JPH04117344A - Production of aromatic carboxylic acid chloride - Google Patents

Abstract

PURPOSE:To produce an aromatic carboxylic acid chloride on an industrial scale at a low cost using a catalyst easily handleable and separable from the product by reacting an aromatic carboxylic acid with trichloromethylbenzenes in the presence of a solid acid catalyst in liquid phase. CONSTITUTION:The objective aromatic carboxylic acid chloride is produced on an industrial scale at a low cost by reacting an aromatic carboxylic acid with trichloromethylbenzenes in liquid phase in the presence of a solid acid catalyst such as crystalline aluminosilicate, amorphous silica.alumina, silica.zirconia, alumina, strongly acidic ion exchange resin, activated clay, montmorillonite, zirconium phosphate and metal oxide supporting oxyacid radical. The process has various merits such as remarkable reduction of the load of waste water disposal in addition to the above-mentioned effects.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing an aromatic carboxylic acid chloride. Specifically, the present invention relates to a method for producing aromatic carboxylic acid chlorides from aromatic carboxylic acids and trichloromethylbenzenes, which is characterized by reacting them under liquid phase conditions using a solid acid catalyst.

(Prior art) Conventional methods for producing aromatic carboxylic acid chlorides include methods using carboxylic acid and chlorinating agents such as thionyl chloride and phosphorous pentachloride, and methods using carboxylic acid and hesitrichloride. A method is known in which the reaction is carried out in contact with a trichloromethyl compound such as. For example, JP-A-53
-53636, Special Publication No. 53-121733, etc.
JP-A-63-14753 describes a method for producing aromatic dicarboxylic acid chloride by reacting bis(trichloromethyl)benzene and aromatic dicarboxylic acid in the presence of a Friedel-Craft catalyst such as iron chloride. A method is described in which a methyl-substituted phenyl ether and an aromatic dicarboxylic acid are reacted in the presence of a Friedel-Kraf catalyst.

(Problems to be Solved by the Invention) However, the method using an inorganic chlorinating agent contains sulfur and phosphorus compounds that are difficult to remove, and the conventional method using a Friedel-Krach type catalyst is a liquid-phase homogeneous system. Because of the reaction form, it is difficult to separate the reaction product and catalyst, and furthermore,
There are problems such as the catalyst cannot be reused and its disposal is difficult.

(Means for Solving the Problems) In order to solve the above-mentioned problems, the present inventors have conducted extensive studies on an industrially advantageous production method using a solid catalyst that is easy to separate from reactants, etc. As a result, aromatic carboxylic acid chlorides can be produced by reacting aromatic carboxylic acids and trichloromethylbenzenes under liquid phase conditions using a solid acid catalyst. We have discovered that aromatic carboxylic acid chloride can be produced in high yield by using silica/alumina and activated clay, and have completed the present invention.

That is, the present invention is a method for producing an aromatic carboxylic acid chloride, which is characterized by reacting an aromatic carboxylic acid and trichloromethylbenzenes under liquid phase conditions in the presence of a solid acid catalyst.

Aromatic carboxylic acids used in the present invention include mono-, di-, tri-, and tetracarboxylic acids of aromatic compounds such as benzene, naphthalene, and biphenyl, and aromatic carboxylic acids containing halogen groups, nitro groups, etc. as substituents. can be mentioned.

Specific examples include benzoic acid, terephthalic acid, isophthalic acid, naphthalene monocarboxylic acid, naphthalene dicarboxylic acid, naphthalene tetracarboxylic acid, biphenyl monocarboxylic acid, biphenyl 4.4'-dicarboxylate, 3.3°
Examples include biphenyl dicarboxylate, p-chlorobenzoic acid, P-fluorobenzoic acid, P-iodobenzoic acid, monochloronaphthalenecarboxylic acid, monochlorobiphenylcarboxylic acid, and the like.

Trichloromethylbenzenes used in the present invention may have substituents other than trichloromethylbenzene, bistrichloromethylbenzene, and trichloromethyl groups that do not inhibit the reaction, such as halogen, alkoxy, alkyl groups, and aryl groups. I can't help it. For example, Balafluorotrimethylbenzene, Parachlorotrimethylbenzene, Balaiodotrichloromethylbenzene, 4.4
Examples include °-trichloromethylbiphenyl, bis(4-trichloromethylphenyl)ether, and the like.

