JPS6112649A - Preparation of aromatic carboxylic acid ester - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as a raw material for polyamide in good yield, by reacting a halogenated diphenyl ether derivative with carbon monoxide, base and alcohol in the presence of a catalyst containing a transition metal compound. CONSTITUTION:A compound (example; 4,4'-dichlorodiphenyl ether) expressed by formula I (X is halogen atom) is reacted with carbon monoxide in the alcohol solvent in the presence of a catalyst containing a transition metal in the presence of a base such as alkylamine at room temperature - 300 deg.C, preferably 80-200 deg.C to obtain the aimed compound expressed by formula II. The catalyst contains 1 or >=2 species selected from transition metals, salts and complexes thereof, preferably both a salt of nickel, palladium or cobalt and an organic phosphine, an organic phosphite or pyridine.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel method for producing aromatic carboxylic acid esters having the following.

The aromatic carboxylic acid ester obtained by the present invention is
It is a compound useful as a raw material for polyamide. In particular, the polyamide using the aromatic dicarboxylic acid having an ether bond according to the present invention is extremely tough and highly flexible, and exhibits excellent properties in fibers, films, and shaped products.

(Prior art) Aromatic carboxylic acid or ester of the present invention "R000"
The conventionally known manufacturing method for ゛()-〇(P0001 is ``te)-L(ri''), in which Br is reacted with copper cyanide to form dinitrile, and [Bu Il.

Soc, Chim, France, (1966) (4
), 1285. ':1 This is hydrolyzed by a conventional method [: J, pharm, Soc.

Japan, 7044 (1950)] (Zh, o
rg.
hem, Soc, .

(1961) 16.04: ], ■ A method of reacting R, NC0 (J with diphenyl ether in the presence of anhydrous aluminum chloride and then hydrolyzing it) CZh, Org, Che
m, 3(1)46 (1967): ], etc. are known.

(Problems to be Solved by the Invention) The conventional production techniques described above have drawbacks such as using toxic cyanide, expensive reaction reagents, and long reaction steps.
Further, there are problems such as low yield and product purity.

(Means for Solving the Problems) The present inventors conducted research on a novel method for producing diphenyl ether dicarboxylic acid ester, which is completely different from the conventional production method which has the above-mentioned drawbacks.

As a result, the diphenyl ether derivative X'
We have completed the present invention by discovering that the desired product can be obtained in high yield by reacting @-o→g with carbon monoxide and alcohol in the presence of a catalyst system containing a transition metal compound. Ta.

That is, the present invention involves reacting a compound represented by the general formula "@)-/El/ゝ (X represents a halogen atom) with carbon monoxide, a base, and an alcohol in the presence of a catalyst system containing a transition metal. This is a novel synthesis method that has not been previously reported, and can be expressed as shown in equation (1).

(1) The starting materials used in the process of the present invention have the general formula = "-@-0R5
It is a compound represented by X (X represents a rogen atom), and bromine and chlorine are often used as the rogen. The substitution position of the norogen atom is 4.4-;
3,4-; or 3,3'- are often used, such as 4,41-dichlorodiphenyl ether, 4,4-cyfuromodiphenyl ether, 3,4-dichlorodiphenyl ether, 3,41-dibromodiphenyl ether, 3
．． 3-) Ri.

Roldiphenyl ether or 3,3-dibromschiffenyl ether are typical starting materials.

These compounds are synthesized by conventional methods, but for example, 4
,41-dibromidiphenyl ether is produced with good selectivity by brominating diphenyl ether in concentrated sulfuric acid.

The catalyst used in the method of the present invention is a catalyst containing a transition metal compound, that is, a catalyst containing one or more selected from a transition metal, a transition metal salt, and a transition metal complex.

As transition metals, those active in carbonylation reactions are generally used, and transition metals of groups 1 and 2, such as palladium, platinum, cobalt, iridium, manganese, rhodium,
Examples include iron.

These transition metals themselves, these inorganic acid salts
An organic acid salt or a complex thereof may be used, or it may be supported on a carrier such as carbon, organic polymer, alumina, or silica. A particularly preferred catalyst system is one in which a salt of nickel, palladium or cobalt is combined with an organic phosphine, an organic phosphite or a pyridine. At this time, organic phosphine such as triphenylphosphine is used to form a complex (if used in excess of the required amount, the catalyst becomes stable and deterioration of the catalyst is less likely to occur, making the reaction smooth and mild). Proceed with conditions.

The carbonylation reaction in the method of the present invention proceeds under normal pressure or elevated pressure of -carbon oxide, but since the reaction is extremely slow and the yield is low at normal pressure, it is usually carried out under elevated pressure. The reaction pressure used is usually in the range of 5 to 300 atmospheres.

As shown in the above formula (1), as the reaction progresses, hydrogen halide is produced as a by-product in addition to the target product. A base is added to the reaction system as an acceptor for by-produced hydrogen halide. The base to be added may be any base as long as it reacts with and neutralizes hydrogen chloride. For example, hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and lithium hydroxide, carbonates such as sodium carbonate and sodium bicarbonate, weak acid salts such as sodium acetate, alkylamines, pyridine, and quinoline. Organic amines such as For example, when a hydroxide such as potassium hydroxide is used as a base, the product is obtained in the form of a carboxylate salt after the cabonylation reaction. If an alkylamine is used as a base and alcohol is present in excess,
The product is obtained as an ester of a carboxylic acid. The alcohol used is a lower aliphatic alcohol, and methyl alcohol or ethyl alcohol is often used.

