JPS6396151A - Production of aromatic alkoxycarboxylic acid - Google Patents

Abstract

PURPOSE:To readily obtain the titled substance from an inexpensive raw material in high yield, by reacting a dihalogenated compound with CO in the presence of a basic substance to form a monocarbonyl compound and subjecting the resultant monocarbonyl compound to alcoholysis in the presence of a basic substance. CONSTITUTION:A compound expressed by formula I (X is I or Br; n is 0 or 1) is reacted with CO in the presence of a basic substance (in an amount of 0.4-3 equivalents based on the compound expressed by formula I) at 100-250 deg.C in the case of a transition metal catalyst used or 180-400 deg.C without using the catalyst under 1-200kg/cm<2> partial pressure of CO to provide a compound expressed by formula II (R is H, alkyl or aromatic group), which is then subjected to alcoholysis in the presence of a basic substance, e.g. Na alcoholate, and a catalyst (copper or iron based catalyst) in an alcoholic solution at 100-300 deg.C to afford the aimed compound expressed by formula III (R' is alkyl or aromatic group). The resultant compound is used as a raw material for liquid crystal compounds or organic synthetic intermediates.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel method for producing aromatic alkoxycardanic acid. Among these target compounds, for example, 4
- (4-rl-butoxyphenyl)benzoic acid is a typical raw material for liquid crystal compounds, and other compounds are also extremely important as intermediates for organic synthesis.

(Prior Art) Conventionally known industrial production methods include, for example, rGray, G, W; Hartley, J, B;
on@s, B, J, Chem, Sac, 1955.14
There is a 12J method. That is, 4-hydroxybiphenyl was converted to 4-methoxybiphenyl with methyl sulfate in a 1.5N sodium hydroxide solution, and diCm-formed RP.
to 4-acetyl-4'-methoxybiphenyl in the presence of dioxane solvent, to 4-(4-methoxyphenyl)benzoic acid with sodium ibobromide in dioxane solvent, and then to 4-(4-methoxyphenyl)benzoic acid in the presence of hydrogen oxide in acetic acid. (4-Hydroxyphenyl)benzoic acid [KL is then reacted with n-butyl bromide in the presence of potassium hydroxide in a mixed solvent of ethanol and water to give 4-(4-n-butylphenyl)benzoic acid. This is the method.

For other compounds, few industrially valuable production methods have been proposed. In any case, output f:
The raw materials are difficult to obtain industrially, and the reaction process is long.
This cannot be said to be an industrially preferable method, and the development of an industrially viable manufacturing method is desired.

(Means and effects for solving the problem) The present inventors
As a result of extensive research from the above viewpoint, we have found that using dibrominated or diiodinated biphenyls or diphenyl ethers, which can be easily synthesized from inexpensive biphenyl or diphenyl ethers, monocarginylation with -carbon oxide produces two halogen groups in biphenyl or diphenyl ethers. By converting one of these into carginic acid or its ester, and then hydrolyzing and replacing the remaining halogen group with an alkoxy group, aromatic alkoxycarmenic acid can be easily prepared in high yield using only inexpensive raw materials. I found that it is possible to obtain The present invention is based on the above knowledge, and is represented by the following general formula (1)
A halogenated compound represented by is reacted with carbon monoxide in the presence of a basic substance to obtain a monocargnyl compound represented by the general formula (2), and then alcoholyzed in the presence of a basic substance to obtain a general A method for producing an aromatic alkoxycarzenic acid represented by formula (3).

Brominated or iodinated biphenyls or diphenyl ethers R used as raw materials of the present invention, examples tR14,4'-dibromubiphenyl, 4,4'-dibromubiphenyl ether, 4,4'-short biphenyl, 4°4'
-Short diphenyl ether, etc., and can be obtained by inoculation.

Iodinated biphenyl or diphenyl ether can be easily obtained by oxidatively iodizing biphenyl or diphenyl ether.

There are methods such as beating, iodination in the presence of nitric acid, or iodination in the presence of acid and hydrogen peroxide or oxygen. Further, brominated biphenyl or diphenyl ether can be easily obtained by reacting biphenyl or diphenyl 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 carbonylation reaction of 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 can proceed satisfactorily even without a catalyst if the reaction conditions are selected. In that sense, it can be said that it is preferable to use iodide as the starting material.

Transition metals used in reactions with catalyst threads include:
Generally, those active in carbonylation reactions are used;
■Group transition metals, such as palladium, platinum, nickel,
Examples include conomalt, iron, manganese, etc., but from the viewpoint of yield, palladium, nickel, cobalt, and iron are preferably used. These transition metals themselves can be used, or their halides, sulfates, nitrates, organic acid salts, etc. can be used. However, these transition metal compounds can also be used as complexes of carbon oxide, triphenylphosphine, and the like. The amount of transition metal compound used is 0.0 of the iodinated diphenyl or brominated diphenyl to be reacted.
It is sufficient if it is 1 to 10 moles.

