JP2002363133A - METHOD FOR PRODUCING alpha CARBON-BONDED AROMATIC COMPOUND CONTAINING AT LEAST ONE OR MORE HYDROGEN ATOMS ON alphaCARBON BONDED TO AROMATIC RING AND METHOD FOR PRODUCING AROMATIC CARBOXYLIC ACID OR AROMATIC CARBOXYLIC ACID ESTER - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently and inexpensively producing aromatic compounds such as an αcarbon-bonded aromatic compound containing at least one or more hydrogen atoms on an α-carbon bonded to an aromatic ring, an aromatic carboxylic acid, an aromatic carboxylic acid ester, etc. SOLUTION: An aromatic carboxylic acid or an aromatic carboxylic acid ester is reacted with an α carbon-bonded aromatic compound containing at least one or more hydrogen atoms on an α carbon bonded to aromatic ring to exchange the hydroxycarbonyl group of the aromatic carboxylic acid or the ester group of the aromatic carboxylic acid ester for a substituent group containing the αcarbon of the α carbon bonded aromatic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel substituent which is suitably used for producing aromatic compounds such as p-acetoxymethylbenzoic acid, p-methylbenzyl acetate, p-xylylene diacetate and the like. The present invention relates to a method for producing an α-carbon-bonded aromatic compound having at least one hydrogen atom at an α-carbon bonded to an aromatic ring, and a method for producing an aromatic carboxylic acid or an aromatic carboxylic acid ester using an exchange reaction. Things.

[0002]

2. Description of the Related Art In general, p-acetoxymethyl benzoic acid, p-methylbenzyl acetate and p-xylylene diacetate, which are a kind of aromatic compounds, are generally used as raw materials for synthetic resins such as polyester resins, and various kinds of fragrances and solvents. It is used as a chemical or a raw material of these chemicals. Further, p-hydroxymethylbenzoic acid, which can be easily produced from p-acetoxymethylbenzoic acid by hydrolysis, is also very useful as a polyester raw material.

As a method for producing the above-mentioned p-acetoxymethyl benzoic acid, for example, Japanese Patent Application Laid-Open No. 2000-290229 discloses a method in which alkyl-substituted aromatics and carboxylic acids are partially oxidized using a catalyst containing a Group VIII element. It has been disclosed.

Various methods have been proposed for producing the above-mentioned p-hydroxymethylbenzoic acid. For example, US Pat. No. 4,130,719 discloses that sodium borohydride is used in a stoichiometric amount or more. (Excess) to reduce the side chains of terephthalic acid monoesters. Also, for example, see US Pat. No. 4,448,987.
Discloses a method for reducing terephthalic acid with hydrogen using rhenium oxide as a catalyst.

[0005] For example, Japanese Patent Application Laid-Open No. 48-96541 discloses that p-hydroxymethylbenzoic acid produced as a by-product when terephthalic acid is synthesized by directly oxidizing the side chain of p-xylene is recovered. A method for doing so is disclosed.

Various methods have also been proposed for producing the above-mentioned p-methylbenzyl acetate and p-xylylene diacetate.
No. 174950 discloses that p-xylene and acetic acid are reacted with p-xylene and acetic acid in the presence of oxygen using a palladium-bismuth compound and / or a palladium-lead compound as a catalyst to obtain p-methylbenzyl acetate and p-methylbenzyl acetate.
-A method for producing xylylene diacetate is disclosed.

Further, for example, Japanese Patent Application Laid-Open No. 62-273927
Japanese Patent Application Laid-Open Publication No. H11-157, discloses a method for producing p-xylylene diacetate by reacting p-xylene and acetic acid in the presence of oxygen using a catalyst containing palladium and bismuth. In addition, for example,
JP-A-70718 discloses a method for producing p-methylbenzyl acetate and p-xylylene diacetate by oxidizing a benzyl compound and a carboxylic acid in the presence of a specific catalyst.

[0008]

SUMMARY OF THE INVENTION However, Japanese Patent Application Laid-Open
The method for producing p-acetoxymethyl benzoic acid disclosed in Japanese Patent Application Publication No. 000-290229 is a method in which one side chain is converted into an acetoxymethyl group and the other side chain is converted into a carboxyl group by oxidation of a side chain. And the selectivity of p-acetoxymethylbenzoic acid is low.

In the method disclosed in US Pat. No. 4,130,719, p-hydroxymethylbenzoic acid must be efficiently and inexpensively produced since an excessive amount of a reducing agent must be used. Can not. Also, in the method disclosed in US Pat. No. 4,448,987,
Since a reduction process using hydrogen must be performed,
Equipment that can withstand the reaction conditions of high temperature and high pressure is required,
It is hard to say that it is an industrial manufacturing method. In addition, JP
In the method disclosed in JP-A-8-96541, p-hydroxymethylbenzoic acid produced as a by-product is recovered, so that the productivity is low and the production cannot be performed stably. Absent.

