JP2002201158A - Aromatic carboxylic acid and its acid halide, and method for synthesis - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new aromatic carboxylic acid and its acid chloride which are useful as raw materials for condensed polymers having high heat resistance. SOLUTION: An aromatic carboxylic acid represented by formula (1) (X is H, R, Ph) and its acid chloride derivative and a method for producing the compounds are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to aromatic carboxylic acids and their acid chloride derivatives which are useful as raw materials for polymers, especially condensation polymers having high heat resistance, and to a method for synthesizing them.

[0002]

2. Description of the Related Art Aromatic carboxylic acids having two carboxyl groups per molecule and acid chlorides thereof are used as raw materials for aromatic polyamide resins, polyarylate resins, polybenzoxazole resins, polybenzothiazole resins, and the like. Resins having various structures have been synthesized and used according to their uses. On the other hand, these resins are generally thermoplastic polymers, but have high heat resistance and are often used for applications exposed to high temperatures. Attempts have been made to introduce a heat-curable substituent as a means for further improving heat resistance, but a raw material used for the purpose has been demanded.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aromatic carboxylic acid and its acid chloride derivative suitable for the above-mentioned applications, and a method for synthesizing them.

[0004]

That is, the present invention provides an aromatic carboxylic acid represented by the general formula (1) and an acid chloride derivative of the carboxylic acid represented by the general formula (2).

[0005]

Embedded image (In the formula, X represents hydrogen, an alkyl group, or an aromatic group.)

[0006]

Embedded image (In the formula, X represents hydrogen, an alkyl group, or an aromatic group.)

Further, the present invention provides a compound represented by the general formula (5) obtained by reacting a compound represented by the general formula (3) with a compound represented by the general formula (4). A compound represented by the general formula (1), which is obtained by treating in the presence of an alkali metal hydroxide to produce a compound represented by the general formula (6), and further subjecting the compound to an acid treatment. A method for synthesizing an aromatic carboxylic acid, preferably using a transition metal catalyst in the reaction between the compound represented by the general formula (3) and the compound represented by the general formula (4). It is a synthesis method.

[0008]

Embedded image (In the formula, Y represents a leaving group.)

[0009]

Embedded image (In the formula, X ₁ represents a trimethylsilyl group, a hydroxypropyl group, an alkyl group, or an aromatic group.)

[0010]

Embedded image (In the formula, X ₁ represents a trimethylsilyl group, a hydroxypropyl group, an alkyl group, or an aromatic group.)

[0011]

Embedded image (In the formula, X represents hydrogen, an alkyl group or an aromatic group, and M represents an alkali metal.)

Further, the present invention relates to a compound represented by the general formula (6) or a compound represented by the general formula (1) obtained by the above synthesis method.
A method for synthesizing an acid chloride derivative of an aromatic carboxylic acid represented by the general formula (2), which is obtained by treating a compound represented by the formula (1) with a chlorinating agent.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The aromatic carboxylic acid represented by the general formula (1) and the acid chloride derivative thereof represented by the general formula (2) of the present invention can be synthesized, for example, by the following route. I can do it.

[0014]

Embedded image Y in the formula (3) represents a leaving group, X ₁ in the formulas (4) and (5) represents a trimethylsilyl group, a hydroxypropyl group, an alkyl group or an aromatic group, and the formulas (1) and (2) ) And X in the formula (6) represent hydrogen, an alkyl group or an aromatic group, and M in the formula (6) represents an alkali metal.

First, as a starting material, a methyl ester compound of isophthalic acid represented by the formula (3) and substituted with a 5-position leaving group Y on a benzene ring, and one side of acetylene is substituted with an X ₁ group. The compound represented by the formula (5) is obtained by performing a coupling reaction with the compound (formula (4)). In the coupling reaction, a catalyst may be used. For example, a transition metal catalyst such as palladium is used. However, at this time, the leaving group Y is preferably a group which is easily removed from an alkyl group or an aromatic ring by a coupling reaction in the presence of a catalyst, and is preferably a halogen such as fluorine, chlorine, bromine or iodine, or trifluoromethanesulfonate. Preferable examples include a nitroxy group. Examples of the substituent X ₁ include a group that functions as a protecting group. In this case, preferably, a trimethylsilyl group, a hydroxypropyl group, or the like is selected, and the substituent X ₁ includes an aromatic group or an alkyl group. Examples of the aromatic group include a phenyl group, a naphthyl group, an anthryl group, a quinoxy group, and a quinoxalyl group.

Next, this compound is subjected to a demethylation reaction from an acetyl group using a basic alkali metal hydroxide, and when the X ₁ group in the compound represented by the formula (5) is a protecting group, Deprotection is performed simultaneously to obtain an alkali metal salt of an isophthalic acid derivative represented by the formula (6).

