DHN) crude was charged in 1000 g of isopropanol-modified ethanol, and then the air inside the kettle was removed under reduced pressure. Nitrogen gas was introduced and heated and dissolved to 60 ° C. with stirring to obtain a solution. In this step, the oxygen concentration in the purification pot was less than 1% by volume.
Next, 1250 g of ion-exchanged water was charged into the purification pot to precipitate crystals, and 1250 g of ion-exchanged water was further charged, cooled to 10 ° C. or lower, and stirred for 2 hours.
Then, after filtration by centrifugation, rinsing and vacuum drying were carried out with 500 g of ion-exchanged water to obtain 450 g (yield 90%) of 2,6-DHN having a purity of 99%.

(Example 3)
In a 3000 L capacity glass-lined refining kettle, 100 kg of a 98% pure 4,4'-biphenol crude was charged in 150 kg of acetone and 200 kg of ion-exchanged water, and then the air inside the kettle was removed under reduced pressure to introduce nitrogen gas. Then, the solution was obtained by heating and dissolving to 50 ° C. with stirring. In this step, the oxygen concentration in the purification pot was less than 1% by volume.
Next, 10 kg of activated carbon that had been deoxidized in advance was added to the obtained solution, the mixture was cooled to room temperature, stirred for 1 hour, and then the activated carbon was filtered off. Subsequently, the filtrate was rinsed with 100 kg of acetone / ion-exchanged water (1/1).
Then, acetone was removed from the filtrate under reduced pressure, filtered by centrifugation, and vacuum dried to obtain 95 kg (yield 95%) of 4,4'-biphenol having a purity of 99%.

(Example 4)
300 g of a 98% pure 4,4'-biphenol crude was charged in 1000 g of isopropanol-modified ethanol in a 5000 mL glass-lined purification kettle, and then the air inside the kettle was removed under reduced pressure to introduce nitrogen gas. A solution was obtained by heating and dissolving to 60 ° C. with stirring. In this step, the oxygen concentration in the purification pot was less than 1% by volume.
Next, 1200 g of ion-exchanged water was charged into the purification pot to precipitate crystals, and 1200 g of ion-exchanged water was further charged, cooled to 10 ° C. or lower, and stirred for 2 hours.
Then, after filtration by centrifugation, it was rinsed with 500 g of ion-exchanged water and vacuum dried to obtain 280 g (yield 95%) of 4,4'-biphenol having a purity of 99%.

(Example 5)
In a 3000 L capacity glass-lined refining kettle, 100 kg of a 90% pure resorcinol (1,3-dihydroxybenzene) crude is charged in 150 kg of acetone and 200 kg of ion-exchanged water, and then the air inside the kettle is removed under reduced pressure to remove nitrogen. A gas was introduced and heated and dissolved to 50 ° C. with stirring to obtain a solution. In this step, the oxygen concentration in the purification pot was less than 1% by volume.
Next, 10 kg of activated carbon that had been deoxidized in advance was added to the obtained solution, the mixture was cooled to room temperature, stirred for 1 hour, and then the activated carbon was filtered off. Subsequently, the filtrate was rinsed with 100 kg of acetone / ion-exchanged water (1/1).
Then, acetone was removed from the filtrate under reduced pressure, filtered by centrifugation, and then vacuum dried to obtain 90 kg (yield 90%) of resorcinol having a purity of 98%.

(Example 6)
In a glass-lined refining kettle with a capacity of 5000 mL, 300 g of a crude solution of 90% pure resorcinol was charged into 1000 g of isopropanol-modified ethanol, and then the air inside the kettle was removed under reduced pressure to introduce nitrogen gas, and the temperature was 60 ° C. with stirring. The solution was obtained by heating and dissolving. In this step, the oxygen concentration in the purification pot was less than 1% by volume.
Next, 1000 g of ion-exchanged water was charged into the purification kettle to precipitate crystals, and 1500 g of ion-exchanged water was further charged, cooled to 10 ° C. or lower, and stirred for 2 hours.
Then, after filtration by centrifugation, it was rinsed with 500 g of ion-exchanged water and vacuum dried to obtain 270 g (yield 90%) of resorcinol having a purity of 98%.