Also, Japanese Patent Application Laid-Open No. Sho 63-174950,
JP-A-62-273927 and JP-A-2000-273927
In the method for producing an aromatic carboxylic acid ester such as p-methylbenzyl acetate or p-xylylene diacetate disclosed in JP-A-70718, it is necessary to use an expensive specific catalyst in order to advance the oxidation reaction. There is.

Therefore, p-acetoxymethylbenzoic acid, p-methylbenzyl acetate, p-xylylene diene can be obtained by a high selectivity reaction which does not require an expensive and special catalyst and does not undergo oxidation or reduction of side chains. There is a demand for a method capable of producing an aromatic compound such as acetate.

The present invention has been made in view of the above-mentioned conventional problems, and has been made without using a catalyst, or
Α-carbon-bonded aromatic compound having at least one hydrogen atom at the α-carbon bonded to the aromatic ring, aromatic carboxylic acid, and aromatic carboxylic acid by a reaction that proceeds by using a general acid catalyst An object of the present invention is to provide a production method capable of producing an aromatic compound such as an ester with high selectivity.

[0013]

SUMMARY OF THE INVENTION The present inventors have developed an α-carbon-bonded aromatic compound having at least one hydrogen atom at the α-carbon bonded to an aromatic ring, an aromatic carboxylic acid, and an aromatic carboxylic acid. The present inventors have conducted intensive studies on a method for producing an aromatic compound such as an ester. As a result, the aromatic carboxylic acid or the aromatic carboxylic acid ester is reacted with an α-carbon-bonded aromatic compound having at least one hydrogen atom at the α-carbon bonded to the aromatic ring to form an aromatic carboxylic acid. A substituent exchange reaction occurs in which the hydroxycarbonyl group of the acid or the ester group of the aromatic carboxylic acid ester and the substituent containing the α-carbon of the α-carbon-bonded aromatic compound are exchanged. It has been found that it proceeds without use or by using a common acid catalyst. That is, a novel exchange reaction, which is a novel exchange reaction that does not require a special catalyst and does not undergo oxidation or reduction of side chains and has high selectivity, has been found. Then, by using the above-mentioned substituent exchange reaction, an α-carbon-bonded aromatic compound having at least one hydrogen atom at the α-carbon bonded to the aromatic ring, an aromatic carboxylic acid, an aromatic carboxylic acid ester and the like The present invention has been completed by confirming that an aromatic compound can be efficiently and inexpensively produced.

That is, the method for producing an α-carbon-bonded aromatic compound having at least one hydrogen atom at the α-carbon bonded to an aromatic ring according to the present invention is intended to solve the above-mentioned problems. An acid or an aromatic carboxylic acid ester is reacted with an α-carbon-bonded aromatic compound having at least one hydrogen atom at an α-carbon bonded to an aromatic ring to form a hydroxycarbonyl group of the aromatic carboxylic acid or It is characterized in that the ester group of the aromatic carboxylic acid ester is replaced with a substituent containing an α-carbon of the above-mentioned α-carbon bond aromatic compound.

In order to solve the above-mentioned problems, the method for producing an aromatic carboxylic acid or an aromatic carboxylic acid ester according to the present invention provides an aromatic carboxylic acid or an aromatic carboxylic acid ester and an α-bonded to an aromatic ring. Reacting an α-carbon-bonded aromatic compound having at least one hydrogen atom on carbon with the hydroxycarbonyl group of the aromatic carboxylic acid or the ester group of the aromatic carboxylic acid ester and the α-carbon-bonded aromatic compound Is substituted with a substituent containing an α-carbon.

The method for producing an α-carbon-bonded aromatic compound having at least one hydrogen atom on the α-carbon bonded to the aromatic ring, or the method for producing an aromatic carboxylic acid or an aromatic carboxylic acid ester is as described above. More preferably, the α-carbon bonded aromatic compound is selected from the group consisting of benzyl acetate, xylylene diacetate, methyl benzyl acetate, acetoxymethyl benzoic acid, acetoxymethyl benzyl alcohol, and acetoxymethyl benzaldehyde.

The method for producing an α-carbon-bonded aromatic compound having at least one hydrogen atom at the α-carbon bonded to the aromatic ring, or the method for producing an aromatic carboxylic acid or an aromatic carboxylic acid ester is as described above. Aromatic carboxylic acid or the above aromatic carboxylic acid ester, benzoic acid, benzoic acid ester, acetoxymethyl benzoic acid, acetoxymethyl benzoic acid ester, toluic acid, toluic acid ester, formyl benzoic acid, formyl benzoic acid ester, hydroxymethyl benzoic acid More preferably, it is selected from the group consisting of an acid, hydroxymethylbenzoate, dihydroxycarbonylbenzene, monoester of dihydroxycarbonylbenzene and diester of dihydroxycarbonylbenzene.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION α bonded to an aromatic ring of the present invention
Used as a raw material in a method for producing an α-carbon bonded aromatic compound or aromatic carboxylic acid or an aromatic carboxylic acid ester having at least one hydrogen atom on carbon (hereinafter, simply referred to as “aromatic compound producing method”). The aromatic carboxylic acid to be obtained is not particularly limited as long as it is a compound having a hydroxycarbonyl group (carboxy group) bonded to an aromatic ring in the molecule. Examples of the aromatic ring here include an aromatic ring composed of a hydrocarbon such as benzene and naphthalene, a nitrogen-containing aromatic ring such as pyridine, quinoline and pyrrole, an oxygen-containing aromatic ring such as furan and pyran, thiophene and thiopyran. Such sulfur-containing aromatic rings are exemplified. Among these exemplified aromatic rings, benzene and naphthalene are preferred. The number of hydroxyl carbonyl groups may be one or more. Further, the aromatic carboxylic acid may have another substituent on the aromatic ring, and the number of the other substituent is not particularly limited.