Furthermore, the alkali metal salt of the isophthalic acid derivative represented by the formula (6) is treated with an acid to treat the aromatic carboxylic acid represented by the formula (1) with a chlorinating agent. The acid chloride derivative represented by (2) can be obtained.

The isophthalic acid in which the 5-position on the benzene ring represented by the formula (3) is substituted with Y, when the leaving group Y is a trifluoromethanesulfonyloxy group, dimethyl 5-hydroxyisophthalate (formula ( 7)) is esterified with trifluoromethanesulfonic anhydride (formula (8)) to give dimethyl 5-trifluoromethanesulfonyloxyisophthalate (formula (3 ′)).

[0019]

Embedded image

However, trifluoromethanesulfonic anhydride (formula (8)) is expensive and requires careful handling, such as use under water-free conditions. here,
Sandme proceeding via diazonium salt (formula (10)) using 5-aminoisophthalic acid (formula (9)) as a raw material
By performing the yer reaction, isophthalic acid in which the leaving group Y represented by the formula (11) is a halogen can be synthesized. Subsequently, the carboxylic acid is subjected to methyl esterification with methanol, whereby dimethyl isophthalate (formula (3)) in which the leaving group Y represented by formula (3) is a halogen can be obtained at low cost and easily.

[0021]

Embedded image

Hereinafter, an example of the manufacturing method will be described. 5-
Dimethyl bromoisophthalate (in the formula (3), Y = B
As an example using r)), first, dimethyl 5-bromoisophthalate is converted to 5-aminoisophthalic acid (formula (9)).
Is reacted with hydrobromic acid and sodium nitrite to obtain diazonium bromate (formula (10)).
By reacting this with cuprous bromide, nitrogen gas is generated, and 5-bromoisophthalic acid (formula (11)) is obtained. Subsequently, in an atmosphere of an inert gas such as nitrogen, argon or helium, the presence of an acidic catalyst such as sulfuric acid or the like, methanol is added, and the mixture is refluxed, whereby the methanol and the carboxylic acid undergo an esterification reaction to give dimethyl 5-bromoisophthalate. Is obtained. At this time, it is desirable to use a large excess of methanol in order to shift the equilibrium of the reaction to the product side. Further, in order to reduce the amount of water in the system, it is better to distill methanol in advance.

When dimethyl 5-trifluoromethanesulfonyloxyisophthalate (Y in the formula (3) is a trifluoromethanesulfonyloxy group),
First, trifluoromethanesulfonic anhydride is added to a solution obtained by dissolving dimethyl 5-hydroxyisophthalate (formula (7)) and a base in a solvent, and cooling the solution to -78 ° C to 10 ° C. The reaction is performed in a temperature range below the boiling point. At this time, the reaction time is not particularly limited. Also,
In the above-mentioned reaction, the reason why cooling is performed before the addition of trifluoromethanesulfonic anhydride is that the reaction is an exothermic reaction, and at a temperature higher than this, the reaction proceeds rapidly, and the solvent may suddenly boil. This is because there is a danger. By subjecting the reaction product thus obtained to ordinary separation means, for example, operations such as extraction, liquid separation, and concentration,
Dimethyl trifluoromethanesulfonyloxyisophthalate can be obtained. Further, this can be purified by recrystallization, column chromatography or the like, if necessary.

The amount of trifluoromethanesulfonic anhydride to be used is preferably 1 to 1.5 equivalent times of dimethyl 5-hydroxyisophthalate.

The base is preferably a tertiary amine having no active hydrogen, and specific examples thereof include pyridines such as pyridine and methylpyridine, and trialkylamines such as triethylamine and tributylamine. The amount used is preferably 1 to 1.5 equivalent times the total amount of dimethyl 5-hydroxyisophthalate and trifluoromethanesulfonic anhydride.

As the solvent, benzene, toluene, n-
Hexane, cyclohexane, petroleum ether, ethyl ether, tetrahydrofuran, dichloromethane, 1,2-
Solvents inert to the reaction, such as aromatic hydrocarbons such as dichloromethane and chloroform, hydrocarbons, ethers, halogenated hydrocarbons, and the like, may be used alone or in a mixture thereof, and the amount thereof is not particularly limited. In addition, if water is present in the solvent, a side reaction occurs with trifluoromethanesulfonic anhydride, which is the reaction reagent, and the actual reaction equivalent ratio changes.Use an anhydrous solvent or determine the amount of water contained in advance. Then, it is desirable to adjust the amount used and to charge more than the theoretical equivalent.