The reaction is preferably carried out at room temperature to 300°C, particularly in the range of 80 to 200°C. Usually the alcohol added acts as a solvent. Other substances besides alcohol can also be used as solvents. For example, hydrocarbons such as benzene, toluene, and xylene, or polar solvents such as N,N-dimethylformamide are used. The amount of starting materials added to the solvent is often in the range of 3 to 20 wt%. The amount of catalyst added to the solvent is 0.05 to 10 wt based on the starting material.
A range of % is suitable. The time required for the reaction is, for example, in the range of 1 to 20 hours in a batch-type reaction.

(Operations and Effects) The advantages of the present invention are that aromatic carboxylic acids or esters can be produced directly from the halide of diphenyl ether, that the reaction conditions are mild, that the reaction proceeds quickly and with good yield, and that there is no by-product of isomers. .

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

Example-1 4,4-dibromidiphenyl ether5. (lwo50-
3.59 of triethylamine, 0.19 of dichlorobis-triphenylphosphine palladium complex and 0.379 of triphenylphosphine were added thereto, and the mixture was charged into an autoclave. Carbon monoxide was pressurized into the autoclave at 20 atm, and the mixture was stirred at 110°C for 5 hours.

The product after the reaction is collected on the r side, and the liquid phase is concentrated by distilling off methanol under reduced pressure to obtain the target product, 44-(diphenyl ether).
Methyl dicarboxylate separates out as a precipitate.

and IR spectra are in good agreement with those of the standard.

Elemental analysis C-H Calculated value (%) 67.1 4.89 Analytical value (correspondence) 66.99 4.78 On the other hand, when the product was analyzed by gas chromatography, it was found that 4.4'-(diphenyl needle) -Methyl dicarboxylate is 3.99 (
Yield: 90%), and a trace amount of 4-from-41-carboxymethyl-diphenyl ether was produced.

Example-2 4,4'-syfurom diphenyl ether 5.0in'5
The solution was dissolved in 0ml of methanol, and 3.5g of triethylamine, 50ml of palladium acetate and 0.82ml of triphenylphosphine were added thereto, and the mixture was charged into an autoclave. Carbon oxide was injected into this at 15 atm and heated to 120℃ for 5
The reaction was stirred for hours.

After cooling the autoclave, the contents were analyzed.
．． Methyl 4'-(diphenyl ether)-dicarboxylate was produced in 3.79 (yield: 85).

Example-3 3.4'-dibromidiphenyl ether 5',09 to 7
The mixture was dissolved in 0-methanol, and 3 g of 0.17 dichlorbistriphenylphosphine palladium complex, triphenylphosphine o, and 1.7 g of R acid nodazole were added thereto, and the mixture was charged into an autoclave. - 20 kg of carbon oxide was introduced under pressure and reacted at 125°C for 6 hours.

Analysis of the product revealed that 3.67 methyl 3.4'-(diphenyl ether)-dicarboxylate (83 high yield) was produced.

Example-4 3,3-short diphenyl ether 6.017 and calcium hydroxide 4. Og and tetracarbonyl nickel (0) from 2.0 to 40. d in dimethyl sulfoxide, and methanol 5d was charged into the autoclave.

- Carbon oxide was introduced under pressure at 50 atm and reacted at 150°C for 5 hours. As a result of analysis of the product, 2.19 methyl 3.3'-(diphenyl ether)-dicarboxylate (yield 4
9%).

Example-5 2.2-short-diphenyl ether 6.0 g, triethylamine 3.2 g, di-cobalt octacarbonyl 068 g, 507 nI! of methanol and filled into an autoclave. - Inject carbon oxide under pressure at 100 atmospheres 2
The reaction was carried out at 00'C for 8 hours. Product analysis results 2
．． 2.0 ml of methyl 2'-(sifuenyl ether)dicarboxylate (yield 46%) was produced.

Example-6 4,4-Dichlorodiphenyl ether (59 to 50 mJ) was dissolved in methanol, 4.02 triethylamine, 0.29 dichloro-bis-triphenylphosphine palladium complex, and 0.82 triphenylphosphine were added, and the mixture was autoclaved. was filled.

Carbon monoxide was pressurized into the autoclave at 50 atmospheres, and the temperature was increased to 180
As a result of reacting for 6 hours at
Section 4) Generated.

Example-7 4,4-cyfuromodiphenyl ether5. On'5ml
of methanol and 50-N,N-dimethylformamide, to which 3 g of potassium acetate and 0.02 g of dichlorbistriphenylphosphine para') rum complex L
o, o5q of triphenylphosphine were added and the autoclave was filled. Carbon monoxide was injected into the autoclave at 20 atm, stirred at 115°C for 6 hours, cooled, and the contents were taken out and analyzed. As a result, methyl 4.4-(diphenyl ether)-dicarboxylate was found to be 3.77 (yield: 85%).
generated.

Claims (1)

[Claims] 1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (X is
There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ which are characterized by the reaction of a compound represented by (representing a halogen atom) with carbon monoxide, a base and an alcohol in the presence of a catalyst system containing a transition metal compound. A method for producing an aromatic carboxylic acid ester represented by (R represents a lower alkyl group).