JPS6399036A - Production of aromatic hydroxycarboxylic acid - Google Patents

Abstract

PURPOSE:To obtain the titled compound, by subjecting dibrominated or diiodated biphenyl or diphenyl ether to be readily synthesized from inexpensive biphenyl or diphenyl ether to monocarbonylation with CO and hydrolyzing. CONSTITUTION:A compound (e.g. 4,4'-diiododiphenyl ether, etc.) shown by formula I (X is B or I; n is 0 or 1) is reacted with carbon monoxide in the presence of a basic substance such as n-tributylamine to give a compound shown by formula II (R is H, alkyl or aromatic group), which is then hydrolyzed in the presence of a basic substance such as NaOH, KOH, etc., to give an aromatic hydroxycarboxylic acid [e.g. 4-(4-hydroxyphenoxy)benzoic acid, etc.] sown by formula III. The compound shown by formula I is obtained by oxidatively iodating biphenyl or diphenyl ether. The aromatic hydroxycarboxylic acid is a raw material for fibers and resins having excellent heat resistance and chemical resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel method for producing aromatic hydroxycarzenic acid. The object compound of the present invention c, for example c,
4 (4-hydroxyphenyl)benzoic acid and 4-(4
-Hydroxyphenoxy)benzoic acid is attracting attention as a raw material for fibers and resins with excellent heat resistance and chemical resistance. In particular, for wholly aromatic polyesters, asymmetric hydroxyfurzenic acid can be called a pot material of polymer physical properties.

Furthermore, 4-(4-hydroxyphenyl)benzoic acid is also useful as a basic raw material for biphenyl-based liquid crystal synthesis.

(Prior Art) Conventionally known industrial production methods include, for example, in the case of 4-(4-hydroxyphenyl)benzoic acid, [Gray, G.W.; Hartley, J.
B. 1 Jones.

B, J, Chem, Soc, 1955.1412J
There is a method. That is, 4-hydroxybiphenyl is 1.
4-methoxybiphenyl with methyl sulfate in 5N aqueous sodium hydroxide solution, 4-acetyl-4'-methoxybiphenyl in the presence of aluminum chloride and acetyl chloride in carbon disulfide solvent, and sodium hypopromite in dioxane solvent. 4-(4-methoxyphenyl)benzoic acid, and then 4-(4-hydroxyphenyl)benzoic acid in acetic acid in the presence of specific hydrogen. For other compounds, few industrially valuable production methods have been proposed. In any case, it is difficult to obtain the raw materials industrially, and the reaction process is also difficult, so it cannot be said that it is an industrially preferable method, and there is a desire to develop an industrially viable production method.

(Means and effects for solving the problem) The present inventors
As a result of intensive research from the above viewpoint, we have found that using dibrominated or diiodinated biphenyls or diphenyl ethers that can be easily synthesized from inexpensive biphenyl or diphenyl ethers, mono-ruzenylation with carbon oxide can be used to convert the two halogen groups of biphenyl or diphenyl ether into By converting one of them into a carboxylic acid or its ester, and then hydrolyzing and replacing the remaining halogen group with a hydroxyl group, aromatic hydroxyfurzenic acid can be easily obtained in high yield using only inexpensive raw materials. I found out that it is possible. The present invention is based on the above findings, by reacting a compound represented by iodine (n is 0 or 1) with carbon monoxide in the presence of a basic substance, where n = O or 1, R is hydrogen, an alkyl group, or an aromatic group. This method is characterized by producing an aromatic hydroxycarboxylic acid which is then hydrolyzed in the presence of a basic substance.

The brominated or iodinated biphenyls or diphenyl ethers used as raw materials in the present invention are, for example, 4,4'-sif-1'rom biphenyl, 4,4'-dibrom diphenyl ether, 4,4'-,)iothohyphenyl, .4
' --) iododiphenylethernato, which can be obtained by various methods.

Biphenyls or diphenyl ethers can be easily obtained by oxidative iodination of biphenyl or diphenyl ethers, i.e., by iodination in the presence of nitric acid, or by combining acid with hydrogen peroxide or There are methods such as iodination in the presence of oxygen. Further, it can be easily obtained by reacting hydrogenated biphenyl or diphenyl ether, biphenyl or hasiphenyl ether with bromine at low temperature. These methods make it possible to advantageously produce para-substituted halides.

The details of the carsenylation reaction of the present invention will be explained.