Next, as a method for obtaining the compound represented by the formula (5), the dimethyl 5-bromoisophthalate or the dimethyl 5-trifluoromethanesulfonyloxyisophthalate obtained above is represented by the formula (4). A compound in which one side of acetylene is substituted with a protecting group X ₁ , an alkyl group or an aromatic group X ₁ in an inert gas atmosphere of nitrogen, argon, helium or the like in the presence of a catalyst at 20 to 150 ° C. A reaction product is obtained by performing a coupling reaction in a temperature range. At this time, the reaction time is not particularly limited. By subjecting the reaction product thus obtained to a separation operation such as concentration and reprecipitation, the compound represented by the formula (5) can be obtained. It can be purified by chromatography, recrystallization and the like.

The compound in which _one side of the acetylene represented by the formula (4) is protected with the protecting group X ₁ is not limited as long as the protecting group X ₁ can be deprotected with an alkali metal hydroxide. , and trimethylsilylacetylene protecting group X ₁ is a trimethylsilyl group, is a hydroxypropyl group 3-methyl-1-butyn-3-ol are preferred.
The compound represented by the formula (4) is calculated to be equivalent to 1 equivalent equivalent to the compound represented by the formula (3), but in order to allow the reaction to proceed completely, the equivalent of 1 to 2 equivalents is required. It is advisable to adjust the amount added.

As the catalyst system, any catalyst system capable of forming a carbon-carbon bond can be used without any particular limitation, but a catalyst system comprising dichlorobis (triphenylphosphine) palladium, copper iodide and triphenylphosphine is used. It is desirable. The addition amount of dichlorobis (triphenylphosphine) palladium is not particularly limited, but 0.1 to 1 mol% based on the compound represented by the formula (5). Triphenylphosphine is added to dichlorobis (triphenylphosphine) palladium. The amount is 1 to 20 equivalent times, and the amount of copper iodide is 1 to 5 equivalent times.

As a solvent used in this reaction, an amine-based solvent is used in order to capture a generated acid and promote a catalytic reaction. Examples of such a solvent include tertiary amines such as diethylamine, triethylamine, butylamine and tributylamine, and cyclic amines such as pyridine and piperidine. These solvents are used alone or in combination of two or more. Although the amount of use is not particularly specified, it is 2 to 50 times the weight of the raw material. In addition, it is desirable that these solvents are distilled in advance in order to prevent side reactions and deactivation of the catalyst.

Next, as a method for obtaining an alkali metal salt of an isophthalic acid derivative represented by the formula (6), a compound represented by the formula (5) is treated in a solvent in the presence of an alkali metal hydroxide. In the compound represented by the formula (5), when the X group is a protecting group such as a trimethylsilyl group or a hydroxypropyl group, the ethynyl group is simultaneously deprotected. Yields a reaction product. At this time, the reaction temperature and the reaction time are not particularly limited, but the reaction temperature is preferably from room temperature to the reflux temperature of the solvent. The obtained reaction product, the crystals precipitated by cooling were separated, methanol, ethanol, butanol, washed with an alcoholic solvent such as isopropanol, and then dried,
An alkali metal salt of an isophthalic acid derivative represented by the formula (6) can be obtained.

As the alkali metal hydroxide, potassium hydroxide and sodium hydroxide are preferable, and the amount of addition is 3 equivalent times or more of the compound represented by the formula (5).
More than this is fine.

The reaction solvent is not particularly limited as long as it is other than an ester capable of reacting with the alkali metal hydroxide, but it has a high solubility for the alkali metal hydroxide, such as methanol, ethanol, butanol and isopropanol. Alcohol solvents are preferred. Although the amount of the solvent is not particularly limited, it is preferable to use 5 to 50 times by weight of dimethyl isophthalate due to the problem of operability.

The aromatic carboxylic acid represented by the formula (1) of the present invention is obtained by dissolving the alkali metal salt of the isophthalic acid derivative (formula (6)) obtained above in water, and adding hydrochloric acid, sulfuric acid, nitric acid, and the like. The precipitate can be obtained by acidifying treatment with an acid such as described above, preferably to pH 1, to obtain a precipitate, which is collected by filtration, washed and dried. In this case, if the ethynyl moiety is exposed to a strong acid for a long period of time, an ethynyl moiety may undergo a side reaction such as an addition reaction or polymerization.

The acid chloride derivative of the carboxylic acid of the present invention represented by the formula (2) is obtained by converting the alkali metal salt of the isophthalic acid derivative (formula (6)) obtained above into a solvent or
After reacting in a temperature range of 0 to 70 ° C. using an excess amount of a chlorinating agent as a solvent, the solvent is distilled off, and the obtained solid is washed with a solvent and further recrystallized to obtain a solid. Can be done. Further, instead of the alkali metal salt of the isophthalic acid derivative represented by the formula (6), an aromatic carboxylic acid represented by the formula (1) may be used.

