JPS62242648A - Production of aromatic carboxylic acid aryl ester - Google Patents

Abstract

PURPOSE:To obtain the titled compound economically in high yield and in high selectivity without requiring processes for separating and recovering a catalyst after reaction, by reacting an aromatic iodine compound with carbon monoxide and an alkali metallic salt of an aromatic hydroxy compound in the absence of a catalyst. CONSTITUTION:An aromatic iodine compound is reacted with carbon monoxide and an alkali metallic salt (preferably sodium salt or potassium salt) of an aromatic hydroxy compound in an amount to give 0.5-2.0 equivalents, more preferably 0.8-1.5 equivalent based on the alkali metallic atom of iodine atom in a solvent such as hexane, etc., usually at 50-350 deg.C, preferably 100-300 deg.C at 1-500kg/cm<2>, preferably 5-300kg/cm<2> to give the aimed compound. A compound obtained by replacing one or more hydrogens of aromatic ring of an aromatic hydrocarbon such as benzene, etc., with one or more iodines may be cited as the aromatic iodine compound.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing aromatic carboxylic acid aryl ester t-.

(Prior art) Aromatic halide and carbon monoxide are reacted with a hydroxyl group-containing substance such as water or alcohol.

The synthesis of the corresponding aromatic carboxylic acids and esters is well known. However, in these methods reported so far.

All catalysts containing transition metals are used as essential components. For example, methods using nickel catalysts include Japanese Patent Publication No. 27-2424, Japanese Patent Publication No. 11016-1972, U8P2,565,461. 2.565,46
2. 2,565,465. 2,565,464.

2,640,071. 2,691,670. Same 2,
773,090゜Bulletin of the Chemical Society of Japan (Bull, Chem,
Soc, Japan) Volume 42, Page 1124 (19
69), Vol. 45, p. 569 (1970), Vol. 44,
508 pages (1971).

Journal of Organometallic Chemistry
Allic Chemistry) Volume 51, Page 381 (1975), Journal of the American Chemical Society (J, Amer, Chem, So
c, ) Vol. 91, p. 1255 (1969).1 For example, methods using palladium catalysts include JP-A-49-40339 and JP-A-51-15701.
Publication No. 56-61) 22, % Publication No. 1987-61)
91955, Japanese Patent Application Laid-Open No. 59-29641, U
SP2.636,082. 3,988,558. The·
journal.

of Organic Chemistry (J, Org.

Chem, ) vol. 59, p. 551B (197431 vol. 40, 532 Sada (1975), Pretan of the
Chemical Society Op Japan (Bull,
Chem, Soc, Japan) Volume 48, 207
5 (1975), p. 2091 (1975), Journal of the Chemical Society of Japan, 1974, 1) p. 86.1 For example, as a method using a cobalt catalyst, the Journal of Organic Chemistry (J, Org. , Ch.
Em,) Volume 48, Page 1166 (t983).

Journal of Organometallic Chemistry
tallic Chemistry) Volume 105,
022 pages (1976), etc. are known.

Therefore, when carrying out the reaction using these methods, a troublesome step of separating and recovering the catalyst components is required.

Also, except for Japanese Patent Application Laid-Open No. 59-29641.

In contrast to the above method, there is only a description of aromatic carboxylic acid alkyl esters, and there is no description of the synthesis of aromatic carboxylic acid aryl esters.

b6 was proposed in Japanese Patent Application Laid-open No. 59-29641.
The method involves using substituted or unsubstituted bromobenzene and iodobenzene, the substituted partner being an unsubstituted phenol, and -
This is a method for producing benzoic acid phenyl ester by reacting carbon oxide with a platinum group catalyst in the presence of a base, but a platinum group catalyst having an IWI value must be used.

(Problems to be Solved by the Invention) As mentioned above, in the conventional method, a catalyst must be used as an essential component, and the catalyst component must be separated after one reaction.
A cumbersome recovery process was required, and expensive catalysts had to be used.

