JPS62190145A - Production of hydroxyaromatic carboxylic acid - Google Patents

Abstract

PURPOSE:The reaction of a specific halogenated aromatic hydroxy compound with carbon monoxide is effected in a solvent containing a specific amount of water in the presence of a basic substance and a specific catalyst to give the titled compound which is used as a starting substance for polyester through one step reaction in high yield. CONSTITUTION:A halogenated, preferably brominated or iodinated aromatic hydroxy compound where the compounds bearing halogen and hydroxyl on the adjacent position are excluded is allowed to react with carbon monoxide in water or a solvent containing water in which the amount of water is more than the equivalent amount to the halogen in the aromatic hydroxy compound, in the presence of a base such as n-tributylamine in the presence of a catalyst containing transition metal compounds such as a palladium chloride and triphenyl phosphine complex, at a carbon monoxide partial pressure of 1-200kg/cm<2> and temperature of 50-300 deg.C to give the objective compound. USE:A starting material for preservatives, fungicides, agrochemicals, synthetic fibers, plasticizers or heat-resistant and chemical-resistant fibers and resins.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel method for producing hyP-roxy aromatic carboxylic acid. For example, p-oxybenzoic acid is used in the fields of preservatives, antifungal agents, agricultural chemicals, synthetic fibers, and plasticizers. In recent years, hydroxy aromatic carboxylic acids including p-oxybenzoic acid have attracted attention as fiber and resin raw materials with excellent heat resistance and chemical resistance. In particular, in wholly aromatic polyesters, asymmetric hydroxycardinic acid is a substance that determines the physical properties of the polymer.

(Prior art) Conventionally proposed methods include the Kolbe reaction method in which an alkali metal salt of a hydroxyaromatic compound is reacted with carbon dioxide, and the method in which a halogenated hydroxyaromatic compound is reacted with cyanide to form a nitrile. Various methods have been proposed, including a conventional method of hydrolysis, a method of oxidizing the alkyl group of an alkyl-substituted aromatic hydroxy compound, and a method of hydrolyzing a trichloromethyl-substituted aromatic hydroxy compound. However, these methods have problems such as poor yields, use of toxic or expensive reagents, and long reaction steps, and there is a desire to develop industrially advantageous production methods.

(Means and effects for solving the problem) As a result of intensive research from the above viewpoint, the present inventors have developed a halogenated aromatic hydroxy compound that can be easily synthesized from an aromatic hydroxy compound, a basic substance, a transition In the presence of a catalyst system containing a metal compound, when water is used alone or as a solvent system containing water in an amount equivalent to or more than the halogen of the halogenated aromatic hydroxy compound, and is reacted with carbon monoxide, the halogen group and In the case of aromatic compounds in which the hydroxy groups are in ortho positions directly adjacent to each other, the desired compound could not be obtained, but in the case of aromatic compounds in which the hydroxy groups are in ortho positions that are directly adjacent to each other, the target compound was not obtained. In the case of aromatic compounds, −
We have finally discovered that the target compound can be obtained in high yield. The present invention is based on the above findings, and is based on a catalyst system containing an 'sL'' halogenated aromatic hydroxy compound (excluding those in which the halogen group and the hydroxyl group are in the ortho position), a basic substance, and a transition metal compound. in the presence of water alone or a solvent system containing water, using water in an amount or more equivalent to the amount of the halogenated aromatic hydroxy compound,
This is a method for producing hydroxyaromatic carginic acid, which is characterized by reacting it with carbon monoxide.

As the halogen of the halogenated aromatic hydroxy compound used in the present invention, chlorine, bromine, and iodine are used, but in terms of ease of carbinylation reaction, iodine is the easiest, followed by bromine and chlorine in order of difficulty. Bromine and iodine are preferably used because the reaction conditions are mild. Further, even if a plurality of halogens are present in the aromatic ring, it does not particularly matter as long as they are not directly adjacent to a hydroxy group.

Examples of the halogenated aromatic hydroxy compound used in the present invention include various compounds such as halogenated phenol, halogenated hydroxydiphenyl, halogenated hydroxydiphenyl ether, halogenated hydroxynaphthalene, halogenated hydroxyanthracene, and halogenated hydroxyterphenyl. and so on. More specifically, for example, p-halogenated phenol, m-halogenated phenol, 4-hydroxy-4'-halogenated diphenyl, 4-hydroxy-2'-halogenated diphenyl, 4-hydroxy-3'-halogen Chemical formula 1 phenyl, 2
-hydroxy-5-halogenated diphenyl, 2-hydroxy-4'-halogenated phenol, 1-hyProxy 4-halogenated naphthalene, 2-hyProxy 6-halogenated naphthalene, 4-hydroxy-4'-halogen halogenated diphenyl ether, 4-hydroxy-3'-halogenated diphenyl ether, 2-hydroxy-5-halogenated diphenyl ether, 2-hydroxy-47-halogenated, cuphenyl ether, 4-hydroxy-21,4
1,) halogenated diphenyl, 4-hydroxy-21,
Examples include 41-dihalogenodiphenyl ether. These compounds can be easily synthesized by conventional methods. For example, p-iodophenol can be easily obtained by reacting with iodine in alkaline conditions, and 1-hyproxy-4-iodonaphthalene can be easily obtained by reacting α-naphthol with iodine.