As the chlorinating agent, thionyl chloride and the like are preferable, but the amount of the chlorinating agent to be used is 2 equivalent times or more with respect to the alkali metal salt of the isophthalic acid derivative represented by the formula (6). There is no particular upper limit. When a solvent is not used, it may be used in a large excess of 10 equivalents or more.

The solvent is not particularly restricted but includes, for example, aromatic hydrocarbons such as benzene, toluene and xylene, hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, dichloromethane, chloroform, carbon tetrachloride, and the like. Chlorinated solvents such as 1,2-dichloroethane and chlorobenzene are exemplified. Any of these can be used in an arbitrary amount with respect to the alkali metal salt of the isophthalic acid derivative represented by the formula (6).

In order to accelerate the reaction, a base such as N, N-dimethylformamide, pyridine and the like may be added. Further, a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether may be added in order to suppress polymerization at the ethynyl site.

[0039]

The following examples are provided to illustrate the present invention, but do not limit the present invention.

The obtained compound was subjected to melting point measurement, ¹ H-NMR, ¹³ C ( ¹ H) -NMR, measurement of various spectra of MS and elemental analysis for characteristic evaluation. The measurement conditions for each characteristic were as follows.

Test method (1) Melting point: Using a DSC-200 differential scanning calorimeter (DSC) manufactured by Seiko Denshi Co., Ltd. at 10 ° C./min. The temperature was measured at a rate of temperature rise. (2) Nuclear magnetic resonance spectrum analysis ( ¹ H-NMR, ¹³ C
⁽¹ H) -NMR): JEOL JNM-GSX400
It was measured using a mold. ¹ H-NMR has a resonance frequency of 400
MHz, ¹³ C ( ¹ H) -NMR has a resonance frequency of 100 MH
Each was measured in z. Measurements solvent, 5-ethynyl-isophthalate is dissolved in deuterated solvent deuterated dimethyl sulfoxide DMSO-d _6, 5- (2- phenylethynyl) deuterated acetone isophthalic acid is deuterated solvent (CD ₃ ) ₂ CO, 5-ethynyl isophthalic acid chloride and 5- (2-phenylethynyl) isophthalic acid chloride are deuterated chloroform CDCl ₃ which is a deuterated solvent.
Was used for each. (3) Infrared spectroscopy (IR): JIR manufactured by JEOL Ltd.
It was measured by KBr tablet method using Model-5500. (4) Mass spectrometry (MS): JMS-7 manufactured by JEOL Ltd.
It was measured by a field desorption (FD) method using a Model 00. (5) Elemental analysis: carbon and hydrogen are PERKIN ELM
Chlorine was measured by a flask combustion titration method using Model 2400 manufactured by ER.

(Example 1) [Synthesis of 5-trifluoromethanesulfonyloxy isophthalate from dimethyl 5-hydroxyisophthalate] Thermometer, Dimroth condenser, calcium chloride tube,
In a four-necked 5-liter flask equipped with a stirrer, 190.0 g of dimethyl 5-hydroxyisophthalate (0.90 g) was added.
4 mol), dehydrated toluene 3 liter, dehydrated pyridine 2
14.7 g (2.718 mol) was charged and cooled to −30 ° C. while stirring. Here, 510.2 g (1.808 mol) of trifluoromethanesulfonic anhydride was slowly added dropwise while taking care not to raise the temperature to -25 ° C or higher. In this case, it took one hour to complete the dropping. After the addition, the reaction temperature was raised to 0 ° C. and reacted for 1 hour, and further to room temperature and reacted for 5 hours. The obtained reaction mixture was poured into 4 liters of ice water, and an aqueous layer and an organic layer were separated. Further, the aqueous layer was extracted twice with 500 ml of toluene, and this was combined with the previous organic layer. This organic layer is combined with water 3
L, washed twice with anhydrous magnesium sulfate, dried over 100 g of anhydrous magnesium sulfate, filtered to remove anhydrous magnesium sulfate, distilled off toluene with a rotary evaporator, and dried under reduced pressure to give 5-trifluoromethanesulfonyloxy isophthalic acid as a pale yellow solid. 294.0 g of dimethyl was obtained (95% yield). The crude product was recrystallized from hexane to obtain white needles, which were used in the next reaction.