(Example 7)
300 g of a 98% pure 9,10-dihydroxyanthracene crude is charged into 1000 g of methyl ethyl ketone in a 5000 mL glass-lined refining kettle, and then the air inside the kettle is removed under reduced pressure to introduce nitrogen gas and stirred. While heating and dissolving to 60 ° C., a solution was obtained. In this step, the oxygen concentration in the purification pot was less than 1% by volume.
Next, 1000 g of ion-exchanged water was charged into the purification kettle to precipitate crystals, and 1500 g of ion-exchanged water was further charged, cooled to 10 ° C. or lower, and stirred for 2 hours.
Then, after filtering by centrifugation, it was rinsed with 500 g of ion-exchanged water and vacuum-dried to obtain 255 g (yield 85%) of 9,10-dihydroxyanthracene having a purity of 99%.

(Example 8)
300 g of a 98% pure 1-hydroxypyrene crude is charged in 1000 g of isopropanol-modified ethanol in a 5000 mL glass-lined purification kettle, and then the air inside the kettle is removed under reduced pressure to introduce nitrogen gas and the mixture is stirred. While heating and dissolving to 80 ° C., a solution was obtained. In this step, the oxygen concentration in the purification pot was less than 1% by volume.
Next, 1000 g of ion-exchanged water was charged into the purification kettle to precipitate crystals, and 1500 g of ion-exchanged water was further charged, cooled to 10 ° C. or lower, and stirred for 2 hours.
Then, after filtration by centrifugation, it was rinsed with 500 g of ion-exchanged water and vacuum dried to obtain 280 g (yield 95%) of 1-hydroxypyrene having a purity of 99%.
It is considered that this process can be manufactured in an industrially advantageous manner.

(Comparative Example 1)
The same procedure as in Example 1 was carried out except that the air inside the kettle was removed under reduced pressure and nitrogen gas was not introduced. In this step, the oxygen concentration in the purification pot was 20.8% by volume. As a result, 2,6-DHN having a purity of 95% was obtained in 90 kg (yield 90%).
Since the purity of 2,6-DHN was insufficient, the same operation as in this Comparative Example was carried out again with the aim of further increasing the purity. As a result, 80 kg (yield) of 2,6-DHN having a purity of 98% was obtained. 89%) obtained. From 100 kg of crude to 80 kg of refined product, the total yield was as low as 80%.
This process is considered to be industrially disadvantageous.

(Comparative Example 2)
The procedure was the same as in Example 2 except that the air inside the kettle was removed under reduced pressure and nitrogen gas was not introduced. In this step, the oxygen concentration in the purification pot was 20.8% by volume. As a result, 2,6-DHN having a purity of 95% was obtained in 450 g (yield 90%).
Since the purity of 2,6-DHN was insufficient, the same operation as in this Comparative Example was carried out again with the aim of further increasing the purity. As a result, 400 g (yield) of 2,6-DHN having a purity of 98% was obtained. 89%) obtained. From 500 g of crude product to 400 g of refined product, the total yield was as low as 80%.
This process is considered to be industrially disadvantageous.

(Example 1-1) Production of ethyl acetate solution of the compound represented by the formula (1) in which the metal content is reduced In a 1000 mL volume four-necked flask (bottom punching type), 2,6-dihydroxynaphthalene (bottom punching type) is placed. 150 g of a solution (2.5 mass%) in which "2,6-DHN" is dissolved in ethyl acetate is charged, and then the air inside the flask is removed under reduced pressure to introduce nitrogen gas, and the mixture is stirred. While heating to 25 ° C., a solution was obtained. In this step, the oxygen concentration in the flask was less than 1% by volume. Next, 37.5 g of an aqueous oxalic acid solution (pH 1.3) was added to the obtained solution, and the mixture was stirred for 5 minutes and allowed to stand for 30 minutes. As a result, the oil phase and the aqueous phase were separated, and the aqueous phase was removed. After repeating this operation once, 37.5 g of ultrapure water was added to the obtained oil phase, stirred for 5 minutes, and allowed to stand for 30 minutes to remove the aqueous phase. By repeating this operation three times, a solution of 2,6-DHN in ethyl acetate having a reduced metal content was obtained.