The basic substance used in the present invention may be any type of basic substance, including organic bases and inorganic bases, as long as it reacts with and neutralizes hydrogen chloride.

Examples include aliphatic amine pyridine, aromatic amine, quaternary ammonium hydroxide, alkali metal hydroxide, and the like. Preferably, carbonates such as aliphatic amines, quaternary ammonium hydroxide, alkali metal hydroxides, sodium carbonate, and sodium bicarbonate can be used.

The amount of organic amines such as aliphatic amines, pyridines, aromatic amines, etc. to be used should be at least equivalent to the rogen of the rogenated aromatic hydroxy compound to be reacted, and the amount used should be large. It may also be used as a solvent. On the other hand, when using a strong base such as an alkali metal hydroxide or quaternary ammonium hydroxide, the reaction
- From the viewpoint of yield, it is preferable to use about 1 ft1 for the rogen of the rogenated aromatic hydroxy compound. When the amount exceeds the equivalent amount, a carboxylic acid and a salt are formed.

The transition metal used in the present invention is generally Cal7+
? A substance active in the nylation reaction is used, and ■.

Group (2) transition metals include, for example, ξ radium, platinum, nickel, cobalt, iron, and manganese, but palladium, nickel, cobalt, and iron are preferably used from the viewpoint of yield. Particularly preferred are palladium and nickel. These transition metals themselves can be used in the form of halides, sulfates, sheaths, or organic acid salts. Further, complexes of these with carbon monoxide, organic phosphines such as triphenylphosphine, and organic phosphites can also be used. Of course, more than the amount necessary for the formation of the 11-complex such as organic phosphines and organic phosphites may be used. The transition metal compound used frL may be 0.01 to 10 mol% of the halogenated aromatic hydroxy compound to be reacted.

The carzenylation reaction of the present invention can be carried out in an autoclave under pressure of carbon monoxide, and the pressure is from 1 to 200 dirt/l'ffl'', preferably from 2 to 100 dirt/l'ffl''.

At normal pressure, the reaction rate is extremely slow and the yield is low; if the pressure is too high, side reactions increase. The reaction temperature is 50-30
The temperature range is preferably 0°C, particularly 100 to 250°C. When the temperature is low, the reaction rate is slow, and when the temperature is high, there are many side reactions.

Water is used in the present invention either alone or as a solvent system containing water. As the solvent, a solvent that dissolves the halogenated aromatic hydroxy compound as a raw material or a solvent that is soluble in both water can be used. For example, aliphatic alcohols such as methanol, ethanol, pronominol, and butanol, aromatic alcohols such as hensyl alcohol, phenol, and alkyl-substituted phenols, hydrocarbons such as benzene, toluene, and xylene, and dimethylformamide! , dimethyl sulfoxide, sulfolane, dioxane, tetrahydrofuran, and other polar solvents. Furthermore, organic amines added to the reaction system as a scavenger for hydrogen halide may be used as a solvent.

When water is used alone, it is necessary to use at least an equivalent amount to the halogen of the halogenated aromatic hydroxy compound. Of course, there are many problems with using large amounts as a solvent.

When used as a solvent system containing water, it is necessary to use the same amount as in the case of water alone, and by mixing it with other solvent systems, effects such as making the reaction system uniform can be expected.

(Example) Next, the present invention will be explained in more detail with reference to Examples.

Example 1 p-iodophenol 6.05 f (0,0275 mol), n-)butylamine 10.2 f (0,0
55 mol), para-quam chloride o, 2y (0,001
mole), triphenylphosphine 0.8 t (0,0
03 moles), water (1,67 moles), and ethanol 30 moles (0.66 moles) were placed in an autoclave with a magnetic stirrer, and then carbon monoxide was added at 30 H/wt2 (
It was prepared in a). Next, the temperature was raised to 140°C and a reaction was carried out for 1 hour. During the reaction, the pressure of carbon monoxide was reduced to 30 Ay/cIn.
” I kept it at (G).

After the reaction, unreacted carbon monoxide was purged, and the reaction solution was taken out and quantitatively analyzed by liquid chromatography. As a result, p-hydroxybenzoic acid was produced in a yield of 60%. Raw material p-iodophenol was not detected.

Example 2 p-iodophenol 21.9 t (o, 1 mol),
n-tributylamine 22.2 t (0.12 mol)
, palladium chloride 0.029 (0.1 mmol), triphenylphosphine 0.12 (0.5 mmol), water soy (2.78 mol), phenol 11.3 F
(0.12 mol) was charged into an autoclave equipped with a magnetic stirrer, and then 40 kg of carbon monoxide (G) was charged. Next, the temperature was raised to 150°C and the reaction was allowed to proceed for 1 hour. During the reaction, the pressure of carbon monoxide was maintained at 407 (St/σ2 (G)). The same post-treatment as in Example 1 was carried out and the amount was determined. p-hydroxybenzoic acid was produced at a yield of 55%. .The raw material p-iodophenol was not detected.