(Next means to solve the problem) Therefore, the inventors of the present invention have conducted extensive research into a method for producing aromatic carboxylic acid aryl esters more cheaply and more easily, and have found the following surprising results. In this method, the desired aromatic carboxylic acid can be produced in high yield and with high selectivity without using such metal catalysts at all by using different raw materials and anti-3 forms from those in JP-A No. 59-29641. The present inventors discovered that aryl ester t'' could be produced and completed the present invention.

Specifically, the present invention is a method for producing an aromatic carboxylic acid aryl ester, which is characterized by reacting an aromatic iodine compound with carbon monoxide and an alkali metal salt of an aromatic hydroxy compound in the absence of a catalyst. .

The method of the invention is applicable to the reaction of aromatic monoiodites with alkali metal salts of aromatic monohydroxy compounds.
For example, the method of the present invention is based on the following reaction formula (1) (In the formula, Ar and Ar' represent an aromatic group, and 1M represents an alkali metal atom.) ), only alkali metal iodides are produced as by-products.

It is also very easy to separate the desired aromatic carboxylic acid aryl ester because it does not contain any other catalyst components and the by-product is a simple salt of an inorganic substance. This is a feature of the present invention. For example, if the reaction is carried out in an organic medium that hardly dissolves the alkali metal iodide, the organic solution of the aromatic carboxylic acid aryl ester and the solid alkali metal iodide will be formed after one reaction.

Alkali metal iodides can be easily separated by filtration;
The ester compound in the organic solution can be easily obtained in high purity by distilling off the organic medium. Through a carbonylation reaction system that combines an aromatic iodine compound and an alkali metal salt of an aromatic hydroxyl compound,
The fact that aromatic carboxylic acid aryl esters can be produced without a catalyst, which has been completely unknown until now, in good yield and high selectivity is a great advantage.

What is the aromatic iodine compound used in the present invention?

If it is a compound in which iodine is directly bonded to the aromatic ring.

It can be anything. Examples of such aromatic iodine compounds include benzene and toluene.

xylene, ethylbenzene, diethylbenzene.

Sub-colored compounds in which hydrogen in the aromatic ring of aromatic hydrocarbons such as propylbenzene, cumene, trimethylbenzene, tetramethylbenzene, naphthalene, and anthra7ane are replaced by one or more iodine; Compounds in which hydrogen in the aromatic ring of a teloaromatic compound is replaced by one or more iodine; formula [where A is a simple bond, or -o-, -s-].

-8O,-, -CO-, -CH,-, -C(R)! −(
R represents a divalent group such as a lower alkyl group. Examples include compounds in which the hydrogen in the aromatic ring of an aromatic hydrocarbon shown in ] is substituted with 11 or more iodines. Also, other substituents that do not adversely affect one reaction in these aromatic iodine compounds.

For example, halogen atoms other than iodine, lower alkyl i,
i-class alkoxy group, ester group, nitro group.

It may be substituted with a substituent such as an acyl group, 70yl group, carboxyl group, cyano group, or amide group.

In the present invention, the alkali metal salt of an aromatic hydroxy compound used is a compound in which the hydrogen atom of the hydroxyl group of the aromatic hydroxy compound is substituted with an alkali metal atom. Such a compound may be obtained by any method; for example, it can be easily obtained from a basic substance containing an alkali metal atom and an aromatic hydroxy compound. Examples of basic substances containing alkali metal atoms include alkali metals, alkali metal oxides, alkali metal hydroxides, alkali metal carbonates, and alkali metal bicarbonates.

Among others, aromatic hydroxy compounds and lithium hydroxide,
The easiest method is a reaction with an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, rubidium hydroxide, or cesium hydroxide.

As such aromatic hydroxylated products.