The carsenylation reaction for both iodides and bromides is generally carried out in the presence of a catalyst system containing a transition metal or its compound, and the reaction conditions for the carsenylation reaction of iodides are generally much milder. It is possible to Furthermore, in the case of brominated compounds, the reaction does not proceed unless a catalyst is used. On the other hand, in the case of iodides, the reaction proceeds satisfactorily even in the absence of a catalyst if the reaction conditions are selected. In that sense, it can be said that it is preferable to use an iodide as the raw material for extraction.

Transition metals used in catalytic reactions include:
Generally, those active in the carsenylation reaction are used, and v■
, Vm group transition metals such as palladium, platinum, nickel, cobalt, iron, manganese, etc., but from the viewpoint of yield, preferable metals are ξ radium, nickel, cobalt,
Iron is used for oysters. These transition metals are themselves or
These halides, sulfates, nitrates, organic acid salts, etc. can be used. In addition, these transition metal compounds are
- It can also be used as a complex of carbon oxide or a complex of phosphines such as triphenylphosphine.

The amount of the transition metal compound to be used may be 0.01 to 10 mol of the iodinated diphenyl 5I brominated diphenyl to be reacted.

The basic substance to be used can be either an organic base or an inorganic base, as long as it can capture hydrogen iodide etc. generated in the reaction, such as aliphatic amines, aromatic amines, quaternary hydroxides, etc. class ammonium, alcolades of alkali metals and alkaline earth metals, hydroxides of alkali metals and alkaline earth metals, alkali metal carbonates,
Examples include salts of aromatic or aliphatic carboxylic acids and alkali metals, metals, or alkaline earth metals. Preferably, alkali metal salts of aliphatic amines, quaternary ammonium hydroxides, alkali metal hydroxides, alkali metal carbonate products can be used. The amount used is not particularly limited, but preferably the base is in the range of 0.2 to 10 equivalents, more preferably 0.4 to 3 equivalents ρ, based on the aromatic halide.

If the carsenylation reaction is carried out in the presence of a reaction product, the corresponding cardanic acid will be produced, and if carried out in the presence of an alcohol, the corresponding carzenic acid ester will be produced.

When carried out in the presence of water, water is used alone or as a solvent system containing water.

As the solvent, a solvent that dissolves the raw material iodinated diphenyl or brominated diphenyl or a solvent that is soluble in both water can be used. For example, methanol, ethanol, aliphatic alcohols such as propatool, aromatic alcohols such as benzyl alcohol, phenol, 2,6-xylenol, hexane, octane, benzene,
Examples include hydrocarbons such as toluene, polar solvents such as dimethylformamide and dimethyl sulfoxide, and ethers of dioxa/=4. Furthermore, aliphatic amines and aromatic amines used as basic substances can also be used.

When using water alone in the reaction, it is necessary to use at least 1/2 equivalent or more based on iodinated diphenyl or brominated diphenyl. Of course, there is no problem in using a large amount as a solvent. When using a solvent system containing water, it is necessary to use the same method as when using water alone, and by mixing it with another solvent system, effects such as making the reaction system uniform can be expected.

If the reaction is carried out in the presence of alcohol, the alcohol used is of interest. Can be used depending on the ester. For example, aliphatic alcohols include methanol, ethanol, propatool, inobutanol, octatool, etc., and aromatic alcohols include phenol, benzyl alcohol, phenylphenol, phenoxyphenol, alkyl-substituted phenol, naphthol, etc. can be mentioned. Further, the alcohol does not necessarily have to be m alcohols.

The carbon monoxide used in the calzenylation reaction may be diluted carbon oxide, or may be diluted with other gases that do not adversely affect the reaction, such as nitrogen, aldine, helium, or lower hydrocarbons. -The partial pressure of carbon oxide is 0.1~
300 Kg/cm”, preferably 1-200 K9
/α2. If the pressure is too low, the reaction rate will be slow and the yield will be low. If the pressure is too high, side reactions will increase.

The reaction temperature at which the carginylation reaction is carried out is slightly different depending on whether a catalyst is used or not.

In a reaction system using a catalyst, the reaction temperature is 50 to 300°C.
The temperature range is preferably from 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.

In a reaction system that does not use a catalyst, the reaction is preferably carried out at a temperature of 150°C or higher. More preferably 180
It is carried out at a temperature of 400°C or higher.

At a temperature lower than 150°C, the reaction rate is too slow to be practical, and at a temperature higher than 400°C, side reactions increase and the yield of the desired aromatic carzenic acid decreases.