Examples of the other substituents include hydrocarbon groups such as alkyl group, alkenyl group, aryl group and arylalkyl group; nitrogen-containing functional groups such as nitro group, amino group and amide group; hydroxyl group; Oxygen-containing compounds such as aldehyde groups, ether groups, alkyloxyalkyl groups, aryloxyalkyl groups, alkylcarboxyl groups, arylcarboxyl groups, alkylcarbonyl groups, arylcarbonyl groups, alkylcarboxyalkyl groups, arylcarboxylalkyl groups, and hydroxyalkyl groups Functional group: Halogen-containing functional groups such as halogenated alkyl groups and halogen groups. Among these, a hydrocarbon group and an oxygen-containing functional group are preferable.

Specific examples of the aromatic carboxylic acid include benzoic acid, dihydroxycarbonylbenzene (eg, phthalic acid, isophthalic acid, terephthalic acid), trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid,
Toluic acid, 4,4'-biphenyldicarboxylic acid, 2,
2-bis (4-hydroxycarbonylphenyl) propane, aminobenzoic acid, salicylic acid, formylbenzoic acid,
Examples include methoxymethylbenzoic acid, 4,4'-dihydroxycarbonylbenzophenone, acetoxymethylbenzoic acid, hydroxymethylbenzoic acid, chloromethylbenzoic acid and the like. Among these exemplified aromatic carboxylic acids, benzoic acid, dihydroxycarbonylbenzene (for example, phthalic acid, isophthalic acid, terephthalic acid), o, m, p-
Acetoxymethylbenzoic acid, o, m, p-toluic acid,
o, m, p-Formylbenzoic acid and o, m, p-hydroxymethylbenzoic acid are particularly preferred.

The aromatic carboxylic acid ester used as a raw material in the method for producing an aromatic compound of the present invention is not particularly limited as long as it is a compound having an ester group bonded to an aromatic ring in a molecule. Further, the aromatic ring may have both an ester group and a hydroxycarbonyl group. Further, the aromatic carboxylic acid ester may have another substituent on the aromatic ring, and the number of the other substituent is not particularly limited. Examples of the other substituent include those described as the other substituent which the aromatic carboxylic acid may have.

The aromatic carboxylic acid ester includes:
Examples of the above-mentioned aromatic carboxylic acids include alkyl esters such as methyl ester, ethyl ester and lauryl ester; and aryl esters such as phenyl ester and methylphenyl ester. Among these exemplified aromatic carboxylic acid esters, benzoic acid ester, o, m, p-acetoxymethylbenzoic acid ester, o, m, p-toluic acid ester, o, m, p-formylbenzoic acid ester, o, Particularly preferred are m, p-hydroxymethylbenzoic acid esters and dihydroxycarbonylbenzene monoesters and diesters (for example, phthalic acid monoester, phthalic acid diester, isophthalic acid monoester, isophthalic acid diester, terephthalic acid monoester, terephthalic acid diester). preferable.

In the method for producing an aromatic compound of the present invention, an α-carbon-bonded aromatic compound having at least one hydrogen atom at the α-carbon bonded to the aromatic ring is used as the other raw material. The α-carbon-bonded aromatic compound is a compound in which an α-carbon having at least one hydrogen atom is bonded to an aromatic ring, and is not particularly limited.
Examples of the aromatic ring here include an aromatic ring composed of a hydrocarbon such as benzene and naphthalene, a nitrogen-containing aromatic ring such as pyridine, quinoline and pyrrole, an oxygen-containing aromatic ring such as furan and pyran, thiophene and thiopyran. Such sulfur-containing aromatic rings are exemplified. Among these exemplified aromatic rings, benzene and naphthalene are preferred. Also, α
Α bonded to a benzene ring among carbon-bonded aromatic compounds
A benzylidene compound having one hydrogen atom at carbon or a benzyl compound having two hydrogen atoms at α carbon bonded to a benzene ring is preferable, and a benzyl compound is more preferable. Examples of the substituent other than the hydrogen atom bonded to the α carbon include a hydrocarbon group such as an alkyl group and an aryl group, an oxygen atom, a hydroxyl group, an oxygen-containing functional group such as an acyloxy group and an ether group, an amino group, Examples include a nitrogen-containing functional group such as an amide group and a halogen-containing functional group such as a halogen group. Among these exemplified functional groups, oxygen-containing functional groups are more preferred, and acyloxy groups are even more preferred. In the case of a compound having two substituents other than a hydrogen atom on the α-carbon, those substituents may be the same or different.