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. Examples include class ammonium, alcolades of alkali metals and alkaline earth metals, hydroxides of alkali metals and alkaline earth metals, alkali metal carbonates, salts of aromatic or aliphatic carmenic acids and alkali metals or alkaline earth metals, etc. It will be done. Preferably aliphatic amines, quaternary ammonium hydroxides, alkali metal hydroxides,
Alkali metal salts of alkali metal carbonate products can be used. The amount used is not particularly limited, but preferably the base is 0 for aromatic compounds.
．． 2 to 10 equivalents, more preferably 1 L < tri 0.4
~3 equivalents.

If the carbonylation reaction is carried out in the presence of water, the corresponding carboxylic acid will be produced, and if carried out in the presence of alcohol, the corresponding carboxylic acid ester will be produced.

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

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 dimethylshyl-dr-cyto, and ethers such as dioxane. 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 172 equivalents based on iodinated diphenyl or brominated diphenyl. Of course, there is no problem in using a large amount as a solvent. When used as a solvent thread containing water, it is necessary to use the same amount as when using water alone, and mixing with other solvent systems has the effect of making the reaction system uniform. You can expect it.

When the reaction is carried out in the presence of an alcohol, the alcohol used can be selected depending on the desired ester. For example, aliphatic alcohols include methanol, ethanol, propatool, imbutanol, octatool, etc., and aromatic alcohols include phenol, benzyl alcohol, phenylphenol, phenoxyphenol, alkyl-substituted phenol, naphthol, etc. . Moreover, the alcohol does not necessarily have to be a monohydric alcohol.

The carbon monoxide used in the carbonylation reaction may be pure carbon oxide, or may be diluted with other gases that do not adversely affect the reaction, such as nitrogen, argon, helium, or lower hydrocarbons. -Carbon oxide has a partial pressure of 0.1 to 3
00KP/CI/l, preferably 1 to 200 to 7/c1
Used in the range d. 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 carbonylation 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 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 ℃ or higher and 400℃ or lower. At temperatures as low as 150°C, the reaction rate is slow and impractical;
At temperatures above 0°C, side reactions increase and the yield of the desired aromatic carboxylic acid decreases.

If the carbonylation reaction is allowed to run uncontrolled until completion, both of the two halogen substituents of the biphenyl or diphenyl ether will be carbonylated. Therefore, it is necessary to control the reaction midway. That is, in order to advantageously obtain a monocar-J-nylated product, it is necessary to stop the reaction midway through, and it is preferable to suppress the conversion rate of the dino-loginated raw material to 90% or less. More preferably 7
The goal is to keep it below 0.

The product after the cal-737nylation reaction can be easily separated by recrystallization.

Next, the advantages of reacting diiodides in a non-catalytic system will be described. For example, when obtaining carmenic 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 produced as a base, the following reaction formula (1) I am forced to die.

ArI +CO+H2O+ArCOOM-→2ArCO
OH+MI (1) (In the formula, 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 has no aromatic properties. Since group carboxylic acids are generally solid and not easily soluble in water, the salt of hydrogen iodide and base is removed by washing the reaction product 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 diffusion solution, the aromatic carboxylic acid can be solidified. It is easy to separate as

%l, t is aromatic when obtaining a carboxylic acid aryl ester. ! An example of the reaction between a : group monoiodite and an alkali metal salt of an aromatic monohydroxy compound is represented by the following reaction formula.

ArI+CO+Ar'OM →A r -C-0-A r' + M 1 (in the formula,
Ar and Ar' represent an aromatic group, and K1 represents an alkali metal atom. ) In this case as well, only alkali metal iodide is produced as a by-product. Since no other catalyst components are present 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 alcoholysis reaction of the present invention will be explained.

This is possible by reaction under pressure at a temperature of 100 to 300° C. in an alcoholic solution containing an alcoholade or hydroxide of a metal or an alkaline earth metal.

As a hydrolysis catalyst, Cub, C+gO1Curl
, CuCl2, CuBr, CuBr2, Cu (
CH3Coo) 2, Cu (CH3Coo), Cu
t, CuF, CuF2ll2H10,Cu(O
H) 1, Fe01Fs (OH1z, Fe 203, F
eCl2, F, eI2, Fe (CHsCOO]z, etc., each alone or in a mixture, for example, Cu
Mixtures of O and Cuz O can be used. The amount used is 0.1 to 100 mol, preferably 0.5 to 30 mol, based on the raw material.