[Synthesis of 4- (3,5-bis (methoxycarbonyl) phenyl) -2-methyl-3-butyn-1-ol from dimethyl 5-trifluoromethanesulfonyloxyisophthalate] Thermometer, Dimroth condenser In a four-necked 1-liter flask equipped with a nitrogen inlet tube and a stirrer, 125 g of the above-obtained dimethyl 5-trifluoromethanesulfonyloxyisophthalate (0.365 mol
l), 1.1 g of triphenylphosphine (0.0041
9mol), copper iodide 0.275g (0.00144m
ol), 3-methyl-1-butyn-3-ol 33.7
3 g (0.401 mol) was charged, and nitrogen was passed. 375 ml of anhydrous triethylamine and 20 of anhydrous pyridine
0 ml was added and dissolved by stirring. After continuing to flow nitrogen for 1 hour, 0.3 g (0.000427 mol) of dichlorobis (triphenylphosphine) palladium was quickly added, and the mixture was heated and refluxed for 1 hour in an oil bath. Thereafter, triethylamine and pyridine were distilled off under reduced pressure to obtain a viscous brown solution. This was poured into 500 ml of water, and the precipitated solid was collected by filtration and further washed twice with 500 ml of water, 500 ml of 5N hydrochloric acid and 500 ml of water. The solid was dried at 50 ° C. under reduced pressure to give 98.8 g of 4- (3,5-
Bis (methoxycarbonyl) phenyl) -2-methyl-
3-butyn-1-ol was obtained (yield 98%).

[Synthesis of dipotassium 5-ethynylisophthalate from 4- (3,5-bis (methoxycarbonyl) phenyl) -2-methyl-3-butyn-1-ol] Thermometer, Dimroth condenser, stirrer Was charged into a 5 L four-necked flask equipped with a solution of n-butanol and 182 g (2.763 mol) of potassium hydroxide (85%), and dissolved by heating under reflux. The synthesized 4- (3,5-bis (methoxycarbonyl) phenyl) -2-methyl-3
95 g (0.344 mol) of -butyn-1-ol was added, and the mixture was heated under reflux for 30 minutes. Cool this in an ice bath,
The precipitated crystals were collected by filtration. The crystals were washed twice with 1 liter of ethanol and dried at 60 ° C. under reduced pressure to obtain 88.87 g of dipotassium 5-ethynylisophthalate (97%).

[Synthesis of 5-ethynylisophthalic acid from dipotassium 5-ethynylisophthalate] 5 g (0.019 mol) of dipotassium 5-ethynylisophthalate was dissolved in 20 ml of ion-exchanged water and filtered through a 5C filter paper. By doing so, insolubles were removed. 5 (mol)
/ L) Hydrochloric acid was added with stirring until the pH reached 1.
The precipitated solid is collected by filtration, and further washed with ion-exchanged water,
Filtration was repeated twice. The obtained solid was dried at 50 ° C. under reduced pressure to give 3.6 g of 5-ethynylisophthalic acid.
Was obtained (yield 99.5%).

[Synthesis of 5-ethynylisophthalic acid dichloride from dipotassium 5-ethynylisophthalate] In a 2 L four-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer, dipotassium 5-ethynylisophthalate was added. 80
g (0.3 mol) and 400 liters of chloroform were charged and cooled to 0 ° C. 391 g of thionyl chloride
(4.5 mol) was added dropwise at 5 ° C. or lower over 1 hour. Thereafter, 4 ml of dimethylformamide and 4 g of hydroquinone were added, and the mixture was stirred at 45 to 50 ° C. for 3 hours. After cooling, the crystals were removed by filtration, and the crystals were washed with 150 ml of chloroform. The filtrate and the washing solution were combined and concentrated under reduced pressure at 40 ° C. or lower, and the obtained residue was extracted and filtered twice with 200 m of diethyl ether. Diethyl ether was distilled off from the extract under reduced pressure to obtain a semi-solid crude product. This is dried n
After washing with -hexane and recrystallizing with diethyl ether, 13 g of 5-ethynylisophthaloyl dichloride was obtained (yield 19%).

The spectral data of the obtained 5-ethynylisophthalic acid and 5-ethynylphthalic dichloride are shown below. These data support that the obtained compound is the target compound.

[5-Ethynylisophthalic acid (C ₁₀ H
₆ O ₄ )] Appearance: white powder Melting point: 106.2 ° C. (DSC, 10 ° C./min) ¹ H-NMR (400 MHz, DMSO-d ₆ ): δ8.
16 (s, 2H), 8.45 (s, 1H) 13 C (1 H) -NMR (100MHz, DMSO-
d ₆ ): δ81.5, 82.6, 122.7, 130.
0, 131.9, 135.9, 165.7 IR (KBr, cm ^-1 ): 3272, 3081, 179
7,1741, 1438, 1265, 800, 761 MS (FD) (m / z): 190 (M ⁺ ) Elemental analysis: Theoretical C: 63.16% H: 3.18%
O: 33.66% Found C: 63.24% H: 3.09% O: 3
3.67%