Α having at least one hydrogen atom
The number of substituents containing carbon may be one or more in the molecule. That is, the number of the α carbon atoms bonded to the aromatic ring of the α carbon bonded aromatic compound may be one or more. When the number of substituents containing the α carbon is plural, those substituents may be the same or different.

The α-carbon-bonded aromatic compound may have other substituents on the aromatic ring in addition to the substituent containing the α-carbon, and the number of the other substituents may be smaller. There is no particular limitation. That is, a substituent other than the α-carbon may be bonded to the aromatic ring of the α-carbon-bonded aromatic compound. Examples of the other substituent include a hydrocarbon group such as an alkenyl group, an aryl group, and an alkylaryl group; a nitrogen-containing functional group such as a nitro group, an amino group and an amide group; a hydroxyl group, a hydroxycarbonyl group, and an ether group. Oxygen-containing functional groups such as alkyl carboxyl group, aryl carboxyl group, alkylcarbonyl group and arylcarbonyl group; and halogen-containing functional groups such as halogenated alkyl group and halogen group.

Examples of the α-carbon-bonded aromatic compound include toluene, ethylbenzene, benzyl alcohol, benzyl acetate, benzyl chloride, methoxymethylbenzene, aminomethylbenzene, methylbenzylacetate, acetoxymethylaniline, acetoxymethylphenol, and acetoxymethyl. Benzoic acid, acetoxymethylbenzaldehyde, acetoxymethylbenzyl alcohol, xylylene glycol dimethyl ether, xylylene diacetate, xylylene glycol,
α-chloroxylene, α, α′-xylylene dichloride, 4,4′-diacetoxybiphenyl, 2,2′-bis (4-acetoxymethylphenyl) propane,
4'-diacetoxymethylbenzophenone and the like. Among these exemplified compounds, benzyl acetate, o, m, p-xylylene diacetate, o, m, p
-Methylbenzyl acetate, o, m, p-acetoxymethylbenzoic acid, o, m, p-acetoxymethylbenzyl alcohol, o, m, p-acetoxymethylbenzaldehyde are particularly preferred.

In the method for producing an aromatic compound of the present invention, the molar ratio of the aromatic carboxylic acid or the aromatic carboxylic acid ester to the α-carbon-bonded aromatic compound is not particularly limited. More preferably, the total amount of at least one of the aromatic carboxylic acid and the aromatic carboxylic acid ester per mole of the compound is in the range of 0.01 to 100 mol, more preferably in the range of 0.05 to 30 mol. More preferred. By setting the molar ratio of the two within the above range, it is possible to prevent the reactor and the recovery device for recovering the unreacted raw material from becoming large, and to suppress the production cost.

In the substituent exchange reaction in the method for producing an aromatic compound of the present invention, the α-carbon-bonded aromatic compound, aromatic carboxylic acid and aromatic carboxylic acid ester used as the raw materials may be used alone. Well, 2
It may be used as a mixture of more than one type. That is,
In the method for producing an aromatic compound of the present invention, the α-carbon bonded aromatic compound, aromatic carboxylic acid, and aromatic carboxylic acid ester may be used alone or in combination of two or more. For example, an aromatic compound may be produced by a substituent exchange reaction between one kind of α-carbon bond aromatic compound and one kind of aromatic carboxylic acid, or one of them may be made one kind and the other may be made two or more kinds. As a mixture, both may be a mixture of two or more types. The α-carbon bonded aromatic compound may be reacted with a mixture of an aromatic carboxylic acid and an aromatic carboxylic acid ester.

In the method for producing an aromatic compound according to the present invention, the hydroxycarbonyl group of the aromatic carboxylic acid or the ester group of the aromatic carboxylic acid ester is exchanged for the α-carbon-bonded aromatic compound-containing substituent. The substituent exchange reaction will be described below.

To make the substituent exchange reaction easier to understand,
The aromatic ring of the aromatic carboxylic acid or the aromatic carboxylic acid ester is a benzene ring, and only one hydroxycarbonyl group of the aromatic carboxylic acid or the ester group of the aromatic carboxylic acid ester is bonded to the benzene ring. At least one substituent other than a group or an ester group is bonded to the benzene ring, the aromatic ring of the α-carbon-bonded aromatic compound is a benzene ring, and the substituent containing the α-carbon of the α-carbon-bonded aromatic compound is The case where only one substituent is bonded to the benzene ring and one or more substituents other than the substituent containing the α-carbon are bonded to the benzene ring is exemplified, but the present invention is not limited thereto. .