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

As the alkali metal alcoholade used as the basic substance, sodium and potassium alcoholades are used.

Examples of alkali metal or alkaline earth metal hydroxides include NaOH, KOH, Ca(OH)z, Mg(
0)()2 etc. are used, preferably NaOH and K
OH, 1.0 to 1 based on the halogen atom of the starting material
Use 0.0 equivalent. NaOH, KOH, etc. can be used as an alcohol bath.Although the bath can be used as an aqueous solution,
H)z, Mg(OH)z, etc. are dissolvable in water, @
It can be used as a suspension. Of course, these can be used alone or as a mixture.

As the solvent, alcohol as a reactant is generally used, but it is of course possible to use other solvents. For example, aliphatic hydrocarbons such as hexane and octane, aromatic hydrocarbons such as benzene and toluene,
Ethers such as tetrahydrofuran and 1,4-dioxane, acetate/ketones such as methyl ethyl ketone, and dimethyl sulfoxide are used.

The alcohols used are methanol, ethanol, n
-butanol, imbutanol, n-amyl alcohol, n-hexanol, n-octatool, 2-ethylhexanol, n-nonane 4-l, ny'canol,
Aliphatic alcohols such as n-dodecanol, phenol,
There are aromatic alcohols such as 2,6-xylenol, benzyl alcohol, and phenoxyphenol.

Example C) 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 6.339, tributylamine 6.66, li+, palladium chloride o,
isy.

0.39 jq of triphenylphosphine, 12 I of water, and 551 ml of tetrahydrofuran were placed in a 100 ml stainless steel autoclave equipped with a stirrer, and the inside of the autoclave was replaced with carbon monoxide.
aA was press-fitted. The reaction mixture was stirred at 125° C. for 12 minutes 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
At 2%, the selectivity for 4-(4-iodophenoxy]benzoic acid was 65 or more, and the selectivity for 1,1'-short diphenyl ether-4,4'-dicarboxylic acid was 30%.

The reaction solution was filtered under reduced pressure to remove solid matter in the reaction solution, and then some of the tetrahydrofuran was distilled off and concentrated to about 4 times, whereby 4,41-short diphenyl ether as a raw material was precipitated. This was filtered, and the filtrate was distilled off until almost all tetrahydrofuran was removed, and crystals were precipitated. This precipitate is 4 times the weight of 10]ii% hydroxide) IJ
When the mixture was stirred thoroughly, 4-(4-iodophenoxy)benzoic acid remained undissolved. Filter this and 4-
(4-iodophenoxy)benzoic acid was isolated.

3.4 g of 4-(4-iodophenoxy)benzoic acid, 411 g of sodium hydroxide, 20 g of n-butanol, and steel iodide o, osg were placed in a stainless steel autoclave of 1 ootRt and stirred at 150° C. for 5 hours.

After the reaction was completed, the reaction solution was analyzed by liquid chromatography, and the yield of 4-(4-!l-butoxyphenoxy)benzoic acid was 55%.

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 of dicarboxylic acid was 12.

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

4-(4-iodophenoxy)benzoic acid 3.4y, sodium hydroxide 1.5g, copper powder 0.1. ! i+, 0.19 cuprous iodide, and 20 g of phenol were placed in a 100- autoclave and reacted by heating and stirring at 200° C. for 7 hours. The yield of 4-(4-phenoxy)benzoic acid is 72es
Met.

Example 3 4.4'-dipro-containing biphenyl 15.6,9,n-)liptylamine 13. L9. Con/chloride 0.06ji
, ) rifene dilphosphine 0.40. p, phenol so, v'6100- in an autoclave, -
The reaction was carried out at a carbon oxide pressure of aoKy/d and a temperature of 150° C. for 300 minutes. As a result, the Eft of 4,4'-brompiphenyl.

The selectivity of 4-(4-bromphenyl)benzoic acid phenyl ester was 89.

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

4-(4-bromphenyl) f son fl phenyl xx chill 3. s fis metallic potassium29. n-amyl alcohol: 20p, suboxide steel 0.01.9 to 100
- and reacted at 150°C for 6 hours. As a result, 4-(4-n-amylphenyl)benzoic acid was obtained with a yield of 40%.

Example 4 4.4'-Short biphenyl 6.1 g, triptylamine 6.7 g, palladium chloride 0.18 g, 10 at carbon pressure 2sKy/cj and temperature 115℃
The reaction was allowed to proceed for minutes with stirring. As a result, the conversion rate of 4.4'-short biphenyl was 69 points, the selectivity of 4.4'-biphenyl dicarboxylic acid was 254 points, and the selectivity of 4-(4-iodophenyl)benzoic acid was 70 points. Met.