Examples of the solid acid catalyst used in the present invention include crystalline aluminosilicate, amorphous silica/alumina, silica/zirconia, alumina, strongly acidic ion exchange resin, activated clay, montmorillonite, zirconium phosphate, metal oxide supporting oxygen acid groups, etc. can be mentioned. Specifically, the effective pore diameter of the crystalline aluminosilicate is preferably 6 Å.
Among these, examples include X, Y, and L type zeolites, mordenite, zeolite beta, and ZSM-12. Particularly preferred are Y-type high silica, mordenite, and beta. A preferable silica/alumina ratio is about 4 to 100.

These crystalline aluminosilicates are usually used in the proton form, and include, for example, silver and copper from the lb group, zinc from the 2 group,
Cadmium etc., group 3 gallium, rare earths lanthanum, cerium etc., group 4 tin, zirconium etc., group 6 chromium, molybdenum etc., group 8 iron, cobalt, nickel etc. Exchanged with metal cations may also be used. I can do it.

Specific examples of metal oxides supporting oxygen acid groups of Group 6 elements include sulfuric acid, molybdic acid, molybdic acid,
Examples of metal oxides include zirconia, titania, silica, alumina, hafnium oxide, tin oxide, and iron oxide.

Strongly acidic ion exchange resins include those having -SO3M type exchange groups, such as Amberlite IR-200, IR-120,
Amberlyst 15, Dowex 50, MSC-1,
Diaion 5K-1PK-1HPK-, series, etc. can be mentioned. Among these ion exchange resins, those having a giant network structure called MR type are preferred from the viewpoint of stability.

The present invention can be carried out by a fixed bed method, a fluidized bed method, a suspension method, or the like, which usually uses a solid catalyst.

The reaction conditions of the present invention vary depending on the raw material type, but are usually 30
The temperature is ~300°C, preferably 50~200°C, and the molar ratio of aromatic carboxylic acids/trichloromethylbenzenes as raw materials is carboxyl group/trichloromethyl group = 0.9~1°1. Such a molar ratio is preferable. The reaction time varies depending on the amount of catalyst and reaction temperature, but is about 0°1 to 20 hours. The amount of catalyst used is
Usually 0.01 to 5 for trichloromethylbenzenes
Weight times, preferably 0.05 to 1 times weight is used.

When implementing the distribution method, the weight hourly space velocity (WH3
V) as 0. 01-20Hr-'preferably 0.1
~10 Hr-' is used.

The reaction uses orthodichlorobenzene as a solvent, 1.2.
4-) Halogenated benzenes such as dichlorobenzene, nitrobenzene, etc. may be used. In order to proceed with the reaction, it is preferable to pass an inert gas such as nitrogen through the reaction system to remove the generated hydrogen halide from the system. If water is present, hydrolysis by-products such as trichloromethyl groups will be produced, so the water content in the system should be 500 ppm or less.
Preferably, it is 1100 pp or less.

It is preferable that the catalyst be thoroughly dried using means such as heating before use, and used in a dehydrated state.

(Effects of the Invention) According to the method of the present invention, aromatic carboxylic acid chlorides can be produced from aromatic carboxylic acids and trichloromethylbenzenes using a solid catalyst that is easy to handle. The industrial advantages such as ease of separation and greatly reduced wastewater treatment are extremely large.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Note that the yields shown in Examples are expressed based on aromatic carboxylic acid.

Example 1 Commercially available ultra-stable Y-type zeolite (SiO□/Alto3=6.1°Na2O/
^1z03=0. 01) was used as a catalyst.

20.0 g of P-chlorotrichloromethylbenzene and 1.0 g of P-chlorobenzoic acid. Og was placed in a 50111 three-loaf flask equipped with a cooling tube and a stirrer, and while stirring, 1.8 g of the above-mentioned Y-type zeolite was added, and the mixture was heated to 85°C in an oil bath for reaction. Generation of hydrogen chloride gas was observed as the reaction progressed. After 3 hours of reaction, the reaction solution was sampled and analyzed by gas chromatography. As a result, the yield of p-chlorobenzoic acid chloride was 197n+olχ(p
-chlorobenzoic acid standard).