Example 3 p-bromophenol 17.39 (0.1 mol), n
-Triphthylamine 27.82 (O, IS mol), nickel chloride 0.13 t (o, oot mol), triphenylphosphine 0.792 (0,003 mol), water so
y (2.78 mol) was charged into an autoclave equipped with an 'If IAa stirrer, and then carbon monoxide was added to s o Al
f/cm" (0). Next, the temperature was raised to 200°C and the reaction was carried out for 3 hours. During the reaction, the pressure of carbon monoxide was increased to 50 #
/cm2. After the reaction, the same post-treatment as in Example 1 was carried out, and the amount was determined by gas chromatography. The yield of p-hydroxybenzoic acid was 40%. The conversion rate of p-bromophenol as a raw material was 97%.

Example 4 The reaction, post-treatment and quantitative determination were carried out in the same manner as in Example 2, except that 4-hydroxy 4'-iodophenyl ether was used instead of p-iodophenol. 4'-
Hydroxy-4-diphenylnifcal, l? phenolic acid phenol ester was obtained with a yield of 57%.

Example 5 4-hydroxy-47-bromodiphenyl 24.9 F
(0.1 mol), n-)butylamine 22.2y
(0.12 mol), palladium acetate 0.046 f (
0.2 mmol), triphenylphosphine 1. Ot
(1.0 mmol), 50 g (2.78 mol) of water, and 50 g (1.11 mol) of ethanol were placed in an autoclave equipped with a magnetic stirrer, and then the carbon monoxide pressure was adjusted to
A? , /ffi" (a). Next, the temperature was raised to 180°C and the reaction was carried out for 3 hours. During the reaction, carbon monoxide was removed from SO
It was maintained at seashore/cm2 (G). After the reaction was completed, it was post-treated in the same manner as in Example 1, and analyzed using gas chromatography. 4'-Hyproxy4--. ) Phenylcarboxylic acid was obtained with a yield of 37%. Raw material 4-hydroxy-4'
-The conversion rate of bromodiphenyl was 94%.

Example 6 2-phenyl-4-iodophenol 29.69 (0,
1 mo →, n −) butylamine 20.2 t (0,
2 mol), nickel acetate 0.35 t (0,002 mol), triphenylphosphine 1.57 t (0,0
0.06 mol), 50 f (2.78 mol) of water, and 20 t (0.43 mol) of ethanol at a temperature of 150°C.
, 3 hours, carbon monoxide pressure 40 kf/cm” (G)
The experiment was carried out using the same apparatus and method as in Example 1. the result,
3-phenyl-4-hydroxybenzoic acid was obtained in a yield of 45%. The conversion rate of the raw material 2-phenyl-4-iodophenol was 100%.

Example 7 Instead of using p-iodophenol, 1-hydroxy-
The reaction, post-treatment, and quantitative determination were carried out in the same manner as in Example 1 except that 4-iodonaphthalene was used. the result,
]-Hydroxy-4-naphthalenecarboxylic acid was obtained with a yield of 50%.

Example 8 4-hydroxy-2' instead of p-bromophenol,
The reaction, post-treatment and quantitative determination were carried out in exactly the same manner as in Example 3, except that 4'-short siphenyl ether was used and conomol acetate (If) was used instead of nickel chloride. 4-Hydroxy-27,4/-diphenyl ether dicarboxylic acid was obtained with a yield of 27%.

Example 9 The reaction, post-treatment and quantitative determination were carried out in exactly the same manner as in Example 3, except that p-iodophenol was used in place of p-bromophenol and iron chloride was used in place of nickel chloride. p-Hydroxybenzoic acid was obtained with a yield of 33%.

Example 10 p-Yo)”7-1-/-#21.9F (0.1 mol)
, n-tributylamine 22.2 t (0.12 mol), noradium chloride 0.029 (0.1 mol), and phenol 11.39 t (0.12 mol) were placed in an autoclave equipped with a magnetic stirrer, and then carbon monoxide was added. pressure of 4
The weight was maintained at 0 kg7cm'' (G).The same post-treatment as in Example 1 was carried out and quantification was carried out.

p-hydroxybenzoic acid was produced with a yield of 42%.

Claims (3)

[Claims] (1) Halogenated aromatic hydroxy compounds (excluding those in which the halogen group and hydroxy group are in the ortho position)
In the presence of a catalyst system containing a basic substance and a transition metal compound, water alone or as a solvent system containing water is used in an amount equivalent to or more than the halogen of the halogenated aromatic hydroxy compound, and carbon monoxide and A method for producing aroxyaromatic carboxylic acid, which is characterized by a reaction. (2) The method according to claim 1, wherein the halogenated aromatic hydroxy compound is a brominated aromatic hydroxy compound or an iodinated aromatic hydroxy compound. (3) The transition compound is palladium, nickel, cobalt,
The method according to claim 1, which is an iron compound.