(Example 2-1)
A solution of 2,6-DHN in ethyl acetate was obtained in the same manner as in Example 1-1 except that the air inside the kettle was removed under reduced pressure and the introduction of nitrogen gas was omitted. In this step, the oxygen concentration in the flask was 20.8% by volume.

(Example 3-1)
In a 1000 mL volume four-necked flask (bottom punching type), 300 g of a solution (5.0% by mass) in which a crude material of 4,4'-biphenol was dissolved in ethyl acetate was charged.
Subsequently, the air inside the flask was removed under reduced pressure, nitrogen gas was introduced, and the mixture was heated to 40 ° C. with stirring to obtain a solution. In this step, the oxygen concentration in the flask was less than 1% by volume. Next, 75 g of an aqueous oxalic acid solution (pH 1.3) was added to the obtained solution, and the mixture was stirred for 5 minutes and allowed to stand for 30 minutes. As a result, the oil phase and the aqueous phase were separated, and the aqueous phase was removed. After repeating this operation once, 75 g of ultrapure water was added to the obtained oil phase, stirred for 5 minutes, and allowed to stand for 30 minutes to remove the aqueous phase. By repeating this operation three times, an ethyl acetate solution of 4,4′-biphenol having a reduced metal content was obtained.

(Example 5-1)
In a 1000 mL four-necked flask (bottom punching type), 300 g of a solution (5.0% by mass) of a crude resorcinol dissolved in ethyl acetate was charged, and then the air inside the flask was removed under reduced pressure to remove nitrogen gas. Was introduced and heated to 40 ° C. with stirring to obtain a solution. In this step, the oxygen concentration in the flask was less than 1% by volume. Next, 75 g of an aqueous oxalic acid solution (pH 1.3) was added to the obtained solution, and the mixture was stirred for 5 minutes and allowed to stand for 30 minutes. As a result, the oil phase and the aqueous phase were separated, and the aqueous phase was removed. After repeating this operation once, 75 g of ultrapure water was added to the obtained oil phase, stirred for 5 minutes, and allowed to stand for 30 minutes to remove the aqueous phase. By repeating this operation three times, an ethyl acetate solution of resorcinol having a reduced metal content was obtained.

(Example 7-1)
A 1000 mL volume four-necked flask (bottom punched type) is charged with 300 g of a solution (2.5% by mass) of a crude material of 9,10-dihydroxyanthracene dissolved in ethyl acetate, and then the air inside the flask is depressurized. After removal, nitrogen gas was introduced, and the mixture was heated to 40 ° C. with stirring to obtain a solution. In this step, the oxygen concentration in the flask was less than 1% by volume. Next, 75 g of an aqueous oxalic acid solution (pH 1.3) was added to the obtained solution, and the mixture was stirred for 5 minutes and allowed to stand for 30 minutes. As a result, the oil phase and the aqueous phase were separated, and the aqueous phase was removed. After repeating this operation once, 75 g of ultrapure water was added to the obtained oil phase, stirred for 5 minutes, and allowed to stand for 30 minutes to remove the aqueous phase. By repeating this operation three times, an ethyl acetate solution of 9,10-dihydroxyanthracene having a reduced metal content was obtained.

(Example 8-1)
A 1000 mL volume four-necked flask (bottom punching type) was charged with 300 g of a solution (2.0% by mass) of a crude 1-hydroxypyrene dissolved in ethyl acetate, and then the air inside the flask was removed under reduced pressure. Nitrogen gas was introduced and heated to 40 ° C. with stirring to obtain a solution. In this step, the oxygen concentration in the flask was less than 1% by volume. Next, 75 g of an aqueous oxalic acid solution (pH 1.3) was added to the obtained solution, and the mixture was stirred for 5 minutes and allowed to stand for 30 minutes. As a result, the oil phase and the aqueous phase were separated, and the aqueous phase was removed. After repeating this operation once, 75 g of ultrapure water was added to the obtained oil phase, stirred for 5 minutes, and allowed to stand for 30 minutes to remove the aqueous phase. By repeating this operation three times, an ethyl acetate solution of 1-hydroxypyrene having a reduced metal content was obtained.

