JPH054940A - New dicarboxylic acid, its derivative and production thereof - Google Patents

Abstract

PURPOSE:To obtain a new dicarboxylic acid available for a raw material of high-performance polymer having excellent thermal and mechanical properties and good moldability, heat resistance and chemical resistance or derivative thereof. CONSTITUTION:A dicarboxylic acid [e.g. 4'-[(p-carboxyphenoxy) ethoxyl- diphenyl-4-carboxylic acid ethyl ester] expressed by formula I [n is 2, 4 or 6; R is -ORr (R' is H, lower alkyl, cycloalkyl or aryl) or halogen; Ar is formula II or formula III] and derivative thereof. The compound is obtained by reacting an aromatic hydroxycarboxylic acid expressed by formula IV and/or alkali metal salt of ester thereof with alpha-omega-dihalogenated alkylene (e.g. 1,2- dibromoethane) and then reacting the reaction product with p-hydroxybenzoic acid and/or alkali metal salt of ester thereof.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel dicarboxylic acid,
Derivatives thereof and methods for producing them.

[0002]

2. Description of the Related Art Various aromatic dicarboxylic acids have been known so far, and these are widely used as raw materials for condensation polymers such as polyesters and polyamides. For example, terephthalic acid and its derivatives are industrially used as raw materials for polymers such as polyethylene terephthalate, polytetramethylene terephthalate, and polyparaphenylene terephthalamide. Further, m-substituted dicarboxylic acid of isophthalic acid is also used as a polymer raw material.

On the other hand, a dicarboxylic acid having a biphenyl skeleton such as 4,4'-biphenyldicarboxylic acid enhances the rigidity and orientation of the polymer obtained by using this as a raw material.
It has the effect of providing a high-performance polymer thermally and mechanically.
Further, similar effects have been observed with dicarboxylic acids having a naphthalene skeleton.

[0004]

OBJECT OF THE INVENTION The present inventors arrived at the present invention as a result of extensive studies on a novel dicarboxylic acid that can be used as a raw material for a high-performance polymer having excellent thermal and mechanical properties, moldability and chemical resistance. .

That is, an object of the present invention is to provide a novel dicarboxylic acid and its derivative. More specifically, an object of the present invention is to provide a novel dicarboxylic acid and its derivative which are advantageous for producing a condensation polymer such as polyester and polyimide. Another object of the present invention is to
It is an object of the present invention to provide a method for efficiently producing the above novel dicarboxylic acid and its derivative.

[0006]

That is, the present invention has the following formula (I):

[0007]

[Chemical 4] [In formula, n is 2, 4 or 6. R is -OR 'or a halogen atom. R'is a hydrogen atom, a lower alkyl group,
It is a cycloalkyl group or an aryl group. Ar is

[0008]

[Chemical 5] Is. ] A novel dicarboxylic acid represented by the above, a derivative thereof and a method for producing the same.

The present invention will be described in detail below.

In the above formula (I), n is 2, 4 or 6
And is preferably 2.

In the above formula (I), R'which forms a carboxylic acid ester is a hydrogen atom, a lower alkyl group, a cycloalkyl group or an aryl group. Furthermore, carbon number 1 to 4
Is preferably a lower alkyl group, a cycloalkyl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and specifically methyl, ethyl, propyl, cyclohexyl, phenyl, tolyl and the like.

Of these, methyl, ethyl and phenyl are particularly preferable. Further, when R is a halogen atom in the above formula, examples of R include Cl, Br, and I.

In the above formulas (I) and (II), Ar is

[0014]

[Chemical 6] Is.

Specific examples of the compound represented by the above formula (I) include the followings.

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10]

Preferred methods for producing the above novel dicarboxylic acid and its ester include (a) an alkali metal salt of an aromatic hydroxycarboxylic acid represented by the above formula (II) and / or its ester;
A method of reacting with an α, ω-dihalogenated alkylene and then reacting with an alkali metal salt of P-hydroxybenzoic acid and / or its ester.

(B) The alkali metal salt of P-hydroxybenzoic acid and / or its ester is reacted with α, ω-dihalogenated alkylene, and then the aromatic hydroxycarboxylic acid represented by the above formula (II), And / or a method of reacting with an alkali metal salt of an ester thereof. Etc.