Any type of aromatic group may be used as long as it has a hydroxyl group directly bonded to the aromatic group. For example, phenol; cresol (each isomer),
J1 form), trimethylphenol (each isomer), tetramethylphenol (each isomer), ethylphenol (each isomer), propylphenol (each isomer), and other alkylphenols; anisole (each isomer), Various alkoxyphenols such as ethoxyphenol (each isomer); formula (however, one person is as above, the aromatic ring is lower
may be substituted with a substituent such as a low d alkoxy group, an ester group, a nitro group, or a cyano group. ) Each plant-substituted phenol represented by; naphthol (each isomer) and each dan-substituted naphthol; Aromatic hydroxyl compounds; Aromatic dihydroxy compounds such as hydroquinone, resorcinol, catechol, naphthoquinone, anthraquinone, and their alkyl-substituted dihydroxy compounds; 'F
It may be substituted with a substituent such as an alkyl group, a lower alkoxy group, an ester group, a nitro group, or a cyano group. ) aromatic dihydroxy compounds shown in the following.

Particularly preferred alkali metal salts of aromatic hydroxy compounds are alkali metal salts of phenol and 2,6-dimethylphenol, and particularly preferred alkali metal species include sodium and potassium.

Carbon monoxide may be pure carbon oxide or nitrogen.

It may be diluted with other gases such as argon, helium, lower hydrocarbons, etc., which do not adversely affect the reaction. - Carbon oxide is used at a partial pressure of 0.1 to 300 kf/d, preferably 1 to 200 kf/d.

In carrying out the present invention, the molar ratio of the aromatic iodine compound to the alkali metal salt of the aromatic hydroxy compound is not particularly limited, but preferably the iodine atom is 0.00% to the alkali metal atom. The amount ranges from 5 to 2.0 equivalents, preferably from 0.8 to 1.5 equivalents.

Although the method of the present invention can be carried out without using a reaction solvent, it is preferable to use a solvent that does not adversely affect the reaction. Examples of such a medium include hexane.

8' such as heptane, octane, decane, pentadecane, etc.
tl Rib group hydrocarbons Alicyclic hydrocarbons such as dichlorohexane and methylcyclohexane; benzene.

Aromatic hydrocarbons such as toluene, xylene and mesitylene; Nitriles such as acetonitrile and benzonitrile; Sulfolane and methylsulfolane.

Sulfones such as dimethylsulfolane; ethers such as tetrahydro7rane, l 1,4-dioxane, and 1,2-dimethoxyethane; ketones such as acetone and methyl ethyl keto7; esters such as ethyl acetate and ethyl benzoate; N , N-dimethylformamide, N, N-
Examples include ε-ads such as dimethylacetamide, IN-methylpyrrolidone, and hexamethylphosphoramide.

The reaction of the present invention is 1 usually 50 to 5 soC1 preferably 10
In the range of 0 to 500C, 1-reaction pressure is usually 1 to 50C.
0 kg/d, preferably in the range of 5 to 300 to 9/7.

The duration of IL reaction for 6 hours varies depending on the catalyst system used, the 'a' and amounts of raw materials, and other reaction conditions such as temperature and pressure, but is usually from several minutes to several tens of hours.

As for the anti-16 method, any one of the single-dose method, continuous method, and combinations thereof can be adopted from 4.

(Effects of the Invention) By the method of the present invention, from an aromatic iodine compound, carbon monoxide, and an alkali metal salt of an aromatic hydroxy compound,
This resulted in the production of aromatic carboxylic acid aryl esters in high yield and high selectivity.

(Example) The present invention will be further explained below with reference to Examples.

The present invention is not limited to these examples.

Example 1 Iodobenzene 50 mmot, sodium phenoxide obtained by reacting phenol and atO sodium hydroxide in a water bath rinse, dehydrating and drying 0 mmoj
) Put 30P of luene into an autoclave, replace the inside of the autoclave with carbon monoxide, and then press-inject carbon oxide at 50 kg/d. 2 at 20 G'C under stirring
After reacting for an hour, the reaction mixture was cooled and filtered.
Analysis of the liquid revealed that the iodobenzene reaction rate was 95%.
So, benzoin 11! It was found that phenyl ester was obtained with a yield of 95s1 and a selectivity of 99.8%. F slag is sodium iodide and unreacted sodium phenoxide.