Example 2 Same as Example 1, except that commercially available mordenite (silica/alumina ratio 20) was used as a catalyst for ammonium exchange using an aqueous ammonium chloride solution, and then 4
A proton-type mordenite that was heat-treated at 50° C. was used. Reaction conditions were 110°C for 4 hours.

As a result, the yield of P-chlorobenzoic acid chloride was 180
It was molχ.

Example 3 Using the same apparatus as in Example 1 and using the same catalyst as in Example 1, 2.1 g of catalyst was added to 20 g of p-chlorotrichloromethylbenzene and 1.9 g of terephthalic acid, and the mixture was heated at 115°
The reaction was carried out for 4 hours at a reaction temperature of C. As a result, the yield of P-chlorobenzoic acid chloride was 175 mol.chi., and the yield of terephthalic acid dichloride was 88 smol.chi. Note that each yield is based on terephthalic acid.

Example 4 The reaction was carried out in the same manner as in Example 1, except that 152 g of a commercially available strong acidic ion exchange resin Amberlyst was used instead of Y-type zeolite as a catalyst, and the reaction was carried out at 85° C. for 2 hours. As a result, the yield of p-chlorobenzoic acid chloride was 198 mol.
It was χ.

Example 5 Same as Example 3, but using U.S. Pat.
500 g of a 10% aqueous solution of tetraethylammonium hydroxide according to the method described in No. 308,069.
1.9.9 g of sodium aluminate was mixed with stirring into a solution of 250 g of distilled water, and then 169 g of silica powder was mixed therein. This raw material mixture was charged into 11 Teflon-coated autoclaves and heated to 150°C.
Hydrothermal synthesis was carried out for 6 days under stirring at 20 Orpm to obtain beta zeolite. This product was treated with 1N nitric acid at room temperature for about 4 hours, filtered, washed with water, dried, and reacted with hydrogen-type zeolite (5iOz/A1.zo3=65). As a result, the yield of p-chlorobenzoyl chloride was 198 molχ, and the yield of terephthalic acid dichloride was 97 molχ.

Example 6 Same as Example 3, except that 25 d of ammonia water (26%) was added to 100 d of distilled water while stirring to a solution in which 50 g of zirconium oxychloride as a catalyst was dissolved in 150 g of distilled water.
Add the diluted solution and filter the white precipitate that forms.
It was washed with water and then dried at 110°C for 116 hours. To 10 g of zirconium hydroxide prepared in this way, concentrated sulfuric acid
．． It was impregnated with a solution obtained by diluting 65 g with 71 d of distilled water, and then, after drying, it was calcined at 600°C in an air atmosphere for 3 hours.

This sulfate group-supported zirconia was used. Catalyst 2g, p-
Using 20 g of chlorotrichloromethylbenzene and 2 g of terephthalic acid, the reaction was carried out while maintaining the temperature at 100 to 105'C for 5 hours. As a result, the yield of p-chlorobenzoic acid was 84 molχ, and the yield of terephthalic acid dichloride was 38 molχ (based on terephthalic acid). Ta.

Example 7 The same procedure as in Example 6 was carried out, except that H-type ZSM-5 (silica/alumina ratio 30), which was hydrothermally synthesized by a known method and subjected to proton exchange, was used as the catalyst.

The result is a yield of p-chlorobenzoic acid chloride of 4 a+m.
ol, yield of terephthalic acid dichloride l ++++a
It was OL.

Example 8 In the same manner as in Example 3, 20 g of p-chlorotrichloromethylbenzene and 2 g of p-chlorobenzoic acid were used, except that 2 g of commercially available activated clay calcined at 450°C and dried was used as a catalyst, and heated at 100°C. The reaction was allowed to proceed for 615 hours. the result,
The yield of p-chlorobenzoic acid chloride is 200 solχ
The yield of terephthalic acid dichloride reached 100 solχ. (Yield is based on terephthalic acid) Example 9

Claims (1)

[Claims] A method for producing an aromatic carboxylic acid chloride, which comprises reacting an aromatic carboxylic acid and trichloromethylbenzenes under liquid phase conditions in the presence of a solid acid catalyst.