[5-ethynylisophthalic acid dichloride (C
₁₀ H ₄ O ₂ Cl ₂ )] Appearance: reddish brown solid Melting point: 49 ° C. (DSC, 10 ° C./min) ¹ H-NMR (400 MHz, CDCl ₃ ): δ 8.47
(S, 2H), 8.77 ( s, 1H) 13 C (1 H) -NMR (100MHz, CDCl 3):
δ 80.0, 81.6, 124.9, 133.0, 13
4.7, 139.8, 166.6 IR (KBr, cm ^-1 ): 3465, 3077, 176
6,1736,1151,1022,802,740 MS (FD) (m / z): 190 (M ⁺ -2Cl) Elemental analysis: Theoretical C: 52.86% H: 1.77% Cl: 3
1.21 O: 14.08% Found C: 52.74% H: 1.70% Cl: 3
0.89 O: 14.67%

Example 2 [Synthesis of 1- (3,5-bis (methoxycarbonyl) phenyl) -2-phenylethyne from dimethyl 5-trifluoromethanesulfonyloxy isophthalate] Thermometer
125 g (0.365 mol) of dimethyl 5-trifluoromethanesulfonyloxyisophthalate obtained in the same manner as in Example 1 was placed in a four-necked one-liter flask equipped with a Dimroth condenser, a nitrogen inlet, and a stirrer. 1.1 g (0.00419 mol) of phosphine, 0.275 g (0.00144 mol) of copper iodide, and 40.95 g (0.401 mol) of ethynylbenzene were charged.
Nitrogen was flushed. 375 ml of dehydrated triethylamine and 200 ml of dehydrated pyridine were added and dissolved by stirring. After continuing to flow nitrogen for one hour, 0.3 g of dichlorobis (triphenylphosphine) palladium (0.000427mo)
l) was added quickly, and the mixture was heated under reflux in an oil bath for 1 hour. Thereafter, triethylamine and pyridine were distilled off under reduced pressure to obtain a viscous brown solution. This was poured into 500 ml of water, and the precipitated solid was collected by filtration.
It was washed twice with 500 ml of mol / L hydrochloric acid and 500 ml of water. The solid is dried at 50 ° C. under reduced pressure to give 8
0.8 g of 1- (3,5-bis (methoxycarbonyl)
Phenyl) -2-phenylethyne was obtained (yield 75
%).

[(3,5-bis (methoxycarbonyl)
Synthesis of di-potassium 5- (2-phenylethynyl) isophthalate from phenyl) -2-phenylethyne] 3 L n-butanol in a 5 L four-necked flask equipped with a thermometer, a Dimroth condenser, and a stirrer, 180 g (2.72 mol) of potassium (85%) was charged and dissolved by heating under reflux. (3,5-bis (methoxycarbonyl) phenyl) -2-phenylethyne synthesized therefrom
80 g (0.272 mol) was added, and the mixture was heated under reflux for 30 minutes. This was cooled in an ice bath, and the precipitated crystals were collected by filtration. The crystals were washed twice with 1 liter of ethanol,
By drying under reduced pressure at 0 ° C., 90.35 g of 5-
Dipotassium (2-phenylethynyl) isophthalate was obtained (97%).

[Synthesis of 5- (2-phenylethynyl) isophthalic acid from dipotassium 5- (2-phenylethynyl) isophthalate] 6.5 g of dipotassium 5- (2-phenylethynyl) ethynylisophthalate (0 g .019
mol) was dissolved in 20 ml of ion-exchanged water, and insolubles were removed by filtration through 5C filter paper. To this filtrate, 5 mol / L hydrochloric acid was added with stirring until the pH became 1. The precipitated solid was collected by filtration, and washing with ion-exchanged water and filtration were repeated twice. The obtained solid is
Drying under reduced pressure at 5 ° C. gave 5.0 g of 5- (2-phenylethynyl) isophthalic acid (yield 99.5).
%).

[Synthesis of 5- (2-phenylethynyl) isophthalic acid dichloride from di-potassium 5- (2-phenylethynyl) isophthalate] Two-liter four-holes equipped with a thermometer, a Dimroth condenser, and a stirrer Add 5- (2-
Phenylethynyl) dipotassium isophthalate salt 82.1
g (0.24 mol), 1,2-dichloroethane 400
One liter was charged and cooled to 0 ° C. To this, 391 g (4.5 mol) of thionyl chloride was added dropwise at 5 ° C. or lower over 1 hour. Thereafter, 4 ml of dimethylformamide and 4 g of hydroquinone were added, and the mixture was stirred at 45 to 50 ° C. for 3 hours. After cooling, the crystals were removed by filtration, and the crystals were washed with 150 ml of chloroform. The combined filtrate and washing solution
The mixture was concentrated under reduced pressure at 0 ° C. or lower, and the obtained residue was extracted and filtered twice with 200 m of diethyl ether. Diethyl ether was distilled off from the extract under reduced pressure to obtain a semi-solid crude product. This was washed with dried n-hexane and then recrystallized from diethyl ether to obtain 13.8 g of 5- (2-
(Phenylethynyl) isophthaloyl dichloride was obtained (19% yield).