Both the method (a) and the method (b) can efficiently produce the desired product. Although the method (a) will be described in more detail below, the method (b) is also carried out essentially in the same manner.

The alkali metal salt of the aromatic hydroxycarboxylic acid and / or ester thereof represented by the above formula (II) is the above-mentioned aromatic dicarboxylic acid and / or ester thereof and alkali metal and / or hydroxide of alkali metal and /
Alternatively, it can be obtained by reacting with an alkoxide. After the reaction, the alkali metal salt may be isolated and purified, or the reaction mixture containing the alkali metal salt may be directly subjected to the reaction with the α, ω-dihalogenated alkylene.
Sodium and potassium are preferably selected as the alkali metal salt.

In this case, the amount of the alkali metal and / or the hydroxide and / or alkoxide of the alkali metal used is an amount sufficient to obtain the salt of the above-mentioned hydroxycarboxylic acid and / or its ester, and the above-mentioned hydroxycarboxylic acid. The amount is preferably 2 times mol or more with respect to the acid and 1 mol or more with respect to the ester compound.

Examples of α, ω-dihalogenated alkylene include 1,2-dichloroethane, 1,2-dibromoethane, 1,4-dichlorobutane, 1,4-dichlorobutane, 1,6-bromohexane and 1,6. -Dichlorohexane is preferred.

The amount of these used is preferably an excess amount with respect to the alkali metal salt of the hydroxycarboxylic acid and / or its ester represented by the above (II). That is, it is preferably 2 times or more mols of the alkali metal salt. These may be sequentially added to the above alkali metal salt during the reaction, or may be added all at once at the start of the reaction.

As the solvent used in the reaction, N, N-
Examples thereof include amides such as dimethylformamide and N, N-dimethylacetamide, ethers such as tetrahydrofuran and dioxane, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl isobutyl ketone, and water.

The reaction temperature is preferably 50 to 200 ° C.,
The temperature is particularly preferably 60 to 180 ° C, and the reaction can be carried out under normal pressure to increased pressure.

The time required for the reaction varies depending on the conditions such as reaction temperature, solvent and raw material concentration, but is usually 1 to 100 hours,
It is preferably 2 to 50 hours.

When the alkali metal salt of the ester of hydroxycarboxylic acid is reacted with an excess of α, ω-dihalogenated alkylene, the following formula (III)

[0031]

[Chemical 11] [Where X is a halogen atom. Ar has the same definition as in formula (I). R ″ is a lower alkyl group, a cycloalkyl group, or an aryl group. ”The compound represented by the formula is efficiently obtained. This can be purified by a purification method such as recrystallization.

As the ester recrystallization solvent, N, N-
Amides such as dimethylformamide and N, N-dimethylacetamide, ethers such as tetrahydrofuran and dioxane, alcohols such as ethanol and propanol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, methylene chloride, chloroform and tetra Halogenated hydrocarbons such as carbon chloride are preferred.

On the other hand, when the alkali metal salt of hydroxycarboxylic acid represented by the above formula (II) is reacted with an excess of α, ω-dihalogenated alkylene, the product is obtained as a carboxylic acid salt. Carboxylic acid can be obtained by acid precipitation.

Next, the compound and / or carboxylic acid represented by the above formula (III) thus obtained is reacted with an alkali metal salt of P-hydroxybenzoic acid and / or its ester.

The alkali metal of P-hydroxybenzoic acid and / or its ester is obtained by reacting P-hydroxybenzoic acid and / or its ester with alkali metal and / or hydroxide and / or alkoxide of alkali metal. Can be obtained at. After the reaction, the alkali metal salt may be isolated and purified, or the reaction mixture containing the alkali metal salt may be directly subjected to the reaction.

As the alkali metal, sodium and potassium are preferably selected. In this case, the amount of alkali metal and / or alkali metal hydroxide used is P-
It is an amount sufficient to obtain a salt of hydroxybenzoic acid and / or an ester thereof, and is preferably 2-fold moles or more with respect to P-hydroxybenzoic acid and equimolar or more with respect to the ester.
The amount of the alkali metal salt of P-hydroxybenzoic acid and / or its ester used is preferably equimolar or more based on the compound represented by the above formula (III) and / or the carboxylic acid.

The above alkali metal salts may be added sequentially during the reaction, or may be added all at once at the start of the reaction.