If the carzenylation reaction is allowed to run uncontrolled until completion, both of the two halogen substituents of the biphenyl or -)phenyl ether will be carsenylated. Therefore,
It is necessary to control the reaction midway. That is, in order to advantageously obtain a monocarnylated product, it is necessary to stop the reaction midway through, and it is preferable to suppress the conversion rate of the raw material halide to 90% or less. More preferably 7
The goal is to keep it below 1.

The product after the carsenylation reaction can be easily separated by recrystallization.

Next, the advantage K of reacting a diiodide in a non-catalytic system will be described. For example, when obtaining calzenic acid,
To illustrate the reaction in the case of aromatic monoiodite using an alkali metal salt of an aromatic carboxylic acid having the same skeleton as the aromatic carboxylic acid to be generated as a base, the following reaction formula (1) It is expressed as

ArI+CO+H20+ArCOOM −→2ArCOOH+MI (1) (wherein, Ar
represents an aromatic group, and M represents an alkali metal atom.

) In this case, the by-product is alkali metal iodide, which is easily soluble in water, but aromatic carboxylic acids are generally solid and not easily soluble in water, so the reaction product is The salt of hydrogen iodide and base is removed by washing with water. Of course, if an excessive amount of base is used, the aromatic carboxylic acid produced may also form a salt with the base, but in that case, by treating with an aqueous mineral acid solution, the aromatic carboxylic acid can be converted to the isomer. It is easy to separate.

For example, when obtaining a carboxylic acid aryl ester, the following reaction formula (2) is used to illustrate the reaction between an aromatic monoiodite and an alkali metal salt of an aromatic monohydroxy compound.

A　r　　　+CO+A　r’OM Represents an alkali metal atom. ) In this case as well, only the alkali metal iodide is used as an auxiliary material.

Since it does not contain any other catalyst components and the by-product is a simple salt of an inorganic substance, it is very easy to separate the desired aromatic carboxylic acid aryl ester.

The details of the hydrolysis reaction of the present invention will be explained.

The hydrolysis reaction is basically carried out in the presence of a copper-based catalyst in an aqueous solution containing a basic substance, particularly an alkali metal and/or alkaline earth metal hydroxide, at a temperature of 100 to 300°C. This is possible.

Hydrolysis catalysts include Cub, Cu2O, CuC1
, CuCl2゜CuBr, CuBr2, Cu (
CH3COO), Cu (CH3COO)2, C
ul.

CuF, CuF2 ・2H20, Cu(OR)2. Fe
d, Fe2O3, Fe (OH)! .

FeC12, Fe I2, Fe (CHICOO)
2, etc., and each can be used alone or in a mixture, for example, a mixture of CuO and Cu2O. The amount used is 0.1 to 100 mole based on the raw material.
Preferably it is 0.5 to 20 mol.

Other alkali metal or alkaline earth metal peroxides may also be used as catalysts.

Examples of the alkali metal or alkaline earth metal hydroxide used as the basic substance include NaOH and KOH.

Ca(OH)2, Mg(OH)z etc. are used, preferably NaOH and KOH to
It is used in an amount of 1.0 to 10.0 equivalents based on the rogen atom.

NaOH and KOH etc. dissolve well in water and can be used as an aqueous solution, but Ca(OH)2, Mg(OH)
2 and the like are dissolvable in water and can be used as a suspension. Of course, these can be used alone or as a mixture.

Of course, the solvent does not have to be used, but it is also possible to use it. The solvent used may be any solvent as long as it has an affinity for both water and the intermediate raw material, such as alcohols such as methanol and ethanol, dimethyl sulfoxide, and the like.

(Effects of the invention) As described above, according to the present invention, inexpensive raw materials are used,
In addition, aromatic hydroxycarboxylic acids can be produced with good yield through short reaction steps, providing an advantageous industrial production method.

(Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 4.4'-short diphenyl ether 6.33 g5 tributylamine 6.66 g, radium chloride 0.18
g5 triphenylphosphine o, 3c+g, water 12 g
, Tetrahydrofuran 55g/100g with stirring
After placing it in a stainless steel autoclave and replacing the inside of the autoclave with carbon monoxide, -carbon oxide 25Kq/
The reaction mixture was reacted at 125° C. for 12 minutes with stirring, and then rapidly cooled to stop the reaction.