The aromatic carboxylic acid or aromatic carboxylic acid ester as a raw material in the method for producing an aromatic compound of the present invention is, for example, a compound represented by the following general formula (1):

[0032]

Embedded image

(Wherein R ¹ represents a hydrogen atom or an alkyl group, and X represents an alkyl group, alkenyl group, aryl group, arylalkyl group, nitro group, amino group, amide group, hydroxyl group, aldehyde group, ether group, alkyl group An oxyalkyl group, an aryloxyalkyl group, an alkylcarboxyl group, an arylcarboxyl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylcarboxyalkyl group, an arylcarboxylalkyl group, a hydroxyalkyl group, a halogenated alkyl group or a halogen group; Is an integer of 1 to 5 indicating the number of X).

For convenience of description of the substituent exchange reaction, the hydroxycarbonyl group or ester group in the above general formula (1) is represented by A1, and a portion (residue) excluding the hydroxycarbonyl group or ester group is represented by A1. Is represented as A2.

The α-carbon-bonded aromatic compound having at least one hydrogen atom on the α-carbon bonded to the aromatic ring as the other raw material in the method for producing an aromatic compound of the present invention includes, for example, The following general formula (2)

[0036]

Embedded image

(Wherein R ² and R ³ each independently represent an alkyl group, an aryl group, an oxygen atom, a hydroxyl group, an acyloxy group, an ether group, an amino group, an amide group or a halogen group, Y is an alkenyl group, Represents an aryl group, alkylaryl group, nitro group, amino group, amide group, hydroxyl group, hydroxycarbonyl group, ether group, alkylcarboxyl group, arylcarboxyl group, alkylcarbonyl group, arylcarbonyl group, halogenated alkyl group or halogen group. , N is an integer of 1 to 5 indicating the number of Y).

For convenience of explanation of the substituent exchange reaction, the substituent containing an α-carbon in the above general formula (2) is represented by B1, and the substituent containing the α-carbon is converted from the α-carbon-bonded aromatic compound. The removed portion (residue) is represented as B2.

The reaction of the aromatic carboxylic acid or the aromatic carboxylic acid ester represented by the above general formula (1) with the α-carbon-bonded aromatic compound represented by the above general formula (2) is used for the present invention. The substituent exchange reaction in the method for producing an aromatic compound will be described below.

In the above substituent exchange reaction, a residue A2 obtained by removing a hydroxycarbonyl group or an ester group A1 from an aromatic carboxylic acid or an aromatic carboxylic acid ester represented by the above general formula (1), which is one of the raw materials, is used. Then, a product is formed in which the substituent B1 containing the α-carbon of the α-carbon-bonded aromatic compound represented by the above general formula (2), which is the other raw material, is bonded.

That is, by the above substituent exchange reaction, the residue A2 of the aromatic carboxylic acid or the aromatic carboxylic acid ester represented by the above general formula (1) is added to the above general formula (2)
Is bonded to the substituent B1 containing an α-carbon of the α-carbon-bonded aromatic compound represented by the following general formula (3):

[0042]

Embedded image

(Wherein R ² and R ³ each independently represent an alkyl group, an aryl group, an oxygen atom, a hydroxyl group, an acyloxy group, an ether group, an amino group, an amide group or a halogen group; X represents an alkyl group; Alkenyl, aryl, arylalkyl, nitro, amino, amide, hydroxyl, aldehyde, ether, alkyloxyalkyl, aryloxyalkyl, alkylcarboxyl, arylcarboxyl, alkylcarbonyl, aryl A carbonyl group, an alkylcarboxyalkyl group, an arylcarboxylalkyl group, a hydroxyalkyl group, a halogenated alkyl group or a halogen group, and m is an integer of 1 to 5 representing the number of X) Having at least one hydrogen atom on the alpha carbon An α-carbon bonded aromatic compound is obtained as a product.

Similarly, by the above-mentioned substituent exchange reaction,
The residue B2 obtained by removing the substituent B1 containing an α-carbon from an α-carbon-bonded aromatic compound having at least one hydrogen atom on an α-carbon bonded to an aromatic ring represented by the general formula (2) Then, a product in which the hydroxycarbonyl group or the ester group A1 of the aromatic carboxylic acid or the aromatic carboxylic acid ester as the other raw material is bonded is produced.

That is, the residue of the α-carbon-bonded aromatic compound having at least one hydrogen atom on the α-carbon bonded to the aromatic ring represented by the general formula (2) by the above-mentioned substituent exchange reaction. By bonding the hydroxycarbonyl group or ester group A1 of the aromatic carboxylic acid or the aromatic carboxylic acid ester represented by the above general formula (1) to B2, the following general formula (4)

[0046]

Embedded image

(Wherein R ¹ represents a hydrogen atom or an alkyl group, Y represents an alkenyl group, an aryl group, an alkylaryl group, a nitro group, an amino group, an amide group, a hydroxyl group, a hydroxycarbonyl group, an ether group, an alkylcarboxyl group) , Aryl carboxyl group, alkylcarbonyl group,
An aromatic carboxylic acid or an aromatic carboxylic acid ester represented by an arylcarbonyl group, a halogenated alkyl group or a halogen group, wherein n is an integer of 1 to 5 representing the number of Y) is obtained as a product.

