JP2948012B2 - 4',4'-(alkylenedioxy)-bis(biphenyl-4-carboxylic acid), its derivative and production thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel 4 ', 4'-
The present invention relates to (alkylenedioxy) -bis (biphenyl-4-carboxylic acid), derivatives thereof, and methods for producing them.

[0002]

2. Description of the Related Art Various aromatic dicarboxylic acids have been known, 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. Also, m-substituted dicarboxylic acid of isophthalic acid has been used as a polymer raw material.

On the other hand, a dicarboxylic acid having a biphenyl skeleton, such as 4,4'-biphenyldicarboxylic acid, increases rigidity and orientation of a polymer obtained from the dicarboxylic acid,
It has the effect of providing a thermally and mechanically high-performance polymer.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies on a novel dicarboxylic acid which can be used as a raw material for a high-performance polymer having excellent thermal and mechanical properties and good moldability and chemical resistance. .

That is, an object of the present invention is to provide a novel 4 ′,
4 '-(alkylenedioxy) -bis (biphenyl-4
-Carboxylic acid) and derivatives thereof.
More specifically, an object of the present invention is to provide 4 ', 4'-(alkylenedioxy) -bis (biphenyl-4-carboxylic acid) which is advantageous for producing condensation polymers such as polyester and polyimide.
And its derivatives. Another object of the present invention is to provide the above 4 ', 4'-(alkylenedioxy)
-To provide a method for efficiently producing bis (biphenyl-4-carboxylic acid) and its derivatives.

[0006]

That is, the present invention provides the following formula (I)

[0007]

Embedded image

Wherein n is an integer from 2 to 6.
R is -OR 'or a halogen atom. R 'is a hydrogen atom, a lower alkyl group, a cycloalkyl group or an aryl group. Represented by, 4 ', 4' - (alkylenedioxy) - bis (biphenyl-4-carboxylic acid), a derivative thereof and their preparation.

Hereinafter, the present invention will be described in detail.

In the above formula (I), n is an integer from 2 to 6.

In the above formula (I), R 'forming a carboxylic acid ester is a hydrogen atom, a lower alkyl group, a cycloalkyl group or an aryl group. Furthermore, carbon number 1-4
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 specific examples include methyl, ethyl, propyl, cyclohexyl, phenyl and tolyl.

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

Specific examples of the compound represented by the above formula include 4 ', 4'-(ethylenedioxy) -bis (biphenyl-4-carboxylic acid), 4 ', 4'-(ethylenedioxy) -bis (Biphenyl-4-carboxylic acid methyl ester), 4 ', 4'-(ethylenedioxy) -bis (biphenyl-4-carboxylic acid ethyl ester), 4 ',
4 '-(ethylenedioxy) -bis (biphenyl-4-)
Carboxylic acid phenyl ester), 4 ', 4'-(ethylenedioxy) -bis (biphenyl-4-carboxylic acid cyclohexyl), 4 ', 4'-(ethylenedioxy) -bis (biphenyl-4-carboxylic acid chloride) ), 4 ',
4 '-(tetramethylenedioxy) -bis (biphenyl-4-carboxylic acid), 4', 4 '-(tetramethylenedioxy) -bis (biphenyl-4-carboxylic acid methyl ester), 4', 4 ' ― (Tetramethylenedioxy) ―
Bis (biphenyl-4-carboxylic acid ethyl ester),
4 ', 4'-(tetramethylenedioxy) -bis (biphenyl-4-carboxylic acid phenyl ester), 4 ',
4 '-(tetramethylenedioxy) -bis (biphenyl-4-carboxylic acid cyclohexyl), 4', 4 '-(tetramethylenedioxy) -bis (biphenyl-4-carboxylic acid chloride), 4', 4 ' -(Hexamethylenedioxy) -bis (biphenyl-4-carboxylic acid),
4 ', 4'-(hexamethylenedioxy) -bis (biphenyl-4-carboxylic acid methyl ester), 4 ', 4'
-(Hexamethylenedioxy) -bis (biphenyl-4)
-Carboxylic acid ethyl ester), 4 ', 4'-(hexamethylenedioxy) -bis (biphenyl-4-carboxylic acid phenyl ester), 4 ', 4'-(hexamethylenedioxy) -bis (biphenyl-4) -Cyclohexyl carboxylate), 4 ', 4'-(hexamethylenedioxy)
-Bis (biphenyl-4-carboxylic acid chloride),
4 ', 4'-(butylenedioxy) -bis (biphenyl-4-carboxylic acid ethyl ester) and the like are exemplified.

A preferred method for producing the compound represented by the above formula (I) is 4'-hydroxy-biphenyl-4
A method of reacting an alkali metal salt of a carboxylic acid and / or an ester thereof with an α, ω-dihalogenated alkylene.

The alkali metal salt of 4'-hydroxy-biphenyl-4-carboxylic acid and / or its ester is
4'-hydroxy-biphenyl-4-carboxylic acid and / or
Alternatively, it can be obtained by reacting an ester thereof with an alkali metal salt and / or an alkali metal hydroxide. 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 a reaction with an α, ω-alkylene halide.

As the alkali metal, sodium and potassium are preferably selected.

In this case, the amount of the alkali metal and / or the hydroxide of the alkali metal to be used is an amount sufficient to obtain a salt of 4'-hydroxybiphenyl-4-carboxylic acid and / or an ester thereof. The molar amount is preferably at least 2 moles with respect to the acid and at least equimolar with respect to the ester compound.