After the reaction was completed, unreacted carbon monoxide was purged, and then the reaction solution was taken out. The reaction solution was taken out and analyzed by gas chromatography and liquid chromatography. As a result, the conversion rate of 4.4'-short diphenyl ether was 8
2, the selectivity for 4-(4-iodophenoxy)benzoic acid is 65ts, and the selectivity for 1.1'-,)iododiphenyl ether-4°4'-dicarzenic acid is 30ts.
It was Chi.

The reaction solution was filtered under reduced pressure to remove solid matter in the reaction solution, and then a portion of tetrahydrofuran was distilled off and concentrated to about 4 times, whereby 4,4'-short diphenyl ether as a raw material was precipitated. This was subjected to Pi, and when tetrahydrofuran was distilled off from the F solution until it was almost completely eliminated, crystals were precipitated. When 4 times the weight of 10-t sodium thihydroxide was added to this precipitate and thoroughly stirred, 4-(4-iodophenoxy)benzoic acid remained undissolved. This was filtered to isolate 4-(4-iodophenoxy)benzoic acid.

3.4 g of 4-(4-iodophenoxy)benzoic acid.

20g of 20% by weight aqueous sodium hydroxide solution, 20g of dimethyl sulfoxide, 0.05g of steel iodide for 1o.

- placed in a stainless steel autoclave at 150°C.
The mixture was stirred for 2 hours. After the reaction was completed, the reaction solution was analyzed by liquid chromatography, and the yield of 4-(4-hydroxyphenoxy)benzoic acid was 77%.

Example 2 The reaction was carried out in the same manner as in Example 1 except that the reaction time was changed from 12 minutes to 9 minutes. As a result, the conversion rate of 4,4'-short diphenyl ether was 63%, the selectivity of 4-(4-iodophenoxy)benzoic acid was 81%, and the conversion rate of 4,4'-short diphenyl ether was 81%. The selectivity for dicarzenic acid was 12.

4-(4-iodophenoxy)benzoic acid was isolated in the same manner as in Example 1.

3.4 g of 4-(4-iodophenoxy)benzoic acid.

Sodium hydroxide 1.5g, copper powder 0.1g, 1st chloride
Copper 0.05g, sodium peroxide 0.2K% water 2g
was charged into an autoclave with a rate of 100 stations per hour and heated at 190°C for 4 hours. After the reaction was completed, 20 g of water was added to the reaction solution and the reaction solution was taken out. The yield of 4-(4-hydroxyphenoxy)benzoic acid was 57%.

Example 3 4.4'-Dibrompiphenyl 15.6 g, n-)butylamine 219 g5 Conolt chloride 0.06 g s
) Riphenylphosphine 70.40g, 7x Nork 5
0 g was placed in a Zoom autoclave and reacted for 30 minutes at a carbon oxide pressure of 30 Kg/crn2 and a temperature of 150°C. As a result, the conversion rate of 4.4'-zoromubiphenyl was 1430%, and the conversion rate of 4-(4-bromphenyl) was 1430%.
The selectivity for benzoic acid phenyl ester was 89%.

4-(4-bromphenyl)benzoic acid phenyl ester was isolated in the same manner as in Example 1.

3.5 g of 4-(4-bromphenyl>benzoic acid phenyl ester, 20 g of 200 weight potassium hydroxide aqueous solution, 0.01 g of suboxide steel) were charged in an IQO*/ autoclave, and reacted at 250°C for 3 hours. Result, 4-
(4-Hydroxyphenyl)benzoic acid was obtained in a yield of 81%.

Example 4 4.4'-Short biphenyl 6.1g5) Butylamine 6.7g, Palladium chloride 0.18g,) Riphenylphosphine 0.39g, Water 12g1 Tetrahydrofuran 55g were charged in a 100*t autoclave, -carbon oxide The reaction was carried out under stirring for 10 minutes at a pressure of 25 kg/cm" and a temperature of 115°C. As a result, the conversion rate of 4,41-short biphenyl was 69%, and the selectivity of 4,4'-biphenyldicarzenic acid was 25%, and the selectivity for 4-(4-iodophenyl)benzoic acid was 70%.

4-(4-iodophenyl)benzoic acid was isolated in the same manner as in Example 1.

3.2 g of 4-(4-mortar-dofenyl)benzoic acid, ZOg of potassium hydroxide, 29 g of water 1 0.5 g of steel iodide to 10
The mixture was placed in a No. 01e autoclave and stirred at 250° C. for 6 hours to react. As a result, the yield of 4-(4-hydroxyphenyl)benzoin was 75%.