Therefore, as described above, the hydroxycarbonyl group or the ester group of the aromatic carboxylic acid or the aromatic carboxylic acid ester as the raw material and the substituent containing the α-carbon of the α-carbon-bonded aromatic compound are replaced. The product of the above substituent exchange reaction of an aromatic compound such as an α-carbon-bonded aromatic compound having at least one hydrogen atom at an α-carbon bonded to an aromatic ring, an aromatic carboxylic acid, an aromatic carboxylic acid ester, etc. Can be obtained as

In the process for producing an aromatic compound of the present invention, the reaction conditions such as the reaction temperature and the reaction time for the substituent exchange reaction between the aromatic carboxylic acid or the aromatic carboxylic acid ester and the α-carbon-bonded aromatic compound are as follows: The type of the α-carbon bond aromatic compound used in the reaction, the aromatic carboxylic acid, the type and amount of the aromatic carboxylic acid ester, and the type and amount of the catalyst used in the reaction vary depending on the type of the catalyst. The temperature is preferably in the range of 50C to 300C. When the reaction temperature is lower than 50 ° C., the reaction rate may be too slow to produce an aromatic compound efficiently. On the other hand, when the reaction temperature exceeds 300 ° C.,
Side reactions are likely to occur, and efficient production of an α-carbon-bonded aromatic compound having at least one hydrogen atom on the α-carbon bonded to the aromatic ring, or an aromatic carboxylic acid or an aromatic carboxylic acid ester can be achieved. It may not be possible. The reaction time of the above-mentioned substituent exchange reaction is usually in the range of 0.1 hour to 30 hours.

The reaction pressure in the above substituent exchange reaction is as follows:
It can be carried out under any of normal pressure, increased pressure and reduced pressure conditions. In addition, the method of the reaction is not particularly limited,
It can be carried out by any of batch, semi-batch and continuous methods. Separation of an aromatic compound such as an α-carbon-bonded aromatic compound having at least one hydrogen atom at the α-carbon bonded to the generated aromatic ring, aromatic carboxylic acid, or aromatic carboxylic acid ester from the reaction solution. -The method of collecting is not particularly limited, and a known method can be used.

The above substituent exchange reaction proceeds without a catalyst, and it is not always necessary to use a catalyst. However, if it is desired to increase the reaction rate, a catalyst may be added. The reaction rate can be increased by allowing the above substituent exchange reaction to proceed in the presence of a catalyst. When an aromatic carboxylic acid is used as a raw material, the reaction often proceeds without a catalyst as compared with a case where an aromatic carboxylic acid ester is used as a raw material. For this reason, when performing a reaction without adding a catalyst, it is more preferable to use an aromatic carboxylic acid as a raw material.

Examples of the catalyst used in the above-mentioned substituent exchange reaction include an acid catalyst, and specific examples thereof include sulfuric acid, hydrochloric acid, nitric acid, heteropolyacid, p-toluenesulfonic acid, phosphoric acid, formic acid, acetic acid and benzoic acid. Homogeneous catalysts such as acids; and heterogeneous catalysts such as acidic ion exchange resins, zeolites, clays and acidic solid oxides. The amount of the catalyst used is not particularly limited, but the amount of the catalyst to be added is preferably from 0.01% by weight to the raw material.
It is preferably within a range of 20% by weight, more preferably within a range of 0.1% by weight to 10% by weight.

An aromatic carboxylic acid or an aromatic carboxylic acid ester in the method for producing an aromatic compound of the present invention,
The substituent exchange reaction with the α-carbon-bonded aromatic compound can be carried out in the presence of a solvent or in the absence of a solvent. It may be preferable to carry out the reaction in the presence of As the solvent used in the above-mentioned substituent exchange reaction, those which are inert to the reaction are preferable, and specifically, for example, saturated hydrocarbons such as octane, decane and undecane, and aromatic hydrocarbons such as benzene ;
Ethers such as diphenyl ether and diethylene glycol dimethyl ether; and chlorinated hydrocarbons such as orthodichlorobenzene and dichloroethane.

[0054]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 In a 100 ml three-necked flask equipped with a reflux tube, 25 g of p-xylylene diacetate as an α-carbon bond aromatic compound as a raw material and p-toluyl as an aromatic carboxylic acid as a raw material were placed. 1.5 g of acid
And a sulfonic acid type ion exchange resin Dow- as a catalyst.
X 50w (trade name, manufactured by Dow Chemical Co., USA) 0.25
g, and reacted under a nitrogen stream at a reaction temperature of 150 ° C. and a reaction time of 3 hours. After the completion of the reaction, the composition of the reaction solution was analyzed by gas chromatography and liquid chromatography. As a result, the reaction solution contained 0.1% of p-acetoxymethylbenzoic acid, which is an aromatic carboxylic acid as a product.
68 g, and 0.72 g of p-methylbenzyl acetate, which is an α-carbon bonded aromatic compound as a product, was contained.