The spectrum data of the obtained 5- (2-phenylethynyl) isophthalic acid and 5- (2-phenylethynyl) isophthalic acid dichloride are shown below. These data support that the obtained compound is the target compound.

[5- (2-phenylethynyl) isophthalic acid (C ₁₆ H ₁₀ O ₄ )] Appearance: White powder Melting point: 99.7 ° C. (DSC, 10 ° C./min) ¹ H-NMR (400 MHz, (CD ₃ ) ₂ CO): δ
7.44 (m, 3H), 7.64 (m, 2H), 8.3
5 (d, 2H, J = 1.6 Hz), 8.63 (t, 1
H, J = 1.6 Hz) ¹³ C ( ¹ H) -NMR (100 MHz, (CD ₃ ) ₂ CO
): Δ 88.0, 91.7, 123.2, 125.
0, 129.5, 129.5, 129.9, 131.
0, 132.5, 132.7, 132.7, 136.
8, 166.2 IR (KBr, cm ^-1 ): 3549, 2968, 236
5,1722,1492,1446,1276,91
7,756,674 MS (FD) (m / z): 266 (M ⁺ ) Elemental analysis: Theory C: 72.18% H: 3.79%
O: 24.04% Observed value C: 70.86% H: 3.64% O: 2
5.50%

[5-ethynylisophthalic acid dichloride (C
₁₆ H ₈ O ₂ Cl ₂ )] Appearance: White solid Melting point: 124 ° C. (DSC, 10 ° C./min) ¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.40
(M, 3H), 7.57 (m, 2H), 8.50 (d,
2H, J = 1.6 Hz), 8.73 (t, 2H, J =
(1.6 Hz) ¹³ C ( ¹ H) -NMR (100 MHz, CDCl ₃ ):
δ 85.7, 93.6, 121.6, 126.2, 12
8.6, 129.5, 131.9, 132.2, 13
4.6, 139.2, 166.8 IR (KBr, cm ^-1 ): 3489, 3075, 221
6,1756,1580,1489,1440,132
9, 1218, 1145, 1000, 819, 690 MS (FD) (m / z): 266 (M ⁺ -2Cl) Elemental analysis: Theoretical C: 63.39% H: 2.66% Cl: 2
3.39 O: 10.56% Found C: 63.04% H: 2.49% Cl: 2
2.69 O: 11.78%

(Example 3) [Synthesis of 5-bromoisophthalic acid] In a four-necked one-liter flask equipped with a thermometer, a stirrer, and a dropping funnel, 99.18 g (0.55 mol) of 5-hydroxyisophthalic acid was placed.
And 165 mL of 48% hydrobromic acid and 150 mL of distilled water were added and stirred. The flask was cooled to 5 ° C. or lower, and a solution of 39.4 g (0.57 mol) of sodium nitrite dissolved in 525 mL of distilled water was added dropwise over 1 hour to obtain a diazonium salt aqueous solution. In a four-necked 3-liter flask equipped with a thermometer, a Dimroth condenser, a dropping funnel, and a stirrer, 94.25 g (0.66 mol) of cuprous bromide was placed.
l) and 45 mL of 48% hydrobromic acid were added and stirred. The flask was cooled to 0 ° C. or lower, and the above diazonium salt aqueous solution was added dropwise over 2 hours. After the completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes and continuously refluxed for 30 minutes. After cooling, the precipitate was separated by filtration and washed twice with 2 L of distilled water.
It was dried under reduced pressure at 0 ° C. for 2 days to obtain 117 g of a crude product. Used for the next reaction without purification.

[Synthesis of dimethyl 5-bromoisophthalate from 5-bromoisophthalic acid] In a 500 mL flask equipped with a stirrer and a Dimroth condenser, 110 g of the above obtained 5-bromoisophthalic acid, methanol 50
0 mL and 10 g of concentrated sulfuric acid were added and refluxed for 6 hours. After cooling, the solution was dropped into 1 L of distilled water, and neutralized with a 5% aqueous sodium hydrogen carbonate solution. The precipitate is separated by filtration and 2 L with 2 L of distilled water.
After washing twice, the resulting white solid was dried under reduced pressure at 50 ° C. for 2 days, and 109 g of dimethyl 5-bromoisophthalate was obtained.
(0.4 mol). (89% yield)

[Synthesis of 4- (3,5-bis (methoxycarbonyl) phenyl) -2-methyl-3-butyn-1-ol from dimethyl 5-bromoisophthalate] In Example 1, 5-trifluoromethane 125 g of dimethyl sulfonyloxy isophthalate (0.365 mol
l) with 99.7 g of dimethyl 5-bromoisophthalate
(8.85 mol) in the same manner as in Example 1 to obtain 98.8 g of 4- (3,5-bis (methoxycarbonyl) phenyl) -2-methyl-3-butyn-1-ol. (Yield 98%).