Various metal contents were measured by ICP-MS for each solution before and after the treatment obtained in Examples 1 to 8 and Examples 1-1 to 8-1. The measurement results are shown in Table 1.

Subsequently, before the treatment, the purity of 2,6-DHN was measured by liquid chromatography (LC) for each of the solutions of 2,6-DHN obtained in Examples 1-1 and 2-1. As a result, what was 99% pure before the treatment was maintained at 99% purity in Example 1-1. In Example 2-1 the purity was 91%. Example 2-1 was the same as that of Example 1-1 except that the air inside the kettle was decompressed and the nitrogen gas was introduced, and the effect of carrying out in a nitrogen gas atmosphere was shown. ..

According to the present invention, a hydroxy-substituted aromatic compound, for example, a compound represented by the formula (1) can be produced industrially advantageously.
Further, according to the present invention, a hydroxy-substituted aromatic compound having a reduced metal content, for example, a compound represented by the formula (1) can be industrially advantageously produced.

Claims (19)

A method for producing a hydroxy-substituted aromatic compound, which comprises a step (contact step) of contacting the hydroxy-substituted aromatic compound with an organic solvent and / or water in an atmosphere having an oxygen concentration of less than 20% by volume. The method for producing a hydroxy-substituted aromatic compound according to claim 1, wherein the hydroxy-substituted aromatic compound is a hydroxy-substituted aromatic compound represented by the following formulas (A ₀ ) and / or (B ₀ ).
(In the above equation (A ₀ ), n ⁰ is an integer of ⁰ to 9, m ⁰ is an integer of ⁰ to 2, p ⁰ is an integer of ⁰ to 9, and Ra is independently hydrogen. An atom, a hydroxyl group, a halogen group, a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms which may have a substituent, or an aryl group having 2 to 40 carbon atoms. It is a group consisting of an alkenyl group and a combination thereof, and the alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond.
In the above formula (B ₀ ), n ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and R _b is independently a hydrogen atom, a hydroxyl group, a halogen group, and 1 to 1 carbon atoms. A group consisting of 40 linear, branched or cyclic alkyl groups, aryl groups having 6 to 40 carbon atoms which may have substituents, or alkenyl groups having 2 to 40 carbon atoms and combinations thereof. , The alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond. ) The hydroxy-substituted aromatic compound represented by the formula (A ₀ ) is a compound represented by the following formula (A), and the hydroxy-substituted aromatic compound represented by the formula (B ₀ ) is the following formula (B). The production method according to claim 2, which is a compound represented by.
(In the above equation (A), n ⁰ is an integer of ⁰ to 9, m ⁰ is an integer of ⁰ to 2, p ⁰ is an integer of ⁰ to 9, and R ₀ is an independent carbon. A linear, branched or cyclic alkyl group of numbers 1 to 30, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms.
In the above formula (B), n ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and R ₁ is independently linear, branched or branched with 1 to 30 carbon atoms. It is a cyclic alkyl group, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms. ) The hydroxy-substituted aromatic compound represented by the formula (A) is a compound represented by the following formula (A-1), a compound represented by the following formula (A-2), and a compound represented by the following formula (A-3). It is one or more selected from the group consisting of the compound represented by the compound and the compound represented by the following formula (A-4).
The production method according to claim 3, wherein the hydroxy-substituted aromatic compound represented by the formula (B) is a compound represented by the following formula (B-1).
(In the above formulas (A-1) to (A-4), n ⁰ is an integer of ⁰ to 9, and in the above formula (B-1), n ¹ is an integer of 0 to 9.) The production method according to claim 3, wherein the hydroxy-substituted aromatic compound represented by the formula (A) is a compound represented by the following formula (1).