Example 2 A p-xylylene diacetate was used in an amount of 27 g, terephthalic acid was used instead of p-toluic acid, and 1.2 g of terephthalic acid was used.
The reaction was carried out under the same conditions as in Example 1 except that 0.3 g of p-toluenesulfonic acid was used instead of X50w, and the composition of the reaction solution obtained by the reaction was analyzed. As a result, the reaction solution contained 0.11 g of p-acetoxymethylbenzoic acid, which corresponds to both the aromatic carboxylic acid and the α-carbon bonded aromatic compound as products.

Example 3 1.3 g of terephthalic acid was used in place of p-toluic acid, and a reaction temperature of 200 ° C. and a reaction time of 7 hours were used without using a sulfonic acid type ion exchange resin Dow-X 50w as a catalyst. A reaction was performed under the same conditions as in Example 1 except that the reaction was performed, and the composition of a reaction solution obtained by the reaction was analyzed. As a result, the reaction solution contained 0.61 g of p-acetoxymethylbenzoic acid, which corresponds to both the aromatic carboxylic acid and the α-carbon bonded aromatic compound as products.

Example 4 p-xylylene diacetate was used in an amount of 24 g, and benzoic acid was used instead of p-toluic acid.
g and a sulfonic acid type ion exchange resin D as a catalyst
ow-X 50w instead of p-toluenesulfonic acid 0.1%.
The reaction was carried out under the same conditions as in Example 1 except that 25 g was used, and the composition of the reaction solution obtained by the reaction was analyzed.
As a result, the reaction solution contained 0.31 g of p-acetoxymethylbenzoic acid, which is an aromatic carboxylic acid as a product,
The product contained 0.33 g of benzyl acetate, an α-carbon bonded aromatic compound.

Example 5 In place of p-xylylene diacetate and p-toluic acid, 25 g of p-acetoxymethyl benzoic acid, which corresponds to both an α-carbon bonded aromatic compound and a carboxylic acid, was used as a raw material. The reaction was carried out under the same conditions as in Example 1 except that 0.24 g of sulfonic acid type ion exchange resin Dow-X 50w was used, and the composition of the reaction solution obtained by the reaction was analyzed. as a result,
The reaction solution contained 8.6 g of terephthalic acid, an aromatic carboxylic acid as a product, and 10.9 g of p-xylylene diacetate, an α-carbon bonded aromatic compound as a product.
g.

Example 6 In place of p-xylylene diacetate and p-toluic acid, 26 g of p-acetoxymethylbenzoic acid, which corresponds to both an α-carbon bonded aromatic compound and a carboxylic acid, was used as a raw material. The reaction was carried out under the same conditions as in Example 1 except that the sulfonic acid type ion exchange resin Dow-X 50w was not used as a catalyst.
The composition of the reaction solution obtained by the reaction was analyzed. As a result, 4.6 g of terephthalic acid as an aromatic carboxylic acid as a product and 6.5 g of p-xylylene diacetate as an α-carbon bonded aromatic compound as a product in the reaction solution.
g was included.

Example 7 15 g of p-methylbenzyl acetate was used instead of p-xylylene diacetate.
Instead of p-toluic acid, 12.4 g of methyl benzoate, which is an aromatic carboxylic acid ester, was used as a raw material, and 0.26 w of a sulfonic acid type ion exchange resin Dow-X 50w was used.
g, and the reaction was performed under the same conditions as in Example 1 except that the reaction temperature was 120 ° C., and the composition of the reaction solution obtained by the reaction was analyzed. As a result, the reaction solution contained 1.1 g of methyl p-methylbenzoate, which is an aromatic carboxylate as a product, and 1.4 g of benzyl acetate, which is an α-carbon bond aromatic compound as a product. I was

Example 8 In place of p-xylylene diacetate, 20 g of p-methylbenzyl acetate was used.
Using 4.7 g of p-acetoxymethylbenzoic acid instead of p-toluic acid, a sulfonic acid type ion exchange resin Dow-
The reaction was performed under the same conditions as in Example 1 except that X50w was changed to 0.24 g, and the composition of the reaction solution obtained by the reaction was analyzed. As a result, the reaction liquid contained 1.4 g of p-toluic acid, which is an aromatic carboxylic acid as a product, and 2.7 g of p-xylylene diacetate, which is an α-carbon-bonded aromatic compound as a product. I was

[Example 9] In place of p-xylylene diacetate, 25 g of p-methylbenzyl acetate was used.
Using 1.7 g of terephthalic acid instead of p-toluic acid,
Sulfonic acid type ion exchange resin Dow-X 50w was added to 0.
The reaction was carried out under the same conditions as in Example 1 except that the amount was 28 g, and the composition of the reaction solution obtained by the reaction was analyzed. As a result, 0.18 g of p-toluic acid, which is an aromatic carboxylic acid as a product, and α as a product were contained in the reaction solution.
0.14 g of p-acetoxymethylbenzoic acid, which is a carbon-bonded aromatic compound, was contained.

