JPH07173125A - Benzenedicarboxylic acid and its ester and production thereof - Google Patents

Abstract

PURPOSE:To provide a method for producing a benzenedicarboxylic acid useful as a raw material for polymer, etc., and its ester and to obtain a new compound prepared by the method. CONSTITUTION:A benzonitriles of formula I (X is a halogen) is reacted with carbon monoxide and water or an alcohol of formula R-OH (R is H or a lower alkyl) in the presence of a palladium compound and a phosphine compound as catalysts, and a base to obtain a benzenedicarbonic acid of formula II and its ester. A compound of formula III, e.g. diethyl 2-cyanobenzene-1,3- dicarboxylate is a new compound among the resultant compounds. As the palladium compound, palladium metal, palladium metal supported with a solid or a complex of palladium having a valency of 0 or two is exemplified. As the phosphine compound, a trialkylphosphine, triphenylphosphine or a compound of formula IV (R<1> is an alkyl or phenyl; A is a 1-6C alkylene, formula IV, formula VI, etc.) or formula VII or formula VIII (n is 1-5) is exemplified.

Description

Detailed Description of the Invention

[0001]

The present invention relates to the general formula (I)

[Chemical 14] (Wherein R represents a hydrogen atom or a lower alkyl group), benzenedicarboxylic acid and its esters, and general formula (I ′) including the dicarboxylic acid and esters.

[Chemical 15] (In the formula, R is the same as above.) The present invention relates to a method for producing benzenedicarboxylic acid and its esters.

[0002]

2. Description of the Related Art As a method for producing benzenedicarboxylic acid and its esters, for example, US Pat.
358, JP 61-233648 A, JP 6
No. 1-293950 is known.

[0003]

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies as to a method for producing benzenedicarboxylic acid and its esters, and as a result, found the production method of the present invention and completed the present invention. Some of the benzenedicarboxylic acids represented by the general formula (I) and their esters produced by the present production method are novel compounds not described in the literature, and are useful compounds as starting compounds for polymers and the like.

[0004]

As a method for producing the benzenedicarboxylic acid and its esters of the present invention, for example, the method shown in the following can be used.

[Chemical 16] (In the formula, X represents a halogen atom which may be the same or different and R represents a hydrogen atom or a lower alkyl group.) A benzonitrile represented by the general formula (II) is used as a catalyst for a palladium compound and a phosphine compound. And benzenedicarboxylic acid of the general formula (I ') by reacting with carbon monoxide and water or alcohols of the general formula (III) in the presence of Can be produced, and then a benzenedicarboxylic acid ester in which R represents a lower alkyl group is hydrolyzed with a compound represented by the general formula (I ′) to be represented by the general formula (I ″) It is also possible to produce benzenedicarboxylic acid.

1. General formula (II) → general formula (I ') The palladium compound used as a catalyst in this reaction may be used in combination with a phosphine compound, and as the palladium compound, palladium metal, palladium metal supported on a solid or palladium zero-valent may be used. Alternatively, a divalent complex can be used, for example, metal palladium, palladium carbon, palladium alumina, palladium chloride, palladium bromide, palladium acetate, dichlorobis (cyanophenyl) palladium, tetrakis (triphenylphosphine) palladium, dichlorobis. (Benzonitrile) palladium, dichlorobis (triphenylphosphine) palladium, dichloro [bis (diphenylphosphino) butane] palladium and the like can be used.

As the phosphine compound used in combination with the palladium compound, trialkylphosphine,
Triphenylphosphine which may have a substituent, a general formula
One or more compounds selected from the phosphine compounds represented by (IV), (V) and (VI) can be used. General formula (IV)

Embedded image (R ¹ ) ₂ -PAP- (R ¹ ) ₂ (IV) (In the formula, R ¹ represents an alkyl group or a phenyl group which may have a substituent, and A represents 1 to 1 carbon atoms. An alkylene group of 6,

[Chemical 18] ,

[Chemical 19] ,

[Chemical 20] ,

[Chemical 21] Alternatively, it represents a binaphthyl group. ) General formula (V)

[Chemical formula 22] (In the formula, R ¹ is the same as above.) General formula (VI)

[Chemical formula 23] (In the formula, n represents an integer of 1 to 5.)

Trialkylphosphine, optionally substituted triphenylphosphine, general formulas (IV), (V) and
Examples of the phosphine compound represented by (VI) include triethylphosphine, tripropylphosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphine, 1,1-bis (dimethylphosphino) methane, 1,1-bis (diethyl). Phosphino) methane, 1,2-bis (dimethylphosphino) ethane, 1,
2-bis (diethylphosphino) ethane, 1,3-bis (dimethylphosphino) propane, 1,3-bis (diisopropylphosphino) propane, 1,4-bis (dimethylphosphino) butane, 1,4- Bis (dialkylphosphino) alkanes such as bis (diisopropylphosphino) butane, 1,1-bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphine) Fino) propane, 1,4-bis (diphenylphosphino) butane,
1,5-bis (diphenylphosphino) pentane, 1,
6-bis (diphenylphosphino) hexane, 2,3-
O-isopropylidene-2,3-dihydroxy-1,4
-Bis (diphenylphosphino) butane, bis (diphenylphosphino) ferrocene, bis (diphenylphosphino) binaphthyl, 1,2-bis (diphenylphosphino) benzene, methyldibenzophosphole, ethyldibenzophosphole, propyl Dibenzophosphole, butyldibenzophosphole, pentyldibenzophosphole, phenyldibenzophosphole, 1,1-bis (dibenzophosphoryl) methane, 1,2-bis (dibenzophosphoryl) ethane, 1,3-bis (Dibenzophosphoryl) propane, 1,4-bis (dibenzophosphoryl) butane,
Examples thereof include 1,5-bis (dibenzophosphoryl) pentane and diphenylphosphinobenzene-m-monosulfonic acid sodium salt, but the present invention is not limited thereto.

The amount of the phosphine compound used may be selected from the range of 0.01 to 10000 times by mole, and preferably 0.1 to 100 times by mole with respect to the palladium compound. This reaction may use a combination of a palladium compound and a phosphine compound,
Each of them may be used alone in the reaction system, or may be prepared in the form of a complex in advance and used.

The amount of the palladium compound and the phosphine compound used is not particularly limited, but 0.0001 relative to 1 mol of the benzonitrile represented by the general formula (II).
It may be used in the range of mol to 0.5 mol, preferably 0.001 to 0.1 mol. As the base that can be used in this reaction, an inorganic base, an organic base, an organic acid salt, or the like can be used.Examples of the inorganic base include sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and other inorganic bases, triethylamine. , Tributylamine, diisopropylethylamine, triisooctylamine, pyridine, N-methylpyrrolidine, N-methylmorpholine, N-ethylmorpholine, and other organic bases. As the organic acid salt, for example, sodium acetate can be used. The amount used may be the amount necessary to neutralize the hydrogen chloride produced in the reaction system, but it may be used more than the required amount. In the esterification reaction of this reaction, the alcohols represented by the general formula (III) are used by appropriately selecting from the range of 2 times to excess moles with respect to the benzonitriles represented by the general formula (II). However, it is preferable to use an excess molar amount. Also, in the reaction to acid, the general formula
Instead of using the water represented by (III), the alcohol represented by the general formula (III) and an excess of bases can be used to induce an acid by the water produced in the reaction system.

This reaction can be carried out in the presence or absence of an inert solvent, and the usable inert solvent may be any inert solvent which does not significantly inhibit the progress of this reaction.
For example, hexane, benzene, toluene, diethyl ether, tetrahydrofuran, acetonitrile, dimethylformamide, dimethylacetamide, hexamethylenephosphorotriamide, acetone, water and the like can be exemplified, and these inert solvents can be used alone or in combination of two or more. It can also be used as a mixture. This reaction can be carried out under atmospheric pressure to increased pressure, and the pressure of carbon monoxide may be appropriately selected from the range of 1 to 200 atm, preferably 1 to 50 atm.

The reaction temperature of this reaction is usually 100 to 300 ° C.
Can be performed in the range of, preferably 150 ~ 250 ℃
Is the range. The reaction vessel used in this reaction may be any reaction vessel used in the reaction under normal pressure to pressure,
For example, in the case of pressure reaction, a reaction container that can withstand the reaction pressure may be used, and a metal or glass reaction container is usually used. The reaction time is not constant depending on the amount of the reactants, the reaction temperature, etc., but may be selected from the range of several minutes to 48 hours. After completion of the reaction, the desired product may be isolated from the reaction system by a conventional method, and can be used in the next reaction without isolation.

2. General formula (I ') → General formula (I'') This reaction is carried out by hydrolyzing a benzenedicarboxylic acid ester in which R represents a lower alkyl group in the compound represented by the general formula (I'). The benzenedicarboxylic acid represented by (I '') can be produced, and the reaction is carried out by a conventional hydrolysis reaction, for example, an alkali hydrolysis reaction using a base such as sodium hydroxide or potassium hydroxide. good.

[0013]

EXAMPLES Representative examples of the present invention will be illustrated below, but the present invention is not limited to these examples. Example 1 Preparation of diethyl 2-cyanobenzene-1,3-dicarboxylate.

[Chemical formula 24]

8.6 g (50 mmol) of 2,6-dichlorobenzonitrile and 0.0 of dichlorobis (triphenylphosphine) palladium were added to a stainless steel autoclave.
351 g (0.05 mmol), 1,4-bis (diphenylphosphino) butane 0.64 g (1.5 mmol), sodium carbonate 5.83 g (55 mmol), ethanol 11.5 g (250 mmol) and Toluene 5
Add 0 ml and add carbon monoxide to 5 while stirring at 300 rpm.
After purging 3 times with kg / cm ^2, reaction was conducted for 3 hours at 200 ° C. and filled into 35 kg / cm ^2. After completion of the reaction, the reaction solution was filtered to remove insoluble materials, and the filtrate was concentrated to obtain 11.4 g of the desired product. Physical properties m. p. 54-56 ° C Yield 91.9%

Example 2 2-Cyanobenzene-1,3-
Production of dimethyl dicarboxylate.

[Chemical 25]

8.6 g (50 mmol) of 2,6-dichlorobenzonitrile and 0.0 of dichlorobis (triphenylphosphine) palladium were added to a stainless steel autoclave.
175 g (0.025 mmol), 1,4-bis (diphenylphosphino) butane 0.64 g (1.5 mmol), sodium carbonate 5.83 g (55 mmol), methanol 8.0 g (250 mmol) and Toluene 50
Add 5 ml of carbon monoxide under stirring at 300 rpm to 5 k
After substituting 3 times with g / cm ^2, it was filled with 35 kg / cm ² and reacted at 200 ° C. for 1 hour. After completion of the reaction, the reaction solution was filtered to remove insoluble matter, and the filtrate was concentrated to recrystallize the obtained crystals to obtain 4.7 g of the desired product. . Physical properties m. p. 112-113 ° C Yield 42.9
%

Example 3 2-Cyanobenzene-1,3-
Production of dicarboxylic acids. 3-1

[Chemical formula 26]

8.6 g (50 mmol) of 2,6-dichlorobenzonitrile and 0.0 of dichlorobis (triphenylphosphine) palladium were added to a stainless steel autoclave.
351 g (0.05 mmol), 1,4-bis (diphenylphosphino) butane 0.64 g (1.5 mmol), sodium carbonate 21.2 g (200 mmol) and ethanol 50 ml were added, and the mixture was stirred at 300 rpm. After replacing carbon monoxide with 5 kg / cm ² for 3 times,
It was filled with g / cm ² and reacted at 200 ° C. for 3 hours.
After completion of the reaction, the precipitated potassium salt is collected by filtration and dissolved in water, insoluble matters are removed from the solution, concentrated hydrochloric acid is added to the filtrate to make it acidic, and the precipitated crystals are collected by filtration and washed with water. 3.73 g of the product was obtained. Physical properties m. p. > 300 ° C Yield 39.1%

3-2

[Chemical 27]

8.6 g (50 mmol) of 2,6-dichlorobenzonitrile and 0.0 of dichlorobis (triphenylphosphine) palladium were added to a stainless steel autoclave.
351 g (0.05 mmol), 1,4-bis (diphenylphosphino) butane 0.64 g (1.5 mmol), sodium carbonate 5.83 g (55 mmol), water 4.5 g (250 mmol) and toluene 50 ml. And add carbon monoxide at 5 kg / cm with stirring at 300 rpm.
After replacing with ² times 3 times, fill it with 35 kg / cm ² and
The reaction was carried out at 0 ° C for 3 hours. After the completion of the reaction, water was added to the reaction system to extract the desired product, and the resulting aqueous layer was acidified by adding concentrated hydrochloric acid, and the precipitated crystals were collected by filtration and dried to obtain 3.20 g of the desired product. . (Yield 33.5%)

3-3

[Chemical 28]

In a three-necked flask equipped with a condenser and a stirrer, 7.41 g (30 mmol) of diethyl 2-cyanobenzene-1,3-dicarboxylate, 4.75 g (72 mmol) of 85% potassium hydroxide and ethanol were added. 60 ml was added and the reaction was carried out under reflux for 2 hours. After completion of the reaction, the precipitated potassium salt is collected by filtration and dissolved in water, insoluble matters are removed from the solution, concentrated hydrochloric acid is added to the filtrate to make it acidic, and the precipitated crystals are collected by filtration and washed with water. 2.4 g of the product was obtained. (Yield 41.9%)

Example 4 5-Cyanobenzene-1,3-
Production of dicarboxylic acids. 4-1

[Chemical 29]

In a stainless steel autoclave, 6.88 g (40 mmol) of 3,5-dichlorobenzonitrile, dichlorobis (triphenylphosphine) palladium.
0281 g (0.04 mmol), 1,4-bis (diphenylphosphino) butane 0.51 g (1.2 mmol), sodium carbonate 19.96 g (160 mmol)
And 40 ml of ethanol were added, and carbon monoxide was replaced with 5 kg / cm ² three times with stirring at 300 rpm, and then 35
It was filled with kg / cm ² and reacted at 200 ° C. for 3 hours. After completion of the reaction, the precipitated potassium salt is collected by filtration and dissolved in water, insoluble matters are removed from the solution, concentrated hydrochloric acid is added to the filtrate to make it acidic, and the precipitated crystals are collected by filtration and washed with water. 2.09 g of the product was obtained. Physical properties m. p. 252 to 254 ° C Yield 27.4%

4-2

[Chemical 30]

In a stainless steel autoclave, 6.88 g (40 mmol) of 3,5-dichlorobenzonitrile, dichlorobis (triphenylphosphine) palladium.
0281 g (0.04 mmol), 1,4-bis (diphenylphosphino) butane 0.51 g (1.2 mmol), sodium carbonate 4.66 g (44 mmol), water 3.6 g (200 mmol) and toluene 40 ml. And add carbon monoxide at 5 kg / cm with stirring at 300 rpm.
After replacing with ² times 3 times, fill it with 35 kg / cm ² and
The reaction was carried out at 0 ° C for 3 hours. After the reaction was completed, water was added to the reaction system to extract the desired product, and the resulting aqueous layer was acidified by adding concentrated hydrochloric acid, and the precipitated crystals were collected by filtration and dried to obtain 1.90 g of the desired product. . (Yield 24.9%)

4-3

[Chemical 31]

1. In a 3-necked flask equipped with a condenser and a stirrer, diethyl 5-cyanobenzene 1,3-dicarboxylate 2.
47 g (10 mmol), 85% potassium hydroxide 1.5
8 g (24 mmol) and 20 ml ethanol were added,
The reaction was carried out under reflux for 2 hours. After completion of the reaction, the precipitated potassium salt is collected by filtration and dissolved in water, insoluble matters are removed from the solution, concentrated hydrochloric acid is added to the filtrate to make it acidic, and the precipitated crystals are collected by filtration and washed with water. 0.85 g of the product was obtained. (Yield 44.5%)

Example 5 5-Cyanobenzene-1,3-
Production of diethyl dicarboxylate.

[Chemical 32]

In a stainless steel autoclave, 6.88 g (40 mmol) of 3,5-dichlorobenzonitrile, and dichlorobis (triphenylphosphine) palladium.
0281 g (0.04 mmol), 1,4-bis (diphenylphosphino) butane 0.51 g (1.2 mmol), sodium carbonate 4.66 g (44 mmol) and ethanol 9.2 g (200 mmol). Toluene 4
Add 0 ml and add carbon monoxide to 5 while stirring at 300 rpm.
After purging 3 times with kg / cm ^2, reaction was conducted for 3 hours at 200 ° C. and filled into 35 kg / cm ^2. After completion of the reaction, the reaction solution was filtered to remove insoluble materials, and the filtrate was concentrated to recrystallize the obtained crystals to recrystallize from 2-propanol-n-hexane to obtain 4.42 g of the desired product. . Physical properties m. p. 80-81 ° C Yield 44.7%

Claims (9)

[Claims] 1. A compound represented by the general formula (I): (In the formula, R represents a hydrogen atom or a lower alkyl group.) A benzenedicarboxylic acid and its ester. 2. A compound represented by the general formula (II): (Wherein X represents a halogen atom which may be the same or different), carbon monoxide and a general formula (in the presence of a palladium compound and a phosphine compound as catalysts and a base) III) [Image Omitted] R-OH (III) (wherein R represents a hydrogen atom or a lower alkyl group) and water or an alcohol represented by the general formula (I ') [Chemical 4] (In the formula, R is the same as above.) A method for producing benzenedicarboxylic acid and esters thereof. 3. The method for producing benzenedicarboxylic acid esters according to claim 2, wherein X is a chlorine atom. 4. The method for producing benzenedicarboxylic acid esters according to claim 3, wherein X is substituted at the 2- and 6-positions. 5. The method for producing benzenedicarboxylic acid and its esters according to claim 2, wherein the palladium compound is palladium metal, palladium metal supported on a solid, or a palladium zero-valent or divalent complex. 6. The method for producing benzenedicarboxylic acid and its esters according to claim 2, wherein the palladium compound is palladium carbon, palladium chloride, palladium acetate or dichlorobis (triphenylphosphine) palladium. 7. The phosphine compound is a trialkylphosphine, optionally substituted triphenylphosphine,
The method for producing benzenedicarboxylic acid and its esters according to claim 2, which is one or more selected from the compounds represented by the general formulas (IV), (V) and (VI). Formula (IV) embedded image (R ¹ ) ₂ -PAP- (R ¹ ) ₂ (IV) (In the formula, R ¹ represents an alkyl group or a phenyl group which may have a substituent, and A represents An alkylene group having 1 to 6 carbon atoms, embedded image , , , Alternatively, it represents a binaphthyl group. ) General formula (V) (In the formula, R ¹ is the same as above.) General formula (VI) (In the formula, n represents an integer of 1 to 5.) 8. A compound represented by the general formula (I ′): (Wherein R ′ represents a lower alkyl group), benzenedicarboxylic acid ester represented by the general formula (I ″) embedded image is hydrolyzed. A method for producing benzenedicarboxylic acid represented by: 9. The method for producing benzenedicarboxylic acid esters according to claim 8, wherein the dicarboxylic acid is substituted at the 2- and 6-positions.