Thereafter, dipotassium 5-ethynylisophthalate, 5-ethynylisophthalic acid,
5-Ethynylisophthalic acid dichloride was obtained. Appearance, melting point and ¹ H-NMR, ¹³ C ( ¹ H) -NM of 5-ethynylisophthalic acid and 5-ethynylisophthalic acid dichloride
The R, IR, MS, and spectral data of elemental analysis were all consistent with Example 1, indicating that the same compound was obtained.

(Example 4) [Synthesis of 1- (3,5-bis (methoxycarbonyl) phenyl) -2-phenylethyne]
The same procedure was repeated except that 125 g (0.365 mol) of dimethyl 5-trifluoromethanesulfonyloxyisophthalate was changed to 99.7 g (0.365 mol) of dimethyl 5-bromoisophthalate obtained in the same manner as in Example 3. 80.8 g of dimethyl- (2-phenylethynyl) isophthalate was obtained as 1- (3,5-bis (methoxycarbonyl) phenyl) -2-phenylethyne (yield 75).
%).

Thereafter, in the same manner as in Example 2, 5- (2-
As a result, dipotassium phenylethynyl) isophthalate, 5-ethynylisophthalic acid, and 5- (2-phenylethynyl) isophthalic acid dichloride were obtained. Appearance, melting point and ¹ H-NM of 5- (2-phenylethynyl) isophthalic acid and 5- (2-phenylethynyl) isophthalic acid dichloride
The spectrum data of R, ¹³ C ( ¹ H) -NMR, IR, MS, and elemental analysis were all consistent with Example 2, indicating that the same compound was obtained.

[0063]

According to the present invention, an aromatic carboxylic acid represented by the formula (1) and an acid chloride of the formula (1) represented by the formula (2) can be obtained. It is useful as a raw material for system polymers.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 67/343 C07C 67/343 // C07B 61/00 300 C07B 61/00 300 (72) Inventor Naofumi Eno 2-5-8 Higashishinagawa, Shinagawa-ku, Tokyo Sumitomo Bakelite Co., Ltd. F-term (reference) 4G069 AA06 BA27A BA27B BB08A BB08B BC29A BC31A BC31B BC72A BC72B BD14A BD14B BE27A BE27B BE46A BE46B CB25 CB62 4H006 AC46 AC46 BA25 BA37 BA48 BA53 BE01 BE02 BE03 BE10 BE51 BJ50 BS30 BS90 4H039 CA31 CD10 CD40

Claims (5)

[Claims] 1. An aromatic carboxylic acid represented by the general formula (1). Embedded image (In the formula, X represents hydrogen, an alkyl group, or an aromatic group.) 2. An acid chloride derivative of an aromatic carboxylic acid represented by the general formula (2). Embedded image (In the formula, X represents hydrogen, an alkyl group, or an aromatic group.) 3. A compound represented by the general formula (5) obtained by reacting a compound represented by the general formula (3) with a compound represented by the general formula (4) is converted into an alkali metal water. An aromatic carboxylic acid represented by the general formula (1), which is obtained by treating the compound in the presence of an oxide to produce a compound represented by the general formula (6), and further performing an acid treatment. Synthesis method. Embedded image (In the formula, Y represents a leaving group.) (In the formula, X ₁ represents a trimethylsilyl group, a hydroxypropyl group, an alkyl group or an aromatic group.) (In the formula, X ₁ represents a trimethylsilyl group, a hydroxypropyl group, an alkyl group, or an aromatic group.) (In the formula, X represents hydrogen, an alkyl group or an aromatic group, and M represents an alkali metal.) 4. The aromatic carboxylic acid according to claim 3, wherein a transition metal catalyst is used in the reaction between the compound represented by the general formula (3) and the compound represented by the general formula (4). Synthetic method of acid. 5. A compound represented by the general formula (6) or a compound represented by the general formula (1) obtained by the synthesis method according to claim 3 or 4.
A method for synthesizing an acid chloride derivative of an aromatic carboxylic acid represented by the general formula (2), which is obtained by treating a compound represented by the formula (1) with a chlorinating agent.