As the solvent used in the reaction, N, N-
Examples thereof include amides such as dimethylformamide and N, N-dimethylacetamide, ethers such as tetrahydrofuran and dioxane, alcohols such as methanol, ethanol and propanol, ketones such as acetone and methyl isobutyl ketone, and water.

The reaction temperature is preferably 50 to 200 ° C.,
The temperature is particularly preferably 60 to 180 ° C, and the reaction can be carried out under normal pressure to increased pressure.

The time required for the reaction varies depending on the conditions such as reaction temperature, solvent and raw material concentration, but is usually 1 to 100 hours,
It is preferably 2 to 50 hours.

The end point of the reaction can be determined by monitoring the raw materials and / or products in the reaction solvent.

The thus-obtained novel dicarboxylic acid and / or ester thereof of the present invention can be purified by a method such as recrystallization.

The acid halide in the present invention can be prepared by synthesizing the above-mentioned novel dicarboxylic acid according to a conventionally known method.

For example, an acid halide can be obtained by reacting the above dicarboxylic acid with thionyl chloride in the presence of pyridine.

[0045]

INDUSTRIAL APPLICABILITY The novel dicarboxylic acid and its derivative of the present invention are useful as a raw material for producing polyester, polyamide and the like.

Further, according to the present invention, there can be provided a method for efficiently producing the above novel carboxylic acid and its derivative.

Therefore, its significance is industrially significant.

[0048]

The present invention will be described in detail below with reference to examples. The infrared absorption spectrum (IR) was measured by the KBr disk method. The magnetic resonance spectrum (NMR) is
The measurement was performed using deuterated chloroform as a solvent and tetramethylsilane as a standard.

The present invention is not limited to these examples.

[0050]

Example 1 Synthesis of 4 '-[(P-carboxyphenoxy) ethoxy] -diphenyl-4-carboxylic acid ethyl ester 37'4'-hydroxybiphenyl-4-carboxylic acid methyl ester, 1,2-dibromoethane 22. 94 g was placed in a 500-ml three-necked flask equipped with a stirring blade together with 260 ml of ethanol in which 3.7 g of metallic sodium was dissolved in advance, and the mixture was subjected to a heating reflux reaction for 4 hours in a nitrogen atmosphere. Then, 100 ml of ethanol in which 3.7 g of metallic sodium was dissolved and 7.0 g of 1,2-dibromoethane were added, and the mixture was heated to reflux for another 4 hours to continue the reaction. After cooling, the resulting precipitate was washed with acetone then ethanol and 28.0 g of 4- (2-bromoethoxy).
-Biphenyl-4'-carboxylic acid ethyl ester was obtained.

Next, 15.0 g of 4- (2-bromoethoxy) -biphenyl-4'-carboxylic acid ethyl ester and P-hydroxybenzoic acid methyl ester 13.1 g
Ethanol 25 in which 2.0 g of metal and sodium natriumm are dissolved
0 ml was placed in a 500 ml autoclave equipped with a stirring blade and reacted at 150 ° C. and 9 atm for 7 hours. The precipitate formed after cooling was washed with ethanol and then with water,
The desired ethyl dicarboxylic acid ester was obtained. Melting 1
It was 56-159 ° C. The IR spectrum and NMR spectrum of this compound are shown in FIGS. 1 and 2, respectively. As a result of elemental analysis, this compound was found to have C 71.7%, O 22.
It was 0% and H 6.3%. It was confirmed by mass spectrometry that the molecular weight of this compound was 434.

[0052]

Example 2 Synthesis of 2-[(P-carboxyphenoxy) ethoxy] -naphthalene-6-carboxylic acid ethyl ester 152 g of P-hydroxybenzoic acid methyl ester, 413.4 g of dibromoethane and 25.3 g of sodium metal in advance. 1000 ml of dissolved ethanol was put into a 3 liter three-necked flask, and heated and reacted for 18 hours while stirring under a nitrogen stream under reflux conditions.

After cooling, the deposited precipitate was separated by filtration, collected, washed twice with alkaline water (NaOH-water) and then once with water to give 4- (2-bromoethyleneoxy) -ethyl benzoate as a white powder. 108 g of ester are obtained.