Example 10 A sulfonic acid type ion exchange resin Dow-X 50w was used in an amount of 0.2 g using 25 g of benzyl acetate instead of p-xylylene diacetate and 2.8 g of terephthalic acid instead of p-toluic acid. The reaction was carried out under the same conditions as in Example 1 except that the amount was 27 g, and the composition of the reaction solution obtained by the reaction was analyzed. as a result,
The reaction solution contained 0.23 g of benzoic acid, which is an aromatic carboxylic acid as a product, and 0.16 g of p-acetoxymethylbenzoic acid, which was an α-carbon bonded aromatic compound as a product.
g.

Example 11 In place of p-xylylene diacetate, 25 g of 1-acetoxymethylnaphthalene synthesized from 1-naphthalenemethanol and acetic anhydride was used, and 1.5 g of benzoic acid was used in place of p-toluic acid. Sulfonic acid type ion exchange resin Dow-X 50w as catalyst
Example 1 was repeated except that the reaction temperature was 170 ° C.
The reaction was performed under the same conditions as described above, and the composition of the reaction solution obtained by the reaction was analyzed. As a result, 1-naphthoic acid, which is an aromatic carboxylic acid as a product, is contained in the reaction solution in an amount of 0.1%.
65 g, and 0.56 g of benzyl acetate as an α-carbon bonded aromatic compound as a product were contained.

[0066]

As described above, the method for producing an aromatic compound according to the present invention comprises the steps of: providing an aromatic carboxylic acid or an aromatic carboxylic acid ester with at least one hydrogen atom at the α-carbon bonded to the aromatic ring; With an α-carbon-bonded aromatic compound having a hydroxycarbonyl group of the aromatic carboxylic acid or an ester group of the aromatic carboxylic acid ester, and a substituent containing an α-carbon of the α-carbon bonded aromatic compound. It will be exchanged.

Therefore, the substituent of the aromatic ring can be exchanged without using a catalyst or by using a general acid catalyst to progress the reaction. Thereby, an α-carbon-bonded aromatic compound having at least one hydrogen atom at an α-carbon bonded to an aromatic ring, an aromatic carboxylic acid, an aromatic compound such as an aromatic carboxylic acid ester, efficiently and There is an effect that a manufacturing method that can be manufactured at low cost can be provided.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yuichi Sato 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. F-term (reference) 4H006 AA02 AC48 BA66 BA72 BC10 BC11 BC31 BJ50 BS30 KA04 KC12 4H039 CA66 CL60

Claims (4)

[Claims] An aromatic carboxylic acid or an aromatic carboxylic acid ester is reacted with an α-carbon-bonded aromatic compound having at least one hydrogen atom at an α-carbon bonded to an aromatic ring to obtain the aromatic compound. A hydroxycarbonyl group of a carboxylic acid or an ester group of the aromatic carboxylic acid ester and the α
A method for producing an α-carbon-bonded aromatic compound having at least one hydrogen atom on an α-carbon bonded to an aromatic ring, wherein the α-carbon-bonded aromatic compound is substituted with an α-carbon-containing substituent. 2. The reaction of an aromatic carboxylic acid or an aromatic carboxylic acid ester with an α-carbon-bonded aromatic compound having at least one hydrogen atom at an α-carbon bonded to an aromatic ring, A hydroxycarbonyl group of a carboxylic acid or an ester group of the aromatic carboxylic acid ester and the α
A method for producing an aromatic carboxylic acid or an aromatic carboxylic acid ester, comprising exchanging a substituent containing an α-carbon of a carbon-bonded aromatic compound. 3. The method according to claim 1, wherein the α-carbon-bonded aromatic compound is selected from the group consisting of benzyl acetate, xylylene diacetate, methyl benzyl acetate, acetoxymethyl benzoic acid, acetoxymethyl benzyl alcohol, and acetoxymethyl benzaldehyde. Item 1. The α-carbon bonded to the aromatic ring according to Item 1 has at least one
A method for producing an α-carbon-bonded aromatic compound having at least one hydrogen atom, or the method for producing an aromatic carboxylic acid or an aromatic carboxylic acid ester according to claim 2. 4. The aromatic carboxylic acid or the aromatic carboxylic acid ester is benzoic acid, benzoic acid ester, acetoxymethyl benzoic acid, acetoxymethyl benzoic acid ester, toluic acid, toluic acid ester, formyl benzoic acid, formyl benzoic acid. The aromatic ring according to claim 1, wherein the aromatic ring is selected from the group consisting of an acid ester, hydroxymethylbenzoic acid, hydroxymethylbenzoic acid ester, dihydroxycarbonylbenzene, a diester of dihydroxycarbonylbenzene and a diester of dihydroxycarbonylbenzene. The method for producing an α-carbon-bonded aromatic compound having at least one hydrogen atom on the α-carbon bonded thereto, or the method for producing an aromatic carboxylic acid or an aromatic carboxylic acid ester according to claim 2.