Example 5 4.4'-short diphenyl ether 42.2 g, n
-tributylamine 20.2g, nickel acetylacetonate 0.51g, )riphenylphosphine 1.57
g.

Benzyl alcohol 16.2 g 100 d (charged in D autoclave, -47 cm2 at carbon oxide pressure 30,
The reaction was carried out at a temperature of 130°C for 1 hour. As a result, 4.4'
- Conversion rate of short diphenyl ether 63%, 4-(
4-iodophenoxy) benzoin 1'! ? The selectivity of Hensyl ester was 75%.

4-(4-iodophenoxy)benzoic acid benzyl ester was isolated in the same manner as in Example 1.

4-(4-iodophenoxy)benzoin IM2 Hensyl ester 4.3g, sodium hydroxide 25g1 water 11,
0 g 1 methanol 180 g, iodized steel 0.05 g 1
00m/Put in an autoclave and heat at 150℃ for 2 hours.
The reaction mixture was stirred for hours. As a result, 4-(4-hydroxyphenoxy)benzoic acid was obtained in a yield of 60 yen.

Example 6 13.5 g of 4.4'-short biphenyl, 4.4'
- Sodium biphenyldicarzenate 19g 1 water 35g
was charged into a 100-y autoclave and reacted with stirring at a carbon oxide pressure of 100 Kf/an'' and a temperature of 250°C for 15 minutes. As a result, the conversion rate of 4,4'-short biphenyl was 48, The selectivity for -(4-iodophenyl)benzoic acid was 88%.

After cooling, carbon monoxide was removed and the product was taken out.

The product is a white solid, which is crushed and thoroughly washed with hot water, and the remaining crystals are thoroughly washed with hot chloroform to obtain 4-(4-iodophenyl)benzoic acid. Ta.

Next, 3.2 g of 4-(4-iodophenyl)benzoic acid.

Potassium hydroxide 10g, water 29g, copper iodide 0.1g,
0.2 g of iron oxide was placed in a 100 kg/cm autoclave and stirred at 240° C. for 6 hours to react. As a result, 4-(4-hydroxyphenyl)benzoin was obtained in a yield of 74 tons.

Example 7 14.1 g of 4.4'-short diphenyl ether, 13 g of tri-n-butylamine, and 35 g of water were charged into a 100 t/autoclave, and the carbon oxide pressure was 100 Kq/
cm2 and a temperature of 250°C for 20 minutes with stirring.

As a result, the conversion rate of 4.4'-short diphenyl ether was 57%, and 4-(4-iodophenoxy)
The selectivity for benzoic acid was 83.

After adding 130 v/l of tetrahydrofuran to the reaction mixture and thoroughly stirring with heating, 4-(4-iodophenox7)benzoic acid was isolated in the same manner as in Example 1. Hydrolysis of 4-(4-iodophenoxy)benzoic acid was carried out in exactly the same manner as in Example 1.

Example 8 20.3 g of 4.4'-short biphenyl, 9 g of sodium 2,6-,:,7 methyl phenol oxide, and 30 g of toluene were charged into a 100 kg/cm autoclave, and the carbon oxide pressure was set to 50 Kq/cm. The reaction was carried out for 30 minutes with stirring at a temperature of 1200°C. As a result, the conversion rate of 4.4'-short biphenyl was 69%, and 4-(4-iodophenyl)benzoate e 2.6-simethylphenyl Ester selectivity was 78%.

After taking out the reactants and removing toluene, 8 g of sodium hydroxide, 40 g of water, 0.5 g of steel iodide, and 0.5 g of sodium peroxide were charged into a 200 kg/cm autoclave.
The mixture was stirred and heated at 220° C. for 5 hours. As a result, 4-(4-
Hydroxyphenyl)benzoic acid was obtained in a yield of 75 g.

Claims (2)

[Claims] (1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼A compound represented by (X is bromine or iodine, n is 0 or 1) is reacted with carbon monoxide in the presence of a basic substance, and the general formula▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (X is bromine or iodine, n is 0 or 1, R is hydrogen or an alkyl group or aromatic group), and then hydrolyzed in the presence of a basic substance to obtain the ▲ formula , chemical formula, table, etc. ▼ Method for producing aromatic hydroxycarboxylic acid represented by (n is 0 or 1) (2) The method according to claim 1, wherein X is iodine, and the reaction with carbon monoxide in the presence of a basic substance is carried out without using a catalyst.