Then, 27.3 g of 4- (2-bromoethyleneoxy) -benzoic acid methyl ester obtained and 32.5 g of oxynaphthoic acid methyl ester were dissolved in advance with sodium hydroxide 6.43 g of ethanol 5
It was put together with 00 ml in a 1-liter three-necked flask, and heated and reacted under reflux conditions for 7.5 hours while stirring under a nitrogen stream. The precipitate generated during the reaction was filtered and collected after cooling. This was washed with water then methanol and recrystallized from chloroform to give 23.5 g of product. This compound had a melting point of 140-145 ° C.

IR spectrum and NMR spectrum of this compound are shown in FIGS. As a result of elemental analysis, this compound was found to be C 70.6%, O 23.5%, H 5.9.
%Met.

[Brief description of drawings]

1 is an IR spectrum of the compound obtained in Example 1. FIG.

FIG. 2 is an'H-NMR spectrum of the compound obtained in Example 1.

3 is an IR spectrum of the compound obtained in Example 2. FIG.

FIG. 4 is an'H-NMR spectrum of the compound obtained in Example 2.

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[Procedure amendment]

[Submission date] August 6, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

The alkali metal salt of the aromatic hydroxycarboxylic acid and / or ester thereof represented by the above formula (II) is the above-mentioned aromatic dicarboxylic acid and / or ester thereof and alkali metal and / or hydroxide of alkali metal and /
Alternatively, it can be obtained by reacting with an alkoxide. After the reaction, the alkali metal salt may be isolated and purified, or the reaction mixture containing the alkali metal salt may be directly subjected to the reaction with the α, ω-dihalogenated alkylene.
Sodium and potassium are preferably selected as the alkali metal .

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

When the alkali metal salt of the ester of hydroxycarboxylic acid is reacted with an excess of α, ω-dihalogenated alkylene, the following formula (III)

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

The alkali metal of P-hydroxybenzoic acid and / or its ester is obtained by reacting P-hydroxybenzoic acid and / or its ester with alkali metal and / or hydroxide and / or alkoxide of alkali metal. Can be obtained at. After the reaction, the alkali metal salt may be isolated and purified, or the reaction mixture containing the alkali metal salt may be directly subjected to the reaction .

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0051

[Correction method] Change

[Correction content]

Next, 15.0 g of 4- (2-bromoethoxy) -biphenyl-4'-carboxylic acid ethyl ester and P-hydroxybenzoic acid methyl ester 13.1 g
Ethanol 25 in which 2.0 g of metal and sodium natriumm are dissolved
0 ml was placed in a 500 ml autoclave equipped with a stirring blade and reacted at 150 ° C. and 9 atm for 7 hours.
The precipitate formed after cooling was washed with ethanol and then with water to obtain the desired ethyl dicarboxylic acid ester. Fusion
The point was 156-159 ° C. The IR spectrum and NMR spectrum of this compound are shown in FIGS. 1 and 2, respectively.
As a result of elemental analysis, this compound was C 71.7%, O 2
It was 2.0% and H 6.3%. It was confirmed by mass spectrometry that the molecular weight of this compound was 434.

[Procedure Amendment 5]

[Document name to be corrected] Drawing

[Name of item to be corrected] Figure 3

[Correction method] Change

[Correction content]

[Figure 3]

Claims (3)

[Claims] 1. The following formula (I): [In formula, n is 2, 4 or 6. R is -OR 'or a halogen atom. R'is a hydrogen atom, a lower alkyl group,
It is a cycloalkyl group or an aryl group. Ar is [Chemical formula 2] Is. ] The new dicarboxylic acid and its derivative represented by these. 2. The following formula (II): [Where Ar is as defined in formula (I). ] The alkali metal salt of an aromatic hydroxylcarboxylic acid and / or its ester represented by the following is reacted with α, ω-dihalogenated alkylene, and then the alkali metal salt of P-hydroxybenzoic acid and / or its ester is reacted. The method for producing the novel dicarboxylic acid and its derivative according to claim 1, wherein 3. An alkali metal salt of P-hydroxybenzoic acid and / or its ester is reacted with an α, ω-dihalogenated alkylene, and then an aromatic hydroxycarboxylic acid represented by the above formula (II), and 2. The method for producing the novel dicarboxylic acid and its derivative according to claim 1, which comprises reacting with an alkali metal salt of an ester thereof.