The production method according to any one of claims 1 to 5, which comprises a step of dissolving the hydroxy-substituted aromatic compound in an organic solvent. The production method according to claim 6, further comprising a step of dissolving the hydroxy-substituted aromatic compound in an organic solvent and then bringing activated carbon into contact with a solution of the hydroxy-substituted aromatic compound. The production method according to claim 6 or 7, which comprises a step of dissolving the hydroxy-substituted aromatic compound in an organic solvent and then crystallizing the hydroxy-substituted aromatic compound. The group in which the organic solvent consists of methanol, ethanol, isopropanol, acetone, N-methylpyrrolidone, propylene glycol monomethyl ether, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate and ethyl acetate. The production method according to any one of claims 1 to 8, which is one or more selected from the above. A hydroxy-substituted aromatic compound comprising a step of contacting a solution (α) containing an organic solvent and a hydroxy-substituted aromatic compound that is optionally immiscible with water with an acidic aqueous solution to extract a metal component in the hydroxy-substituted aromatic compound. Manufacturing method. The production method according to claim 10, wherein the hydroxy-substituted aromatic compound is a hydroxy-substituted aromatic compound represented by the following formulas (A ₀ ) and / or (B ₀ ).
(In the above equation (A ₀ ), n ⁰ is an integer of ⁰ to 9, m ⁰ is an integer of ⁰ to 2, p ⁰ is an integer of ⁰ to 9, and Ra is independently hydrogen. An atom, a hydroxyl group, a halogen group, a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, an aryl group having 6 to 40 carbon atoms which may have a substituent, or an aryl group having 2 to 40 carbon atoms. It is a group consisting of an alkenyl group and a combination thereof, and the alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond.
In the above formula (B ₀ ), n ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and R _b is independently a hydrogen atom, a hydroxyl group, a halogen group, and 1 to 1 carbon atoms. A group consisting of 40 linear, branched or cyclic alkyl groups, aryl groups having 6 to 40 carbon atoms which may have substituents, or alkenyl groups having 2 to 40 carbon atoms and combinations thereof. , The alkyl group, the aryl group or the alkenyl group may contain an ether bond, a ketone bond, or an ester bond. ) The hydroxy-substituted aromatic compound represented by the formula (A ₀ ) is a compound represented by the following formula (A), and the hydroxy-substituted aromatic compound represented by the formula (B ₀ ) is the following formula (B). The production method according to claim 11, which is a compound represented by).
(In the above equation (A), n ⁰ is an integer of ⁰ to 9, m ⁰ is an integer of ⁰ to 2, p ⁰ is an integer of ⁰ to 9, and R ₀ is an independent carbon. A linear, branched or cyclic alkyl group of numbers 1 to 30, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms.
In the above formula (B), n ¹ is an integer of 0 to 9, p ¹ is an integer of 0 to 9, and R ₁ is independently linear, branched or branched with 1 to 30 carbon atoms. It is a cyclic alkyl group, an aryl group having 6 to 15 carbon atoms which may have a substituent, or an alkenyl group having 2 to 15 carbon atoms. ) The hydroxy-substituted aromatic compound represented by the formula (A) is a compound represented by the following formula (A-1), a compound represented by the following formula (A-2), and a compound represented by the following formula (A-3). It is one or more selected from the group consisting of the compound represented by the compound and the compound represented by the following formula (A-4).
The production method according to claim 12, wherein the hydroxy-substituted aromatic compound represented by the formula (B) is a compound represented by the following formula (B-1).
(In the above formulas (A-1) to (A-4), n ⁰ is an integer of ⁰ to 9, and in the above formula (B-1), n ¹ is an integer of 0 to 9.) The production method according to claim 12, wherein the hydroxy-substituted aromatic compound represented by the formula (A) is a compound represented by the following formula (1).
The production method according to any one of claims 10 to 14, which is carried out in an atmosphere having an oxygen concentration of less than 20% by volume. The production method according to any one of claims 10 to 15, further comprising an extraction treatment of a metal component in a hydroxy-substituted aromatic compound with water after the extraction step. Claims 10 to 10 that the organic solvent which is not miscible with water is at least one selected from the group consisting of toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate and ethyl acetate. The production method according to any one of 16. The acidic aqueous solution is one or more mineral acid aqueous solutions selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, or acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid and maleic acid. , Tartrate acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid and one or more organic acid aqueous solutions selected from the group consisting of trifluoroacetic acid, according to any one of claims 10 to 17. The manufacturing method described. The production method according to any one of claims 10 to 18, wherein the hydroxy-substituted aromatic compound is at least one selected from the group consisting of 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene.