JPH08104661A - Production of aromatic carboxylic acids - Google Patents

Abstract

PURPOSE: To obtain an aromatic carboxylic acid useful e.g. as a raw material for pharmaceuticals and agrochemicals in high efficiency and improved catalytic activity by reacting an aromatic chlorine compound with carbon monoxide and water in the presence of a specific catalyst and a base. CONSTITUTION: This aromatic carboxylic acid is produced by reacting (A) an aromatic chlorine compound such as (poly)chlorobenzene with (B) carbon monoxide and (C) water in the presence of (D) a Pd-phosphine catalyst such as a catalyst of formula, PdCl2 (PCy3 )2 (Cy is cyclohexyl) and (E) an alkali metal carbonate, a t-amine such as triethylamine or N,N-dimethylpiperazine or a quaternary ammonium salt such as tetraethylammonium chloride. Preferably, the amounts of the Pd compound and the phosphine of the component D are 0.0001-0.005mol and 0.0001-0.01mol and the amounts of the components E, B and C are 0.01-0.05mol, 0.4-10mol and 3-5mol based on 1mol of the component A, respectively, the reaction temperature is 130-200 deg.C and the reaction pressure is 3-10-kg/cm<2> G.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing aromatic carboxylic acids, and more particularly to a method for producing aromatic carboxylic acids by reacting an aromatic chlorine compound with carbon monoxide and water.

[0002]

BACKGROUND OF THE INVENTION Aromatic carboxylic acids are useful as raw materials for medicines, agricultural chemicals, etc., and they are converted into aromatic chlorine compounds by using a palladium-phosphine catalyst in the presence of a base. It is also well known to produce carbon oxide by reacting water with water.

For example, as the base, a method using an inorganic base such as sodium carbonate, potassium carbonate, sodium hydroxide or potassium hydroxide or an organic base such as triethylamine, pyridine, N-methylpyrrolidine or N-methylmorpholine (Japanese Patent Laid-open Publication No. Sho. 64-47), a method using potassium hydroxide (J.Chem.Soc., Chem.Commun., 611 (1992)), a method using sodium acetate (J.Am.Chem.Soc., 111 , 8742 ( 1989)) etc. are known.

However, these methods have an industrial drawback that the catalytic activity is not sufficient and the amount of aromatic carboxylic acids produced per catalyst is low.

[0005]

Means for Solving the Problems As a result of intensive studies on the catalyst system in order to solve the above problems, the present inventors have found that
As a base, it was found that the combined use of alkali metal carbonates and specific amines improves the catalytic activity and significantly improves the production amount of aromatic carboxylic acids per catalyst. In addition, the present invention has been completed.

That is, in the present invention, when a palladium-phosphine-based catalyst is used in the presence of a base to react an aromatic chlorine compound with carbon monoxide and water to produce an aromatic carboxylic acid, an alkali metal base is used. Carbonates and 3
A method for producing an industrially excellent aromatic carboxylic acid characterized by using a secondary amine and / or a quaternary ammonium salt.

Hereinafter, the present invention will be described in detail. As the aromatic chlorine compound used in the present invention, it is sufficient that at least one chlorine atom is substituted on the aromatic ring, and in addition to the chlorine atom, for example, an alkyl group, a haloalkyl group, an alkoxy group, a phenoxy group, an acyl group. May be replaced.
Examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl and decyl.

Examples of the haloalkyl group include haloalkyl groups such as trifluoromethyl and 2-chloroethyl. As the alkoxy group, for example, methoxy,
Examples thereof include alkoxy groups having 1 to 10 carbon atoms such as ethoxy, butoxy, pentoxy, cyclopentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, nonyloxy and decyloxy.

As the acyl group, for example, acetyl,
Total carbon number of propionyl, benzoyl, toluyl etc. is 1
~ 10 acyl groups.

More specific compounds include, for example, chlorobenzene, dichlorobenzene, trichlorobenzene,
Tetrachlorobenzene, pentachlorobenzene, hexachlorobenzene, chlorofluorobenzene, chlorodifluorobenzene, dichlorofluorobenzene, chlorobenzotrifluoride, chlorotoluene, dichlorotoluene, ethylchlorobenzene, chloroxylene, dichloroxylene, chloroanisole, dichloroanisole ,
Examples thereof include chlorodiphenyl ether, chlorodimethoxybenzene, chloro-1,2-methylenedioxybenzene, chloroacetophenone, chlorobenzophenone, chloronaphthalene and chloroanthraquinone.

In the present invention, alkali metal carbonates are used as bases in the production of aromatic carboxylic acids by reacting the above-mentioned aromatic chlorine compounds with carbon monoxide and water using a palladium-phosphine catalyst. And tertiary amines and / or quaternary ammonium salts are allowed to coexist with each other. Examples of the alkali metal carbonates include carbonates such as sodium and potassium, and hydrogen carbonates. The alkali metal carbonate is generally used in an amount of 0.1 to 1 mol times, preferably 0.3 to 0.5 mol times, of the aromatic chlorine compound. Usually, it is used as an aqueous solution of about 20 to 40%.

The tertiary amines include, for example, trialkylamines having 1 to 6 carbon atoms such as trimethylamine, triethylamine and tripropylamine, N, N'-dimethylpiperazine, N, N'-diethylpiperazine and 4-dimethyl. Aminopyridine, 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), N-methylpyrrolidine, N-methylmorpholine,
Heterocyclic amines such as triethylenediamine, N-methylimidazole, N-ethylimidazole and the like can be mentioned.

Examples of the quaternary ammonium salts include tetraethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, benzyltrimethylammonium chloride and phenyltrimethylammonium chloride.

The tertiary amines and quaternary ammonium salts are
Normally 0.001 to 0.1 mole times the aromatic chlorine compound,
It is preferably used at 0.01 to 0.05 molar times.

The palladium-phosphine catalyst used in the present invention comprises a palladium compound and phosphines. Examples of the palladium compound include palladium chloride, palladium acetate (Pd (AcO) ₂ ), and palladium acetyl. Acetonate (Pd (acac) ₂ ) and the like can be mentioned. The amount used is usually 0 with respect to the aromatic chlorine compound.
It is used in an amount of 00001 to 0.1 times, preferably 0.0001 to 0.005 times.

The phosphines include, for example, phosphines having a cyclohexyl group such as tricyclohexylphosphine (Cy ₃ P), dicyclohexylphosphinoethane and didylohexylphosphinopropane. The amount of phosphine used is usually based on the aromatic chlorine compound.
It is used in an amount of 0.00001 to 0.2 times, preferably 0.0001 to 0.01 times.

In the present invention, it can be carried out either without solvent or under solvent. As the solvent, any solvent which does not inhibit the reaction may be used, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane, heptane and cyclohexane, ethers such as diethyl ether, dioxane and tetrahydrofuran. And the like. When a solvent is used, the amount thereof is usually about 1 to 5 times the weight of the aromatic chlorine compound.

Water is usually 0.
It is used in an amount of 2-10 mol times, preferably 3-5 mol times. The corresponding aromatic carboxylic acid esters and aromatic carboxylic acid amides can also be produced by allowing alcohols or primary amines and secondary amines to be present instead of or together with water. Here, as the alcohols, for example, methanol, ethanol, propanol, butanol, octanol, decanol and the like aliphatic alcohols having 1 to 10 carbon atoms, phenol, cresol,
Examples include xylenol, methoxyphenol, benzyl alcohol and the like. When using alcohols,
It is usually used in an equimolar amount or more with respect to the aromatic chlorine compound.

Examples of primary amines and secondary amines include methylamine, ethylamine, propylamine, butylamine, octylamine, decylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dioctylamine and didecylamine. Examples thereof include aliphatic amines having an alkyl group having 1 to 10 carbon atoms, aromatic amines such as benzylamine, aniline, lower alkylaniline and lower alkoxyaniline, and cyclic amines such as pyrrole, imidazole, aminopyridine and aminoimidazole. When such an amine is used, it is usually used in an equimolar amount or more with respect to the aromatic chlorine compound.

Carbon monoxide is usually used in an amount of 0.2 mol times or more, preferably 0.4 to 10 mol times, relative to the aromatic chlorine compound. The reaction temperature is generally 100 to 230 ° C, preferably 130 to 200 ° C. Reaction pressure is usually 1 kg / cm ² · G
The above is preferably 3 to 10 kg / cm ² · G.

[0021]

As described above, aromatic carboxylic acids can be obtained from aromatic chlorine compounds. According to the present invention, palladium-phosphine catalysts are used as alkali metal carbonates and tertiary amines and / or quaternary ammonium salts. By coexisting with, the catalytic activity can be remarkably improved, and the aromatic carboxylic acids can be efficiently produced.

[0022]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 3.38 g of chlorobenzene and PdCl were placed in a 100 ml autoclave.
₂ (Cy ₃ ) ₂ 7.1 mg (0.03 mol%), triethylamine 0.13 g, 40
% ^3. Aqueous potassium carbonate solution (3.75 g) was added, the system was replaced with carbon monoxide, and the pressure was increased to 5 kg / cm ² · G. Then, the temperature was raised to 180 ° C. with stirring, and stirring was continued at the same temperature for 2.5 hours. After the reaction, cool to room temperature, then water 20g and ether 20g
Was added to separate the aqueous layer, and ether (20 g, 10%) was added to the aqueous layer.
Hydrochloric acid was added until the pH reached 2 for extraction, the ether layer was dried over magnesium sulfate, and the low-boiling fraction was distilled off.
1.01 g of benzoic acid was obtained. TON (turnover number) is 860
Met.

Examples 2-5, Comparative Examples 1-5 3.38 g of chlorobenzene and PdCl were added to a 100 ml autoclave.
₂ (Cy ₃ ) ₂ 6.9 mg, an aqueous solution of inorganic bases shown in Table 1, tertiary amines, quaternary ammonium salts, etc. were added, and after the system was replaced with carbon monoxide, the pressure was adjusted to 5 kg / cm ² · G. Pressurized. Then, the temperature was raised to 180 ° C. with stirring, and stirring was continued at the same temperature for 2.5 hours. After the reaction was cooled to room temperature, ether 20g,
10% aqueous hydrochloric acid was added until the pH reached 2, and the mixture was extracted, and the ether layer was analyzed by gas chromatography. The results are shown in Table 1.

Table 1 Examples Inorganic bases Amines, ammonium salts TON Carboxylic acid selectivity Example 2 40% K ₂ CO ₃ 0.36 mol times ^{* 1} Et ₃ N 4.4 mol% ^{* 1} 1000 97% Example 3 40% K ₂ CO ₃ 0.36 Et ₄ NCl 1 967 98 Example 4 28% Na ₂ CO ₃ 0.36 Et ₃ N 4.4 658 96 Example 5 25% KHCO ₃ 0.5 Et ₄ NCl 1 802 99 Comparative Example 1 40% K ₂ CO ₃ 0.36 − − 446 99 Comparative Example 2 25% KHCO ₃ 0.5 − − 276 89 Comparative Example 3 − − Et ₃ N 4.4 0 0 Comparative Example 4 20% KOH 0.36 Et ₃ N 4.4 370 58 Comparative Example 5 20% KOH 0.36 − − 283 53 * 1: To chlorobenzene

Examples 6 to 10 In Example 2, instead of triethylamine, triethylenediamine (TED 4.4 mol%), N, N'-dimethylpiperazine (DMP 4.4 mol%), 1,8-diazabicyclo [5,4] , 0] -7-Undecene (DBU 4.4 mol%), 4-dimethylaminopyridine
(DAP 4.4 mol%) and benzyltrimethylammonium chloride (BAC 1 mol%) were used in the same manner as in Example 2. The results are shown in Table 2.

Table 2 Examples Amine, ammonium salts TON Carboxylic acid selectivity Example 6 TED 957 95% Example 7 DMP 971 95 Example 8 DBU 999 92 Example 9 DAP 865 97 Example 10 BAC 699 94

[0028] In Examples 11-13 Example 2, PdCl ₂ (Cy _{3) 2} of PdCl instead ₂ (dicyclohexylphosphino _{ethane) (PdCl 2 (DCPE))} , Pd (aca
c) ₂ (Cy ₃ ) ₂ and Pd (AcO) ₂ (Cy ₃ ) ₂ were used at 0.03 mol%, respectively,
It carried out based on Example 2 except having used the amount of potassium carbonate shown in Table 3. The results are shown in Table 3.

[0029] Table 3 Example catalysts K ₂ CO ₃ TON Karubonsan selectivity Example 11 PdCl ₂ (DCPE) 1 mole times ^{* 1} 576 91% Example _{12 Pd (acac) 2 (Cy} 3) 2 0.5 957 81 embodiment Example 13 Pd (AcO) ₂ (Cy ₃ ) ₂ 0.5 348 92 * 1: to chlorobenzene

Examples 14 to 20 In Example 2, instead of chlorobenzene, o-chlorotoluene, 2,4-dichlorotoluene, m-chlorofluorobenzene, m-chloroanisole, m-dichlorobenzene, 1,
The same procedure as in Example 2 was carried out except that 30 mmol of 2,4-trichlorobenzene and 1-chloronaphthalene were used, to obtain a monocarboxylic acid corresponding to each. The results are shown in Table 4. When 1,2,4-trichlorobenzene was used, the total value of the three types of monocarboxylic acid isomers was shown. Also
When m-chlorofluorobenzene was used, tetraethylammonium chloride (1 mol%) was used instead of triethylamine.

Table 4 Examples Aromatic chlorine compounds TON Carboxylic acid selectivity Example 14 o-chlorobenzene 146 96% Example 15 2,4-dichlorotoluene 408 86 Example 16 m-chlorofluorobenzene 781 91 Example 27 m- Chloroanisole 436 90 Example 28 m-Dichlorobenzene 722 94 Example 29 1,2,4-Trichlorobenzene 336 70 Example 20 1-Chloronaphthalene 826 88

Example 21 The procedure of Example 2 was repeated, except that 3.75 g of 40% aqueous potassium carbonate solution was replaced by 3.75 g of 40% aqueous potassium carbonate solution and 1.8 g of isopropanol. The results were as follows. Product TON selectivity Benzoic acid 217 38% Isopropyl benzoate 230 41

Example 22 In Example 2, 0.05 g of tetraethylammonium chloride was used instead of triethylamine, and 3.75 g of 40% aqueous potassium carbonate solution and 3.88 g of di-n-butylamine were used instead of 3.75 g of 40% aqueous potassium carbonate solution. It carried out based on Example 2 except using it. The results were as follows. Product TON selectivity Benzoic acid 251 61% N, N-di-n-butylbenzamide 108 26

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[Procedure amendment]

[Submission date] December 18, 1995

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[0016] As phosphines, for example, tricyclohexylphosphine (PCy _3), dicyclohexyl phosphino ethane, phosphines containing a cyclohexyl group such as di-Sik b hexyl phosphino propane. The amount of phosphine used is usually 0.00001 to 0.2 mol times, preferably 0.0001 to 0.01 mol times, relative to the aromatic chlorine compound.

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Examples of primary amines and secondary amines include methylamine, ethylamine, propylamine, butylamine, octylamine, decylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dioctylamine and didecylamine. aliphatic amines having an alkyl group having 1 to 10 carbon atoms, benzylamine, aniline, lower alkyl aniline, aromatic amines such as lower Arukokishianiri down, pyrrole, imidazole, aminopyridine, and the like cyclic amines and amino imidazole . When such an amine is used, it is usually used in an equimolar amount or more with respect to the aromatic chlorine compound.

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Example 1 3.38 g of chlorobenzene and PdCl were placed in a 100 ml autoclave.
₂ ( P Cy ₃ ) ₂ 7.1 mg (0.03 mol%), triethylamine 0.13 g, 4
After adding 3.75 g of 0% potassium carbonate aqueous solution and replacing the inside of the system with carbon monoxide, the pressure was increased to 5 kg / cm ² · G. Then, the temperature was raised to 180 ° C. with stirring, and stirring was continued at the same temperature for 2.5 hours. After the reaction, cool to room temperature, then water 20g and ether 20g
Was added to separate the aqueous layer, and ether 20 g, 10% was added to the aqueous layer.
Hydrochloric acid was added until the pH reached 2 for extraction, the ether layer was dried over magnesium sulfate, and the low-boiling fraction was distilled off.
1.01 g of benzoic acid was obtained. TON (number of turnovers ^{* 2} ) is 86
It was 0. * 2. Turnover number: Aromatic carboxylic acid per catalyst
Amount of production (mol / mol)

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Examples 2-5, Comparative Examples 1-5 3.38 g of chlorobenzene and PdCl were added to a 100 ml autoclave.
₂ ( P Cy ₃ ) ₂ 6.9 mg, an aqueous solution of inorganic bases shown in Table 1, 3
Primary amines, quaternary ammonium salts, etc. were added, the system was replaced with carbon monoxide, and the pressure was increased to 5 kg / cm ² · G. Then, the temperature was raised to 180 ° C. with stirring, and stirring was continued at the same temperature for 2.5 hours. After the reaction was cooled to room temperature, ether 20g,
10% aqueous hydrochloric acid was added until the pH reached 2, and the mixture was extracted, and the ether layer was analyzed by gas chromatography. The results are shown in Table 1.

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Table 1 _{* 3} Examples Inorganic bases Amines, ammonium salts TON Carboxylic acid selectivity Example 2 40% K ₂ CO ₃ 0.36 mol times ^{* 1} Et ₃ N 4.4 mol% ^{* 1} 1000 97% Example 3 40% K ₂ CO ₃ 0.36 Et ₄ NCl 1 967 98 Example 4 28% Na ₂ CO ₃ 0.36 Et ₃ N 4.4 658 96 Example 5 25% KHCO ₃ 0.5 Et ₄ NCl 1 802 99 Comparative Example 1 40% K ₂ CO ₃ 0.36 − − 446 99 Comparative Example 2 25% KHCO ₃ 0.5 − − 276 89 Comparative Example 3 − − Et ₃ N 4.4 0 0 Comparative Example 4 20% KOH 0.36 Et ₃ N 4.4 370 58 Comparative Example 5 20% KOH 0.36 − − 283 53 * 1: To chlorobenzene * 3. Carboxylic acid selectivity: Amount of aromatic carboxylic acids produced relative to the total amount of reaction products (mol%)

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[0028] In Examples 11-13 Example 2, PdCl ₂ (P Cy _{3) 2} of PdCl instead ₂ (dicyclohexylphosphino _{ethane) (PdCl 2 (DCPE))} , Pd (a
cac) ₂ ( P Cy ₃ ) ₂ and Pd (AcO) ₂ ( P Cy ₃ ) ₂ 0.03 mol%
It was carried out in accordance with Example 2 except that potassium carbonate was used in the amounts shown in Table 3. The results are shown in Table 3.

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[0029] Table 3 Example catalysts K ₂ CO ₃ TON Karubonsan selectivity Example 11 PdCl ₂ (DCPE) 1 mole times ^{* 1} 576 91% Example _{12 Pd (acac) 2 (P} Cy 3) 2 0.5 957 81 Example 13 Pd (AcO) ₂ ( P Cy ₃ ) ₂ 0.5 348 92 * 1: to chlorobenzene

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Table 4 Examples Aromatic chlorine compounds TON Carboxylic acid selectivity Example 14 o- chlorotoluene 146 96% Example 15 2,4-dichlorotoluene 408 86 Example 16 m-chlorofluorobenzene 781 91 Example 27 m - chloroanisole 436 90 example 28 m-dichlorobenzene 722 94 example 29 1,2,4-trichloro b benzene 336 70 example 20 1-chloronaphthalene 826 88

Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 51/10 9450-4H 63/04 9450-4H 63/36 9450-4H 67/08 67/36 69/78 9546-4H 231/02 233/65 9547-4H // C07B 61/00 300

Claims (3)

[Claims] 1. An aromatic chlorine compound is reacted with carbon monoxide and water in the presence of a palladium-phosphine-based catalyst, an alkali metal carbonate, a tertiary amine and / or a quaternary ammonium salt. Process for producing aromatic carboxylic acids. 2. A method of reacting an aromatic chlorine compound with carbon monoxide, water and alcohols in the presence of a palladium-phosphine catalyst, an alkali metal carbonate, a tertiary amine and / or a quaternary ammonium salt. A method for producing an aromatic carboxylic acid ester, which is characterized. 3. In the presence of a palladium-phosphine-based catalyst, an alkali metal carbonate, a tertiary amine and / or a quaternary ammonium salt, an aromatic chlorine compound contains carbon monoxide, water, ununia and primary amines. A method for producing aromatic carboxylic acid amides, which comprises reacting at least one amine selected from secondary amines.