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

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

Potassium hydroxide 2-0. ! 1ISn-Octatool 30
I.

Copper iodide o, 5,! 9 was placed in a 100Md autoclave and stirred at 200°C for 6 hours to react. As a result, the yield of 4-(4-n-octoxyphenyl)benzoic acid was 41%.

Example 5 4.4'-Short diphenyl ether 42.2. ! ?
, n-tributylamine 20.29. Nickel acetylacetonate 0.51. ! l;', triphenylphosphine 1.57y, benzyl alcohol 16.2!9
was placed in a 100-degree autoclave and reacted for 1 hour at a carbon oxide pressure of 30 Kp/c1A and a temperature of 130°C. As a result, the conversion rate of 4°4/-short diphenyl ether was 63%.

The selectivity for 4-(4-iodophenoxy)benzoic acid benzyl ester was 75 scratches.

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

4-(4-iodophenoxy)benzoic acid benzyl ester 4.3. @1 Sodium hydroxide 2.5g, n-hex/- 20g, Ei uride tno, os, ywo 100
The mixture was charged into a Go autoclave and stirred at a temperature of 200° C. for 6 hours to react. As a result, 4-(4-n-hexanoxyphenoxy)benzoic acid was obtained with a yield of 50%.

Example 6 4.4'-Short biphenyl 13.59.4.4'-
Sodium biphenyl cardate 19/! , Water 35E
The mixture was charged into a 100-degree autoclave and reacted with stirring at a carbon oxide pressure of 100 K9/d and a temperature of 250 DEG C. for 15 minutes. As a result, the conversion rate of 4,4'-jotobi7enyl was 489, and the selectivity of 4-(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.
C washing to obtain 4-(4-iodophenyl)benzoic acid.

Next, 4-(4-iodophenyl)benzoic acid 3.2 g 1 potassium 2.0. lit, n-nonanol, copper iodide 0
．． 1,9. 0.15 g of iron oxide was placed in a 100-liter autoclave, and the mixture was stirred at 220° C. for 6 hours to react.

As a result, 4-(4-n-nonatukidiphenyl)benzoic acid was obtained with a yield of 47%.

Example 7 4.4'-Short diphenyl ether 14. L9.
tri-n-butylamine 13,9. water 359 to 100
The mixture was charged into an autoclave, and reacted with stirring at a carbon oxide pressure of Zoos/d and a temperature of 250° C. for 20 minutes. As a result, the conversion rate of 4.4'-short diphenyl ether was 57%, 4-(4-iodophenoxy)
The selectivity for benzoic acid was 83%.

After adding 130 mj of tetrahydrofuran to the reaction mixture and thoroughly stirring with heating, 4-(4-iodophenoxy)benzoic acid was isolated in the same manner as in Example 1.

4-(4-Iodophenoxy)benzoic acid 3.4.9.

Sodium methylate 2g, methanol 25. il,
Put 0.5g of iodized steel into a 100m autoclave,
The mixture was stirred and reacted at 150° C. for 8 hours. As a result, 4-
(4-Methoxyphenoxy)benzoic acid was obtained with a yield of 46%.

Example 8 4.4I-short biphenyl 20.3,9. Sodium-2,6-dimethylphenoxy) 19g, toluene 3
0.9 for 100r! Pour into Lt autoclave, -
The carbon oxide pressure was set to 501'-p,/j, and the temperature was 200°C.
The mixture was reacted for 30 minutes with stirring. As a result, the conversion rate of 4.4'-short biphenyl was 69 scratches, and 4-(4-
The selectivity of benzoic a,2,6-cymethy#phenyl ester was 78. ``After taking out the reactants and removing toluene, 8 g of potassium, n-decanol, 0, s g of copper iodide, 0 g of sodium peroxide.
．． Put 5g into a 200-℃ autoclave and heat at 220℃.
The mixture was stirred and heated for 5 hours.

As a result, +-(4-hydroxyphenyl)benzoic acid was obtained in a yield of 40 tons.

Claims (2)

[Claims] (1) A dihalogenated compound represented by the following general formula (1) is reacted with carbon monoxide in the presence of a basic substance to obtain a monocarbonyl compound represented by the general formula (2), and then in the presence of a basic substance The general formula (
3) Method for producing aromatic alkoxycarboxylic acid represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼…………(1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼…………(2) However, X is bromine or iodine, R is hydrogen, an alkyl group or an aromatic group, R' is an alkyl group or an aromatic group, and 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.