Example 2 Parafluoroiodobenzene, potassium hydroxide in an amount equivalent to phenol were stirred in an aqueous solution for 46 minutes, then dehydrated and dried. Potassium phenoxide and toluene were placed in an autoclave. , the reaction is carried out in the same manner as in Example 1. When the potassium iodide was removed by bubbling the reaction mixture, a mostly colorless and transparent toluene solution was obtained. The results of analyzing this solution.

The reaction rate of parafluoroiodobenzene was 100%, and the yield of parafluoroamne J and aromatic acid phenyl ester was 99.
9% and a selectivity of 99.9%.

When toluene is distilled off from this solution, white crystals 10
．． 78 t was obtained friend.

Example 3 The reaction was carried out in the same manner as in Example 2 except that sodium phenoxide was used instead of potassium phenoxide. As a result, the reaction rate of rosefluoroiodobenzene was 100%, and the reaction rate of rosefluoroiodobenzene was 100%, and the reaction rate of rosefluoroiodobenzene was 100%. It was found that the yield was 99.8% and the selectivity was 99.8%.

Comparative Example: Rose fluorobromobenzene was used instead of rose fluoroiodobenzene, and the reaction temperature was 250C.
The reaction was carried out in the same manner as in Example 2, except that the reaction did not proceed at all, and almost all of the parafluorobrombenzene was recovered.

Example 4 Parachloroiodobenzene s instead of iodobenzene
The reaction was carried out in the same manner as in Example 1 using o mmot. As a result, the anti-16 & of parachloroiodobenzene was 1
Parachlorobenzoic acid phenyl ester was obtained with a yield of 95% and a selectivity of 95%.

Example 5 Balaiodotoluene 50 mm instead of iodobenzene
The same reaction as in Example 1 was carried out using 7 oL, and the result was 1 o of balayodotoluene.

In this case, the yield of rose methyl female zoic acid phenyl ester was 9B.
qb, was obtained with a selectivity of 98%.

Example 6 4.4'-Short diphenyl ether 25mmotS
Sodium phenoxide 0mmot, toluene 30t
(Put it in an autoclave, replace the inside of the autoclave with carbon monoxide, and then - carbon oxide t-50 with 9/CI
/1 was press-fitted. After reacting at 200C for 2 hours under stirring, the reaction mixture was filtered, and the F solution was analyzed.The following results showed that diphenylnyf-4,4'-dicarboxylic acid diphenyl ester was obtained in a yield of 921%. .

Next, I found out that the selection rate was 97.

Example 7 Lithium phenoxide obtained from lithium hydroxide and phenol instead of potassium phenoxide 0 mmo
The reaction was carried out in the same manner as in Example 2, except that L was used, and as a result, parafluorobenzoic acid phenyl ester was obtained in a yield of 99.5% and a selectivity of 99.5%.

Example 8 Sodium-2,6-dimethylphenoxide 6 obtained by reacting 2,6-dimethylphenol and an equivalent amount of sodium hydroxide in an aqueous solution instead of potassium phenoxide
The reaction was carried out in the same manner as in Example 2 except that 0 mmoA was used.
2,6-dimethylphenyl ester yield 99.2%1
Friend obtained with 499.2% selection.

Example 9 Anti-IEHT was carried out in the same manner as in Example 1, except that sodium β-naphthoxide was used in place of sodium phenoxide.
The naphthyl ester yield was 96% and the selectivity was 98%.

Example 10 The reaction was carried out in the same manner as in Example 5, except that 50 mmol of K2-fluoro-6-iodonaphthalene was used instead of rosefluoroiodobenzene.
-Fluoronaphthalene-6-carboxylic acid phenyl ester was obtained with a yield of 90% in 1 selected 92 samples.

Claims (2)

[Claims] (1) A method for producing an aromatic carboxylic acid aryl ester, which comprises reacting an aromatic iodine compound with carbon monoxide and an alkali metal salt of an aromatic hydroxy compound in the absence of a catalyst. (2) The method according to claim 1, wherein the alkali metal salt of the aromatic hydroxy compound is a sodium salt or/and a potassium salt.