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

The amount of these used is stoichiometrically 4'-
The molar amount is 1/2 times as much as that of the alkali metal salt of hydroxy-biphenyl-4-carboxylic acid and / or an ester thereof, but is preferably 0.3 to 0.4 times in order to increase the conversion efficiency to the intended product. . These may be added to the above alkali metal salt sequentially during the reaction, or may be added 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 from 60 to 180 ° C., and the reaction can be carried out under normal pressure to pressure.

The time of contact with the reaction varies depending on conditions such as the reaction temperature, the solvent and the concentration of the raw materials, but is usually 1 to 100 hours.
Preferably, it is 2 to 20 hours.

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

When an alkali metal salt of 4'-hydroxybiphenyl-4-carboxylic acid ester is reacted with an α, ω-dihalogenated alkylene, 4 ', 4'-(alkylenedioxy) -bis (biphenyl-4-) Carboxylic acid ester), which can be purified by a purification method such as recrystallization. Examples of the solvent for recrystallization of the ester include amides such as N, N-dimethylformamide and N, N-dimethylacetamide; ethers such as tetrahydrofuran and dioxane; alcohols such as ethanol and propanol; methyl ethyl ketone and methyl isobutyl ketone. And the like are preferred.

On the other hand, 4'-hydroxybiphenyl-4-
When an alkali metal salt of a carboxylic acid is reacted with an α, ω-dihalogenated alkylene, the product is obtained as a carboxylic acid salt, which can be converted to a carboxylic acid by acid precipitation.

Further, 4 ', 4'-(alkylenedioxy) -bis (biphenyl-4-carboxylic acid) of the present invention, 4 ', 4'-(alkylenedioxy)-obtained by the above-mentioned method. It can be easily obtained by hydrolyzing bis (biphenyl-4-carboxylic acid ester). This hydrolysis is preferably carried out in the presence of an alkali or an acid, particularly preferably in the presence of an alkali such as sodium hydroxide or potassium hydroxide. In this hydrolysis, it is also preferable to use a water-soluble organic solvent such as methanol, ethanol, dioxane, or dimethylformamide in order to increase the affinity between the ester and water.

The preferred reaction temperature is between 50 and 250 ° C.

The reaction is usually carried out under normal pressure to elevated pressure.

Further, the acid halide in the present invention can be synthesized from the above dicarboxylic acid according to a conventionally known method. For example, by reacting the above dicarboxylic acid with thionyl chloride in the presence of pyridine, 4 ', 4'-
(Alkylenedioxy) -bis (biphenyl-4-carboxylic acid chloride) can be obtained.

[0030]

The 4 ', 4'-(alkylenedioxy) -bis (biphenyl-4-carboxylic acid) and derivatives thereof of the present invention are useful as raw materials for producing polyesters, polyamides and the like.

According to the present invention, the above 4 ', 4'-
A method for efficiently producing (alkylenedioxy) -bis (biphenyl-4-carboxylic acid) and a derivative thereof can be provided.

Therefore, its significance is industrially significant.

[0033]

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

The present invention is not limited by these embodiments.

[0035]

Example 1 Synthesis of 4 ′, 4 ′-(ethylenedioxy) -bis (biphenyl-4-carboxylic acid ethyl ester) 4′-hydroxybiphenyl-4-carboxylic acid ethyl ester 17.6 g, sodium metal 1. 67g, 1,2
6.77 g of dibromoethane and 275 ml of ethanol were charged into a 500 ml autoclave equipped with stirring blades, and reacted at 150 ° C. in a nitrogen atmosphere for 10 hours. After completion of the reaction, the precipitated solid was separated by filtration, washed with water, and recrystallized with dioxane to give 4 ', 4'-(ethylenedioxy)
-Bis (biphenyl-4-carboxylic acid ethyl ester)
14.0 g were obtained. The melting point of this ethyl ester is 222
２225 ° C. IR and NMR are as shown in FIGS. In addition, the mass spectrometry spectrum confirmed that the molecular weight was 510. As a result of elemental analysis, this compound was found to have 75.1% of C, 18.8% of O, and 6.1 of H.
%Met.

[0036]

Example 2 Synthesis of 4 ′, 4 ′-(butylenedioxy) -bis (biphenyl-4-carboxylic acid ethyl ester) Except that 1,4-dibromobutane was used instead of 1,2-dibromoethane In the same manner as in Example 1, 4 ′,
4 '-(Butylenedioxy) -bis (biphenyl-4-)
Carboxylic acid ethyl ester). The melting point of this ethyl ester was 183 ° C. In addition, the mass spectrometry spectrum confirmed that the molecular weight was 538.

[Brief description of the drawings]

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

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

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

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

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-1-204926 (JP, A) Chem. Abstr. , (1990) vol. 112 abstract No. 78965 (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 65/21 C07C 51/367 C07C 67/31 C07C 69/94 CAPLUS (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A compound represented by the following formula (I): [In the formula, n is an integer of 2 to 6. R is -OR '
Or a halogen atom. R 'is a hydrogen atom, carbon number 1
4 lower alkyl groups, cycloalkyl having 6 to 10 carbon atoms
And aryl groups having 6 to 10 carbon atoms . 4 ', 4'-(alkylenedioxy) -bis (biphenyl-4-carboxylic acid) and derivatives thereof. 2. An alkali metal salt of 4'-hydroxy-biphenyl-4-carboxylic acid and / or an ester thereof,
2. The method for producing a compound represented by the formula (I) according to claim 1, wherein the compound is reacted with an α, ω-dihalogenated alkylene.